WO2013182023A1 - Carbon fiber surface modifier, modified carbon fiber, composite material and preparation methods therefor - Google Patents
Carbon fiber surface modifier, modified carbon fiber, composite material and preparation methods therefor Download PDFInfo
- Publication number
- WO2013182023A1 WO2013182023A1 PCT/CN2013/076655 CN2013076655W WO2013182023A1 WO 2013182023 A1 WO2013182023 A1 WO 2013182023A1 CN 2013076655 W CN2013076655 W CN 2013076655W WO 2013182023 A1 WO2013182023 A1 WO 2013182023A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon fiber
- group
- surface modifier
- fiber surface
- hydrogen
- Prior art date
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 352
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 261
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 261
- 239000003607 modifier Substances 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 35
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 10
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 10
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 114
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 79
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- 238000006243 chemical reaction Methods 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- -1 2-ethyl-hexyloxy group Chemical group 0.000 claims description 22
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- 239000000126 substance Substances 0.000 claims description 16
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 13
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- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 125000004185 ester group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000006612 decyloxy group Chemical group 0.000 claims description 7
- 125000000468 ketone group Chemical group 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
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- 125000004429 atom Chemical group 0.000 claims description 4
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
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- HUTITODAYBWJRG-UHFFFAOYSA-N 2,3,5-trihydroxybenzaldehyde Chemical group OC1=CC(O)=C(O)C(C=O)=C1 HUTITODAYBWJRG-UHFFFAOYSA-N 0.000 claims description 2
- AGEJIFIPSQCTCL-UHFFFAOYSA-N 2-hydroxy-4,6-dipropoxybenzaldehyde Chemical group CCCOC1=CC(O)=C(C=O)C(OCCC)=C1 AGEJIFIPSQCTCL-UHFFFAOYSA-N 0.000 claims description 2
- BWHGDPKOFVNGFQ-UHFFFAOYSA-N 4-(dibutylamino)-2-hydroxybenzaldehyde Chemical group CCCCN(CCCC)C1=CC=C(C=O)C(O)=C1 BWHGDPKOFVNGFQ-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 150000003935 benzaldehydes Chemical class 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920006375 polyphtalamide Polymers 0.000 claims description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 1
- 229940080818 propionamide Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
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- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 25
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
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- DOLVFFGLNYMIPV-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=NCCCN=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O DOLVFFGLNYMIPV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
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- 238000012795 verification Methods 0.000 description 2
- 0 *C(*)(C(*)(*)NCC1=C(*)C=CC#CC1)NCc1c(*)cccc1 Chemical compound *C(*)(C(*)(*)NCC1=C(*)C=CC#CC1)NCc1c(*)cccc1 0.000 description 1
- OPCJOXGBLDJWRM-UHFFFAOYSA-N 1,2-diamino-2-methylpropane Chemical compound CC(C)(N)CN OPCJOXGBLDJWRM-UHFFFAOYSA-N 0.000 description 1
- UIOMNPYQUBMBOJ-UHFFFAOYSA-N 2-hydroxy-3,4-dimethoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(O)=C1OC UIOMNPYQUBMBOJ-UHFFFAOYSA-N 0.000 description 1
- XSDFKHGTHUPMQX-UHFFFAOYSA-N 2-hydroxy-4-octadecylbenzaldehyde Chemical compound C(CCCCCCCCCCCCCCCCC)C=1C=C(C(C=O)=CC=1)O XSDFKHGTHUPMQX-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
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- KWUHSYYEWSOMSO-UHFFFAOYSA-N CC(C)(CNCc1cc(O)cc(O)c1O)NCc1cc(O)cc(O)c1O Chemical compound CC(C)(CNCc1cc(O)cc(O)c1O)NCc1cc(O)cc(O)c1O KWUHSYYEWSOMSO-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
- C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
- C07C215/80—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring containing at least two amino groups bound to the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
- C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/20—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
- C07C219/22—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Definitions
- Carbon fiber surface modifier modified carbon fiber, composite material and preparation method thereof
- the invention relates to a modifier, in particular to a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier and a preparation method of the modified carbon fiber, and a modified carbon fiber and a resin system.
- Carbon fiber has outstanding mechanical properties, and carbon fiber is widely used in composite materials for reinforcement. In recent years, improving the interface properties between carbon fiber and matrix resin has become a research hotspot.
- the surface active carbon fiber of the carbon fiber is small, and the effective chemical bond formed when the composite is combined with the matrix resin is small, and the compatibility is poor, which results in the formation of a brittle interface layer structure in the carbon fiber composite material.
- the surface of the carbon fiber is usually oxidized in the industry to impart active oxygen-containing functional groups such as hydroxyl groups and carbonyl groups on the surface of the carbon fiber. Anodizing, nitric acid oxidation, and potassium permanganate oxidation are common. Etc.
- the technical solution adopted by the present invention is a carbon fiber surface modifier whose structural formula is as shown in formula (I):
- R 2 and R 2 ' each independently represent a hydrogen group, a hydroxyl group, or a fluorenyl group.
- the alkyl group of C r C 3 means a linear or branched fluorenyl group having 1 to 3 carbon atoms.
- R 2 , R, ' represents methyl, ethyl, propyl and hydrogen, particularly preferably methyl, ethyl and hydrogen, most preferably methyl and in formula (I),
- R 3 and R 4 are each independently of one another Represents C r C 18 fluorenyl, ⁇ alkoxy, hydroxy, amino, halogen, hydrogen, amide, ester, or siloxy, with the proviso that R 3 and R 4 are not hydrogen at the same time.
- Preferred are a hydroxyl group, an amino group, and a decyloxy group, a siloxy group, an ester group, and an amide group of dC ls .
- the alkyl group of dC 18 means a linear or branched fluorenyl group having 1 to 18 carbon atoms.
- the mercapto group and the stearyl group and the like are preferably 12 to 18, particularly preferably 14 to 18 carbon atoms. Most preferred are myristyl, octadecyl, which include both linear and branched isomers.
- the decyloxy group of C r C 18 means a linear or branched alkoxy group having 1 to 18 carbon atoms.
- the dodecyloxy group or the like is preferably 1 to 12, particularly preferably 3 to 12 carbon atoms. Most preferred are propoxy, (2-ethyl)-hexyloxy, decyloxy, which include both straight and branched isomers.
- the amino group includes -NH 2 , -NHRj, -NR X R 2 , wherein R 2 each independently represents each other
- the halogen means a fluorine, chlorine, bromine or iodine atom.
- a fluorine atom is preferred.
- the amide group has the formula -(CH 2 ) n CONH-R, and n includes an integer of from 1 to 15.
- n is taken A linear or branched chain of 1-10, and n is most preferably 2 and 3.
- R is a linear or branched fluorenyl group of C1-C18, hydrogen, preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, hydrogen, and R is most preferably a methyl group, an ethyl group or a hydrogen.
- the amide group is most preferably an acetamide group or a propionamide group.
- the ester group has the formula -(CH 2 ) n CO 2 -R, and n includes an integer of from 1 to 15. Preferably, n takes from 1 to 10 linear or branched, and n is most preferably 2.
- a linear or branched fluorenyl group wherein R is 18 preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, most preferably a methyl group and an ethyl group.
- the ester group is most preferably an ethyl acetate methyl ester or an ethyl alcohol ethyl ester.
- the siloxy group includes a siloxane derivative, and examples thereof are trimethylsiloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH 3 ) 3 , - (CH 2 ) 2 OSi (CH 3 ) 2 (CH2 ) 3 CH 3 , -(CH 2 ) 6 Si (C3 ⁇ 4) 2 0-CH 3 .
- Most preferred is -(CH 2 ) 3 Si (OCH3 ) 3 , - CCH 2 ) 2 OSi[CH 3 ) 2 C(CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 .
- the formula (I) includes hydrogen, a hydroxyl group, an amino group, a halogen, and a decyloxy group. Preferred are a hydroxyl group, a hydrogen group, and most preferably a hydroxyl group.
- R 2 , RA R 2 ' represents hydrogen and methyl; and represents tetradecyl, octadecyl, acetamido, propionamido, methyl acetate, ethanol Ethyl ester, selected propoxy, (2-ethyl)-hexyloxy, decyloxy, N,N-di-2-methoxy-ethylamino, N,N-diethylhydroxyamino, - ⁇ 2 , hydroxyl, hydrogen, fluorine, trimethylsilyloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH3 ) 3, - (CH 2 ) 2 OSi (CH 3 ) 2 C (CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 ; R 5 represents a hydroxyl group.
- the carbon fiber surface modifier of the present invention comprises a large cavity composed of 12 atoms of carbon, nitrogen, hydrogen and/or oxygen, and a plurality of amino functional groups in the cavity, including hydrogen, hydroxyl and amino groups. , halogen or decyloxy group, these functional groups and amino groups can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers, which are adsorbed on the surface of carbon fibers by chemical bonds;
- the R 3 and R 4 functional substituent groups of the modifier have good compatibility with the resin, and the resin matrix undergoes chemical reaction and physical crosslinking with the molecular chain of the resin to form a network structure under melt processing conditions.
- the appropriate modifier of the invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the invention can effectively improve the interface between the carbon fiber and the resin.
- the above R5 and the functional groups of the amino functional group and the carbon fiber surface may have various reaction mechanisms, such as mechanism 1: the surface modifier amino group is polycondensed with the ketone group on the surface of the carbon fiber to produce an enamine, so that the modifier is firmly adsorbed on the surface of the carbon fiber. .
- Mechanism 2 Surface modification agent hydroxyl group and carbon fiber surface carboxyl group undergo esterification reaction during heating and drying process, acid dehydroxy alcohol dehydrogenation, ROHOH remove -OH, ROH remove hydrogen, then RCO- and -OR are connected together to generate RCOOR allows the modifier to adhere firmly to the surface of the carbon fiber.
- Mechanism 3 The ammonia of the surface modifier undergoes a ring-opening substitution reaction with the epoxy group on the surface of the carbon fiber to form an amino alcohol. The surface modifier is firmly adsorbed on the surface of the carbon fiber.
- the surface modifier is firmly adsorbed on the surface of the carbon fiber.
- the surface modifier can chemically react with the oxygen-containing functional groups on the surface of the carbon fiber through mechanisms 1-3, and a chemical bond is formed between them to allow the surface modifier to be attached to the surface of the carbon fiber.
- a chelating base Sali-cylaldehydoethylenediamine
- Salen 0 and Salen a chelating base formed by condensation of two identical aldehyde molecules and one diamine molecule
- the imine becomes saturated.
- amino groups such compounds are referred to as Salan.
- the central position of Salen and Salan is 0, N, N, 0 4 atoms, and the large cavity is composed of 12 atoms of carbon, nitrogen, hydrogen and oxygen.
- the invention necessitates a method for preparing a carbon fiber surface modifier, comprising the following steps:
- the component A is an ethylenediamine derivative such as ethylenediamine, 1,1-dimethylethylenediamine, 1,2-dimethylethylenediamine, hydroxyethylenediamine, tetramethyl Ethylenediamine, tetraethylethylenediamine; can be obtained by known conventional experimental methods and commercially available.
- the carbon fiber surface modifier C is prepared by the component A and the component B, and the reaction process is as follows:
- Condensation reaction Component A and component B are dissolved in an ethanol solution at a molar ratio of 1:2-1:4, the temperature is 0-70 ° C, and the reaction time is l-8 h ;
- Reduction reaction After the condensation reaction is completed, an excess of Na 2 BH 4 and dimethyl sulfoxide (DMSO) are added to continue the reaction, the reaction temperature is 0-10 ° C, the reaction time is l-6 h, and the product is further extracted and dried. The solution was rotary evaporated to obtain a carbon fiber surface modifier C.
- DMSO dimethyl sulfoxide
- the present invention necessites a method for preparing a modified carbon fiber by using the carbon fiber surface modifier, which comprises the following steps:
- the carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
- the carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
- the resulting surface-modified carbon fibers are well suited for reinforcing polymers, particularly thermoplastics, and resins for preparing modified carbon fiber/resin composites. It is therefore necessary in the present invention to provide a method of preparing a composite material from the modified carbon fiber and resin.
- the preparation method is as follows: The following weight percentage components are provided,
- thermoplastic or thermosetting resin as a matrix component B, B: 60-95%;
- the components A, B, and C were extruded into a water-cooled strand in a twin-screw extruder (ZSK 25, Wemer & Pfleiderer) for granulation.
- Extruder heating zone 1-6 zone temperature control range 180-420 ⁇
- resin and additive mixed main feed carbon fiber side feed
- speed 100-200rpm capacity 4-20kg / hour.
- the modified carbon fiber comprises: the carbon fiber in the national standard GB T26752-2011 is modified by the modifier of the invention.
- the lipids include: PC, POM; PE, PP, ABS, SAN, PS PA, PBT, PET, PPO, LCP, TPU; PPSU, PPA, PEEK, PEI, PPS, PSU, PI; Thermosettingplastics-Epoxy .
- the auxiliary agent comprises: a flame retardant, a toughening agent, a conductive agent, an antioxidant, a light stabilizer, a lubricant, a coloring agent, a nucleating agent, an antistatic agent, and a filler.
- Aerospace industry used as missile heat protection and structural materials such as rocket nozzles, nose cones, large-area heat protection layers; satellite structures, antennas, solar fin base plates, satellite-rocket combined components; space shuttle noses, machines Parts such as the leading edge of the wing and the hatch; the measuring frame of the Hubble Space Telescope, solar panels and radio antennas.
- the aviation industry is used as the main bearing structural material, such as the main wing, the empennage and the body; the secondary bearing members, such as the rudder, the landing gear, the aileron, the spoiler, the engine compartment, the fairing and the seat plate, etc.
- the secondary bearing members such as the rudder, the landing gear, the aileron, the spoiler, the engine compartment, the fairing and the seat plate, etc.
- Transportation is used as parts for automobile drive shafts, leaf springs, frames and brake pads; ships and marine engineering are used to manufacture fishing boats, torpedo boats, speedboats and patrol boats, as well as masts, navigation rods and casings for racing boats. And water-jetting; submarine cables, submarines, radomes, lifts and pipelines in deep-sea oil fields.
- Biomedical and medical equipment such as artificial bones, teeth, ligaments, X-ray machine bed plates and film boxes.
- Other materials such as electromagnetic shielding, electrode degree, acoustics, anti-wear, energy storage and anti-static have also been widely used.
- the interlaminar shear strength of the material can be used to determine the interfacial bonding properties of carbon fiber with the resin matrix. It is verified that the functional groups in the macrocavity can chemically react with or form chemical bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups and hydroxyl groups inherent on the carbon fiber surface. Adsorption on the surface of carbon fibers; also verified that the R3, R4 functional substituents of the species of the invention have good compatibility with a certain resin.
- the carbon fiber is modified by a carbon fiber surface modifier to greatly improve the bonding force between the carbon fiber and the resin.
- the activity of the surface of the carbon fiber is improved, and the interface property between the carbon fiber and the resin matrix is remarkably improved.
- Example 1 is a comparison diagram of shear strength of a test composite material before and after modification in Example 1;
- Example 2 is a comparison diagram of shear strength of a test composite material before and after modification in Example 2;
- Fig. 3 is a graph showing the comparison of the shear strength of the test composite material before and after the modification in Example 3. Detailed ways
- the invention discloses a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier, a modified carbon fiber preparation method, a composite material prepared by modifying a carbon fiber and a resin, and a preparation method of the composite material, and a preparation method thereof The application of composite materials.
- a surface modification of carbon fiber the structural formula of which is as shown in formula (I):
- R 2, R 2 ' include hydrogen, hydroxy, or C r C 3 alkyl;
- R 3, R4 comprises a C r C ls ⁇ alkyl, C r C 18 embankment group, a hydroxyl group , amino, halogen, hydrogen, amide, ester, or siloxy, including hydrogen, hydroxy, amino, halogen, decyloxy.
- the hydroxyl group, the modified carbon fiber improver has the structural formula:
- the preparation method of the carbon fiber surface modifier is as follows.
- reaction temperature is 0-70 ° C
- reaction time is l-8h ;
- the product obtained after the reduction reaction is further subjected to extraction, dried, and the solution is rotary-screwed to obtain a carbon fiber surface modifier C.
- the carbon fiber surface modifier is used to prepare the modified carbon fiber as follows:
- the carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
- the carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
- the fibers are unidirectionally arranged in the matrix of the composite; 3.
- the carbon reference resin is formulated according to the ISO reference standard. Manufacturing conditions, sample specifications for composite samples. 4.
- the carbon fiber defined in the composite material cannot be sheared, so the test composite material cannot be prepared using a twin-screw extruder.
- Component 1 Modified carbon fiber;
- Component 2 PA6 resin;
- the modified carbon fiber has good interfacial properties in combination with a certain resin, and the R 3 and R 4 functional substituent pairs of the species of the present invention are also verified.
- a certain resin has the characteristics of good compatibility.
- the method for preparing a modified carbon fiber/resin composite material using modified carbon fiber and resin is as follows:
- thermoplastic or thermosetting resin as a matrix component B, B: 60-95 wt% ;
- the processing conditions can be arbitrary, the fiber is cut by a twin-screw extruder, the fibers are arranged disorderly in the resin, and an auxiliary agent (flame retardant, toughening agent, pigment) can be added.
- auxiliary agent flame retardant, toughening agent, pigment
- the temperature is controlled by extrusion in the extruder, and the strands are cut into small particles.
- the particles are produced modified carbon fiber composite materials, namely: modified T700 PA6 composite material.
- the composite materials obtained can be widely used in the production of aerospace equipment, transportation equipment, sports equipment, civil construction materials, daily necessities and medical equipment.
- the carbon fiber surface modifier of the present invention comprises a large cavity, and the large cavity is composed of carbon, nitrogen, hydrogen and/or oxygen.
- the 12-atom open-loop structure has a plurality of amino functional groups in the cavity, which can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers.
