CN106988120A - Intelligent real silk fabric of a kind of hydrophilic and hydrophobic and preparation method thereof - Google Patents
Intelligent real silk fabric of a kind of hydrophilic and hydrophobic and preparation method thereof Download PDFInfo
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- CN106988120A CN106988120A CN201710284282.6A CN201710284282A CN106988120A CN 106988120 A CN106988120 A CN 106988120A CN 201710284282 A CN201710284282 A CN 201710284282A CN 106988120 A CN106988120 A CN 106988120A
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- Prior art keywords
- silk fabric
- real silk
- solution
- hydrophilic
- hydrophobic
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- 239000004744 fabric Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 acrylic ester Chemical class 0.000 claims abstract description 31
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000012047 saturated solution Substances 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 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 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 230000009466 transformation Effects 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000004804 winding Methods 0.000 abstract description 4
- 230000007812 deficiency Effects 0.000 abstract description 2
- 230000002940 repellent Effects 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 26
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 19
- 239000007787 solid Substances 0.000 description 12
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001649 bromium compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 125000003383 isobutyric acid ester group Chemical group 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 108010022355 Fibroins Proteins 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- TXSUKTSBCRQJII-UHFFFAOYSA-N (2-phenyldiazenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1N=NC1=CC=CC=C1 TXSUKTSBCRQJII-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- CHKYYLRUSUXGFU-UHFFFAOYSA-N C(CCC)C1=CC=CC=C1.[F] Chemical class C(CCC)C1=CC=CC=C1.[F] CHKYYLRUSUXGFU-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses intelligent real silk fabric of a kind of hydrophilic and hydrophobic and preparation method thereof.With the acrylic ester grafted modified silk of perfluoroalkyl azobenzene, surface becomes hydrophilic after ultraviolet light, receive again high temperature bake/visible light stimulus after then and be changed into water repellent surface, so can repeatedly circulate the close and distant property of transfer surface.The present invention uses atom transfer radical polymerization method, by controlling grafting processing time, can be controlled the degree of polymerization on cocoon fiber surface grafting, molecular weight distribution very narrow fluorine-contaninig polyacrylate chain；Grafted chain is regular in silk surface alignment, grafting molecules main chain is overcome because molecular weight and molecualr weight distribution is uncontrollable and produces winding, the deficiency for causing side base light isomery efficiency low, obtained modification silk has the performance of good reversible transformation hydrophilic and hydrophobic, and repeatedly circulating and reversible can reply, the hydrophilic and hydrophobic for realizing real silk fabric is intelligent.
Description
Technical field
The present invention relates to a kind of intelligent real silk fabric and preparation method thereof, and in particular to a kind of hydrophilic and hydrophobic is intelligent true
Silk fabrics and preparation method thereof, the real silk fabric surface hydrophilic hydrophobic performance of preparation can repeatedly circulate conversion under environmental stimuli,
And conversion is controllable, belongs to intelligent textile and its manufacture field.
Background technology
The wetability of the surface of solids is made up of surface topography and surface chemistry and together decided on, and changes surface texture or table
Face chemical composition, can realize the reversible transformation of surface wettability.At present for by directly changing surface of solids structure come real
The research of existing surface wettability reversible transformation is less, and more is by controlling the external condition such as factor such as light, temperature, PH come real
The reversible transformation of existing surface wettability, wherein, material surface wetability reversible transformation is realized using azobenzene optical Response
Most study.
The last layer acrylate polymer film of azobenzene containing perfluoroalkyl is covered in substrate material surface, control can be passed through
The Sys-trans isomerism of azobenzene in polymer film, reaches the perfluoroalkyl of control azo group bonding in the poly- of matrix surface
Collection degree, so that the hydrophilic-hydrophobic property of controllable processed material.Prior art synthesizes perfluor alkane using radical polymerization
During base azobenzene acrylate polymer emulsion type surface conditioning agent, quick chain occurs during due to conventional radical polymerization and increases
Cause molecular weight uncontrollable, and there is chain tra nsfer causes molecular structure uncontrollable, Raolical polymerizable has chain in addition
Property, i.e. rapid growth is to high level within the extremely short time for the degree of polymerization, and these shortcomings cause the polymer molecular weight to be formed
Bigger than normal, molecular weight distribution is wide, and obtained emulsion polymer is handled to substrate material surface, and longer main polymer chain is mutual
Winding causes side base azobenzene to be difficult to effectively occur light isomery, therefore isomerisation degree is low under the stimulation of extraneous optical and thermal.
