CN105862396A - Surface-modified aramid fiber and preparation method thereof - Google Patents
Surface-modified aramid fiber and preparation method thereof Download PDFInfo
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- CN105862396A CN105862396A CN201610292606.6A CN201610292606A CN105862396A CN 105862396 A CN105862396 A CN 105862396A CN 201610292606 A CN201610292606 A CN 201610292606A CN 105862396 A CN105862396 A CN 105862396A
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 271
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000001338 self-assembly Methods 0.000 claims abstract description 108
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 75
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 75
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 75
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 75
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 79
- 239000000843 powder Substances 0.000 claims description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 52
- 230000004048 modification Effects 0.000 claims description 47
- 238000012986 modification Methods 0.000 claims description 46
- 230000004087 circulation Effects 0.000 claims description 41
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 150000003948 formamides Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 108
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 229910002651 NO3 Inorganic materials 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 30
- 150000001450 anions Chemical class 0.000 description 29
- 238000005119 centrifugation Methods 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 20
- 239000004202 carbamide Substances 0.000 description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 18
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 18
- 239000012300 argon atmosphere Substances 0.000 description 16
- 238000012546 transfer Methods 0.000 description 16
- 229920003369 Kevlar® 49 Polymers 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 12
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000004134 energy conservation Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
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- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
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- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
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- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M2101/34—Polyamides
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Abstract
The invention discloses a surface-modified aramid fiber and a preparation method thereof. The preparation method comprises the steps that an aramid fiber with hydroxyl is immersed into a SiO2 colloid aqueous solution, after washing and drying are completed, the aramid fiber is immersed into MgAlFe layered bi-hydroxide suspension liquid, and after washing and drying are completed, a self-assembly cycle is completed on the surface of the aramid fiber, wherein in the self-assembly cycle, a layer of SiO2 negative charges serve as a first assembly, and a layer of MgAlFe layered bi-hydroxide nanosheet positive charges serve as a second assembly; repetitive operation is conducted, and multiple self-assembly cycles are completed, so that the surface-modified aramid fiber is obtained. The modified aramid fiber has the triple uvioresistant functions and is higher in heat resistance, high in mechanical performance and good in surface activity, the preparation process is green and environmentally friendly, the technology is easy to control, and the surface-modified aramid fiber and the preparation method thereof are suitable for large-scale production.
Description
Technical field
The present invention relates to the process for modifying surface of a kind of aramid fiber, be specifically related to aramid fiber of a kind of surface modification and preparation method thereof.
Background technology
Aramid fiber occupies critical role with the combination property (such as superhigh intensity and modulus, good heat resistance and chemical resistance, light weight, having extended cycle life) of its excellence in some sophisticated industry fields.But, aramid fiber also exists the deficiencies such as high, the ultra-violet resistance difference of surface inertness.
In order to overcome drawbacks described above, people expand numerous studies, and its Research Thinking is that aramid fiber is introduced ultraviolet absorber.There is the factors such as thermally-stabilised difference owing to common are machine ultraviolet absorber, therefore, the modified preferably inorganic UV absorbent of aramid fiber.Common inorganic UV absorbent (e.g., TiO2And ZnO) there is photocatalytic activity, then exist with sacrificial fiber mechanical property to the problem improving uvioresistant performance when for synthetic fibers.In order to solve this problem, document " Unique
UV-resistant and surface active aramid fibers with simultaneously enhanced
mechanical and thermal properties by chemically coating Ce0.8Ca0.2O1.8
Having low photocatalytic activity " (Xiaoling Zhu, Li Yuan, Guozheng Liang, Aijuan Gu. Journal
Of Materials Chemistry A, 2014,2,11286-11298) disclose one by Ce0.8Ca0.2O1.8The method grafting on aramid fiber surface, achieves prominent modified effect.But it is the most perfect that this is operated in following 2 needs: one is that reaction needs to carry out 18h at 65 DEG C；Two is Ce0.8Ca0.2O1.8For zero dimension particle, it is difficult to fiber surface is completely covered.To this end, researcher introduces hyperbranched polyorganosiloxane, by its good film forming in modification of aramid fiber surface all standing, improve uvioresistant performance (see document: Xiaoling Zhu, Li Yuan, Guozheng Liang,
Aijuan Gu. Unique surface modified aramid fibers with improved flame
retardancy,tensile properties,surface activity and UV-resistance through in
situ formation of hyperbranched polysiloxane-Ce0.8Ca0.2O1.8 hybrids. Journal of
Materials Chemistry A, 2015,3,12515-12529).But reaction temperature is high, the problem of time length does not still have been resolved；Hyperbranched polyorganosiloxane contains the organic matter easily decomposing and burning simultaneously.