- the R5 and the amino group chemically react with the oxygen-containing carboxyl group, the aldehyde group, the ketone group, and the hydroxyl group on the surface of the carbon fiber, and form a chemical bond therebetween, whereby the surfactant is firmly adsorbed on the surface of the carbon fiber through a chemical bond; or R5 and The amino group forms hydrogen bonds with the oxygen-containing carboxyl group, aldehyde group, ketone group, and hydroxyl group on the surface of the carbon fiber, and they are firmly bonded by van der Waals force.
- the R3 and R4 functional substituent groups of the carbon fiber surface modifier have good compatibility with the resin selection, and they undergo chemical reaction and physical crosslinking with the molecular chain of the resin matrix in the hot working molten state.
- the selection of a suitable modifier of the present invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the present invention can effectively improve the interfacial properties of the carbon fiber and the resin.
- the carbon fiber surface modifier of the present invention the preparation method of the carbon fiber surface modifier, the modified carbon fiber prepared by the carbon fiber surface modifier, the preparation method of the modified carbon fiber, the modified carbon fiber and the resin are prepared in combination with the examples and the comparative examples.
- the composite material, the method of preparing the composite material, and the application of the composite material are described in detail, but the embodiment of the invention is not limited thereto.
- Preparation of carbon fiber surface modifier Add 1.5 mol of 1-dimethyl-1,2-diamine (A1) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3, 5- Dihydroxysalicylaldehyde (0.2mol) in 300 mL ethanol solution (Bl), control the polymerization temperature of 55 °C, reflux for 6h, add 300 mL of DMSO solution, control the polymerization temperature 0 °C, then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A1 1-dimethyl-1,2-diamine
- Carbon fiber surface modifier for preparing modified carbon fiber Dissolving carbon fiber surface modifier Cl with dimethyl sulfoxide (DMSO) and water, carbon fiber surface modifier C1 concentration is 1.2 wt%, for model T700 carbon fiber surface The infiltration modification is carried out, and the surface-modified carbon fiber is obtained after drying.
- DMSO dimethyl sulfoxide
- the composite material is prepared by using modified T700 carbon fiber and PA6, and the preparation method is as follows: carbon fiber modified by modifier II is used as reinforcing component A: 10wt% ; PA6 resin as matrix component B: 85wt%; processing aid as component C: 5wt% (N, bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)) Propionyl) hexamethylenediamine: lwt%, 2-(2H-benzotriazol-2)-4,6-bis(1-methylbenzophenethyl)phenol: lwt%, Licomont® CaV 102: lwt% , erucamide: 2wt%);
- the components A, B and C were extruded in a twin-screw extruder (ZSK 25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1 Zone 6 (230 ⁇ 280.C), with a speed of 150 rpm and a capacity of 6kg/hour.
- the composite materials of T700 carbon fiber and PA6 can be applied in the fields of automotive, medical, food processing, and chemical industry.
- the specific components include: the motive part includes the air intake system and the fuel system, such as the engine cylinder cover and section. Valves, air filter housings, automotive air horns, automotive air conditioning hoses, cooling fans and their enclosures, inlet pipes, brake oil tanks and gluing, etc.
- Body part zero The components are: car fenders, rear view frames, bumpers, dashboards, luggage racks, door handles, wiper brackets, seat belt buckles, various decorative parts in the car, and more.
- In-car electrical appliances such as electronically controlled doors and windows, connectors, crisper boxes, cable ties, etc.
- Preparation of carbon fiber surface modifier Add 1.5 mol of 1-dimethyl-1,2-diamine (A2) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4,6- Dipropoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B2), control the polymerization kettle temperature 55 ° C, reflux 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ⁇ , then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A2 1-dimethyl-1,2-diamine
- the aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C2.
- the carbon fiber surface modifier C2 was white solid.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C2 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- the composite material is prepared by using modified T700 carbon fiber and PEEK, and the preparation method is as follows: providing modified carbon fiber as modified by formula (III) Component A: 10wt%; PEEK resin as matrix component B: 85wt% ; processing aid is component C: 5wt% (bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite: lwt %, 2-(2H-benzotriazol-2)-4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont NaV101: lwt%. erucamide: 2wt%) ;
- the components A, B, and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 ( 330 ⁇ 420 °C), the speed is 200rpm, and the capacity is 8kg/hour.
- ZSK25 Werner & Pfleiderer
- water-cooled granulation resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 ( 330 ⁇ 420 °C)
- the speed is 200rpm
- the capacity is 8kg/hour.
- PEEK in the aerospace, medical, pharmaceutical and food processing industries, chemical industry, for the fabrication of gas analyzer structural components such as satellites, heat exchanger blades; chemical industry such as sleeve bearings, Sliding bearings, valve seats, seals, pump wear rings, solenoid valves, precision gears, pipes, etc.
- a carbon fiber surface modifier and a preparation method thereof, the steps are as follows:
- Preparation of carbon fiber surface modifier Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A3) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 4-(dibutylamino)salicylaldehyde (0.2mol) in 300 mL ethanol solution (B3), control the polymerization temperature of 55 °C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization temperature 0 °C Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A3 1,1,2-tetramethyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C3 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- modified carbon fiber/resin composite material by modified carbon fiber and resin The composite material is prepared by using modified T700 carbon fiber and ABS, and the preparation method is as follows: providing modified carbon fiber modified by formula (IV) As reinforcing component A: 10wt%; ABS resin as matrix component B: 85wt%; processing aid as component C: 5wt% (Igganox® 245: 1 wt%, 2- (2H-benzotriazole-2) -4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont
- the components A, B and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 (180 ⁇ 220 °C), the speed is lOOrpm, the capacity is 4kg/hour.
- Applications for this composite include: commercial machinery, electronic components, communication facilities, personal computers, electrical appliances, automotive parts, showers, luggage, faucets and other household items. Such as large appliances, cars, computer casings and accessories.
- the composite material obtained by modifying the carbon fiber and the resin, and the composite material prepared by the unmodified carbon fiber and the resin are compared with each other, and it is known that the carbon fiber surface modifier is passed.
- Modification of carbon fiber greatly enhances the bonding force between carbon fiber and resin.
- the modified carbon fiber can be widely used as a thermoplastic resin such as PA, PU, PEEK, or polyolefin to prepare a carbon fiber reinforced composite material having excellent mechanical properties.
- the following Examples 4-17 focus on the preparation of the carbon fiber surface modifier, and the method for preparing the modified carbon fiber by using the prepared carbon fiber modifier to fully support the general structure of the carbon fiber surface modifier in the present invention;
- the method for preparing composite materials of carbon fiber and resin and the verification and verification are not described in detail.
- the carbon fiber surface modifier and the modified carbon fiber prepared by the modifier can be selected according to the need to prepare a composite material between the resin and the modified carbon fiber.
- the modified carbon fiber and composite material obtained can measure the interlaminar shear strength (ILSS) of the composite before and after carbon fiber modification at 20 °C according to the national building materials industry standard: JC T 773-2010/ISO 14130: 1997. It is known that the shear strength of the modified carbon fiber is greatly improved compared to the shear strength of the unmodified carbon fiber.
- ILSS interlaminar shear strength
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A4) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - octadecyl salicylaldehyde (0.2mol) in 300 mL ethanol solution (B4), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until anti The reaction is completed until the liquid is colorless. 500 mL of water was added to the reaction system, and the mixture was separated.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C4 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-molar, 2-diamine (A5) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-pentyl-2-hydroxy- Salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B5), control the polymerization temperature of the reactor at 65 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH4, stir, The reaction was completed until the reaction solution was colorless. 500 mL of water was added to the reaction system, and the mixture was separated.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C5 at a concentration of 1.6 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A6) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 1-formyl-2-hydroxy-4-phenylethylethyl ester (0.2 mol) in 300 mL ethanol solution (B6), control the polymerization kettle temperature 60 ° C, reflux for 8 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the liquid was separated.
- A6 1,1,2-tetramethyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C6 is dissolved in DMSO and water at a concentration of 1.5 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A7) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 5 -formyl-6-hydroxy-phenylacetic acid methyl ester (0.2mol) in 300 mL ethanol solution (B7), control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- Formula (VIII) Method for preparing modified carbon fiber by carbon fiber surface modifier: The carbon fiber surface modifier C7 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A8) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 - Jiuhexylbenzaldehyde (0.2mol) in 300 mL ethanol solution (B8), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents Na 2 BH 4 was stirred until the reaction mixture was colorless and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C8 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A9) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 -formyl-4-hydroxy-phenylpropanamide (0.2mol) 300mL ethanol solution (B9), control the polymerization temperature of the reactor at 60 °C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 BH 4 , stir , until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C9 is dissolved in DMSO and water at a concentration of 1.7 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C10 at a concentration of 1.9 wt%>, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
- the carbon fiber surface modifier is used for preparing the modified carbon fiber: the carbon fiber surface modifier C11 is dissolved in DMSO and water at a concentration of 2.4 wt%, and the surface of the T700 carbon fiber is infiltrated and modified, and the surface modified carbon fiber is obtained after drying.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A12) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B12 dropwise. (0.2mol) 300mL ethanol solution, control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 B, stir until the reaction solution The color is complete and the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A12 2-dimethyl-1,2-diamine
- Method for preparing modified carbon fiber by carbon fiber surface modifier The carbon fiber surface modifier C12 is dissolved in DMSO and water at a concentration of 2.2 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-methyl-1,2-diamine (A13) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B13 (0.2 mol). 300 mL ethanol solution, control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until the reaction liquid is colorless The reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A13 1-methyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C13 at a concentration of 2.2 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-ethyl-1,2-diamine (A14) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-(N) , N-diethylhydroxyamino)-salicylaldehyde (0.2mol) in 300 mL ethanol solution (B14), control the polymerization temperature of 70 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- A14 1-ethyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C14 is dissolved in DMSO and water at a concentration of 2.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 0.1-dimethyl-1,2-diamine (A15) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - (N, N-di-2-methoxy-ethylamino)-salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B15), control the temperature of the polymerization vessel at 65 ° C, reflux for 6 h, add 300 mL The DMSO solution controls the temperature of the polymerization vessel to 0. C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed.
- A15 0.1-dimethyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C15 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-methyl-1,2-diamine (A16) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4- (2) -ethyl)-hexaneoxy-3-hydroxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B16), control the temperature of the polymerization vessel at 67 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization. The temperature of the kettle was 0 ° C, and 4 equivalents of Na 2 BH 4 was added thereto, and the mixture was stirred until the reaction mixture was colorless, and the reaction was completed.
- A16 1-methyl-1,2-diamine
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C16 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
- Preparation of a carbon fiber surface modifier Add 1.5 mol of 1,1,2,2-tetramethyl-1,2-diamine (A17) to a 1.5 L polymerization vessel, and dissolve it by adding 300 mL of ethanol. Then add 3, 4-dimethoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B17), control the temperature of the polymerization vessel at 70 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization kettle. At a temperature of 0 ° C, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
- a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C17 is dissolved in DMSO and water at a concentration of 1.5 wt%>, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
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Abstract
The present invention provides a carbon fiber surface modifier, a modified carbon fiber, composites, and preparation methods therefor. The general structural formula of the carbon fiber surface modifier is as represented by formula (I): in formula (I), R1, R2, R1' and R2' respectively and independently represent hydrogen, hydroxyl, or the alkyl of C1-C3; R3 and R4 respectively and independently represent C1-C18 alkyl, C1-C18 alkoxyl, hydroxyl, amino, halogen, hydrogen, amide, ester, or siloxyl, wherein R3, R4 are not simultaneously hydrogen; R5 represents hydrogen, hydroxyl, amino, halo, or alkoxyl. The carbon fiber surface modifier of the present invention extends the field of application for carbon fibers. The modified carbon fiber can be widely used in thermoplastic resins such as PA, ABS, PEEK, polyolefin, and for the preparation of carbon fiber resin composite material with excellent mechanical properties.
Description
碳纤维表面改性剂、 改性碳纤维、 复合材料以及它们的制备方法 技术领域 Carbon fiber surface modifier, modified carbon fiber, composite material and preparation method thereof
本发明涉及一种改性剂， 尤其涉及碳纤维表面改性剂及其制备方法、 碳纤 维表面改性剂制得的改性碳纤维及改性碳纤维制备方法、 改性碳纤维与树脂制 说 The invention relates to a modifier, in particular to a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier and a preparation method of the modified carbon fiber, and a modified carbon fiber and a resin system.
备的复合材料及复合材料的制备方法、 以及复合材料的应用。 Preparation of composite materials and composite materials, and application of composite materials.
书 Book
背景技术 Background technique
碳纤维具有突出的力学性能， 在复合材料中广泛使用碳纤维进行增强， 近 年来改善碳纤维与基体树脂间的界面性能成为研究的热点。 碳纤维表面活性官 能团少， 与基体树脂复合时形成的有效化学键少、 相容性差， 导致碳纤维复合 材料中易形成脆性界面层结构。 为提高碳纤维与基体树脂间的界面性能， 工业 上通常对碳纤维表面进行氧化处理， 赋予碳纤维表面羟基、 羰基等活性含氧官 能团， 常见的有阳极氧化法、 硝酸氧化法、 高锰酸钾氧化法等， 但这类方法容 易损伤碳纤维表面， 破坏其力学性能。 为了不损伤纤维表面提高碳纤维与基体 树脂界面性能， 中国专利申请 CN1944783A使用聚合物接枝技术对碳纳米纤维 表面改性， 使纤维表面富有多种活性官能团， 但是， 这种方法工艺复杂， 条件 苛刻， 生产运行成本高， 在一定程度上限制了工业化生产。 发明内容 Carbon fiber has outstanding mechanical properties, and carbon fiber is widely used in composite materials for reinforcement. In recent years, improving the interface properties between carbon fiber and matrix resin has become a research hotspot. The surface active carbon fiber of the carbon fiber is small, and the effective chemical bond formed when the composite is combined with the matrix resin is small, and the compatibility is poor, which results in the formation of a brittle interface layer structure in the carbon fiber composite material. In order to improve the interfacial properties between the carbon fiber and the matrix resin, the surface of the carbon fiber is usually oxidized in the industry to impart active oxygen-containing functional groups such as hydroxyl groups and carbonyl groups on the surface of the carbon fiber. Anodizing, nitric acid oxidation, and potassium permanganate oxidation are common. Etc. However, such methods are prone to damage the surface of carbon fibers and destroy their mechanical properties. In order to improve the interfacial properties of carbon fiber and matrix resin without damaging the fiber surface, Chinese patent application CN1944783A uses polymer grafting technology to modify the surface of carbon nanofibers, so that the surface of the fiber is rich in various reactive functional groups. However, this method is complicated in process and harsh in conditions. The high production and operation costs limit the industrial production to a certain extent. Summary of the invention
鉴于以上所述， 本发明有必要提供一种可改善碳纤维表面活性的碳纤维表 面改性剂。 In view of the above, it is necessary for the present invention to provide a carbon fiber surface modifier which improves the surface activity of carbon fibers.
本发明所采用的技术方案是， 一种碳纤维表面改性剂， 其结构通式如式（I) 所示：
The technical solution adopted by the present invention is a carbon fiber surface modifier whose structural formula is as shown in formula (I):
( I ) (I)
式 （I) 中， R2、 R2'各自彼此独立地代表氢、 羟基、 或^-^的垸 基。所述 CrC3的烷基是指具有 1-3个碳原子的直链或支链的垸基。 R2、 R, '代表甲基、 乙基、 丙基和氢， 特别优选为甲基、 乙基和氢， 最优选为甲基和 式 （I) 中， R3、 R4各自彼此独立地代表 CrC18垸基、 ^^^烷氧基、 羟基、 氨基、 卤素、 氢、 酰胺基、 酯基、 或硅氧基， 条件是 R3、 R4不同时是氢。 优选 羟基、 氨基和 d-Cls的垸氧基、 硅氧基、 酯基以及酰胺基。 In the formula (I), R 2 and R 2 ' each independently represent a hydrogen group, a hydroxyl group, or a fluorenyl group. The alkyl group of C r C 3 means a linear or branched fluorenyl group having 1 to 3 carbon atoms. R 2 , R, ' represents methyl, ethyl, propyl and hydrogen, particularly preferably methyl, ethyl and hydrogen, most preferably methyl and in formula (I), R 3 and R 4 are each independently of one another Represents C r C 18 fluorenyl, ^^^ alkoxy, hydroxy, amino, halogen, hydrogen, amide, ester, or siloxy, with the proviso that R 3 and R 4 are not hydrogen at the same time. Preferred are a hydroxyl group, an amino group, and a decyloxy group, a siloxy group, an ester group, and an amide group of dC ls .
所述 d-C18的烷基是指具有 1-18个碳原子的直链或支链的垸基。 例如， 甲 基、 乙基、 丙基、 异丙基、 丁基、 异丁基、 叔丁基、 仲丁基、 戊基、 新戊基、 己基、 庚基、 辛基、 壬基、 十二垸基和硬脂基等， 优选 12-18 个， 特别优选是 14-18个碳原子。 最优选十四烷基、 十八垸基， 其包括直链和支链化的异构体。 The alkyl group of dC 18 means a linear or branched fluorenyl group having 1 to 18 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, twelve The mercapto group and the stearyl group and the like are preferably 12 to 18, particularly preferably 14 to 18 carbon atoms. Most preferred are myristyl, octadecyl, which include both linear and branched isomers.
所述 CrC18的垸氧基是指具有 1-18个碳原子的直链或支链的烷氧基。例如， 甲氧基、 乙氧基、 丙氧基、 异丙氧基、 丁氧基、 异丁氧基、 叔丁氧基、 仲丁氧 基、 戊氧基、 新戊氧基、 己氧基、 十二烷氧基等， 优选 1-12个， 特别优选 3-12 个碳原子。 最优选丙氧基、 （2-乙基） -己氧基、 癸氧基， 其包括直链和支链化的 异构体。 The decyloxy group of C r C 18 means a linear or branched alkoxy group having 1 to 18 carbon atoms. For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, sec-butoxy, pentyloxy, neopentyloxy, hexyloxy The dodecyloxy group or the like is preferably 1 to 12, particularly preferably 3 to 12 carbon atoms. Most preferred are propoxy, (2-ethyl)-hexyloxy, decyloxy, which include both straight and branched isomers.