The ATRP proposed using nineteen ninety-five doctor Wang Jinshan（ATRP）Controllable activity poly can be realized
Close, so as to realize the structure control of macromolecular chain in radical polymerization, moreover, this method has, reaction condition is gentle, it is more to be adapted to
The advantages of planting polymerization system and strong MOLECULE DESIGN ability, is a kind of effective way for realizing controllable living polymerization.
The content of the invention
The present invention is for when Raolical polymerizable prepares finishing agent or graft modification silk in the prior art, existing poly-
Right big, degree of polymerization distribution is wide, and the winding of grafted chain molecular backbone causes the fluorine-containing azobenzene light isomeric effect difference of side base
Deficiency is there is provided a kind of degree of polymerization of controllable cocoon fiber surface grafting chain and degree of polymerization distribution is narrow, makes to contain perfluoroalkyl poly third
Olefin(e) acid ester grafted chain the regular graft modification silk of silk surface alignment method so that it is intelligent to obtain a kind of hydrophilic and hydrophobic
Real silk fabric.
Realize that the technical scheme of foregoing invention purpose is to provide a kind of intelligent real silk fabric of hydrophilic and hydrophobic, the silk is knitted
The fiber surface of thing is by the acrylic ester grafted modification by copolymerization of perfluoroalkyl azobenzene；Perfluoroalkyl azobenzene polyacrylate
The grafted chain degree of polymerization is 2~20；Perfluoroalkyl is included in pentafluoroethyl group, nine fluorine butyl, ten trifluoro hexyls or 17 fluorine octyl groups
Any one.
Technical solution of the present invention also includes a kind of preparation method of the intelligent real silk fabric of hydrophilic and hydrophobic, and step is as follows：
（1）p- perfluoroalkyl-p′- azophenol is synthesized
By weight, 0.3~1 part of phenol is dissolved in the sodium hydrate aqueous solution that 10~40 parts of concentration are 1 mol/L, matched somebody with somebody
Phenol sodium solution is made；4~8 parts of natrium nitrosums are dissolved in 8~12 parts of deionized waters, sodium nitrite in aqueous solution is configured to；
Willp- Perfluoroalkylanilin is suspended in the dilute hydrochloric acid solution that concentration is 2mol/L, treats that Perfluoroalkylanilin is complete under heating condition
After dissolving, 5~10 DEG C are cooled to, sodium nitrite in aqueous solution, insulation reaction 2~5 hours is slowly added dropwise, then that sodium phenate is added dropwise is molten
Liquid, controlling reaction temperature is maintained at 5~10 DEG C；The pH for adjusting reaction solution with saturated solution of sodium bicarbonate is filtrated to get to 6~7p- perfluoroalkyl-p′- azophenol product；
（2）Perfluoroalkyl azobenzene acrylate monomer is synthesized
0.2~1 part of acryloyl chloride is dissolved in 5~20 parts of dry chlorinated paraffin solvents, acryloyl chloride solution is configured to；By 1
~3 partsp- perfluoroalkyl-p′- azophenol is dissolved in 10~30 parts of dry chlorinated paraffin solvents, adds 0.4~1 part of three second
Under amine, stirring condition, -10~0 DEG C is cooled to；Acryloyl chloride solution is slowly added dropwise under conditions of temperature is -20~0 DEG C again,
Time for adding is controlled in 30min~2h；After completion of dropping, reactant is warmed to room temperature, then reacts 2~10h under agitation；Stop
After only reacting, reaction solution separates organic phase after washing process, adds 0.2~0.5 part of anhydrous magnesium sulfate drying process 1~8
h；Drier is removed, is evaporated off after solvent, obtains perfluoroalkyl azobenzene acrylate monomer；
（3）The preparation of silk macromole evocating agent
1 part of real silk fabric is placed in tetrahydrofuran and soaks, stir, is cleaned up after taking-up, then real silk fabric is placed in vacuum
In drying box, vacuum drying handles 1~12 h under conditions of temperature is 30~70 DEG C, takes out dried real silk fabric, puts
It is placed in 2~24h of Balance Treatment in drier；