It should be noted that green, energy-conservation is the important trend of current material development.For surface modification aramid fiber, this development trend means that the material used by not only modification should have a characteristic of environmental protection, and the technique taked of modification should have low temperature, time short power savings advantages.Obviously, modification of aramid fiber of the prior art is all unsatisfactory for green, energy-conservation condition.In sum, in the case of keeping fiber original excellent mechanical performance and hot property not to reduce, green energy conservation method development of new surface modification aramid fiber is used to have important using value.
Summary of the invention
For the problem overcoming prior art to exist, it is contemplated that on the premise of keeping the original mechanical property of fiber and hot property not reduce, it is provided that a kind of have a surface-active and the aramid fiber of surface modification that ultra-violet resistance can significantly improve and green, energy-conservation preparation method.
In order to realize goal of the invention of the present invention, the present invention adopts the technical scheme that the preparation method of the aramid fiber providing a kind of surface modification, comprises the steps:
(1) by mass, 1 part of hydroxyl aramid fiber is immersed the SiO that mass concentration is 0.5%～5.0%2In colloid aqueous solution, after concussion 30min～1h, through washing, being dried, obtaining surface-assembled a kind of assembling thing is one layer of SiO2The aramid fiber of negative electrical charge, is denoted as aramid fiber A；
(2) aramid fiber A is immersed in MgAlFe layered double-hydroxide suspension after 30min～1h, through washing, it is dried, assembled again the aramid fiber that another kind of assembling thing is one layer of cation MgAlFe layered double-hydroxide, i.e. aramid fiber completes self assembly circulation, is denoted as aramid fiber B；
(3) aramid fiber B is carried out the most successively step (1) and the operation of step (2), complete second time self assembly circulation；Repeat the self assembly circulation of n number, obtain the aramid fiber of a kind of surface modification.
Aramid fiber of the present invention is para-aramid fiber, meta-aramid fibers.
Described hydroxyl aramid fiber, its preparation method comprises the steps: by mass, is placed in by the aramid fiber that 1 part clean in the aqueous acid that concentration is 20%～40wt%, and described acid is phosphoric acid, nitric acid or sulfuric acid；Impregnation process 1h～2h under conditions of temperature is 30～50 DEG C, more scrubbed, dry, obtain the aramid fiber that surface is hydroxyl.
Self assembly cycle-index n is 9 n 1.
The suspension of described MgAlFe layered double-hydroxide, its preparation method is: by mass, under inert gas shielding, by 0.05～0.3 part of MgAlFe-NO3Layered double-hydroxide powder is scattered in 110 parts of formamides, mechanical agitation 1～4 days under conditions of temperature is 15～40 DEG C.
Described inert gas is nitrogen or argon gas.
Technical solution of the present invention also includes the aramid fiber of a kind of surface modification that the method that is prepared as described above obtains.:
Compared with prior art, the present invention obtains and provides the benefit that:
1, the material modified of present invention employing is MgAlFe layered double-hydroxide and SiO2, they are nontoxic, and without easily decomposing and the organic matter of burning, and chemical property is more stable, meets the production theory of environmental protection.
2, the modification of aramid fiber that the present invention prepares has triple uvioresistant function.One, MgAlFe layered double-hydroxide can stop whole UV absorption scope, good stability completely, can play the effect absorbing ultraviolet for a long time；Its two, SiO2Si-O bond energy far above UV radiation can, also give aramid fiber good uvioresistant performance；3rd, MgAlFe layered double-hydroxide forms film at fiber surface, by with zero dimension SiO2Self assembly realize all standing of fiber surface, thus obtain high uvioresistant performance.
3, two kinds of assembling things of the present invention are MgAlFe layered double-hydroxide and SiO2, they are heat resistant inorganic thing, it can be ensured that modification of aramid fiber has higher heat resistance.It is coated on the SiO of fiber surface2Particle and MgAlFe laminated double hydroxide nanometer sheet have high mechanical property and compensate for the defect of fiber surface, thus improve the mechanical property of fiber.
4、SiO2With MgAlFe layered double-hydroxide layer all containing substantial amounts of hydroxyl, improve the surface-active of aramid fiber；Meanwhile, the existence of the inorganic material being self-assembled to surface too increases the roughness of fiber, provides material base for the most modified of fiber and application.
5, two kinds of different inorganic material of the modification of aramid fiber surface self assembly that prepared by the present invention, can be conveniently by the structure of content regulation modified fibre and the performance controlling ultraviolet absorber.
6, the partial routine of the LBL self-assembly that the present invention provides is with water as medium, the most simple to operate, favorable repeatability, and self assembly temperature is not higher than 40 DEG C, and the time of a self assembly circulation, less than 2h, has energy-conservation, to be suitable to large-scale production advantage.