所述的氨基包括 -NH2、 -NHRj, -NRXR2, 其中 、 R2各自彼此独立地代表The amino group includes -NH 2 , -NHRj, -NR X R 2 , wherein R 2 each independently represents each other
Cr C18垸基及其衍生物， 它们最优选的个例是 N， N-二 -2-甲氧基 -乙基氨基、 N, N-二乙羟基氨基， -N¾。 C r C 18 fluorenyl and its derivatives, the most preferred examples of which are N, N-di-2-methoxy-ethylamino, N, N-diethylhydroxyamino, -N3⁄4.
所述卤素是指氟、 氯、 溴或碘原子。 优选氟原子。 The halogen means a fluorine, chlorine, bromine or iodine atom. A fluorine atom is preferred.
所述酰胺基分子式为 -(CH2)nCONH-R， n包括 1-15 的整数。 优选地， n取
1-10的直链或支链， n最优选 2和 3。 其中， R是 C1-C18的直链或支链的垸基、 氢，优选具有 1-6个碳原子的直链或支链的垸基、氢， R最优选甲基、 乙基、氢。 酰胺基最优选为乙酰胺基、 丙酰胺基。 The amide group has the formula -(CH 2 ) n CONH-R, and n includes an integer of from 1 to 15. Preferably, n is taken A linear or branched chain of 1-10, and n is most preferably 2 and 3. Wherein R is a linear or branched fluorenyl group of C1-C18, hydrogen, preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, hydrogen, and R is most preferably a methyl group, an ethyl group or a hydrogen. The amide group is most preferably an acetamide group or a propionamide group.
所述酯基的分子式为 -(CH2)nCO2-R， n包括 1-15的整数。 优选地， n取 1-10 的直链或支链， n最优选 2。 其中 R是 ^ 18的直链或支链的垸基， 优选具有 1-6个碳原子的直链或支链的垸基， 最优选甲基和乙基。 酯基最优选为乙酸基甲 酯、 乙醇基乙酯。 The ester group has the formula -(CH 2 ) n CO 2 -R, and n includes an integer of from 1 to 15. Preferably, n takes from 1 to 10 linear or branched, and n is most preferably 2. A linear or branched fluorenyl group wherein R is 18 , preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, most preferably a methyl group and an ethyl group. The ester group is most preferably an ethyl acetate methyl ester or an ethyl alcohol ethyl ester.
所述硅氧基包括硅氧垸衍生物， 它们的个例是三甲基硅氧基、 叔丁基二甲 基硅氧基、 - (CH2) 3Si (OCH3) 3、 - (CH2) 2OSi (CH3) 2(CH2 ) 3CH3、 -(CH2)6Si (C¾) 20-CH3。 最优选- (CH2) 3Si (OCH3 ) 3、 - CCH2) 2OSi〔CH3) 2C(CH3 ) 3、 -(CH2)6Si (CH3) 20-CH3。 The siloxy group includes a siloxane derivative, and examples thereof are trimethylsiloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH 3 ) 3 , - (CH 2 ) 2 OSi (CH 3 ) 2 (CH2 ) 3 CH 3 , -(CH 2 ) 6 Si (C3⁄4) 2 0-CH 3 . Most preferred is -(CH 2 ) 3 Si (OCH3 ) 3 , - CCH 2 ) 2 OSi[CH 3 ) 2 C(CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 .
式 （I ) 中， 包括氢、 羟基、 氨基、 卤素、 垸氧基。 优选羟基、 氢， 最优 选羟基。 The formula (I) includes hydrogen, a hydroxyl group, an amino group, a halogen, and a decyloxy group. Preferred are a hydroxyl group, a hydrogen group, and most preferably a hydroxyl group.
优选地， 式 （I ) 中， 、 R2、 RA R2'代表氢和甲基； 与 代表十四垸 基、十八烷基、 乙酰胺基、 丙酰胺基、 乙酸基甲酯、 乙醇基乙酯、选丙氧基、 （2- 乙基） -己氧基、 癸氧基、 N， N-二 -2-甲氧基 -乙基氨基、 N， N-二乙羟基氨基， -ΝΗ2、羟基、氢、氟、三甲基硅氧基、叔丁基二甲基硅氧基、 - (CH2) 3Si (OCH3 ) 3、 - (CH2) 2OSi (CH3) 2C(CH3) 3、 -(CH2)6Si (CH3 ) 20-CH3; R5代表羟基。 Preferably, in formula (I), R 2 , RA R 2 ' represents hydrogen and methyl; and represents tetradecyl, octadecyl, acetamido, propionamido, methyl acetate, ethanol Ethyl ester, selected propoxy, (2-ethyl)-hexyloxy, decyloxy, N,N-di-2-methoxy-ethylamino, N,N-diethylhydroxyamino, -ΝΗ 2 , hydroxyl, hydrogen, fluorine, trimethylsilyloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH3 ) 3, - (CH 2 ) 2 OSi (CH 3 ) 2 C (CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 ; R 5 represents a hydroxyl group.
本发明的碳纤维表面改性剂含一个大腔体， 大腔体由碳、 氮、 氢和 /或氧共 12个原子构成， 腔体内有多个 与氨基官能团， 所述 包括氢、 羟基、 氨基、 卤素或垸氧基， 该等官能团以及氨基能与碳纤维表面固有的含氧羧基、 醛基、 酮基、 羟基等官能团发生化学反应或形成氢键， 它们通过化学键吸附在碳纤维 表面； 同时碳纤维表面改性剂的 R3、 R4功能取代基团对树脂的选择相容性好， 与树脂基体在熔融加工条件下， 它们与树脂的分子链间发生化学反应和物理交 联形成网络结构。 针对不同种类树脂， 选用合适的本发明改性剂能使碳纤增强 树脂材料的层间剪切强度提升 9-30% ,本发明能有效提高碳纤维与树脂的界面性
上述 R5以及氨基官能团与碳纤维表面固有的官能团可有多种反应机理，如 机理 1 : 表面改性剂氨基与碳纤维表面酮基发生缩聚反应， 生产烯胺， 使得改性 剂牢固地吸附在碳纤维表面。机理 2: 表面改性剂羟基与碳纤维表面羧基在加热 烘干过程中发生酯化反应，酸脱羟基醇脱氢， RCOOH中去掉 -OH， ROH去掉氢， 然后 RCO-与 -OR连接在一起生成 RCOOR, 使得改性剂牢固地吸附在碳纤维表 面。机理 3: 表面改性剂的氨与碳纤维表面的环氧基发生开环取代反应， 生成氨 基醇。使得表面改性剂牢固地吸附在碳纤维表面。机理 4:表面改性剂中的 -OH、 -NH活泼氢能与碳纤维表面的含氧官能团 -C=O、 -OH、 -COOH、 -C-O-C-等的氧 生成 RO----H-OR氢键。使得表面改性剂牢固地吸附在碳纤维表面。表面改性剂 通过机理 1-3能与碳纤维表面含氧官能团发生化学反应， 他们之间形成化学键， 使得表面改性剂接在碳纤维表面。 尤其， 当 取羟基时， 由 2个相同的醛分子 和 1 个二胺分子缩合生成的螯合席夫碱 (Sali-cylaldehydoethylenediamine)简称为 Salen0与 Salen类似的是， 当亚胺变成饱和的氨基时， 这类化合物则称为 Salan。 Salen和 Salan的中心位置有 0、 N、 N、 0 4个原子， 大腔体由碳、 氮、 氢和氧 共 12个原子组成的 Salan结构。 The carbon fiber surface modifier of the present invention comprises a large cavity composed of 12 atoms of carbon, nitrogen, hydrogen and/or oxygen, and a plurality of amino functional groups in the cavity, including hydrogen, hydroxyl and amino groups. , halogen or decyloxy group, these functional groups and amino groups can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers, which are adsorbed on the surface of carbon fibers by chemical bonds; The R 3 and R 4 functional substituent groups of the modifier have good compatibility with the resin, and the resin matrix undergoes chemical reaction and physical crosslinking with the molecular chain of the resin to form a network structure under melt processing conditions. For different kinds of resins, selecting the appropriate modifier of the invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the invention can effectively improve the interface between the carbon fiber and the resin. The above R5 and the functional groups of the amino functional group and the carbon fiber surface may have various reaction mechanisms, such as mechanism 1: the surface modifier amino group is polycondensed with the ketone group on the surface of the carbon fiber to produce an enamine, so that the modifier is firmly adsorbed on the surface of the carbon fiber. . Mechanism 2: Surface modification agent hydroxyl group and carbon fiber surface carboxyl group undergo esterification reaction during heating and drying process, acid dehydroxy alcohol dehydrogenation, ROHOH remove -OH, ROH remove hydrogen, then RCO- and -OR are connected together to generate RCOOR allows the modifier to adhere firmly to the surface of the carbon fiber. Mechanism 3: The ammonia of the surface modifier undergoes a ring-opening substitution reaction with the epoxy group on the surface of the carbon fiber to form an amino alcohol. The surface modifier is firmly adsorbed on the surface of the carbon fiber. Mechanism 4: -OH, -NH active hydrogen in the surface modifier can form RO----H-OR with oxygen-containing functional groups -C=O, -OH, -COOH, -COC-, etc. on the surface of carbon fiber Hydrogen bond. The surface modifier is firmly adsorbed on the surface of the carbon fiber. The surface modifier can chemically react with the oxygen-containing functional groups on the surface of the carbon fiber through mechanisms 1-3, and a chemical bond is formed between them to allow the surface modifier to be attached to the surface of the carbon fiber. In particular, when a hydroxyl group is taken, a chelating base (Sali-cylaldehydoethylenediamine) formed by condensation of two identical aldehyde molecules and one diamine molecule is abbreviated as Salen 0 and Salen, when the imine becomes saturated. In the case of amino groups, such compounds are referred to as Salan. The central position of Salen and Salan is 0, N, N, 0 4 atoms, and the large cavity is composed of 12 atoms of carbon, nitrogen, hydrogen and oxygen.
本发明有必要提供一种碳纤维表面改性剂的制备方法， 包括如下步骤： The invention necessitates a method for preparing a carbon fiber surface modifier, comprising the following steps:
提供组分 A:
； 所述的组分 A: 为乙 二胺衍生物， 如乙二胺、 1， 1-二甲基乙二胺、 1， 2-二甲基乙二胺、羟基乙二胺、 四甲基乙二胺、 四乙基乙二胺； 可以通过已知常规的实验方法和商购得到。 所 述的组分 B: 为水杨醛衍生物或苯甲醛衍生物， 优选水杨醛衍生物， 它们都是可 以通过已知常规的实验方法和商购得到。 Provide component A: The component A: is an ethylenediamine derivative such as ethylenediamine, 1,1-dimethylethylenediamine, 1,2-dimethylethylenediamine, hydroxyethylenediamine, tetramethyl Ethylenediamine, tetraethylethylenediamine; can be obtained by known conventional experimental methods and commercially available. The component B: is a salicylaldehyde derivative or a benzaldehyde derivative, preferably a salicylaldehyde derivative, which are all commercially available by known conventional experimental methods.
通过组分 A和组分 B制备碳纤维表面改性剂 C， 制备过程反应式如下：
The carbon fiber surface modifier C is prepared by the component A and the component B, and the reaction process is as follows:
反应式中包括縮合反应与还原反应的步骤： The steps of the condensation reaction and the reduction reaction are included in the reaction formula:
缩合反应： 组分 A和组分 B按摩尔比 1:2-1:4溶解在乙醇溶液中， 温度为 0-70 °C , 反应时间为 l-8h; Condensation reaction: Component A and component B are dissolved in an ethanol solution at a molar ratio of 1:2-1:4, the temperature is 0-70 ° C, and the reaction time is l-8 h ;
还原反应： 缩合反应完成后， 加入过量的 Na2BH4和二甲基亚砜 （DMSO) 继续反应， 反应温度为 0-10°C， 反应时间为 l-6h， 产物再经萃取， 干燥， 溶液 旋蒸， 得到一种碳纤维表面改性剂 C。 Reduction reaction: After the condensation reaction is completed, an excess of Na 2 BH 4 and dimethyl sulfoxide (DMSO) are added to continue the reaction, the reaction temperature is 0-10 ° C, the reaction time is l-6 h, and the product is further extracted and dried. The solution was rotary evaporated to obtain a carbon fiber surface modifier C.
本发明有必要提供一种所述碳纤维表面改性剂制备改性碳纤维的方法， 包 括以下步骤： The present invention necessites a method for preparing a modified carbon fiber by using the carbon fiber surface modifier, which comprises the following steps:
碳纤维表面改性剂溶解至有机溶剂或水中形成改性剂溶液， 浓度为 1.2-2.4wt%, The carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
将碳纤维置入改性剂溶液内进行浸润， 碳纤维与改性剂反应； The carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
取出、 烘干后， 得到表面改性的碳纤维。 After being taken out and dried, surface-modified carbon fibers are obtained.
制得的表面改性的碳纤维非常适合增强聚合物特别是热塑性塑料， 与树脂 制备改性碳纤维 /树脂的复合材料。 本发明有必要提供一种所述改性的碳纤维与 树脂制备制复合材料的方法。 The resulting surface-modified carbon fibers are well suited for reinforcing polymers, particularly thermoplastics, and resins for preparing modified carbon fiber/resin composites. It is therefore necessary in the present invention to provide a method of preparing a composite material from the modified carbon fiber and resin.
制备方法如下： 提供如下重量百分比的组分， The preparation method is as follows: The following weight percentage components are provided,
改性碳纤维作为增强组分甲， 甲： l-40wt%; Modified carbon fiber as a reinforcing component A, A: l-40wt%;
热塑性或热固性树脂作为基体组分乙， 乙： 60-95^%; a thermoplastic or thermosetting resin as a matrix component B, B: 60-95%;
加工助剂作为组分丙， 丙： 0-15wt%; Processing aid as a component C, C: 0-15wt% ;
将组分甲、 乙、 丙在双螺杆挤出机 (ZSK 25， Wemer&Pfleiderer)中挤出水 冷拉条造粒。挤出机加热区 1-6区（温度控制范围 180-420Ό ), 树脂与助剂混合 主喂料， 碳纤维侧喂料， 转速为 100-200rpm， 产能 4-20kg/小时。
所述的改性碳纤维包含： 国标 GB T26752-2011类别中的碳纤维经过本发明 改性剂改性。 The components A, B, and C were extruded into a water-cooled strand in a twin-screw extruder (ZSK 25, Wemer & Pfleiderer) for granulation. Extruder heating zone 1-6 zone (temperature control range 180-420 Ό), resin and additive mixed main feed, carbon fiber side feed, speed 100-200rpm, capacity 4-20kg / hour. The modified carbon fiber comprises: the carbon fiber in the national standard GB T26752-2011 is modified by the modifier of the invention.
所述的才对脂包含： PC、 POM; PE、 PP、 ABS、 SAN、 PS PA、 PBT、 PET, PPO 、 LCP、 TPU； PPSU、 PPA、 PEEK、 PEI、 PPS 、 PSU、 PI； Thermosettingplastics-Epoxy。 The lipids include: PC, POM; PE, PP, ABS, SAN, PS PA, PBT, PET, PPO, LCP, TPU; PPSU, PPA, PEEK, PEI, PPS, PSU, PI; Thermosettingplastics-Epoxy .
所述的助剂包含： 阻燃剂、 增韧剂、 导电剂、 抗氧化剂、 光稳定剂、 润滑 剂、 着色剂、 成核剂、 抗静电剂， 填料。 The auxiliary agent comprises: a flame retardant, a toughening agent, a conductive agent, an antioxidant, a light stabilizer, a lubricant, a coloring agent, a nucleating agent, an antistatic agent, and a filler.
另外， 本发明有必要提供制得的复合材料的用途， 复合材料用于制作： In addition, it is necessary for the present invention to provide for the use of composite materials produced by the use of composite materials for:
(1)宇航工业用作导弹防热及结构材料， 如火箭喷管、 鼻锥、 大面积防热层; 卫星构架、 天线、 太阳能翼片底板、 卫星-火箭结合部件； 航天飞机机头， 机翼 前缘和舱门等制件； 哈勃太空望远镜的测量构架， 太阳能电池板和无线电天线。 (1) Aerospace industry used as missile heat protection and structural materials, such as rocket nozzles, nose cones, large-area heat protection layers; satellite structures, antennas, solar fin base plates, satellite-rocket combined components; space shuttle noses, machines Parts such as the leading edge of the wing and the hatch; the measuring frame of the Hubble Space Telescope, solar panels and radio antennas.
(2)航空工业用作主承力结构材料， 如主翼、 尾翼和机体； 次承力构件， 如 方向舵、 起落架、 副翼、 扰流板、 发动机舱、 整流罩及座板等， 此外还有 C/C 刹车片。 (2) The aviation industry is used as the main bearing structural material, such as the main wing, the empennage and the body; the secondary bearing members, such as the rudder, the landing gear, the aileron, the spoiler, the engine compartment, the fairing and the seat plate, etc. There are C/C brake pads.
(3)交通运输用作汽车传动轴、 板簧、 构架和刹车片等制件； 船舶和海洋工 程用作制造渔船、 鱼雷快艇、 快艇和巡逻艇， 以及赛艇的桅杆、 航杆、 壳体及 划水浆； 海底电缆、 潜水艇、 雷达罩、 深海油田的升降器和管道。 (3) Transportation is used as parts for automobile drive shafts, leaf springs, frames and brake pads; ships and marine engineering are used to manufacture fishing boats, torpedo boats, speedboats and patrol boats, as well as masts, navigation rods and casings for racing boats. And water-jetting; submarine cables, submarines, radomes, lifts and pipelines in deep-sea oil fields.