0.1~0.5 part of DMAP and 10~100 parts of ether solvents are added in reactor, stirring and dissolving；Add
After real silk fabric and 0.1~1.0 part of triethylamine, then 0.1~1.0 part of 2- bromine isobutyl acylbromide is slowly added dropwise, time for adding control is
30min~2h；After insulation reaction under conditions of temperature is 40~80 DEG C 1~24 hour, real silk fabric is taken out, with water and ethanol
Clean successively, then it is 1~12 h of vacuum drying processing under conditions of 30~70 DEG C that the real silk fabric after cleaning is placed in into temperature,
2~24h of Balance Treatment in drier is placed in, silk macromole evocating agent is prepared；
（4）Graft copolymerization
0.006 part of pentamethyl-diethylenetriamine is dissolved in 3~8 parts of aromatic hydrocarbon solvents, pentamethyl-diethylenetriamine is obtained molten
Liquid；By 1~3 part of step（2）The perfluoroalkyl azobenzene acrylate monomer of synthesis is dissolved in 5~30 parts of aromatic hydrocarbon solvents
In, obtain perfluoroalkyl azobenzene acrylate monomer solution；
By 1 part of step（3）Obtained silk macromole evocating agent, 0.01~0.05 part of copper bromide and 0.05~0.2 part of bromination
Cuprous, 30 parts of toluene are added in reactor, after vacuumizing under nitrogen protection, add pentamethyl-diethylenetriamine solution,
Temperature is 10~120 min of reaction under conditions of 25~65 DEG C；
Perfluoroalkyl azobenzene acrylate monomer solution is added, 50~105 DEG C are warming up to, 10~120 min are reacted；Take out
Real silk fabric, is embathed after 10~60 min with 0.01 mol/L dilute HCl solution, and real silk fabric is entered respectively with ethanol and acetone
Row extraction is embathed, then is washed with deionized, and is obtained being grafted real silk fabric, is placed in vacuum drying oven, is 20~85 DEG C in temperature
Under conditions of the h of drying and processing 1~12, then at 12~48 h are balanced at room temperature, obtain the intelligent real silk fabric of hydrophilic and hydrophobic.
The preferred scheme of technical solution of the present invention is：
Step（2）Described chlorinated paraffin solvent is any one in dichloromethane, dichloroethanes or tetrachloroethanes；It is added dropwise third
The temperature of alkene solution of acid chloride is -10~-5 DEG C.
Step（3）Described ether solvent is any one in tetrahydrofuran, 1,4- dioxane, ether.
Step（4）Described aromatic hydrocarbon solvent is any one in toluene, dimethylbenzene.
The present invention mechanism be：First real silk fabric is reacted in 2- bromine isobutyl acylbromides, macromole evocating agent is prepared into, then
Pass through ATRP（ATRP）Method is with the acrylic ester grafted modified silk of perfluoroalkyl azobenzene.It is grafted silk
Fiber surface contains multiple perfluoroalkyl azobenzene acrylate polymer grafted chains, and these fluoropolymer grafted chains are ultraviolet
Under light stimulus, side base azo group occurs isomerization and is transformed into cis-configuration, and perfluoroalkyl weakens in silk surface enrichment degree, table
Face is transformed into hydrophily；Then azo group is set to be turned by cis-configuration again with radiation of visible light real silk fabric in a heated condition again
Become anti-configuration, perfluoroalkyl is in the increase of surface enrichment degree, and surface is changed into hydrophobic；So circulation changes the structure of azo group
Type, can repeatedly realize real silk fabric surface hydrophilic to hydrophobic again to hydrophilic transformation, and transformation is controllable.
The controllability that the present invention is reacted using ATRP polymerization, by perfluoroalkyl azobenzene polyacrylate grafting to silk
Fiber surface, the light isomery characteristic having using perfluoroalkyl azobenzene polyacrylate side base azobenzene, by outer
Boundary stimulates the azobenzene light heterogeneous states on control real silk fabric surface to control the space conformation of side base perfluoroalkyl, so as to control
The surface hydrophilic and hydrophobic feature of real silk fabric processed can repeatedly circulate the intelligent of conversion there is provided a kind of surface hydrophilic-hydrophobic property
Fabric.