Accompanying drawing explanation
Fig. 1 is MgAl layered double-hydroxide and X-ray diffraction (XRD) spectrogram of MgAlFe layered double-hydroxide of the embodiment of the present invention 1 offer；
Fig. 2 is MgAl layered double-hydroxide and UV absorption (UV-Vis) spectrogram of MgAlFe layered double-hydroxide of the embodiment of the present invention 1 offer；
Fig. 3 is the cross-sectional view of the aramid fiber of the surface modification that Example 1 and Example 2 of the present invention provides；
Fig. 4 is aramid fiber and infrared (IR) spectrogram of clean aramid fiber of the surface modification that the embodiment of the present invention 1～3 provides；
Fig. 5 is aramid fiber and SEM (SEM) photo of clean aramid fiber of the surface modification that the embodiment of the present invention 1～3 provides；
The clean aramid fiber tensile property before and after ultraviolet light irradiation respectively that Fig. 6 is the surface modification aramid fiber that provides of the embodiment of the present invention 1～3 and embodiment 1 provides.
Specific implementation method
With embodiment, technical solution of the present invention is described further below in conjunction with the accompanying drawings.
Embodiment 1
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 60 DEG C, the petroleum ether of 75 DEG C and 115 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 65g deionized water that 35g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 2g step (1) obtained is immersed in the weak solution of phosphoric acid, 40 DEG C of back flow reaction 2h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.05g magnesium nitrate hexahydrate, 1.38g ANN aluminium nitrate nonahydrate and 0.13g Fe(NO3)39H2O are added 30mL methyl alcohol to dissolve, obtain the methyl alcohol mixed solution of nitrate；0.96g NaOH is added 100mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 200mL, under conditions of temperature is 150 DEG C, reacts 18h；By centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.Its X-ray diffraction (XRD) spectrogram, UV absorption (UV-Vis) spectrogram see accompanying drawing 1,2 respectively.
2.05g magnesium nitrate hexahydrate and 1.50g ANN aluminium nitrate nonahydrate are added 30mL methyl alcohol dissolve, obtain the methyl alcohol mixed solution of nitrate；0.96g NaOH is added 100mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 200mL, under conditions of temperature is 150 DEG C, reacts 18h；By centrifugation, wash, be dried, obtain MgAl-NO3Layered double-hydroxide powder.Its X-ray diffraction (XRD) spectrogram, UV absorption (UV-Vis) spectrogram see accompanying drawing 1,2 respectively.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 0.3g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%240min in colloid aqueous solution, then washes, 60 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that step (4) is obtained2Aramid fiber (the AF-SiO of self assembly2) 2g immerse step (3) prepare layering MgAlFe layered double-hydroxide suspension in and retain 30min, then wash, 80 DEG C of dry 10min, obtain the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)1, its cross-sectional view, infrared spectrum, SEM (SEM) photo and tensile property see accompanying drawing 3,4,5 and 6 respectively.
2, clean fiber and the ultraviolet irradiation of modified fibre
Modification of aramid fiber AF-(the SiO that clean aramid fiber step (1) obtained and step (5) obtain2/ MgAlFe layered double-hydroxide)1It is exposed to (Q-Lab company of the U.S.) in QUV/spray type ultraviolet light accelerated weathering accelerator to carry out the UV irradiation of 24h (radiant illumination is 1.55W/m2, test temperature is 60 DEG C), obtain the clean aramid fiber through 24h irradiation and modification of aramid fiber, be designated as UV-AF and UV-AF-(SiO respectively2/ MgAlFe layered double-hydroxide)1, its tensile property sees accompanying drawing 6.
Seeing accompanying drawing 1, it is the MgAl-NO of synthesis in the present embodiment3Layered double-hydroxide and MgAlFe-NO3X-ray diffraction (XRD) spectrogram of layered double-hydroxide.There it can be seen that both diffraction maximums are sharp-pointed, showing that they define crystalline layered structure well, it is 3R rhombohedron symmetrical structure, and space group is R-3m.D (110) reflects the atom arranging density at laminate.Relative to MgAl-NO3Layered double-hydroxide, MgAlFe-NO3(110) crystal face of layered double-hydroxide there occurs that the skew of 0.4033 °, i.e. arranging density reduce.
Seeing accompanying drawing 2, it is the MgAl-NO of the present embodiment synthesis3Layered double-hydroxide and MgAlFe-NO3UV absorption (UV-Vis) spectrogram of layered double-hydroxide.Where it can be seen that Fe3+Incorporation cause MgAl-NO3The ultraviolet absorption curve generation red shift of layered double-hydroxide, then has width and strong absorption in 200-400nm ultraviolet range, this is because Fe3+Hydroxide is in the absorption of shepardite layer.Go out MgAlFe-NO as available from the above3Layered double-hydroxide is a kind of good ultraviolet absorber, can be used for aramid fiber modified.