(4)运动器材用作网球、 羽毛球和壁球拍及杆、 棒球、 曲棍球和高尔夫球杆、 自行车、 赛艇、 钓杆、 滑雪板、 雪车等。 (4) Sports equipment used for tennis, badminton and squash rackets and poles, baseball, hockey and golf clubs, bicycles, rowing, fishing rods, snowboards, snowmobiles, etc.
(5)土木建筑幕墙、 嵌板、 间隔壁板、 桥梁、 架设跨度大的管线、 海水和水 轮结构的增强筋、 地板、 窗框、 管道、 海洋浮杆、 面状发热嵌板、 抗震救灾用 补强材料。 (5) Civil engineering curtain walls, panels, partitions, bridges, erected pipelines, reinforced ribs for sea and water wheel structures, floors, sashes, pipes, marine floating slabs, planar heating panels, earthquake relief Use reinforcing materials.
(6)其它工业化工用的防腐泵、 阀、 槽、 罐； 催化剂， 吸附剂和密封制品等。 生体和医疗器材如人造骨骼、 牙齿、 韧带、 X光机的床板和胶卷盒。 编织机用 的剑竿头和剑竿防静电刷。 其它还有电磁屏蔽、 电极度、 音响、 减磨、 储能及 防静电等材料也已获得广泛应用。 (6) Anti-corrosion pumps, valves, tanks, tanks for other industrial chemicals; catalysts, adsorbents and sealing products. Biomedical and medical equipment such as artificial bones, teeth, ligaments, X-ray machine bed plates and film boxes. Anti-static brush for swords and swords for knitting machines. Other materials such as electromagnetic shielding, electrode degree, acoustics, anti-wear, energy storage and anti-static have also been widely used.
按国建材行业标准 ΚΥΓ 773-2010/ISO 14130： 1997测量碳纤维 /树脂复合材
料的层间剪切强度。 通过层间剪切强度可判定碳纤维能与树脂基体的界面结合 性能， 验证了大腔体内的官能团能与碳纤维表面固有的含氧羧基、 醛基、 酮基、 羟基等官能团发生化学反应或形成化学键吸附在碳纤维表面； 也验证本发明物 种的 R3、 R4功能取代基对某种树脂具有选择相容性好的特点。通过碳纤维表面 改性剂对碳纤维进行改性， 大大提高碳纤维与树脂的结合力。 利用本发明产品 对碳纤维改性后， 提高了碳纤维表面的活性， 使碳纤维能与树脂基体的界面性 能得到明显地改善。 说明书附图 Measurement of carbon fiber/resin composites according to national building materials industry standards 773 773-2010/ISO 14130: 1997 The interlaminar shear strength of the material. The interfacial shear strength can be used to determine the interfacial bonding properties of carbon fiber with the resin matrix. It is verified that the functional groups in the macrocavity can chemically react with or form chemical bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups and hydroxyl groups inherent on the carbon fiber surface. Adsorption on the surface of carbon fibers; also verified that the R3, R4 functional substituents of the species of the invention have good compatibility with a certain resin. The carbon fiber is modified by a carbon fiber surface modifier to greatly improve the bonding force between the carbon fiber and the resin. After the carbon fiber is modified by the product of the invention, the activity of the surface of the carbon fiber is improved, and the interface property between the carbon fiber and the resin matrix is remarkably improved. Instruction sheet
图 1是实施例 1中改性前后的测试用复合材料的剪切强度比较图; 1 is a comparison diagram of shear strength of a test composite material before and after modification in Example 1;
图 2是实施例 2中改性前后的测试用复合材料的剪切强度比较图; 2 is a comparison diagram of shear strength of a test composite material before and after modification in Example 2;
图 3是实施例 3中改性前后的测试用复合材料的剪切强度比较图。 具体实施方式 Fig. 3 is a graph showing the comparison of the shear strength of the test composite material before and after the modification in Example 3. Detailed ways
本发明公开一种碳纤维表面改性剂及其制备方法、 碳纤维表面改性剂制得 的改性碳纤维及改性碳纤维制备方法、 改性碳纤维与树脂制备的复合材料及复 合材料的制备方法、 以及复合材料的应用。 The invention discloses a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier, a modified carbon fiber preparation method, a composite material prepared by modifying a carbon fiber and a resin, and a preparation method of the composite material, and a preparation method thereof The application of composite materials.
一种碳纤维表面改性 ， 其结构通式如式 （I) 所示： A surface modification of carbon fiber, the structural formula of which is as shown in formula (I):
( I ) (I)
式 （I) 中， 、 R2、 R2 '包括氢、 羟基、 或 CrC3的烷基； R3、 R4包括 CrCls^烷基、 CrC18的垸氧基、 羟基、 氨基、 卤素、 氢、 酰胺基、 酯基、 或硅 氧基， 包括氢、 羟基、 氨基、 卤素、 垸氧基。 In formula (I),, R 2, R 2 ' include hydrogen, hydroxy, or C r C 3 alkyl; R 3, R4 comprises a C r C ls ^ alkyl, C r C 18 embankment group, a hydroxyl group , amino, halogen, hydrogen, amide, ester, or siloxy, including hydrogen, hydroxy, amino, halogen, decyloxy.
优选地， 所述 为羟基， 所述改性碳纤维改进剂结构式为：
Preferably, the hydroxyl group, the modified carbon fiber improver has the structural formula:
所述碳纤维表面改性剂的制备方法如下，
The preparation method of the carbon fiber surface modifier is as follows.
尔比 1:2-1:4溶解在乙醇溶液中进行缩合反应： 反应温度为 0-70°C， 反应时间为 l-8h; Erbi 1:2-1:4 dissolved in ethanol solution for condensation reaction: reaction temperature is 0-70 ° C, reaction time is l-8h ;
缩合反应完成后， 加入过量的 Na2BH4和 DMSO进行还原反应， 反应温度 为 0-10°C， 反应时间为 l-6h; After the condensation reaction is completed, an excess of Na 2 BH 4 and DMSO is added for reduction reaction, the reaction temperature is 0-10 ° C, the reaction time is l-6h;
还原反应后获得的产物再经萃取， 干燥， 溶液旋蒸， 得到一种碳纤维表面 改性剂 C。 The product obtained after the reduction reaction is further subjected to extraction, dried, and the solution is rotary-screwed to obtain a carbon fiber surface modifier C.
缩合反应和还原反应的反应总式如下： The general reaction of the condensation reaction and the reduction reaction is as follows:
碳纤维表面改性剂制备改性碳纤维的方法如下： The carbon fiber surface modifier is used to prepare the modified carbon fiber as follows:
碳纤维表面改性剂溶解至有机溶剂或水中形成改性剂溶液， 浓度为 1.2-2.4wt%, The carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
将碳纤维置入改性剂溶液内进行浸润， 碳纤维与改性剂反应； The carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
取出、 烘干后， 得到表面改性的碳纤维。 After being taken out and dried, surface-modified carbon fibers are obtained.
为了判断上述碳纤维表面改性剂制备改性碳纤维的方法中制备的表面改性 碳纤维的改性效果， 有必要按国建材行业标准： JC T 773-2010 ISO 14130: 1997 测量改性碳纤维一树脂材料的层间剪切强度。 所述层间剪切强度是判断碳纤维
与树脂界面结合效果的一种测试方法， 此方法的国建材行业标准是： JC/T 773-2010 ISO 14130： 1997, 纤维增强塑料短梁法测定层间剪切强度。 单向纤维 增强塑料层间剪切强度试验方法中具体要求为： 1.碳纤维与树脂重量比固定； 2. 纤维在复合材料基体中是单向排列的； 3.含有 ISO引用标准，制定碳纤维树脂复 合材料样品的制造条件， 样品规格。 4.此复合材料中界定了碳纤维不能被剪断， 所以不能使用双螺杆挤出机制备这种测试用复合材料。 举例： 改性 T700 PA6测 试用复合材料。 组分 1 : 改性碳纤维； 组分 2: PA6树脂； 步骤： 将改性碳纤维 放入模具中， 纤维单向排列， 将 PA6树脂涂覆在碳纤维表面， 一段时间后固化 得到改性 T700/PA6测试用复合材料， 最后测层间剪切强度。 如此， 通过测量改 性碳纤维-树脂材料的层间剪切强度， 从而断定该改性碳纤维与某种树脂结合有 很好的界面性能， 也验证本发明物种的 R3、 R4功能取代基对某种树脂具有选择 相容性好的特点。 In order to judge the modification effect of the surface-modified carbon fiber prepared by the above method for preparing the modified carbon fiber by the carbon fiber surface modifier, it is necessary to measure the modified carbon fiber-resin material according to the national building materials industry standard: JC T 773-2010 ISO 14130: 1997 Interlaminar shear strength. The interlaminar shear strength is the judgment of carbon fiber A test method for the interface effect with the resin. The national building materials industry standard for this method is: JC/T 773-2010 ISO 14130: 1997, Determination of interlaminar shear strength by fiber reinforced plastic short beam method. The specific requirements for the test method for the interlaminar shear strength of unidirectional fiber reinforced plastics are as follows: 1. The weight ratio of carbon fiber to resin is fixed; 2. The fibers are unidirectionally arranged in the matrix of the composite; 3. The carbon reference resin is formulated according to the ISO reference standard. Manufacturing conditions, sample specifications for composite samples. 4. The carbon fiber defined in the composite material cannot be sheared, so the test composite material cannot be prepared using a twin-screw extruder. Example: Modified T700 PA6 test composite. Component 1: Modified carbon fiber; Component 2: PA6 resin; Step: The modified carbon fiber is placed in a mold, the fibers are unidirectionally aligned, PA6 resin is coated on the surface of the carbon fiber, and cured for a period of time to obtain a modified T700/PA6 Test the composite material and finally measure the interlaminar shear strength. Thus, by measuring the interlaminar shear strength of the modified carbon fiber-resin material, it is concluded that the modified carbon fiber has good interfacial properties in combination with a certain resin, and the R 3 and R 4 functional substituent pairs of the species of the present invention are also verified. A certain resin has the characteristics of good compatibility.
改性的碳纤维与树脂制备改性碳纤维 /树脂的复合材料的方法如下： The method for preparing a modified carbon fiber/resin composite material using modified carbon fiber and resin is as follows:
1 ) 提供如下重量百分比的组分， 1) Provide the following weight percentage components,
改性碳纤维作为增强组分甲， 甲： l-40wt%; Modified carbon fiber as a reinforcing component A, A: l-40wt%;
热塑性或热固性树脂作为基体组分乙， 乙： 60-95wt%; a thermoplastic or thermosetting resin as a matrix component B, B: 60-95 wt% ;
加工助剂作为组分丙， 丙： 0-15wt%; Processing aid as a component C, C: 0-15wt% ;
2) 将组分甲、 乙、 丙通过挤出机挤出成型制得复合材料。 2) The components A, B, and C are extruded through an extruder to obtain a composite material.
在改性碳纤维 /树脂制备复合材料时， 加工条件可任意， 纤维被双螺杆挤出 机剪断， 纤维在树脂中排列无序， 可添加助剂（阻燃剂， 增韧剂， 颜料）。 举例： 制备改性后的碳纤维 T700与 PA6的复合材料， 组分 1 : 改性碳纤维； 组分 2: PA6树脂； 组分 3 : 助剂； 具体步骤为： 将组分 1、 2、 3在挤出机中控制温度挤 出， 拉条切成小粒子， 这种粒子就是生产的改性碳纤维复合材料， 即： 改性 T700 PA6复合材料。 When the composite material is prepared by modifying the carbon fiber/resin, the processing conditions can be arbitrary, the fiber is cut by a twin-screw extruder, the fibers are arranged disorderly in the resin, and an auxiliary agent (flame retardant, toughening agent, pigment) can be added. Example: Preparation of modified carbon fiber composite of T700 and PA6, component 1: modified carbon fiber; component 2: PA6 resin; component 3: auxiliary; specific steps are: component 1, 2, 3 The temperature is controlled by extrusion in the extruder, and the strands are cut into small particles. The particles are produced modified carbon fiber composite materials, namely: modified T700 PA6 composite material.
制得的复合材料可广泛应用于制作航空航天器材、 交通运输器材、 运动器 材、 土木建筑材料、 日常生活用品以及医疗器材等。 The composite materials obtained can be widely used in the production of aerospace equipment, transportation equipment, sports equipment, civil construction materials, daily necessities and medical equipment.
本发明的碳纤维表面改性剂含一个大腔体， 大腔体由碳、 氮、 氢和 /或氧共
12个原子组成的开环结构， 腔体内有多个 与氨基官能团， 能与碳纤维表面固 有的含氧羧基、 醛基、 酮基、 羟基等官能团发生化学反应或形成氢键， 它们通 过化学键吸附在碳纤维表面； 所述 R5和氨基与碳纤维表面的含氧羧基、 醛基、 酮基、 羟基官能团发生化学反应， 它们之间形成化学键， 以此表面活性剂通过 化学键牢固吸附在碳纤维表面； 或 R5和氨基与碳纤维表面的含氧羧基、 醛基、 酮基、 羟基官能团形成氢键 ， 它们通过范德华力， 牢固结合在一起。 同时碳纤 维表面改性剂的 R3、 R4功能取代基团对树脂的选择相容性好， 热加工熔融状态 下， 它们与树脂基体的分子链间发生化学反应和物理交联。 针对不同种类树脂， 选用合适的本发明改性剂能使碳纤增强树脂材料的层间剪切强度提升 9-30%，本 发明能有效提高碳纤维与树脂的界面性能。 The carbon fiber surface modifier of the present invention comprises a large cavity, and the large cavity is composed of carbon, nitrogen, hydrogen and/or oxygen. The 12-atom open-loop structure has a plurality of amino functional groups in the cavity, which can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers. a carbon fiber surface; the R5 and the amino group chemically react with the oxygen-containing carboxyl group, the aldehyde group, the ketone group, and the hydroxyl group on the surface of the carbon fiber, and form a chemical bond therebetween, whereby the surfactant is firmly adsorbed on the surface of the carbon fiber through a chemical bond; or R5 and The amino group forms hydrogen bonds with the oxygen-containing carboxyl group, aldehyde group, ketone group, and hydroxyl group on the surface of the carbon fiber, and they are firmly bonded by van der Waals force. At the same time, the R3 and R4 functional substituent groups of the carbon fiber surface modifier have good compatibility with the resin selection, and they undergo chemical reaction and physical crosslinking with the molecular chain of the resin matrix in the hot working molten state. For different types of resins, the selection of a suitable modifier of the present invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the present invention can effectively improve the interfacial properties of the carbon fiber and the resin.
下面结合实施例和对比例对本发明碳纤维表面改性剂、 碳纤维表面改性剂 的制备方法、 碳纤维表面改性剂制得的改性碳纤维、 改性碳纤维的制备方法、 改性碳纤维与树脂制备的复合材料、 复合材料的制备方法、 以及复合材料的应 用作进一歩详细的描述， 但本发明的实施方式不限于此。 Hereinafter, the carbon fiber surface modifier of the present invention, the preparation method of the carbon fiber surface modifier, the modified carbon fiber prepared by the carbon fiber surface modifier, the preparation method of the modified carbon fiber, the modified carbon fiber and the resin are prepared in combination with the examples and the comparative examples. The composite material, the method of preparing the composite material, and the application of the composite material are described in detail, but the embodiment of the invention is not limited thereto.
实施例 1， Example 1,
一种碳纤维表面改性剂及其制备方法， 其歩骤如下： A carbon fiber surface modifier and a preparation method thereof, the steps of which are as follows:
碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol l, 1-二甲基 -1， 2- 二胺 (A1), 加入 300mL 乙醇将其溶解， 再滴加 3， 5-二羟基水杨醛 (0.2mol) 的 300 mL 乙醇溶液 (Bl)， 控制聚合釜温度 55 °C， 回流 6h后， 加入 300 mL DMSO溶液， 控制聚合签温度 0 °C， 再加入 4当量的 Na2BH4， 搅拌， 直到反 应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12 萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳 纤维表面改性剂 Cl， 碳纤维表面改性剂 C1为白色固体， 熔点 183-184Ό; 核磁 数据为： 1HNMR(CDC13， 500 MHz, TMS) (56.36(s, 2H)， 6.13 (s, 2H)， 5.35(s， 6H)， 3.76 (d, 4H)， 2.61(d, 2H)， 2.23(s, 2H), 1.27 (s, 6H); 13C NMR (CDC13, 125 MHz, TMS)^ 150.9, 146.1, 138.5， 126.3, 110.5， 106.5, 64.2, 58.3, 49.2, 43.2, 17.6， 分子结构式如式 （II) 所示。
Preparation of carbon fiber surface modifier: Add 1.5 mol of 1-dimethyl-1,2-diamine (A1) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3, 5- Dihydroxysalicylaldehyde (0.2mol) in 300 mL ethanol solution (Bl), control the polymerization temperature of 55 °C, reflux for 6h, add 300 mL of DMSO solution, control the polymerization temperature 0 °C, then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The water layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier Cl. The carbon fiber surface modifier C1 was white solid. , mp 183-184 Ό; NMR data: 1H NMR (CDC1 3 , 500 MHz, TMS) (56.36 (s, 2H), 6.13 (s, 2H), 5.35 (s, 6H), 3.76 (d, 4H), 2.61 (d, 2H), 2.23(s, 2H), 1.27 (s, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS)^ 150.9, 146.1, 138.5, 126.3, 110.5, 106.5, 64.2, 58.3, 49.2 , 43.2, 17.6, the molecular structural formula is shown in formula (II).