Compared with prior art, the beneficial effects of the present invention are：
1st, perfluoroalkyl azobenzene polyacrylate polymers chain is grafted to real silk fabric surface, grafted chain side base by the present invention
On azo group can be transformed into cis-configuration in isomerization under ultraviolet light, receive again after visible ray/thermostimulation then again
It is transformed into anti-configuration, and can repeatedly circulates conversion, and inducing terminal perfluoroalkyl conformation also changes simultaneously every time.Therefore, may be used
By controlling environmental stimuli to obtain the controllable real silk fabric of content of the fluoropolymer chain on silk surface.
2nd, silk is modified as a result of controllable polymerization reactive grafting, control grafting processing time can control cocoon fiber table
The degree of polymerization of face grafted chain and degree of polymerization distribution is narrow, so that the chain of polyacrylate grafting containing perfluoroalkyl can be arranged on silk surface
Row are regular, overcome when preparing finishing agent or graft modification silk by traditional conventional radical polymerization reaction, the degree of polymerization is big, poly-
Right distribution is wide, and the winding of grafted chain molecular backbone causes the defect of the fluorine-containing azobenzene light isomeric effect difference of side base, thus
Obtained graft modification real silk fabric shows good hydrophilic and hydrophobic reversible transformation performance.
3rd, to prepare perfluoroalkyl azobenzene acrylate polymer graft modification true using ATRP controllable polymerizations by the present invention
Silk fabrics, the real silk fabric product of the controllable conversion of intelligent hydrophilic-hydrophobic of preparation is adapted to industrialized production and popularization and application.
Brief description of the drawings
Fig. 1 is the Silk Fabrics Graft modified-reaction flow chart that the present invention is provided.
Fig. 2 is untreated former silk, silk macromole evocating agent, the intelligent silk of preparation of the embodiment of the present invention
The infrared spectrum comparison diagram of fabric.
Fig. 3 is the structural representation for the intelligent real silk fabric that various embodiments of the present invention are provided.
Fig. 4 is the intelligent real silk fabric prepared by technical scheme of the embodiment of the present invention in ultraviolet light, again with visible
Light irradiation, repeatedly after circulation, to the water contact angle result figure that iterative cycles change between 122.2 °/77.8 °.
Fig. 5 be the embodiment of the present invention 1 provide former silk, silk macromole evocating agent and graft modification after it is intelligent very
The SEM comparison diagrams of silk fabrics.
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
The present invention provides the preparation method that a kind of surface hydrophilic-hydrophobic property can repeatedly circulate the intelligent real silk fabric of conversion,
First real silk fabric is reacted in 2- bromine isobutyl acylbromides, macromole evocating agent is prepared into, then passes through ATRP
（ATRP）Method is with the acrylic ester grafted modified silk of perfluoroalkyl azobenzene.Graft polymerization reaction flow referring to accompanying drawing 1, wherein, m
=2~20；N=2,4,6 or 8.
The present embodiment is comprised the following steps that：
（1）Synthesisp- nine fluorine butyl- p′- azophenol
The fluorine butyl benzenes of 0.93 g4- nine are added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dilute hydrochloric acid solution of amine and 10 ml（2 mol/L）, it is heated with stirring to all dissolvings of 4- Perfluoroalkylanilins.Then will mixing
Solution is placed on the aqueous solution that 10 DEG C are cooled in ice bath and 4.5 g natrium nitrosums are slowly added dropwise using constant pressure funnel, 10
Reaction solution after 2 h is reacted at DEG C and becomes faint yellow.0.42 g phenol is dissolved in 20 ml sodium hydrate aqueous solution（1 mol/
L）Middle formation phenol sodium solution.Then the reaction before the phenol sodium solution configured is slowly dropped into using constant pressure funnel
In, temperature is maintained at less than 10 DEG C, gradually has orange-red solid to separate out.Reaction solution is adjusted with saturated solution of sodium bicarbonate
PH to 6~7, natural filtration obtains crude product, in methanol/water（1：1）Mixed solution in be recrystallized to give 0.74 g pure
Orange red solid, is dried into powder, and yield is 59.3%.Product FT-IR: 3419.5, 1595.2, 1354.6, 1231.7,
1198.8, 1136.8, 1096.5 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 19.1, 8.6
Hz, 4H), 7.74 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.7 Hz, 2H), 5.32 (s, 1H, -
OH)。
（2）Synthesize the fluorine butyl -4 of 4- nine '-acrylate-based azobenzene
- 4 '-azobenzenes of fluorine butyl of 1.66 g4- nine are added in equipped with magnetic stir bar, 100 ml three-necked flasks of thermometer
Phenol, the dichloromethane solution and 0.83 g triethylamine solutions of 30 mL water removals.Then three-necked flask is fixed on into cryogenic thermostat to stir
Mix and 30 min are stirred in reactive bath technique, temperature control is -5 DEG C.0.54 g acryloyl chlorides are dissolved in the dichloromethane of 15 mL water removals
In, and pour into constant pressure funnel, keep low temperature to be slowly dropped into above-mentioned reaction solution.Stirred after completion of dropping from cryogenic thermostat
Three-necked flask is taken out in reactive bath technique, is placed under normal temperature and reacts 6 h.Then reaction solution is poured into 100 mL separatory funnel, water
Wash 3 times（3×30 mL）, organic phase is taken out, 8 h are dried in anhydrous magnesium sulfate, suction filtration, vacuum rotary steam obtain orange/yellow solid
1.42 g, yield is 77.4%.