Embodiment 2
1, the preparation of surface modification aramid fiber
Take the aramid fiber that surface that 3g embodiment 1 obtains is hydroxyl, and carry out the step (4) in embodiment 1 and step (5) successively, complete second self assembly circulation；It is further continued for self assembly, completes five self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The ten layers of mineral-modified aramid fiber occurred respectively with MgAlFe five times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)5.Its cross-sectional view, infrared spectrum, SEM (SEM) photo and tensile property see accompanying drawing 3,4,5 and 6 respectively.
2, the ultraviolet irradiation of modified fibre
According to the same steps in embodiment 1 and condition, to the aramid fiber AF-(SiO obtained in embodiment 22/ MgAlFe layered double-hydroxide)5Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)5, its tensile property sees accompanying drawing 6.
Seeing accompanying drawing 3, it is the cross-sectional view of the aramid fiber of the surface modification that Example 1 and Example 2 of the present invention provides, and this figure clearly depicts at fiber surface self assembly one circulation (A figure) AF-(SiO2/ MgAlFe layered double-hydroxide)1With 5 circulations (B figure) AF-(SiO2/ MgAlFe layered double-hydroxide)5The composition of each layer of rear self assembly.
Embodiment 3
1, the preparation of surface modification aramid fiber
Take the aramid fiber that surface that 3g embodiment 1 obtains is hydroxyl, and carry out the step (4) in embodiment 1 and step (5) successively, complete second self assembly circulation；It is further continued for self assembly, completes nine self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The 18 layers of mineral-modified aramid fiber occurred respectively with MgAlFe nine times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)9.Its infrared spectrum, SEM (SEM) photo and tensile property see accompanying drawing 4,5 and 6 respectively.
2, the ultraviolet irradiation of modified fibre
According to the same steps in embodiment 1 and condition, to the aramid fiber AF-(SiO obtained in embodiment 32/ MgAlFe layered double-hydroxide)9Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)9, its tensile property sees accompanying drawing 6.
Seeing accompanying drawing 4, it is clean aramid fiber and embodiment 1, embodiment 2, the infrared spectrum of embodiment 3 modified fibre.It can be seen that compared to clean aramid fiber, the spectrogram of the modified fibre that embodiment 1, embodiment 2 and embodiment 3 provide occurs in that new peak, is the lattice vibration peak (654cm of Al-O respectively-1), the asymmetric stretching vibration peak (1000-1130cm of Si-O-Si-1), show layered double-hydroxide and SiO2Successfully it is assembled into aramid fiber surface.And the vibration peak of embodiment 1, embodiment 2 and embodiment 3 strengthens successively, show LBL self-assembly success.
Seeing accompanying drawing 5, it is clean aramid fiber (A figure) and embodiment 1(B is schemed), embodiment 2(C schemes), embodiment 3(E schemes) Scanning Electron microscope (SEM) photo of modified fibre.It can be seen that the smooth surface of clean aramid fiber (A figure), roughness are little；And embodiment 1(B figure), embodiment 2(C figure) and embodiment 3(E scheme) surface roughness of modified fibre that provides substantially increases.Scheme from embodiment 2(C) the partial enlarged drawing (D figure) of modified fibre it can be seen that, be uniformly covered with laminated double hydroxide nanometer lamella, particle diameter is about 60nm, it was demonstrated that the inventive method can the surface of coated fiber completely.
See accompanying drawing 6, the comparison diagram of the modified fibre that it is clean aramid fiber and embodiment 1, embodiment 2, embodiment 3 provide tensile property before and after 24h ultraviolet irradiation.Where it can be seen that compare clean fiber, the hot strength of the modified fibre that embodiment 1, embodiment 2 and embodiment 3 provide has been respectively increased 5.9%, 9.8% and 8.8%, the modified tensile property being favorably improved fiber is described, but there is an optimal assembling number of times.After 24h ultraviolet irradiation, the hot strength of clean aramid fiber have dropped 12.6%, and the hot strength of embodiment 1, embodiment 2, embodiment 3 have dropped 3.3%, 0.6%, 0.5% respectively, show that the modified fibre that embodiment 1, embodiment 2, embodiment 3 provide not only increases tensile property, and demonstrating the resistance to uviol lamp performance significantly improved, the fall of tensile property significantly reduces；And along with fiber surface assembles the increase of the number of plies, after UV irradiation, the fall of tensile strength of fiber reduces.This is because coating is the most, cladding is the most complete, the ultraviolet-resistent property of modified fibre is the best.