C1 C1
式 （II) Formula (II)
碳纤维表面改性剂制备改性碳纤维的方法： 利用二甲基亚砜（DMSO)和水 溶解碳纤维表面改性剂 Cl， 碳纤维表面改性剂 C1的浓度为 1.2wt%， 对型号为 T700碳纤维表面进行浸润改性， 烘干后得到表面改性碳纤维。 Carbon fiber surface modifier for preparing modified carbon fiber: Dissolving carbon fiber surface modifier Cl with dimethyl sulfoxide (DMSO) and water, carbon fiber surface modifier C1 concentration is 1.2 wt%, for model T700 carbon fiber surface The infiltration modification is carried out, and the surface-modified carbon fiber is obtained after drying.
为了判断上述碳纤维表面改性剂制备改性碳纤维的方法中制备的表面改性 碳纤维的改性效果： 在 20 °C下， 按国建材行业标准： JC/T 773-2010/ISO 14130: 1997测量碳纤维改性前后与 PA6树脂结合的层间剪切强度 (ILSS)。 请参阅图 1， 改性前碳纤维的剪切强度为 76.83MPa， 改性后碳纤维的剪切强度为 84.41MPa， 可见碳纤维经 C1物质改性后， 改性 T700碳纤维提高了 9.86%。 印证了本发明 物质 C1的 R3、 R4功能取代基对 PA6树脂具有选择相容性好的特点。 In order to judge the modification effect of the surface-modified carbon fiber prepared by the above method for preparing the modified carbon fiber by the carbon fiber surface modifier: at 20 ° C, according to the national building materials industry standard: JC/T 773-2010/ISO 14130: 1997 Interlaminar shear strength (ILSS) combined with PA6 resin before and after carbon fiber modification. Referring to Figure 1, the shear strength of the modified carbon fiber is 76.83 MPa, and the shear strength of the modified carbon fiber is 84.41 MPa. It can be seen that the modified T700 carbon fiber is improved by 9.86% after the carbon fiber is modified by the C1 substance. It is confirmed that the R 3 and R 4 functional substituents of the substance C1 of the present invention have the characteristics of good compatibility with the PA6 resin.
改性的碳纤维与树脂制备改性碳纤维 /树脂的复合材料的方法： 采用改性的 T700碳纤维与 PA6制备复合材料， 其制备方法如下： 经改性剂式 II改性后的碳纤维作为增强组分甲： 10wt%; PA6树脂作为基体组 分乙： 85wt%; 加工助剂作为组分丙： 5wt%( N, 双 -(3-(3,5-二叔丁基 -4-羟基 苯基)丙酰基)己二胺: lwt%、 2- (2H-苯并三唑 -2) -4， 6-二 ( 1-甲基小苯乙基) 苯酚: lwt%、 Licomont® CaV 102:lwt%, 芥酸酰胺: 2wt%); Method for preparing modified carbon fiber/resin composite material by modified carbon fiber and resin: The composite material is prepared by using modified T700 carbon fiber and PA6, and the preparation method is as follows: carbon fiber modified by modifier II is used as reinforcing component A: 10wt% ; PA6 resin as matrix component B: 85wt%; processing aid as component C: 5wt% (N, bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)) Propionyl) hexamethylenediamine: lwt%, 2-(2H-benzotriazol-2)-4,6-bis(1-methylbenzophenethyl)phenol: lwt%, Licomont® CaV 102: lwt% , erucamide: 2wt%);
将组分甲、 乙、 丙在双螺杆挤出机 (ZSK 25， Werner & Pfleiderer)中挤出 水冷造粒：树脂与助剂混合主喂料，碳纤维侧喂料，挤出机加热区 1-6区（230〜 280。C )， 转速为 150 rpm， 产能 6kg/小时。 制得的 T700碳纤维与 PA6的复合材料可应用领域包括： 汽车、 医疗、 食品 加工业、 化工领域； 具体制备的零部件包括： 动机部位包括进气系统和燃油系 统， 如发动机气缸盖罩、 节气门、 空气滤清器机器外壳， 车用空气喇叭、 车用 空调软管、 冷却风扇及其外壳、 进水管、 刹车油罐及灌盖， 等等。 车体部位零
部件有： 汽车挡泥板、 后视镜架、 保险杠、 仪表盘、 行李架、 车门手柄、 雨刷 支架、 安全带扣搭、 车内各种装饰件等等。 车内电器方面如电控门窗、 连接 器、 保鲜盒、 电缆扎线等。 The components A, B and C were extruded in a twin-screw extruder (ZSK 25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1 Zone 6 (230~ 280.C), with a speed of 150 rpm and a capacity of 6kg/hour. The composite materials of T700 carbon fiber and PA6 can be applied in the fields of automotive, medical, food processing, and chemical industry. The specific components include: the motive part includes the air intake system and the fuel system, such as the engine cylinder cover and section. Valves, air filter housings, automotive air horns, automotive air conditioning hoses, cooling fans and their enclosures, inlet pipes, brake oil tanks and gluing, etc. Body part zero The components are: car fenders, rear view frames, bumpers, dashboards, luggage racks, door handles, wiper brackets, seat belt buckles, various decorative parts in the car, and more. In-car electrical appliances such as electronically controlled doors and windows, connectors, crisper boxes, cable ties, etc.
实施例 2， Embodiment 2,
一种碳纤维表面改性剂及其制备方法， 其歩骤如下： A carbon fiber surface modifier and a preparation method thereof, the steps of which are as follows:
碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol l, 1-二甲基 -1， 2- 二胺 （A2), 加入 300mL 乙醇将其溶解， 再滴加 4， 6-二丙氧基水杨醛（0.2mol) 的 300mL 乙醇溶液 (B2), 控制聚合釜温度 55°C, 回流 6h后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 Ό， 再加入 4当量的 Na2BH4， 搅拌， 直到反 应液无色为止， 反应完毕。 向反应体系加入 500mL 水， 分液。 水层用 CH2C12 萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳 纤维表面改性剂 C2， 碳纤维表面改性剂 C2为白色固体， 熔点 191-193O; 核磁 数据为 1HNMR(CDC13， 500 MHz, TMS) 36.18(s， 2H), 5.98 (s, 2H)， 5.29(s， 2H), 4.06(m， 8H), 3.75(d, 4H)， 2.58(d， 2H), 2.05(s, 2H), 1.74(m， 8H), 1.32(s, 6H), 0.85(m, 12H); 13C NMR (CDC13， 125 MHz, TMS) δ 160.2， 157.8， 156.3, 110.3， 106.5, 69.8， 63.4, 58.2， 42.7， 37.5, 22.5, 17.3, 10.6， 分子结 （III) 所示。
式 (III) Preparation of carbon fiber surface modifier: Add 1.5 mol of 1-dimethyl-1,2-diamine (A2) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4,6- Dipropoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B2), control the polymerization kettle temperature 55 ° C, reflux 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 Ό, then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C2. The carbon fiber surface modifier C2 was white solid. , mp 191-193O; NMR data: 1H NMR (CDC1 3 , 500 MHz, TMS) 36.18 (s, 2H), 5.98 (s, 2H), 5.29 (s, 2H), 4.06 (m, 8H), 3.75 (d , 4H), 2.58(d, 2H), 2.05(s, 2H), 1.74(m, 8H), 1.32(s, 6H), 0.85(m, 12H); 13 C NMR (CDC1 3 , 125 MHz, TMS ) δ 160.2, 157.8, 156.3, 110.3, 106.5, 69.8, 63.4, 58.2, 42.7, 37.5, 22.5, 17.3, 10.6, molecular knot (III). Formula (III)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C2， 浓度为 1.2wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C2 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
为了判断上述碳纤维表面改性剂制备改性碳纤维的方法中制备的表面改性 碳纤维的改性效果： 在 20 °C下， 按国建材行业标准： JC/T773-2010/ISO 14130:
1997测量碳纤维改性前后与 PEEK树脂结合的层间剪切强度 (ILSS)。请参阅图 2， 改性前碳纤维的剪切强度为 67.52MPa， 改性后碳纤维的剪切强度为 81.07MPa， 可见碳纤维经 C2物质改性后， 改性 T700碳纤维提高了 20.06%。 印证了本发明 物质 C2的 R3、 R4功能取代基对 PEEK树脂具有选择相容性好的特点。 In order to judge the modification effect of the surface-modified carbon fiber prepared by the above method for preparing the modified carbon fiber by the carbon fiber surface modifier: at 20 ° C, according to the national building materials industry standard: JC/T773-2010/ISO 14130: 1997. The interlaminar shear strength (ILSS) combined with PEEK resin before and after carbon fiber modification was measured. Referring to Figure 2, the shear strength of the modified carbon fiber is 67.52 MPa, and the shear strength of the modified carbon fiber is 81.07 MPa. It can be seen that the modified T700 carbon fiber is improved by 20.06% after the carbon fiber is modified by the C2 substance. It is confirmed that the R 3 and R 4 functional substituents of the substance C2 of the present invention have the characteristics of good compatibility with the PEEK resin.
改性的碳纤维与树脂制备改性碳纤维 /树脂的复合材料的方法： 采用改性 T700碳纤维与 PEEK制备复合材料， 其制备方法如下： 提供经改性剂式 （III) 改性后的碳纤维作为增强组分甲： 10wt%; PEEK树脂做 为基体组分乙： 85wt% ; 加工助剂为组分丙： 5wt%(双 (2，4-二叔丁基苯基)季戊 四醇二亚磷酸酯: lwt%、 2- (2H-苯并三唑 -2) -4， 6-二 ( 1-甲基 -1-苯乙基) 苯 酚: lwt%、 Licomont NaV101: lwt%. 芥酸酰胺: 2wt%); Method for preparing modified carbon fiber/resin composite material by modified carbon fiber and resin: The composite material is prepared by using modified T700 carbon fiber and PEEK, and the preparation method is as follows: providing modified carbon fiber as modified by formula (III) Component A: 10wt%; PEEK resin as matrix component B: 85wt% ; processing aid is component C: 5wt% (bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite: lwt %, 2-(2H-benzotriazol-2)-4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont NaV101: lwt%. erucamide: 2wt%) ;
将组分甲、 乙、 丙在双螺杆挤出机 (ZSK25， Werner&Pfleiderer)中挤出水冷 造粒： 树脂与助剂混合主喂料， 碳纤维侧喂料， 挤出机加热区 1-6 区 （330〜 420 °C ) ， 转速为 200rpm， 产能 8kg/小时。 The components A, B, and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 ( 330~ 420 °C), the speed is 200rpm, and the capacity is 8kg/hour.
该复合材料的应用领域包括： PEEK在航天、 医疗、 制药和食品加工业、 化工领域， 用于制作如， 卫星上的气体分析仪结构件、 热交换器刮片； 化工领 域如套筒轴承、 滑动轴承、 阀门座、 密封圈、 泵耐磨环、 电磁阀、 精密齿轮、 管材等。 Applications for this composite include: PEEK in the aerospace, medical, pharmaceutical and food processing industries, chemical industry, for the fabrication of gas analyzer structural components such as satellites, heat exchanger blades; chemical industry such as sleeve bearings, Sliding bearings, valve seats, seals, pump wear rings, solenoid valves, precision gears, pipes, etc.
实施例 3， Example 3,
一种碳纤维表面改性剂及其制备方法， 其步骤如下： A carbon fiber surface modifier and a preparation method thereof, the steps are as follows:
碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol l , 1， 2, 2-四甲基 -1， 2-二胺 （A3)， 加入 300 mL 乙醇将其溶解， 再滴加 4- (二丁氨基)水杨醛 (0.2mol) 的 300 mL 乙醇溶液 (B3)， 控制聚合釜温度 55 °C， 回流 6 h后， 加 入 300 mL DMSO溶液， 控制聚合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅 拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层 用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C3， 碳纤维表面改性剂 C3 为白色固体， 熔点
198-201 °C， 核磁数据为 1 H NMR (CDC13， 500 MHz , TMS) δ 6.88(m, 4H)， 6.15 (s， 2H)， 5.35(s， 2H)， 3.78(m, 8H)， 3.76(d, 4H)， 2.05(s， 2H)， 1.49(m, 8H)， 1.33(s , 12H), 1.31(m， 8H)， 0.89(m, 12H); 13C NMR (CDC13 , 125 MHz, TMS) 3 160.1， 149.8， 130.3 , 112.3， 105.5 , 98.9， 72.4， 53.5 , 30.2, 20.6， 15.3， 13.2, 分子结构式如式 （IV ) 所示。 Preparation of carbon fiber surface modifier: Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A3) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 4-(dibutylamino)salicylaldehyde (0.2mol) in 300 mL ethanol solution (B3), control the polymerization temperature of 55 °C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization temperature 0 °C Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C3 as a white solid. , melting point 198-201 °C, NMR data for 1 H NMR (CDC1 3 , 500 MHz , TMS) δ 6.88 (m, 4H), 6.15 (s, 2H), 5.35 (s, 2H), 3.78 (m, 8H), 3.76(d, 4H), 2.05(s, 2H), 1.49(m, 8H), 1.33(s, 12H), 1.31(m, 8H), 0.89(m, 12H); 13 C NMR (CDC1 3 , 125 MHz, TMS) 3 160.1, 149.8, 130.3, 112.3, 105.5, 98.9, 72.4, 53.5, 30.2, 20.6, 15.3, 13.2, The molecular structural formula is as shown in formula (IV).
式 （IV ) Formula (IV)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C3， 浓度为 1.2wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C3 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
为了判断上述碳纤维表面改性剂制备改性碳纤维的方法中制备的表面改性 碳纤维的改性效果： 在 20 °C下， 按国建材行业标准： JC/T 773-2010/ISO 14130： 1997测量碳纤维改性前后与 ABS树脂结合的层间剪切强度 (ILSS)。 请参 阅图 3， 改性前碳纤维的剪切强度为 71. 33MPa， 改性后碳纤维的剪切强度为 89. 06MPa, 可见碳纤维经 C3物质改性后， 改性 T700碳纤维的剪切强度提高了 24.85%。 印证了本发明物质 C3的 R3、 R4功能取代基对 ABS树脂具有选择相容性 好的特点。 In order to judge the modification effect of the surface-modified carbon fiber prepared by the above method for preparing the modified carbon fiber by the carbon fiber surface modifier: at 20 ° C, according to the national building materials industry standard: JC/T 773-2010/ISO 14130: 1997 Interlaminar shear strength (ILSS) combined with ABS resin before and after carbon fiber modification. Referring to Fig. 3, the shear strength of the modified carbon fiber is 71.33 MPa, and the shear strength of the modified carbon fiber is 89. 06 MPa. It can be seen that the shear strength of the modified T700 carbon fiber is improved after the carbon fiber is modified by the C3 substance. 24.85%. It is confirmed that the functional substituents of R 3 and R 4 of the substance C3 of the present invention have good compatibility with ABS resin.
改性的碳纤维与树脂制备改性碳纤维 /树脂的复合材料的方法： 采用改性后 的 T700碳纤维与 ABS制备复合材料， 其制备方法如下： 提供经改性剂式 （IV ) 改性后的碳纤维作为增强组分甲： 10wt% ; ABS树脂作 为基体组分乙： 85wt% ; 加工助剂作为组分丙： 5wt%( Irganox® 245: 1 wt%、 2-
(2H-苯并三唑 -2) -4， 6-二 ( 1-甲基 -1-苯乙基) 苯酚: lwt%、 Licomont Method for preparing modified carbon fiber/resin composite material by modified carbon fiber and resin: The composite material is prepared by using modified T700 carbon fiber and ABS, and the preparation method is as follows: providing modified carbon fiber modified by formula (IV) As reinforcing component A: 10wt%; ABS resin as matrix component B: 85wt%; processing aid as component C: 5wt% (Igganox® 245: 1 wt%, 2- (2H-benzotriazole-2) -4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont
NaV101:lwt%, 芥酸酰胺: 2wt%)。 NaV101: 1 wt%, erucamide: 2 wt%).
将组分甲、 乙、 丙在双螺杆挤出机 (ZSK25, Werner &Pfleiderer)中挤出水冷 造粒： 树脂与助剂混合主喂料， 碳纤维侧喂料， 挤出机加热区 1-6 区 （180〜 220 °C ) , 转速为 lOOrpm, 产能 4kg/小时。 The components A, B and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 (180~220 °C), the speed is lOOrpm, the capacity is 4kg/hour.
该复合材料的应用领域包括： 商业机械、 电子零件、 通讯设施、 个人计算 机、 电气器具、 汽车零件、 淋浴用具、 行李箱、 水龙头及其它家居用品。 如大 型家电、 汽车、 计算机外壳及配件壳。 Applications for this composite include: commercial machinery, electronic components, communication facilities, personal computers, electrical appliances, automotive parts, showers, luggage, faucets and other household items. Such as large appliances, cars, computer casings and accessories.
从上述实施例 1-3中， 改性后的碳纤维与树脂制得的复合材料， 与未改性的 碳纤维与树脂制得的复合材料进行剪切强度的比较， 可知， 通过碳纤维表面改 性剂对碳纤维进行改性， 大大提髙碳纤维与树脂的结合力。 经改性过的碳纤维 可广泛用于 PA、 PU、 PEEK, 聚烯烃等热塑性树脂， 制备力学性能优异的碳纤 维增强复合材料。 From the above Examples 1-3, the composite material obtained by modifying the carbon fiber and the resin, and the composite material prepared by the unmodified carbon fiber and the resin are compared with each other, and it is known that the carbon fiber surface modifier is passed. Modification of carbon fiber greatly enhances the bonding force between carbon fiber and resin. The modified carbon fiber can be widely used as a thermoplastic resin such as PA, PU, PEEK, or polyolefin to prepare a carbon fiber reinforced composite material having excellent mechanical properties.