（3）The preparation of silk macromole evocating agent
10 g real silk fabrics are put into immersion and stirring and washing in tetrahydrofuran (THF) solution, it is true after then cleaning up
Silk fabrics is transferred in vacuum drying chamber, the h of vacuum drying 4 under the conditions of 50 DEG C, is taken out dried real silk fabric, is placed on dry
24h is balanced in dry device.
The real silk fabric after 1g cooling balances is weighed to add in single-necked flask.Weigh 0.2g DMAP
(DMAP) add in the single-necked flask equipped with 50 mL THF solutions, stirring and dissolving, 0.25g triethylamines (TEA) are then added dropwise molten
Liquid, 0.56g 2- bromine isobutyl acylbromides then be slowly added in single-necked flask and shaken up.
Reaction system is sealed, is put into water-bath constant temperature oscillator, at 50 DEG C after oscillating reactions 2h, real silk fabric is taken out simultaneously
Cleaned successively 3 times with 30ml water and 30ml ethanol.Then the real silk fabric after cleaning is put into vacuum drying chamber, 50 DEG C of conditions
The lower h of vacuum drying 4, finally places into and balance is cooled down in drier, obtain silk macromole evocating agent.Measure silk macromolecular
The infrared spectrum of initiator is referring to the curve b in accompanying drawing 2.
（4）Graft copolymerization
Weigh 0.5 g silks macromole evocating agent, 0.06 g copper bromides（CuBr2）With 0.6 g cuprous bromides（CuBr）It is added to
In single-necked flask equipped with 30 mL toluene solutions, rubber stopper seal is used.
Nitrogen is passed through after closed system is vacuumized, operation is repeated 3 times, makes to be full of nitrogen in single-necked flask.Then will
0.006g ligand pentamethyl-diethylenetriamines（PMDETA）It is dissolved in 5 mL toluene solutions, is added with disposable syringe above-mentioned
In sealing system.
Single-necked flask is put into water-bath constant temperature oscillator, solution colour in 30 min, closed system is vibrated at 45 DEG C and is become
To be blackish green and with there is floccule generation.Weigh 2 g perfluoroalkyl azobenzene acrylate monomers（The fluorine butyl -4 of 4- nine ' -
Acrylate-based azobenzene）, in the toluene solution for being dissolved in 10 mL, equally it is added to obturator with disposable syringe
In system, temperature was increased to after 80 DEG C, reaction a period of time, real silk fabric is taken out.
15 min are embathed with 0.01 mol/L dilute HCl solution, then 15ml ethanol and 15ml acetone solns are successively to true
Silk fabrics carry out extraction embathe, repeatedly operate 4 times, fully remove autopolymer and no reaction monomer, finally gone with 15ml from
Sub- water washing 3 times.Grafting real silk fabric is put into vacuum drying oven, dries 6 hours, balances 24 hours at room temperature in 35 DEG C,
Surface hydrophilic-hydrophobic controllable intelligent real silk fabric is obtained, it is 12.70% to measure modified real silk fabric surface fluorine element content.Connect
As shown in Figure 3, in formula, R is isobutyric acid ester group to the chemical constitution schematic diagram on branch silk surface, and m is 3~5.