Embodiment 4
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 80 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) nitric acid and 80g deionized water that 20g mass concentration is 65% are mixed, prepare the weak solution of nitric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of nitric acid, 30 DEG C of back flow reaction 1.5h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.05g magnesium nitrate hexahydrate, 1.32g ANN aluminium nitrate nonahydrate, 0.19g Fe(NO3)39H2O and 1.18g urea are dissolved in 80mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 150mL, under conditions of temperature is 110 DEG C, reacts 24h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains the NaNO of 0.1M3The aqueous solution further processes, and stirs 24h in a nitrogen atmosphere, obtains MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 0.1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 1 day under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 5%230min in colloid aqueous solution, then washes, 90 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 30min, then washes, 60 DEG C of dry 20min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes three self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The six layers of mineral-modified aramid fiber occurred respectively with MgAlFe three times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)3。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 4 is obtained2/ MgAlFe layered double-hydroxide)3Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)3。
Embodiment 5
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 70 DEG C and 110 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 50g deionized water that 30g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.03g Magnesium dichloride hexahydrate, 1.10g Aluminium chloride hexahydrate, 0.16g ferric chloride hexahydrate and 2.1g urea are dissolved in 100mL deionized water, obtain muriatic aqueous solution of urea；Transfer it in the reactor of 150mL, under conditions of temperature is 130 DEG C, reacts 20h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains 1.5MNaNO3And 5mMHNO3The aqueous solution further process, stir 24h under an argon atmosphere, obtain MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 0.3g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 1 day under conditions of 40 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 5%21h in colloid aqueous solution, then washes, 60 DEG C of dry 10min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 60 DEG C of dry 20min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes eight self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The 16 layers of mineral-modified aramid fiber occurred respectively with MgAlFe eight times and be alternately present, are designated as AF-(SiO2/MgAlFe layered double-hydroxide)8。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 5 is obtained2/ MgAlFe layered double-hydroxide)8Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)8。
Embodiment 6
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 60 DEG C, the petroleum ether of 75 DEG C and 115 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) sulfuric acid and 90g deionized water that 30g mass concentration is 98% are mixed, prepare the weak solution of sulfuric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of sulfuric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.03g Magnesium dichloride hexahydrate, 1.19g Aluminium chloride hexahydrate, 0.07g ferric chloride hexahydrate and 2.1g urea are dissolved in 100mL deionized water, obtain muriatic aqueous solution of urea；Transfer it in the reactor of 150mL, under conditions of temperature is 110 DEG C, reacts 24h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains 0.9MNaNO3And 5mMHNO3The aqueous solution further process, stir 24h under an argon atmosphere, obtain MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 0.1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 4 days under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 0.5%230min in colloid aqueous solution, then washes, 60 DEG C of dry 30min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 80 DEG C of dry 10min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes four self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The eight layers of mineral-modified aramid fiber occurred respectively with MgAlFe four times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)4。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 6 is obtained2/ MgAlFe layered double-hydroxide)4Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)4。
Embodiment 7
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 65 DEG C, the petroleum ether of 75 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 80g deionized water that 30g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 40 DEG C of back flow reaction 2h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.05g magnesium nitrate hexahydrate, 1.36g ANN aluminium nitrate nonahydrate, 0.16g Fe(NO3)39H2O and 1.17g urea are dissolved in 120mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 200mL, under conditions of temperature is 160 DEG C, reacts 20h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.2gMgAlFe-CO3Layered double-hydroxide powder 200mL contains the NaNO of 0.5M3The aqueous solution further processes, and stirs 24h under an argon atmosphere, obtains MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 0.1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 4 days under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 1%21h in colloid aqueous solution, then washes, 50 DEG C of dry 20min, obtains anion SiO2The aramid fiber of (negative electrical charge), is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of (negative electrical charge) immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 60 DEG C of dry 30min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes five self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The ten layers of mineral-modified aramid fiber occurred respectively with MgAlFe five times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)5。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 7 is obtained2/ MgAlFe layered double-hydroxide)5Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)5。
Embodiment 8
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 75 DEG C and 110 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 60g deionized water that 25g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 50 DEG C of back flow reaction 1.5h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.02g magnesium nitrate hexahydrate, 0.71g ANN aluminium nitrate nonahydrate, 0.04g Fe(NO3)39H2O and 0.59g urea are dissolved in 60mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 100mL, under conditions of temperature is 180 DEG C, reacts 14h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.2gMgAlFe-CO3Layered double-hydroxide powder 200mL contains the NaNO of 1M3The aqueous solution further processes, and stirs 24h under an argon atmosphere, obtains MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 3 days under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 1%240min in colloid aqueous solution, then washes, 90 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 30min, then washes, 90 DEG C of dry 20min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes two self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The four layers of mineral-modified aramid fiber occurred respectively twice with MgAlFe and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)2。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 8 is obtained2/ MgAlFe layered double-hydroxide)2Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)2。