以下实施例 4-17重点描述碳纤维表面改性剂的制备， 以及制得的碳纤维改 性剂制备改性碳纤维的方法， 以充分支持本发明中碳纤维表面改性剂的通式结 构； 对改性的碳纤维与树脂制备复合材料的方法以及检测验证不再重点描述， 通过制得碳纤维表面改性剂以及由改性剂制备的改性碳纤维可根据需要而选择 树脂与该改性碳纤维制备复合材料。 制得的改性碳纤维以及复合材料可通过在 20°C下， 按国建材行业标准： JC T 773-2010/ISO 14130： 1997测量碳纤维改性前 后的复合材料层间剪切强度 (ILSS)。可获知改性的碳纤维的剪切强度较未改性的 碳纤维剪切强度大大提高。 The following Examples 4-17 focus on the preparation of the carbon fiber surface modifier, and the method for preparing the modified carbon fiber by using the prepared carbon fiber modifier to fully support the general structure of the carbon fiber surface modifier in the present invention; The method for preparing composite materials of carbon fiber and resin and the verification and verification are not described in detail. The carbon fiber surface modifier and the modified carbon fiber prepared by the modifier can be selected according to the need to prepare a composite material between the resin and the modified carbon fiber. The modified carbon fiber and composite material obtained can measure the interlaminar shear strength (ILSS) of the composite before and after carbon fiber modification at 20 °C according to the national building materials industry standard: JC T 773-2010/ISO 14130: 1997. It is known that the shear strength of the modified carbon fiber is greatly improved compared to the shear strength of the unmodified carbon fiber.
实施例 4， Embodiment 4,
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 （A4)， 加入 300 mL 乙醇将其溶解， 再滴加 4-十八烷基水杨醛 （0.2mol) 的 300 mL 乙醇溶液 (B4)， 控制聚合釜温度 55°C， 回流 6 h后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅拌， 直到反
应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12 萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳 纤维表面改性剂 C4，分子式： C54H96N202;白色固体，熔点 200-20rC ; 1H NMR (CDC13， 500 MHz, TMS) <57.04(m， 2H)， 6.91(s， 2H)， 6.68(m， 2H)， 5.35(m， 2H)， 3.84(d, 4H)， 3.01(m， 2H), 2.62(m, 4H)， 2.03(m, 2H)， 1.59(m， 4H)， 1.32(m, 4H)， 1.28(m， 20H), 1.26(m， 36H)， 1.12(d, 6H)， 0.88(m， 6H); 13C NMR (CDC13， 125 MHz, TMS) 5 154.8, 141.4， 129.1 , 120.5 , 119.3， 114.8， 61.2， 45.7， 36.5， 32.9, 32.6， 32.3 , 31.5， 31.3 , , 31.2, 31.0, 29.9, 29.7， 29.6, 29.5， 29.4， 29.3， 29.2, 22.7， 14.1， 12.3 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-dimethyl-1,2-diamine (A4) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - octadecyl salicylaldehyde (0.2mol) in 300 mL ethanol solution (B4), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until anti The reaction is completed until the liquid is colorless. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C4, molecular formula: C 54 H 96 N 2 0 2; white solid, m.p.: 200-20 s.; NMR (CDC1 3 , 500 MHz, TMS) <57.04 (m, 2H), 6.91 (s, 2H), 6.68 (m, 2H), 5.35 (m, 2H), 3.84(d, 4H), 3.01(m, 2H), 2.62(m, 4H), 2.03(m, 2H), 1.59(m, 4H), 1.32(m, 4H), 1.28(m, 20H), 1.26 (m, 36H), 1.12(d, 6H), 0.88(m, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) 5 154.8, 141.4, 129.1, 120.5, 119.3, 114.8, 61.2, 45.7, 36.5 , 32.9, 32.6, 32.3, 31.5, 31.3, , 31.2, 31.0, 29.9, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 22.7, 14.1, 12.3
C4 C4
式 （V) Formula (V)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C4， 浓度为 1.3wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C4 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 5， Embodiment 5,
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmoll , 2-二胺 (A5)， 加入 300mL乙醇将其溶解，再滴加 4-十五垸基 -2-羟基-水杨醛 (0.2mol)的 300mL 乙醇溶液 (B5)， 控制聚合釜温度 65 °C， 回流 6h后， 加入 300mLDMSO溶液， 控 制聚合釜温度 0°C， 再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反 应完毕。 向反应体系加入 500mL水， 分液。 水层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C5， 分子式： C46H8。N2O4，黄色固体，熔点 240-242°C ; 1H NMR (CDC13, 500 MHz, TMS) ^ 6.57(s, 2H), 5.35(m, 2H), 3.76(d, 4H)， 2.62(m, 4H)， 2.54(m,
4H)， 2.02(m, 2H)， 1.59(m， 4H)， 1.29(m， 20H)， 1.26(m， 24H)， 1.31(m， 6H)， 0.87(m， 6H); 13C NMR (CDC13， 125 MHz, TMS) <5 156.6, 144.4， 107.8 , 48.9, 41.3, 36.3， 36.2， 36.1， 31.9, 31.6, 31.3 , 31.2 , 29.8, 29.6， 29.5， 29.4， 29.3 , 29.2， 22.7 , 14.3 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-molar, 2-diamine (A5) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-pentyl-2-hydroxy- Salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B5), control the polymerization temperature of the reactor at 65 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH4, stir, The reaction was completed until the reaction solution was colorless. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C5, molecular formula: C 46 H 8 . N 2 O 4, as a yellow solid, mp 240-242 ° C; 1H NMR (CDC1 3, 500 MHz, TMS) ^ 6.57 (s, 2H), 5.35 (m, 2H), 3.76 (d, 4H), 2.62 ( m, 4H), 2.54 (m, 4H), 2.02(m, 2H), 1.59(m, 4H), 1.29(m, 20H), 1.26(m, 24H), 1.31(m, 6H), 0.87(m, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) <5 156.6, 144.4, 107.8, 48.9, 41.3, 36.3, 36.2, 36.1, 31.9, 31.6, 31.3, 31.2, 29.8, 29.6, 29.5, 29.4, 29.3, 29.2, 22.7, 14.3
C5 C5
式 （VI) Formula (VI)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C5， 浓度为 1.6wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: using a DMSO and water to dissolve a carbon fiber surface modifier C5 at a concentration of 1.6 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
实施例 6， Example 6
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmoll , 1， 2, 2-四 甲基 -1， 2-二胺 (A6), 加入 300mL乙醇将其溶解， 再滴加 1-甲酰基 -2-羟基 -4-苯 乙醇乙酯（0.2mol)的 300mL乙醇溶液 (B6)，控制聚合釜温度 60°C， 回流 8h后， 加入 300mLDMSO溶液， 控制聚合釜温度 0°C，再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止，反应完毕。向反应体系加入 500mL水，分液。水层用 CH2C12 萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳 纤维表面改性剂 C6， 分子式：C28H40N2O6，白色固体，熔点 180-182°C ; 1H NMR (CDC13 , 500 MHz, TMS) <57.02(m, 2H)， 6.91(s， 2H)， 6.54(m， 2H), 5.35(m, 2H)， 4.42(m， 4H)， 3.78(d, 4H)， 2.86(m, 4H)， 2.02(m, 2H)， 2.22(s, 6H)， 1.32(s , 6H); 13C NMR (CDC13， 125 MHz, TMS) δ 170.2, 154.8 , 137.4, 129.5, 120.3 , 119.4， 114.2， 72.5 , 64.9, 43.5 , 34.7， 20.8, 15.6
Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A6) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 1-formyl-2-hydroxy-4-phenylethylethyl ester (0.2 mol) in 300 mL ethanol solution (B6), control the polymerization kettle temperature 60 ° C, reflux for 8 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the liquid was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C6, molecular formula: C 28 H 40 N 2 O 6 , white solid, melting point 180-182 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) <57.02 (m, 2H), 6.91 (s, 2H), 6.54 (m, 2H), 5.35 (m, 2H) ), 4.42(m, 4H), 3.78(d, 4H), 2.86(m, 4H), 2.02(m, 2H), 2.22(s, 6H), 1.32(s, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) δ 170.2, 154.8, 137.4, 129.5, 120.3, 119.4, 114.2, 72.5, 64.9, 43.5, 34.7, 20.8, 15.6
C6 C6
式 （VII) Formula (VII)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C6, 浓度为 1.5wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C6 is dissolved in DMSO and water at a concentration of 1.5 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 7， Example 7,
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 (A7), 加入 300 mL 乙醇将其溶解， 再滴加 5-甲酰基 -6-羟基-苯乙酸 甲酯（0.2mol)的 300 mL 乙醇溶液 (B7)， 控制聚合釜温度 55°C， 回流 6 h后， 加入 300 mL DMSO溶液，控制聚合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅 拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层 用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C7， 分子式： C22H32N206， 黄色固体， 熔点 188-190 °C ; 1H NMR (CDC13, 500 MHz, TMS) ^ 6.99(m, 2H), 6.88(m， 4H)， 3.76(d, 4H)， 3.72(s, 4H)， 3.68(s， 6H)， 2.59(d, 2H)， 2.02(m, 2H)， 1.34(s， 6H)); 13C NMR (CDC13, 125 MHz, TMS) ^ 171.2, 154.0， 131.2， 128.3 , 126.5 , 124.6, 121.2, 63.8， 58.2, 51.9 , 48.8， 43.2, 36.2, 17.3 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-dimethyl-1,2-diamine (A7) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 5 -formyl-6-hydroxy-phenylacetic acid methyl ester (0.2mol) in 300 mL ethanol solution (B7), control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C7, molecular formula: C 22 H 32 N 2 0 6 , yellow solid, mp 188-190 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) ^ 6.99 (m, 2H), 6.88 (m, 4H), 3.76 (d, 4H), 3.72 (s, 4H ), 3.68(s, 6H), 2.59(d, 2H), 2.02(m, 2H), 1.34(s, 6H)); 13 C NMR (CDC1 3 , 125 MHz, TMS) ^ 171.2, 154.0, 131.2, 128.3, 126.5, 124.6, 121.2, 63.8, 58.2, 51.9, 48.8, 43.2, 36.2, 17.3
C7 C7
式 （VIII)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C7, 浓度为 1.3wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 Formula (VIII) Method for preparing modified carbon fiber by carbon fiber surface modifier: The carbon fiber surface modifier C7 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
实施例 8， Example 8,
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 (A8)， 加入 300 mL 乙醇将其溶解， 再滴加 3-九垸基苯甲醛 (0.2mol) 的 300 mL 乙醇溶液 (B8)， 控制聚合釜温度 55°C， 回流 6 h后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅拌， 直到反 应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12 萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳 纤维表面改性剂 C8， 分子式： C36H6DN2， 白色固体，熔点 171-173 °C ; 1H NMR (CDC13， 500 MHz, TMS) <57.50(m， 2H)， 7.18(m， 2H)， 7.12(m， 2H)， 7.05(m, 2H), 3.82(d, 4H)， 3.02(m, 2H), 2.62(m, 4H)， 2.02(m, 2H)， 1.59(m， 4H)， 1.31(m, 4H) 1.29(m, 20H), 1.12(d, 6H)， 0.88(m, 6H); 13C NMR (CDC13, 125 MHz, TMS) ^ 143.2, 136.4, 128.6， 128.5 , 126.4, 125.2, 61.3， 52.2， 36.0， 31.8， 31.2 , 29.6， 29.5, 29.4, 29.3 , 22.8， 14.3 , 12.5 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-dimethyl-1,2-diamine (A8) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 - Jiuhexylbenzaldehyde (0.2mol) in 300 mL ethanol solution (B8), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents Na 2 BH 4 was stirred until the reaction mixture was colorless and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C8, molecular formula: C 36 H 6D N 2 , White solid, mp 171-173 ° C ; 1H NMR (CDC1 3 , 500 MHz, TMS) <57.50 (m, 2H), 7.18 (m, 2H), 7.12 (m, 2H), 7.05 (m, 2H), 3.82(d, 4H), 3.02(m, 2H), 2.62(m, 4H), 2.02(m, 2H), 1.59(m, 4H), 1.31(m, 4H) 1.29(m, 20H), 1.12( d, 6H), 0.88 (m, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) ^ 143.2, 136.4, 128.6, 128.5, 126.4, 125.2, 61.3, 52.2, 36.0, 31.8, 31.2, 29.6, 29.5 , 29.4, 29.3, 22.8, 14.3, 12.5
C8 C8
式（IX) Formula (IX)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C8， 浓度为 1.2wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C8 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 9， Example 9,
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 (A9), 加入 300 mL 乙醇将其溶解， 再滴加 3-甲酰基 -4-羟基-苯丙酰胺
(0.2mol) 的 300 mL 乙醇溶液 (B9)， 控制聚合釜温度 60 °C， 回流 6 h后， 加 入 300 mL DMSO溶液， 控制聚合釜温度 0 V， 再加入 4当量的 Na2BH4， 搅 拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层 用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C9 , 分子式： C24H34N404， 棕色固体， 熔点 169-171 °C ; 1H NMR (CDC13， 500 MHz, TMS) (5 7.18(s， 4H)， 6.98 (s , 2H)， 6.93(m, 2H)， 6.79(m, 2H)， 5.30(s , 2H)， 3.82(d, 4H)， 3.05(q, 2H)， 2.82(t, 2H)， 2.56(t， 2H)， 2.01(m， 2H)， 1.12(s， 6H); 13C NMR (CDC13， 125 MHz, TMS) 175.2, 153.6， 131.8 , 129.9， 128.6 , 123.5， 115.3 , 61.2, 46.1 , 35.5 , 31.4, 12.5 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-dimethyl-1,2-diamine (A9) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 -formyl-4-hydroxy-phenylpropanamide (0.2mol) 300mL ethanol solution (B9), control the polymerization temperature of the reactor at 60 °C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 BH 4 , stir , until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and then evaporated to give a carbon fiber surface modifier C9. Molecular formula: C 24 H 34 N 4 0 4 , brown solid, melting point 169-171 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) (5 7.18 (s, 4H), 6.98 (s, 2H), 6.93 (m, 2H), 6.79 (m, 2H), 5.30(s, 2H), 3.82(d, 4H), 3.05(q, 2H), 2.82(t, 2H), 2.56(t, 2H), 2.01(m, 2H), 1.12(s, 6H) 13 C NMR (CDC1 3 , 125 MHz, TMS) 175.2, 153.6, 131.8, 129.9, 128.6, 123.5, 115.3, 61.2, 46.1, 35.5, 31.4, 12.5
式 （x) Formula (x)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C9， 浓度为 1.7wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C9 is dissolved in DMSO and water at a concentration of 1.7 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 10 Example 10
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1 , 2-二甲基 -1， 2-二胺 (A10)， 加入 300 mL 乙醇将其溶解， 再滴加 2-甲酰基 - 1-羟基-萘丙酰胺 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1,2-dimethyl-1,2-diamine (A10) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 2 -formyl 1-hydroxy-naphthylpropionamide
(0.2mol) 的 300 mL 乙醇溶液 (B10)， 控制聚合签温度 60。C， 回流 6 h后， 加入 300 mL DMSO溶液，控制聚合签温度 0 V， 再加入 4当量的 Na2BH4， 搅 拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层 用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C10 , 分子式： C32H38N404， 白色固体， 熔点 145-146°C ; 1H NMR (CDC13， 500 MHz, TMS) δ 8.20(m, 2H)， 8.17(m， 2H)，
7.58(m， 2H)， 7.53(m， 2H)， 7.19(s， 4H)， 6.82(s， 2H)， 5.32(s, 2H) , 3.87 (d, 4H)， 3.24(m, 4H)， 2.59(d, 2H)， 2.63(m， 4H)， 2.02(t, 2H), 1.32(s， 6H); 13C NMR (CDC13, 125 MHz, TMS) δ 174.2, 150.6, 131.6, 129.8 , 127.2, 125.9, 125.7， 125.3 , 124.5， 122.8 , 119.3 , 63.8 , 58.6 , 43.6, 35.7 , 29.4， 17.2 (0.2 mol) of 300 mL ethanol solution (B10), controlling the polymerization temperature of 60. C, After refluxing for 6 h, 300 mL of DMSO solution was added to control the polymerization temperature of 0 V, and then 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and the solution was evaporated to give a carbon fiber surface modifier C10. Molecular formula: C 32 H 38 N 4 0 4 , white solid, mp 145-146 ° C; 1 H NMR (CDC1 3 , 500 MHz, TMS) δ 8.20 (m, 2H), 8.17 (m, 2H), 7.58(m, 2H), 7.53(m, 2H), 7.19(s, 4H), 6.82(s, 2H), 5.32(s, 2H), 3.87 (d, 4H), 3.24(m, 4H), 2.59 (d, 2H), 2.63(m, 4H), 2.02(t, 2H), 1.32(s, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) δ 174.2, 150.6, 131.6, 129.8, 127.2, 125.9, 125.7, 125.3, 124.5, 122.8, 119.3, 63.8, 58.6, 43.6, 35.7, 29.4, 17.2
CIO CIO
式（XI) Formula (XI)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C10， 浓度为 1.9wt%>， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: using a DMSO and water to dissolve a carbon fiber surface modifier C10 at a concentration of 1.9 wt%>, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
实施例 11 Example 11
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 (All)， 加入 300 mL 乙醇将其溶解， 再滴加 3-甲酰基 -4-羟基-苯乙酰胺 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1-dimethyl-1,2-diamine (All) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 -formyl-4-hydroxy-phenylacetamide
(0.2mol) 的 300 mL 乙醇溶液 (Bll)， 控制聚合釜温度 55 °C， 回流 6 h后， 加入 300 mL DMSO溶液，控制聚合釜温度 0 V， 再加入 4当量的 Na2BH4， 搅 拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层 用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 Cll， 分子式： C24H34N404， 黄色固体， 熔点 163-165 °C ; 1H NMR (CDC13， 500 MHz, TMS) 7.15(s, 4H)， 6.93(s, 2H)， 6.88(m， 2H), 6.72(m， 2H), 5.35(s， 2H)， 3.85(s， 4H)， 3.77 (d, 4H)， 2.02(t， 2H), 1.28(s， 12H); 13C NMR (CDC13， 125 MHz, TMS) 3 172.4， 156.6， 131.7 , 128.1 , 129.5， 124.2， 116.3 , 72.5 , 43.9, 41.4， 15.4
(0.2mol) 300mL ethanol solution (Bll), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 BH 4 , stir , until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and the solution was evaporated to give a carbon fiber surface modifier C11, molecular formula: C 24 H 34 N 4 0 4 , yellow solid, mp 163-165 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) 7.15 (s, 4H), 6.93 (s, 2H), 6.88 (m, 2H), 6.72 (m, 2H) , 5.35(s, 2H), 3.85(s, 4H), 3.77 (d, 4H), 2.02(t, 2H), 1.28(s, 12H); 13 C NMR (CDC1 3 , 125 MHz, TMS) 3 172.4 , 156.6, 131.7, 128.1, 129.5, 124.2, 116.3, 72.5, 43.9, 41.4, 15.4
Cll Cll
式（XII) Formula (XII)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C11 , 浓度为 2.4wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 The carbon fiber surface modifier is used for preparing the modified carbon fiber: the carbon fiber surface modifier C11 is dissolved in DMSO and water at a concentration of 2.4 wt%, and the surface of the T700 carbon fiber is infiltrated and modified, and the surface modified carbon fiber is obtained after drying.