It is untreated former silk, silk macromole evocating agent manufactured in the present embodiment, intelligent referring to accompanying drawing 2
The infrared spectrum comparison diagram of real silk fabric, wherein, curve a is the infrared spectrogram of untreated former silk, and curve b is true
The infrared spectrogram of silk macromole evocating agent, curve c is the infrared spectrogram of the silk after ATRP is graft-polymerized.By Fig. 2
It can be seen that, the characteristic peak of fibroin can be observed in silk macromole evocating agent and graft modification silk surface, wherein, 1650.5
cm-1、1518.1 cm-1、1228.5 cm-1With 698.5 cm-1The characteristic peak of acid amides in fibroin is belonged to, illustrates that silk is big
Silk after molecule and graft polymerization does not change on primary structure, still keeps beta sheet structure.Contrast is untreated
Silk infrared absorption curve a and silk macromole evocating agent infrared absorption curve b is understood, in 1731.5 cm in curve b-1Place goes out
Showed new absworption peak, the absworption peak belongs to C=O stretching vibration absworption peak, show 2- bromine isobutyl acylbromides and real silk fabric into
Work(reaction generation silk macromolecular.Curve c is then in 1328.9 cm-1Place occurs in that new absworption peak, can belong to stretching for C-F keys
Contracting vibration absorption peak, illustrates that fluorochemical monomer is successfully accessed to real silk fabric surface by ATRP graft polymerization reactions.
Referring to accompanying drawing 5, the intelligence after former silk, silk macromole evocating agent and graft modification that it is provided for the present embodiment
The SEM comparison diagrams of type real silk fabric；Wherein, figure a is untreated silk, and figure b is silk macromole evocating agent, and figure c changes for grafting
Intelligent real silk fabric after property.As seen from Figure 5, after graft modification, perfluoroalkyl azobenzene acrylate is true
Silk fiber surface forms grafted chain, and these grafted chains mutually heap to form coarse surface topography, show that monomer is successfully passed
ATRP is grafted to silk macromolecular surface, and graininess aggregation shape characteristic also demonstrate that the grafted chain degree of polymerization is relatively low, the degree of polymerization point
The narrow architectural feature of cloth.
（5）UV-Visible stimulates azo group isomery
Graft modification real silk fabric is irradiated under spectrum ultraviolet light entirely, makes grafted chain side base azo group isomerization, test silk is knitted
Thing surface contact angle；Then, by real silk fabric in a heated condition with radiation of visible light, test azo group in grafted chain and be transformed into
Fabric face contact angle after anti-configuration.So irradiate isomery through UV-Visible circulation and test real silk fabric surface and connect
Feeler.
Using the full-automatic microscopic droplets wetability measuring instrument of the types of OCAH 200 of dataphysics companies of the U.S. to silicon chip table
Face self-assembled film carries out wetability test, chooses water as test fluid, and droplet size is 3 μ L, and each sample test takes it 3 times
Average value.
Referring to accompanying drawing 4, it is that the intelligent real silk fabric that the present embodiment is provided shines in ultraviolet light, again with visible ray
Penetrate, repeatedly after circulation, to the water contact angle result figure that iterative cycles change between 122.2 °/77.8 °.
Embodiment 2
（1）Synthesized by the preparation technology of embodiment 1p- nine fluorine butyl- p′- azophenol and the fluorine butyl -4 of 4- nine '-acrylate-based
Azobenzene.
（2）The preparation of silk macromole evocating agent
The real silk fabric after 9g cooling balances, 2g4- dimethylamino naphthyridines is weighed to add equipped with 250 mL 1,4- dioxane
In flask, after stirring and dissolving, 2.8g triethylamines are added dropwise, are then slowly added to 5.9g 2- bromine isobutyl acylbromides in single-necked flask simultaneously
Shake up.
Reaction system is sealed, is put into water-bath constant temperature oscillator, at 45 DEG C after oscillating reactions 3h, real silk fabric is taken out simultaneously
Cleaned successively 3 times with 80ml water and 80ml ethanol.Then the real silk fabric after cleaning is put into vacuum drying chamber, 45 DEG C of conditions
The lower h of vacuum drying 8, finally places into and balance is cooled down in drier, obtain silk macromole evocating agent.
（3）Graft copolymerization
Weigh 5 g silks macromole evocating agents, 0.8 g copper bromides and 4.6 g cuprous bromides be added to it is molten equipped with 250 mL toluene
In the flask of liquid, rubber stopper seal is used.