Embodiment 9
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 65 DEG C, the petroleum ether of 80 DEG C and 115 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) nitric acid and 80g deionized water that 25g mass concentration is 65% are mixed, prepare the weak solution of nitric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of nitric acid, 30 DEG C of back flow reaction 2h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.54g magnesium nitrate hexahydrate, 0.99g ANN aluminium nitrate nonahydrate and 0.15g Fe(NO3)39H2O are added 30mL methyl alcohol to dissolve, obtain the methyl alcohol mixed solution of nitrate；0.72g NaOH is added 70mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 150mL, under conditions of temperature is 140 DEG C, reacts 20h；By centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 0.6g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 0.5%21h in colloid aqueous solution, then washes, 50 DEG C of dry 10min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 40min, then washes, 60 DEG C of dry 30min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes five self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The ten layers of mineral-modified aramid fiber occurred respectively with MgAlFe five times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)5。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 9 is obtained2/ MgAlFe layered double-hydroxide)5Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)5。
Embodiment 10
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 80 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) sulfuric acid and 70g deionized water that 30g mass concentration is 98% are mixed, prepare the weak solution of sulfuric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of sulfuric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.03g Magnesium dichloride hexahydrate, 1.20g Aluminium chloride hexahydrate, 0.05g ferric chloride hexahydrate and 1.4g urea are dissolved in 60mL deionized water, obtain muriatic aqueous solution of urea；Transfer it in the reactor of 100mL, under conditions of temperature is 150 DEG C, reacts 19h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains 1.5MNaNO3And 5mMHNO3The aqueous solution further process, stir 24h under an argon atmosphere, obtain MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 0.5g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 4 days under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 1%240min in colloid aqueous solution, then washes, 60 DEG C of dry 20min, obtains anion SiO2The aramid fiber of (negative electrical charge), is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 90 DEG C of dry 30min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes six self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The mineral-modified aramid fiber of Floor 12 occurred respectively with MgAlFe six times and be alternately present, is designated as AF-(SiO2/ MgAlFe layered double-hydroxide)6。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 10 is obtained2/ MgAlFe layered double-hydroxide)6Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)6。
Embodiment 11
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 65 DEG C, the petroleum ether of 75 DEG C and 115 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 60g deionized water that 30g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 50 DEG C of back flow reaction 2h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.02g magnesium nitrate hexahydrate, 0.69g ANN aluminium nitrate nonahydrate and 0.07g Fe(NO3)39H2O are added 25mL methyl alcohol to dissolve, obtain the methyl alcohol mixed solution of nitrate；0.48g NaOH is added 35mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 100mL, under conditions of temperature is 140 DEG C, reacts 20h；By centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 0.5g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 1 day under conditions of 40 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 0.5%240min in colloid aqueous solution, then washes, 90 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 20min, then washes, 90 DEG C of dry 20min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes four self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The eight layers of mineral-modified aramid fiber occurred respectively with MgAlFe four times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)4。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 11 is obtained2/ MgAlFe layered double-hydroxide)4Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)4。
Embodiment 12
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 80 DEG C and 115 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 90g deionized water that 40g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 40 DEG C of back flow reaction 2h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.71g magnesium nitrate hexahydrate, 1.10g ANN aluminium nitrate nonahydrate, 0.16g Fe(NO3)39H2O and 1.4g urea are dissolved in 60mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 100mL, under conditions of temperature is 130 DEG C, reacts 21h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.2gMgAlFe-CO3Layered double-hydroxide powder 200mL contains 1MNaNO3And 5mMHNO3The aqueous solution further process, stir 24h under an argon atmosphere, obtain MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 0.1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%240min in colloid aqueous solution, then washes, 50 DEG C of dry 20min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 40min, then washes, 80 DEG C of dry 10min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes eight self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The 16 layers of mineral-modified aramid fiber occurred respectively with MgAlFe eight times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)8。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 12 is obtained2/ MgAlFe layered double-hydroxide)8Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)8。
Embodiment 13