实施例 12 Example 12
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 2-二甲基 -1， 2-二胺 (A12), 加入 300 mL 乙醇将其溶解， 再滴加 B12 (0.2mol) 的 300 mL 乙 醇溶液， 控制聚合釜温度 55 °C， 回流 6 h后， 加入 300 mL DMSO溶液， 控制 聚合釜温度 0 V， 再加入 4当量的 Na2B ， 搅拌， 直到反应液无色为止， 反 应完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C12, 分子式： C34H60SiN2O4，白色固体，熔点 235-237 °C； ¾ NMR (CDC13， 500 MHz, TMS) δ 7.02(m, 2Η)， 6.53(m, 2Η)， 6.93(s, 2Η)， 5.35(s, 2Η)， 4.12(t, 4Η)， 3.85(d, 4Η)， 3.03(m, 2Η)， 2.76(t， 4Η)， 2.02(m， 2Η) , 1.13(s， 6H)， 0.98(s， 簡)， 0.22(s, 12H); 13C NMR (CDC13， 125 MHz， TMS) 3 154.9， 137.6, 129.2, 120.2， 119.6， 114.3， 61.2, 62.0, 45.8, 39.2， 30.3， 25.6, 12.4, -2.6 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 2-dimethyl-1,2-diamine (A12) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B12 dropwise. (0.2mol) 300mL ethanol solution, control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 B, stir until the reaction solution The color is complete and the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C12, molecular formula: C 34 H 60 SiN 2 O 4 , white solid, melting point 235-237 ° C; 3⁄4 NMR (CDC1 3 , 500 MHz, TMS) δ 7.02 (m, 2 Η), 6.53 (m, 2 Η), 6.93 (s, 2 Η), 5.35 (s, 2 Η ), 4.12(t, 4Η), 3.85(d, 4Η), 3.03(m, 2Η), 2.76(t, 4Η), 2.02(m, 2Η), 1.13(s, 6H), 0.98(s, Jane) , 0.22 (s, 12H); 13 C NMR (CDC1 3 , 125 MHz, TMS) 3 154.9, 137.6, 129.2, 120.2, 119.6, 114.3, 61.2, 62.0, 45.8, 39.2, 30.3, 25.6, 12.4, -2.6
OH OH
B12
B12
C12 C12
式 （XIII) Formula (XIII)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C12，浓度为 2.2wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 Method for preparing modified carbon fiber by carbon fiber surface modifier: The carbon fiber surface modifier C12 is dissolved in DMSO and water at a concentration of 2.2 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
实施例 13 Example 13
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1-甲基 -1， 2- 二胺 (A13), 加入 300 mL 乙醇将其溶解， 再滴加 B13 (0.2mol) 的 300 mL 乙醇 溶液， 控制聚合釜温度 55°C， 回流 6 h后， 加入 300 mLDMSO溶液， 控制聚 合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反应 完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C13, 分子式： C29H40SiN2Os，白色固体，熔点 155-157°C; ¾NMR (CDC13, 500 MHz, TMS)(56.99(s, 2H), 6.93(m, 2H), 6.78(m， 2H), 5.35(s， 2H), 3.83(d, 4H)， 3.55(s， 18H)， 3.03(m， 1H)， 2.76(s, 1H)， 2.61(m， 4H)， 2.56(s， 1H)， 2.02(m, 2H)， 1.76(m, 4H)， 1.12(d， 2H)， 0.56(m， 4H); 13C NMR (CDC13, 125 MHz, TMS)^ 154.8, 135.2, 130.2, 123.8, 121.4, 115.6， 55.7， 55.4， 50.4， 48.3, 45.7， 39.3, 16.8， 15.3, 15.1 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1-methyl-1,2-diamine (A13) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B13 (0.2 mol). 300 mL ethanol solution, control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until the reaction liquid is colorless The reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C13, molecular formula: C 29 H 40 SiN 2 O s , white solid, mp 155-157 ° C; 3⁄4 NMR (CDC1 3 , 500 MHz, TMS) (56.99 (s, 2H), 6.93 (m, 2H), 6.78 (m, 2H), 5.35 (s, 2H) , 3.83(d, 4H), 3.55(s, 18H), 3.03(m, 1H), 2.76(s, 1H), 2.61(m, 4H), 2.56(s, 1H), 2.02(m, 2H), 1.76(m, 4H), 1.12(d, 2H), 0.56(m, 4H); 13 C NMR (CDC1 3 , 125 MHz, TMS)^ 154.8, 135.2, 130.2, 123.8, 121.4, 115.6, 55.7, 55.4, 50.4, 48.3, 45.7, 39.3, 16.8, 15.3, 15.1
B13
B13
C13 C13
式（XIV ) Formula (XIV)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C13， 浓度为 2.2wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: using a DMSO and water to dissolve a carbon fiber surface modifier C13 at a concentration of 2.2 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
实施例 14 Example 14
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1-乙基 -1， 2- 二胺 (A14)， 加入 300 mL 乙醇将其溶解， 再滴加 4- (N， N-二乙羟基氨基） -水 杨醛 （0.2mol) 的 300 mL 乙醇溶液 (B14), 控制聚合釜温度 70°C， 回流 6 h 后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 V， 再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水 层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C14， 分子式： C26H42N406， 米黄色固体， 熔点 197-199 °C ; 1H NMR (CDC13, 500 MHz, TMS) <5 6.98(m, 2H)， 6.25 (m, 2H)，Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1-ethyl-1,2-diamine (A14) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-(N) , N-diethylhydroxyamino)-salicylaldehyde (0.2mol) in 300 mL ethanol solution (B14), control the polymerization temperature of 70 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C14, molecular formula: C 26 H 42 N 4 0 6 , beige solid, mp 197-199 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) <5 6.98 (m, 2H), 6.25 (m, 2H),
6.15(s， 2H)， 5.32(s , 2H)， 4.20(t， 8H)， 3.85(d, 4H)，
6.15(s, 2H), 5.32(s, 2H), 4.20(t, 8H), 3.85(d, 4H),
3.64(s, 4H)， 2.85(m, 1H)， 2.75(m， 1H)， 2.52(m, 1H)， 2.03(m, 2H), 3.64(s, 4H), 2.85(m, 1H), 2.75(m, 1H), 2.52(m, 1H), 2.03(m, 2H),
1.46(m， 2H)， 0.98(t, 3H); 13C NMR (CDC13， 125 MHz, TMS) 5 159.9，1.46 (m, 2H), 0.98 (t, 3H); 13 C NMR (CDC1 3 , 125 MHz, TMS) 5 159.9,
149.3 , 131.2, 111.9， 98.9, 62.3, 61.7, ， 58.9， 52.8, 45.7， 20.9,149.3, 131.2, 111.9, 98.9, 62.3, 61.7, , 58.9, 52.8, 45.7, 20.9,
10.6
10.6
C14 C14
式 （XV) Formula (XV)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C14， 浓度为 2.3wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C14 is dissolved in DMSO and water at a concentration of 2.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 15 Example 15
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1, 2-二甲基 -1， 2-二胺 (A15)， 加入 300 mL 乙醇将其溶解， 再滴加 4- (N， N-二 -2-甲氧基 -乙基 氨基） -水杨醛（0.2mol)的 300mL 乙醇溶液 (B15), 控制聚合釜温度 65°C， 回 流 6 h后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 。C， 再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水层用 CH2C12萃取， 合并有机层， 用无水 Na2SO4干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C15， 分子式： C3。H5。N406， 黄色固体， 熔点 255-257°C; 1HNMR(CDC13， 500 MHz, TMS) 6.78(m， 2H)， 6.24 (m， 2H), 6.15(s, 2H)， 5.35(s, 2H), 4.18(t， 8H)， 3.82(d, 4H)， 3.73(t， 8H)， 3.32(s, 12H)， 3.04(m， 2H), 2.02(m, 2H)， 1.16(d, 6H); 13C NMR (CDC13, 125 MHz, TMS) δ 160.2, 149.1, 130.3, 111.9, 105.6， 98.7, 70.5， 61.3, 59.4, 59.2, 45.8， 12.5
Preparation of a carbon fiber surface modifier: Add 1.5 mol of 0.1-dimethyl-1,2-diamine (A15) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - (N, N-di-2-methoxy-ethylamino)-salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B15), control the temperature of the polymerization vessel at 65 ° C, reflux for 6 h, add 300 mL The DMSO solution controls the temperature of the polymerization vessel to 0. C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C15, molecular formula: C 3 . H 5 . N 4 0 6 , yellow solid, mp 255-257 ° C; 1HNMR (CDC1 3 , 500 MHz, TMS) 6.78 (m, 2H), 6.24 (m, 2H), 6.15 (s, 2H), 5.35 (s, 2H), 4.18(t, 8H), 3.82(d, 4H), 3.73(t, 8H), 3.32(s, 12H), 3.04(m, 2H), 2.02(m, 2H), 1.16(d, 6H 13 C NMR (CDC1 3 , 125 MHz, TMS) δ 160.2, 149.1, 130.3, 111.9, 105.6, 98.7, 70.5, 61.3, 59.4, 59.2, 45.8, 12.5
C15 C15
式 （XVI) Formula (XVI)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C15， 浓度为 2.1wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C15 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 16 Example 16
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1-甲基 -1， 2- 二胺 (A16), 加入 300 mL 乙醇将其溶解， 再滴加 4- (2-乙基） -己烷氧基 -3-羟基 水杨醛 （0.2mol) 的 300 mL 乙醇溶液 (B16), 控制聚合釜温度 67°C， 回流 6 h 后， 加入 300 mL DMSO溶液， 控制聚合釜温度 0 °C， 再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水 层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C16， 分子式： C33H54N206， 淡黄色固体， 熔点 225-226 °C； 1H NMR (CDC13, 500 MHz, TMS) (5 6.58(m, 2H), 6.27 (m, 2H), 5.35(s， 4H)， 4.05(d， 1H)， 3.85(d, 4H)， 3.78(d, 1H)， 3.03(m, 1H)， 2.75(m， 1H)， 2.52(m， 1H)， 2.03(m, 2H)， 1.98(m， 2H)， 1.56(m， 4H)， 1.33(m, 4H)， 1.25(m, 8H), 1.14(d， 3H), 0.98(t, 6H)， 0.88(t, 6H); 13C NMR (CDC13， 125 MHz, TMS) ^ 147.8, 146.7, 136.5 , 122.3 , 116.8, 105.4, 75.6， 55.8， 55.4， 48.9， 48.4， 40.4， 30.9， 29.8， 23.5 , 23.0， 15.4， 14.2, 11.8
Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1-methyl-1,2-diamine (A16) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4- (2) -ethyl)-hexaneoxy-3-hydroxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B16), control the temperature of the polymerization vessel at 67 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization. The temperature of the kettle was 0 ° C, and 4 equivalents of Na 2 BH 4 was added thereto, and the mixture was stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C16, molecular formula: C 33 H 54 N 2 0 6 , pale yellow solid, mp 225-226 ° C; 1H NMR (CDC1 3 , 500 MHz, TMS) (5 6.58 (m, 2H), 6.27 (m, 2H), 5.35 (s, 4H), 4.05 (d , 1H), 3.85(d, 4H), 3.78(d, 1H), 3.03(m, 1H), 2.75(m, 1H), 2.52(m, 1H), 2.03(m, 2H), 1.98(m, 2H), 1.56(m, 4H), 1.33(m, 4H), 1.25(m, 8H), 1.14(d, 3H), 0.98(t, 6H), 0.88(t, 6H); 13 C NMR (CDC1 3 , 125 MHz, TMS) ^ 147.8, 146.7, 136.5, 122.3, 116.8, 105.4, 75.6, 55.8, 55.4, 48.9, 48.4, 40.4, 30.9, 29.8, 23.5, 23.0, 15.4, 14.2, 11.8
C16 C16
式（XVII) Formula (XVII)
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C16， 浓度为 2.1wt%， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C16 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
实施例 17 Example 17
一种碳纤维表面改性剂的制备： 1.5L的聚合釜中加入 O.lmol 1， 1， 2， 2- 四甲基 -1， 2-二胺 （A17), 加入 300 mL 乙醇将其溶解， 再滴加 3， 4-二癸垸氧 基水杨醛 （0.2mol) 的 300 mL 乙醇溶液 (B17), 控制聚合釜温度 70°C， 回流 6 h后，加入 300 mL DMSO溶液，控制聚合釜温度 0°C，再加入 4当量的 Na2BH4， 搅拌， 直到反应液无色为止， 反应完毕。 向反应体系加入 500 mL水， 分液。 水 层用 CH2C12萃取， 合并有机层， 用无水 Na2S04干燥， 静置， 过滤， 溶液旋蒸， 得到一种碳纤维表面改性剂 C17， 分子式： C28H4。N2O6， 白色固体， 熔点 187-189 °C ; 1H NMR (CDC13, 500 MHz, TMS) ^ 6.79(s , 2H), 6.33 (s , 2H), 5.35(s， 2H)， 4.08(m， 8H)， 3.78(d, 4H)， 2.01(m， 2H), 1.78(m， 8H)， 1.46(m， 8H)， 1.34(s， 12H), 1.32(m, 8H)， 1.29(m， 32H), 1.25(m， 8H)， 0.88(m， 12H); 13C NMR (CDC13, 125 MHz, TMS) ^ 147.5 , 146.3 , 141.2, 115.6， 114.3， 98.5， 72.6, 69.1， 43.9， 31.8， 29.6， 29.5， 29.3 , 29.2， 25.8, 23.8, 22.7 , 15.6, 14.3 Preparation of a carbon fiber surface modifier: Add 1.5 mol of 1,1,2,2-tetramethyl-1,2-diamine (A17) to a 1.5 L polymerization vessel, and dissolve it by adding 300 mL of ethanol. Then add 3, 4-dimethoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B17), control the temperature of the polymerization vessel at 70 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization kettle. At a temperature of 0 ° C, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated. The aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , stood, filtered, and evaporated to give a carbon fiber surface modifier C17, molecular formula: C 28 H 4 . N 2 O 6, as a white solid, mp 187-189 ° C; 1H NMR (CDC1 3, 500 MHz, TMS) ^ 6.79 (s, 2H), 6.33 (s, 2H), 5.35 (s, 2H), 4.08 ( m, 8H), 3.78(d, 4H), 2.01(m, 2H), 1.78(m, 8H), 1.46(m, 8H), 1.34(s, 12H), 1.32(m, 8H), 1.29(m , 32H), 1.25 (m, 8H), 0.88 (m, 12H); 13 C NMR (CDC1 3 , 125 MHz, TMS) ^ 147.5 , 146.3 , 141.2 , 115.6 , 114.3 , 98.5 , 72.6 , 69.1 , 43.9 , 31.8 , 29.6, 29.5, 29.3, 29.2, 25.8, 23.8, 22.7, 15.6, 14.3
碳纤维表面改性剂制备改性碳纤维的方法： 利用 DMSO和水溶解碳纤维表 面改性剂 C17， 浓度为 1.5wt%>， 对 T700碳纤维表面进行浸润改性， 烘干后得到 表面改性碳纤维。 A method for preparing a modified carbon fiber by using a carbon fiber surface modifier: a carbon fiber surface modifier C17 is dissolved in DMSO and water at a concentration of 1.5 wt%>, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
以上所述仅为本发明的实施例， 并非因此限制本发明的专利范围， 凡是利 用本发明说明书内容所作的等效结构或等效流程变换， 或直接或间接运用在其 他相关的技术领域， 均同理包括在本发明的专利保护范围内。
The above is only the embodiment of the present invention, and thus does not limit the scope of the patent of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied to other related technical fields, The same is included in the scope of patent protection of the present invention.
Claims
1.一种碳纤维表面改性剂， 其结构通式如式 （I ) 所示: A carbon fiber surface modifier having a structural formula of the formula (I):
( I ) (I)
式 （I ) 中， R2、 R2'各自彼此独立地代表氢、 羟基、 或 CrC3的烷 基； 、 各自彼此独立地代表 CrC18烷基、 （^-( 18烷氧基、 羟基、 氨基、 卤 素、 氢、 酰胺基、 酯基、 或硅氧基， 且 、 R4不同时为氢； R5代表氢、 羟基、 氨基、 卤素、 或垸氧基。 Of formula (I) wherein, R 2, R 2 'each independently of one another represent hydrogen, hydroxy or C r C 3 alkyl; each independently of one another represent C r C 18 alkyl, (^ - (18 alkoxy a group, a hydroxyl group, an amino group, a halogen, a hydrogen, an amide group, an ester group, or a siloxy group, and R 4 is not hydrogen at the same time; and R 5 represents hydrogen, a hydroxyl group, an amino group, a halogen, or a decyloxy group.
2. —种碳纤维表面改性剂， 其结构式中包括一个腔体， 腔体为碳、 氮、 氢、 以及和 /或氧共 12个原子构成， 腔体内有取代基团 与氨基官能团， 所述 包 括氢、 羟基、 氨基、 卤素或烷氧基， 所述 R5和氨基与碳纤维表面的含氧羧基、 醛基、 酮基、 羟基官能团发生化学反应或形成氢键， 使得碳纤维表面改性剂通 过化学键吸附在碳纤维表面。 2. A carbon fiber surface modifier comprising a cavity comprising a carbon, nitrogen, hydrogen, and/or oxygen 12 atoms, a substituent group and an amino functional group in the cavity, Including hydrogen, a hydroxyl group, an amino group, a halogen or an alkoxy group, the R 5 and the amino group chemically react with or form a hydrogen bond with an oxygen-containing carboxyl group, an aldehyde group, a ketone group or a hydroxyl group on the surface of the carbon fiber, so that the carbon fiber surface modifier passes through Chemical bonds are adsorbed on the surface of the carbon fiber.
3. 根据权利要求 2所述的碳纤维表面改性剂， 其特征在于： 所述结构式如 式 （I) 所示： The carbon fiber surface modifier according to claim 2, wherein the structural formula is as shown in the formula (I):
( I ) (I)
式 （I ) 中， R2、 R, '各自彼此独立地代表氢、 羟基、 或 CrC3的垸 基； R3、 各自彼此独立地代表 CrC18烷基、 ^18垸氧基、 羟基、 氨基、 卤 素、 氢、 酰胺基、 酯基、 或硅氧基， 且 、 R4不同时为氢。
Of formula (I) wherein, R 2, R, 'are each independently of one another represent hydrogen, hydroxy or C r C alkyl with 3; R & lt 3, independently of one another represent C r C 18 alkyl group, 18 ^ alkoxy embankment a hydroxyl group, an amino group, a halogen, a hydrogen, an amide group, an ester group, or a siloxy group, and R 4 is not hydrogen at the same time.
4. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述 Ri、 R2、 R R2'各自独立地选择甲基、 乙基或氢。 The carbon fiber surface modifier according to claim 1 or 3, wherein the Ri, R 2 and RR 2 ' each independently select a methyl group, an ethyl group or a hydrogen group.
5. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述 R5 选自羟基。 The carbon fiber surface modifier according to claim 1 or 3, wherein the R 5 is selected from a hydroxyl group.
6.根据权利要求 1或 3所述的碳纤维表面改性剂，其特征在于：所述 d-C18 垸基指具有 1-18个碳原子的直链或支链的烷基。 The carbon fiber surface modifier according to claim 1 or 3, wherein the dC 18 fluorenyl group means a linear or branched alkyl group having 1 to 18 carbon atoms.
7. 根据权利要求 6所述的碳纤维表面改性剂， 其特征在于： 所述 d-dJ^ 基选则十四垸基或十八烷基。 The carbon fiber surface modifier according to claim 6, wherein the d-dJ group is selected from a tetradecyl group or an octadecyl group.
8.根据权利要求 1或 3所述的碳纤维表面改性剂，其特征在于：所述 CrC18 烷氧基是指具有 1-18个碳原子的直链或支链的烷氧基。 The carbon fiber surface modifier according to claim 1 or 3, wherein the C r C 18 alkoxy group means a linear or branched alkoxy group having 1 to 18 carbon atoms.
9. 根据权利要求 8所述的碳纤维表面改性剂， 其特征在于： 所述 d-C18垸 氧基选则丙氧基、 2-乙基-己氧基、 或癸氧基。 The carbon fiber surface modifier according to claim 8, wherein the dC 18 methoxy group is selected from a propoxy group, a 2-ethyl-hexyloxy group, or a decyloxy group.
10. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述卤 素包括氟、 氯、 溴或碘原子。 The carbon fiber surface modifier according to claim 1 or 3, wherein the halogen atom comprises a fluorine, chlorine, bromine or iodine atom.
11 . 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述酰 胺基分子式为 -(CH2)nCONH-R， n取 1-15的任意整数， R是 CrC18的直链或支链 的垸基、 或氢。 The carbon fiber surface modifier according to claim 1 or 3, wherein the amide group has the formula -(CH 2 ) n CONH-R, n is an arbitrary integer of 1-15, and R is C r A linear or branched fluorenyl group of C 18 , or hydrogen.
12. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述酯 基的分子式为 -(CH2)nCO2-R， n取 1-15的整数， R是 CrCls的直链或支链的垸基。 The carbon fiber surface modifier according to claim 1 or 3, wherein the ester group has the formula -(CH 2 ) n CO 2 -R, n is an integer from 1 to 15, and R is C. Linear or branched fluorenyl group of r C ls .
13. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述氨 基包括 -NH2、 -NHR^ -NRiR2, 其中 、 R2各自彼此独立地代表 CrC18烷基及 其衍生物。 The carbon fiber surface modifier according to claim 1 or 3, wherein the amino group comprises -NH 2 , -NHR^ -NRiR 2 , wherein R 2 each independently represents C r C 18 alkane Base and its derivatives.
14. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述 R3、 R4彼此独立地选自十四烷基、 十八垸基、 乙酰胺基、 丙酰胺基、 乙酸基甲酯、 乙醇基乙酯、丙氧基、 （2-乙基） -己氧基、癸氧基、 N, N-二 -2-甲氧基 -乙基氨基、 N, N-二乙羟基氨基， -ΝΗ2、 羟基、 氢、 三甲基硅氧基、 叔丁基二甲基硅氧基、 - (CH2) 3Si (OCH3) 3、 - (CH2) 2OSi (CH3 ) 2C(C¾) 3、 或 -(CH2)6Si (CH3)
The carbon fiber surface modifier according to claim 1 or 3, wherein the R 3 and R 4 are independently selected from the group consisting of tetradecyl, octadecyl, acetamido, and propionamide. Methyl acetate, ethyl ethoxide, propoxy, (2-ethyl)-hexyloxy, decyloxy, N, N-di-2-methoxy-ethylamino, N, N-di Ethylhydroxyamino, -ΝΗ 2 , hydroxy, hydrogen, trimethylsilyloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH 3 ) 3, - (CH 2 ) 2 OSi ( CH 3 ) 2 C(C3⁄4) 3 , or -(CH 2 ) 6 Si (CH 3 )
15. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述改The carbon fiber surface modifier according to claim 1 or 3, wherein:
i i i i
、 I I ^2 I I ^2
f生碳纤维改进剂结构式为：
The structure of the f-carbon fiber improver is:
16. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述改
The carbon fiber surface modifier according to claim 1 or 3, wherein:
f生碳纤维改进剂结构式如式 （C1 ) 所示： The structure of the f-carbon fiber improver is as shown in the formula (C1):
17. 根据权利要求 1或 3所述的碳 ， 其特征在于： 所述改
17. The carbon according to claim 1 or 3, characterized in that:
性碳纤维改进剂结构式如式 （C2) 所示： C2 。 The structural formula of the carbon fiber improver is as shown in formula (C2): C2.
18. 根据权利要求 1或 3所述的碳纤维表面改性剂， 其特征在于： 所述改 The carbon fiber surface modifier according to claim 1 or 3, wherein:
性碳纤维改进剂结构式如式 （C3 ) 所示：
The structural formula of the carbon fiber improver is as shown in formula (C3):
19. 一种权利要求 1-14任意一项所述的碳纤维表面改性剂的制备方法， 包 括如下步骤： 19. A method of preparing a carbon fiber surface modifier according to any of claims 1-14, comprising the steps of:
提供组分 A和组分 B : Provide component A and component B:
其中组分 A为乙二胺衍生物， 其结构式为：
， 组分 B为水杨
醛衍生物或苯甲醛衍生物， 其结构式为：
Wherein component A is an ethylenediamine derivative, the structural formula of which is: , component B is salicy An aldehyde derivative or a benzaldehyde derivative having the structural formula:
通过组分 A和组分 B制备碳纤维表面改性剂 C， 制备过程反应式如下: The carbon fiber surface modifier C is prepared by the component A and the component B, and the reaction process is as follows:
A B c A B c
反应式中包括反应步骤如下 The reaction steps included in the reaction formula are as follows
缩合反应： 组分 A和组分 B按摩尔比 1:2-1:4溶解在乙醇溶液中， 温度为 0-70 °C , 反应时间为 l-8h; Condensation reaction: component A and component B molar ratio 1:2-1:4 dissolved in ethanol solution, the temperature is 0-70 ° C, the reaction time is l-8h;
还原反应： 缩合反应完成后， 加入过量的 Na2BH4和 DMSO继续反应， 反 应温度为 0-10°C， 反应时间为 l-6h。 Reduction reaction: After the condensation reaction is completed, the reaction is continued by adding an excess of Na 2 BH 4 and DMSO at a reaction temperature of 0 to 10 ° C for a reaction time of 1 to 6 hours.
20. 根据权利要求 19所述的碳纤维表面改性剂的制备方法， 其特征在于： 所述还原反应后的产物再经萃取， 干燥， 溶液旋蒸， 得到碳纤维表面改性剂。 The method for preparing a carbon fiber surface modifier according to claim 19, wherein the product after the reduction reaction is further subjected to extraction, drying, and the solution is rotary-screwed to obtain a carbon fiber surface modifier.
21. 根据权利要求 19所述的碳纤维表面改性剂的制备方法， 其特征在于： 所述组分 A为： 1， 1-二甲基 -1， 2-二胺， 所述组分 B为 3， 5-二羟基水杨醛。 The method for producing a carbon fiber surface modifier according to claim 19, wherein the component A is: 1, 1-dimethyl-1,2-diamine, and the component B is 3, 5-dihydroxy salicylaldehyde.
22. 根据权利要求 19所述的碳纤维表面改性剂的制备方法， 其特征在于： 所述组分 A为： 1， 1-二甲基 -1， 2-二胺， 所述组分 B为 4， 6-二丙氧基水杨醛。 The method for producing a carbon fiber surface modifier according to claim 19, wherein the component A is: 1, 1-dimethyl-1,2-diamine, and the component B is 4,6-Dipropoxy salicylaldehyde.
23. 根据权利要求 19所述的碳纤维表面改性剂的制备方法， 其特征在于： 所述组分 A为： 1， 1， 2， 2-四甲基 -1， 2-二胺， 所述组分 B为 4-二丁氨基水杨 醛。 The method for preparing a carbon fiber surface modifier according to claim 19, wherein the component A is: 1, 1, 2, 2-tetramethyl-1,2-diamine, Component B is 4-dibutylaminosalicylaldehyde.
24. 一种改性碳纤维， 通过碳纤维表面改性剂与碳纤维制备， 所述碳纤维表 面改性剂的结构通式如式 （I ) 所示：
24. A modified carbon fiber prepared by a carbon fiber surface modifier and a carbon fiber, the structural formula of the carbon fiber surface modifier being as shown in formula (I):
25. 一种改性碳纤维的制备方法， 由权利要求 1-14任意一项所述的碳纤维 表面改性剂与碳纤维制成， 包括如下步骤： A method of producing a modified carbon fiber, comprising the carbon fiber surface modifier according to any one of claims 1 to 14 and carbon fiber, comprising the steps of:
碳纤维表面改性剂溶解至有机溶剂或水中形成改性剂溶液， 浓度为 1.2-2.4wt% , The carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
将碳纤维置入改性剂溶液内进行浸润， 碳纤维与改性剂反应； The carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
取出、 烘干后， 得到改性碳纤维。 After being taken out and dried, a modified carbon fiber is obtained.
26. 一种改性碳纤维， 其特征在于： 根据权利要求 25所述的碳纤维表面改 性剂的制备方法制得。 A modified carbon fiber obtained by the method for producing a carbon fiber surface modifier according to claim 25.
27.—种复合材料， 通过碳纤维表面改性剂与碳纤维制得改性碳纤维， 改性 碳纤维与树脂制得， 所述 通式如式 （I) 所示： 27. A composite material obtained by a carbon fiber surface modifier and a carbon fiber obtained by modifying a carbon fiber, a modified carbon fiber and a resin, wherein the formula is as shown in the formula (I):
式 （I ) 中， R2、 R, '各自彼此独立地代表氢、 羟基、 或 CrC3的垸 基； R3、 各自彼此独立地代表 d-C18垸基、 - 18烷氧基、 羟基、 氨基、 卤 素、 氢、 酰胺基、 酯基、 或硅氧基， 且 R3、 R4不同时为氢。 Of formula (I) wherein, R 2, R, 'independently represent hydrogen, hydroxy or C r C 3 alkyl with each other; R & lt 3, independently of one another represent alkyl with dC 18, --18 alkoxy, hydroxy An amino group, a halogen, a hydrogen, an amide group, an ester group, or a siloxy group, and R 3 and R 4 are not hydrogen at the same time.
28. 根据权利要求 27所述的复合材料， 其特征在于： 所述复合材料通过结
CI所示的碳纤维改性剂与 T700碳纤维、 PA6、 以及助剂制得， C1结构
The composite material according to claim 27, wherein: the composite material passes through a knot Carbon fiber modifier shown by CI and T700 carbon fiber, PA6, and additives, C1 structure
29. 根据权利要求 27所述的复合材料， 其特征在于： 所述复合材料通过结 构式如 C2 、 T700碳纤维、 PEEK、 以及助剂制得， C2结
The composite material according to claim 27, wherein the composite material is obtained by a structural formula such as C2, T700 carbon fiber, PEEK, and an auxiliary agent, and a C2 junction.
构式如下: The configuration is as follows:
30. 根据权利要求 27所述的复合材料， 其特征在于： 所述复合材料通过结 构式如 C3所 的碳纤维改性剂、 T700碳纤维， ABS、 以及助剂制得， C3结构 The composite material according to claim 27, wherein the composite material is obtained by a carbon fiber modifier of a structural formula such as C3, T700 carbon fiber, ABS, and an auxiliary agent, and the C3 structure.
式如下所示：
。 The formula is as follows: .
31. 一种复合材料， 包括以下重量百分比的组分， 31. A composite material comprising the following weight percentage components,
改性碳纤维： l-40wt%; Modified carbon fiber: l-40wt%;
热塑性树脂基体： 60-95 wt%; Thermoplastic resin matrix: 60-95 wt%;
助剂： 0-15wt%; Additives: 0-15wt% ;
其中， 改性碳纤维由碳纤维改性剂对碳纤维表面改性制得， 所述碳纤维表 面改性剂的结构通式如下式 （I ) 所示： Wherein, the modified carbon fiber is obtained by modifying a carbon fiber surface by a carbon fiber modifier, and the structural formula of the carbon fiber surface modifier is as follows: (I):
32. 根据权利要求 31所述的复合材料，其特征在于：所述的树脂基体包括: PC、 POM; PE、 PP、 ABS、 SAN、 PS、 PA、 PBT、 PET、 PPO、 LCP、 TPU; PPSU、 PPA、 PEEK, PEI、 PPS、 PSU、 或 PI。 The composite material according to claim 31, wherein the resin matrix comprises: PC, POM; PE, PP, ABS, SAN, PS, PA, PBT, PET, PPO, LCP, TPU; PPSU , PPA, PEEK, PEI, PPS, PSU, or PI.
33. 根据权利要求 31所述的复合材料， 其特征在于： 所述的助剂包含： 阻 燃剂、 增韧剂、 导电剂、 抗氧化剂、 光稳定剂、 润滑剂、 着色剂、 成核剂、 抗 静电剂， 或填料。 33. The composite material according to claim 31, wherein: the auxiliary agent comprises: a flame retardant, a toughening agent, a conductive agent, an antioxidant, a light stabilizer, a lubricant, a colorant, a nucleating agent , antistatic agents, or fillers.
34. 一种权利要求 31-33任意一项所述的复合材料的制备方法， 包括如下步 骤： 34. A method of making a composite according to any of claims 31-33, comprising the steps of:
提供如下重量百分比的组分， Provide the following weight percentage components,
改性碳纤维： l-40wt%; Modified carbon fiber: l-40wt%;
热塑性树脂基体： 60-95wt%; 以及 Thermoplastic resin matrix: 60-95% by weight ;
助剂： 0-15wt%; Additives: 0-15wt% ;
将组分改性碳纤维、 树脂基体以及助剂通过挤出机混合并挤出成型。 The component-modified carbon fiber, the resin matrix, and the auxiliary agent are mixed and extruded by an extruder.
35. 一种根据权利要求 1-14任意一项所述的复合材料应用于制作航空航天 器材、 交通运输器材、 运动器材、 土木建筑材料、 日常生活以及医疗器材的用 途。
35. Use of a composite material according to any of claims 1-14 for the manufacture of aerospace equipment, transportation equipment, sports equipment, civil construction materials, daily life and medical equipment.
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| JP2019506447A (en) * | 2015-12-21 | 2019-03-07 | シーカ テクノロジー アクチェンゲゼルシャフト | Polyaldimine and curable polyurethane composition |
| CN109486006A (en) * | 2018-11-07 | 2019-03-19 | 宿迁市春明医疗器材有限公司 | A kind of injector for medical purpose PP material |
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| CN103774424B (en) * | 2014-01-09 | 2015-11-25 | 郎溪普瑞泰渔具制造有限公司 | The corrosion-resistant carbon fiber modifying agent of a kind of fishing rod |
| CN104610725A (en) * | 2014-12-31 | 2015-05-13 | 东莞市高明企业服务有限公司 | Method for extruding enhanced polyurethane cable shroud material |
| CN106283600A (en) * | 2016-08-11 | 2017-01-04 | 西北工业大学 | A kind of preparation method of functionalized carbon fiber |
| CN112482027B (en) * | 2020-11-20 | 2022-10-25 | 南京玻璃纤维研究设计院有限公司 | Carbon fiber surface treating agent and treating method |
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| CN115092927B (en) * | 2022-07-15 | 2023-06-20 | 安徽工程大学 | Carbon fiber composite resin-based activated carbon and preparation method thereof |
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