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 60 DEG C, the petroleum ether of 80 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) sulfuric acid and 75g deionized water that 30g mass concentration is 98% are mixed, prepare the weak solution of sulfuric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of sulfuric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.54g magnesium nitrate hexahydrate, 1.05g ANN aluminium nitrate nonahydrate, 0.08g Fe(NO3)39H2O and 0.79g urea are dissolved in 50mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 100mL, under conditions of temperature is 120 DEG C, reacts 22h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains the NaNO of 1.5M3The aqueous solution further processes, and stirs 24h in a nitrogen atmosphere, obtains MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlFe-NO of 1g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 4 days under conditions of 15 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%240min in colloid aqueous solution, then washes, 50 DEG C of dry 20min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 40min, then washes, 80 DEG C of dry 20min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes seven self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The 14 layers of mineral-modified aramid fiber occurred respectively with MgAlFe seven times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)7。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 13 is obtained2/ MgAlFe layered double-hydroxide)7Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)7。
Embodiment 14
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 75 DEG C and 110 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) nitric acid and 110g deionized water that 30g mass concentration is 65% are mixed, prepare the weak solution of nitric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of nitric acid, 40 DEG C of back flow reaction 1.5h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.05g magnesium nitrate hexahydrate, 1.41g ANN aluminium nitrate nonahydrate and 0.10g Fe(NO3)39H2O are added 30mL methyl alcohol to dissolve, obtain the methyl alcohol mixed solution of nitrate；0.96g NaOH is added 110mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 200mL, under conditions of temperature is 130 DEG C, reacts 22h；By centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 0.6g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%21h in colloid aqueous solution, then washes, 90 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 30min, then washes, 90 DEG C of dry 10min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes five self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The ten layers of mineral-modified aramid fiber occurred respectively with MgAlFe five times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)5。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 14 is obtained2/ MgAlFe layered double-hydroxide)5Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)5。
Embodiment 15
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 60 DEG C, the petroleum ether of 75 DEG C and 110 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 70g deionized water that 35g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 1.54g magnesium nitrate hexahydrate, 1.06g ANN aluminium nitrate nonahydrate and 0.07g Fe(NO3)39H2O are added 20mL methyl alcohol to dissolve, obtain the methyl alcohol mixed solution of nitrate；0.72g NaOH is added 80mL methyl alcohol dissolve, obtain the methanol solution of NaOH；The methanol solution of nitrate is instilled in the methanol solution of NaOH, have floccule to produce, transfer it in the reactor of 150mL, under conditions of temperature is 140 DEG C, reacts 21h；By centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under nitrogen atmosphere is protected, by the MgAlF-NO of 0.4g3E layered double-hydroxide powder is scattered in 100mL formamide, stirs 1 day under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%21h in colloid aqueous solution, then washes, 50 DEG C of dry 10min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 60 DEG C of dry 30min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes six self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The mineral-modified aramid fiber of Floor 12 occurred respectively with MgAlFe six times and be alternately present, is designated as AF-(SiO2/ MgAlFe layered double-hydroxide)6。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 15 is obtained2/ MgAlFe layered double-hydroxide)6Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)6。
Embodiment 16
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 60 DEG C, the petroleum ether of 75 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) phosphoric acid and 80g deionized water that 40g mass concentration is 85% are mixed, prepare the weak solution of phosphoric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of phosphoric acid, 30 DEG C of back flow reaction 1.5h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.03g Magnesium dichloride hexahydrate, 1.16g Aluminium chloride hexahydrate, 0.09g ferric chloride hexahydrate and 2.1g urea are dissolved in 130mL deionized water, obtain muriatic aqueous solution of urea；Transfer it in the reactor of 200mL, under conditions of temperature is 110 DEG C, reacts 24h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.1gMgAlFe-CO3Layered double-hydroxide powder 100mL contains 1.5MNaNO3The aqueous solution further process, stir 24h under an argon atmosphere, obtain MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 2g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 25 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 3%250min in colloid aqueous solution, then washes, 50 DEG C of dry 20min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the surface band SiO that 2g step (4) is obtained2The aramid fiber of (negative electrical charge) immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 80 DEG C of dry 10min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes four self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The eight layers of mineral-modified aramid fiber occurred respectively with MgAlFe four times and be alternately present, are designated as AF-(SiO2/ MgAlFe layered double-hydroxide)4。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 16 is obtained2/ MgAlFe layered double-hydroxide)4Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)4。
Embodiment 17
1, the preparation of surface modification aramid fiber
(1) by 3g aramid fiber (Kevlar-49, diameter 12 μm, density 1.45g/m3, du pont company produces) and it is immersed in the deionized water of the acetone of 70 DEG C, the petroleum ether of 80 DEG C and 130 DEG C reservation 3 hours successively；Then take out fiber, in the vacuum drying oven of 80 DEG C, be dried 12h, obtain clean aramid fiber, be designated as AF.
(2) nitric acid and 85g deionized water that 25g mass concentration is 65% are mixed, prepare the weak solution of nitric acid；Clean aramid fiber AF 3g step (1) obtained is immersed in the weak solution of nitric acid, 40 DEG C of back flow reaction 1h, and reaction is washed after terminating, is dried, and obtains the surface aramid fiber with hydroxyl.
(3) 2.05g magnesium nitrate hexahydrate, 1.44g ANN aluminium nitrate nonahydrate, 0.06g Fe(NO3)39H2O and 1.17g urea are dissolved in 100mL deionized water, obtain the aqueous solution of urea of nitrate；Transfer it in the reactor of 150mL, under conditions of temperature is 180 DEG C, reacts 14h；By centrifugation, wash, be dried, obtain MgAlFe-CO3Layered double-hydroxide powder.
By 0.2gMgAlFe-CO3Layered double-hydroxide powder 200mL contains the NaNO of 0.5M3The aqueous solution further processes, and stirs 24h under an argon atmosphere, obtains MgAlFe-NO3Layered double-hydroxide solution；The most by centrifugation, wash, be dried, obtain MgAlFe-NO3Layered double-hydroxide powder.
Under argon atmosphere is protected, by the MgAlFe-NO of 2g3Layered double-hydroxide powder is scattered in 100mL formamide, stirs 2 days under conditions of 40 DEG C, obtains the MgAlFe layered double-hydroxide suspension of layering.
(4) aramid fiber hydroxyl for 2g being immersed mass concentration is the SiO of 2%240min in colloid aqueous solution, then washes, 90 DEG C of dry 5min, obtains anion SiO2The aramid fiber of self assembly, is designated as AF-SiO2。
(5) the anion SiO that 2g step (4) is obtained2The aramid fiber of self assembly immerses in the MgAlFe layered double-hydroxide suspension of the layering that step (3) prepares and retains 1h, then washes, 80 DEG C of dry 10min, obtains the aramid fiber of cation MgAlFe laminated double hydroxide nanometer sheet self assembly.
(6) repeat step (4) and step (5), complete second self assembly circulation；It is further continued for self assembly, completes six self assembly circulations altogether.Now, SiO is obtained at aramid fiber surface2The mineral-modified aramid fiber of Floor 12 occurred respectively with MgAlFe six times and be alternately present, is designated as AF-(SiO2/ MgAlFe layered double-hydroxide)6。
2, the ultraviolet irradiation of fiber
According to the same steps in embodiment 1 and condition, the aramid fiber AF-(SiO that step (6) in embodiment 17 is obtained2/ MgAlFe layered double-hydroxide)6Carry out the UV irradiation of 24h, obtain 24h ultraviolet irradiation fiber, be designated as UV-AF-(SiO2/ MgAlFe layered double-hydroxide)6。
Claims (7)
1. the preparation method of the aramid fiber of a surface modification, it is characterised in that comprise the steps:
(1) by mass, 1 part of hydroxyl aramid fiber is immersed the SiO that mass concentration is 0.5%～5.0%2In colloid aqueous solution, after concussion 30min～1h, through washing, being dried, obtaining surface-assembled a kind of assembling thing is one layer of SiO2The aramid fiber of negative electrical charge, is denoted as aramid fiber A；
(2) aramid fiber A is immersed in MgAlFe layered double-hydroxide suspension after 30min～1h, through washing, it is dried, assembled again the aramid fiber that another kind of assembling thing is one layer of cation MgAlFe layered double-hydroxide, i.e. aramid fiber completes self assembly circulation, is denoted as aramid fiber B；
(3) aramid fiber B is carried out the most successively step (1) and the operation of step (2), complete second time self assembly circulation；Repeat the self assembly circulation of n number, obtain the aramid fiber of surface modification.
The aramid fiber of a kind of surface modification the most according to claim 1, it is characterised in that: described aramid fiber is para-aramid fiber, meta-aramid fibers.
The aramid fiber of a kind of surface modification the most according to claim 1, it is characterized in that: described hydroxyl aramid fiber, its preparation method comprises the steps: by mass, being placed in by the aramid fiber that 1 part clean in the aqueous acid that concentration is 20%～40wt%, described acid is phosphoric acid, nitric acid or sulfuric acid；Impregnation process 1h～2h under conditions of temperature is 30～50 DEG C, more scrubbed, dry, obtain the aramid fiber that surface is hydroxyl.
The aramid fiber of a kind of surface modification the most according to claim 1, it is characterised in that: self assembly cycle-index n is 9 n 1.
The aramid fiber of a kind of surface modification the most according to claim 1, it is characterised in that: the suspension of described MgAlFe layered double-hydroxide, its preparation method is: by mass, under inert gas shielding, by 0.05～0.3 part of MgAlFe-NO3Layered double-hydroxide powder is scattered in 110 parts of formamides, mechanical agitation 1～4 days under conditions of temperature is 15～40 DEG C.
The aramid fiber of a kind of surface modification the most according to claim 5, it is characterised in that: described inert gas is nitrogen or argon gas.
7. the aramid fiber of a kind of surface modification obtained by claim 1 preparation method.
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| CN106637953A (en) * | 2016-12-14 | 2017-05-10 | 陕西科技大学 | Modification method of p-aramid fiber chopped fiber |
| WO2017190492A1 (en) * | 2016-05-05 | 2017-11-09 | 苏州大学张家港工业技术研究院 | Surface-modified aramid fiber and preparation method therefor |
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| CN109610171B (en) * | 2018-12-14 | 2021-09-03 | 贵州大学 | Method for increasing surface roughness of aramid fiber |
| CN111926612B (en) * | 2020-08-10 | 2022-06-21 | 中国制浆造纸研究院衢州分院 | Preparation method of high-performance aramid fiber nano mica insulation paper |
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