Nitrogen is passed through after closed system is vacuumized, operation is repeated 3 times, makes to be full of nitrogen in single-necked flask.Then will
0.08g ligand pentamethyl-diethylenetriamines are dissolved in 48mL toluene solutions, and above-mentioned sealing system is added with disposable syringe
In.
Single-necked flask is put into water-bath constant temperature oscillator, solution colour in 2h, closed system is vibrated at 45 DEG C and is changed into ink
Green and with there is floccule generation.22 g perfluoroalkyl azobenzene acrylate monomers are weighed, 105 mL are dissolved in
Toluene solution in, be equally added to disposable syringe in closed system, temperature be increased to 75 DEG C, react 20min
Afterwards, real silk fabric is taken out.
30 min are embathed with 0.01 mol/L dilute HCl solution, it is then right successively with 80ml ethanol and 80ml acetone solns
Real silk fabric carries out extraction and embathed, and operates 4 times repeatedly, fully removes autopolymer and the no monomer of reaction, finally uses deionization
Water washing 3 times, grafting real silk fabric is put into vacuum drying oven, is dried in 45 DEG C 5 hours, is balanced 24 hours, obtain at room temperature
To surface hydrophilic-hydrophobic controllable intelligent real silk fabric, it is 10.32% to measure modified real silk fabric surface fluorine element content.Grafting
As shown in Figure 3, in formula, R is isobutyric acid ester group to the chemical constitution schematic diagram on silk surface, and m is 2~4.
（4）Ultraviolet light-can be by light stimulus azo group isomery
Graft modification real silk fabric is irradiated under spectrum ultraviolet light entirely, makes grafted chain side base azo group isomerization, test silk is knitted
Thing surface contact angle；Then, by real silk fabric in a heated condition with radiation of visible light, azo group in its surface grafting chain is tested
It is transformed into fabric contact angle after anti-configuration.So isomery is irradiated through UV-Visible circulation and test real silk fabric surface
Contact angle.
Using the full-automatic microscopic droplets wetability measuring instrument of the types of OCAH 200 of dataphysics companies of the U.S. to silicon chip table
Face self-assembled film carries out wetability test, chooses water as test fluid, and droplet size is 3 μ L, and each sample test takes it 3 times
Average value.
Measuring modified real silk fabric, the iterative cycles between 103.5 °/55.7 ° change to water contact angle.
Embodiment 3
（1）p- ten trifluoro hexyls-p′- azophenol is synthesized
The trifluoro hexyls of 1.23 g4- ten are added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dilute hydrochloric acid solution of aniline and 10 ml（2 mol/L）, all dissolvings of agitating and heating reactant.Then mixed solution is placed on
10 DEG C are cooled in ice bath and the aqueous solution of 4.5 g natrium nitrosums is slowly added dropwise using constant pressure funnel, it is anti-at 10 DEG C
Reaction solution after 2 h is answered to become faint yellow.0.42 g phenol is dissolved in 20 ml sodium hydrate aqueous solution（1 mol/L）Middle shape
Into phenol sodium solution.Then in the reaction before the phenol sodium solution configured is slowly dropped into using constant pressure funnel, temperature
Degree is maintained at less than 10 DEG C, gradually has orange-red solid to separate out.The PH to 6- of reaction solution is adjusted with saturated solution of sodium bicarbonate
7, natural filtration obtains crude product, in methanol/water（1：1）Mixed solution in be recrystallized to give pure orange red solid of 0.81 g
Body, is dried into powder.Yield is 52.3%.Product FT-IR: 3448.0, 1596.6, 1391.68, 1248.1, 1205.0,
1143.8, 1104.7, 1010.0 cm-1。
（2）Trifluoro hexyl-the p ' of p- ten-acrylate-based azobenzene synthesis
- 4 '-azos of trifluoro hexyl of 2.06 g 4- ten are added in equipped with magnetic stir bar, 100 ml three-necked flasks of thermometer
Phenol, the dichloromethane solution and 0.83 g triethylamine solutions of 30mL water removals.Then three-necked flask is fixed on cryogenic thermostat
30 min are stirred in stirring reaction bath, temperature control is -5 DEG C.0.54 g acryloyl chlorides are dissolved in the dichloromethane of 15 mL water removals
In alkane, and pour into constant pressure funnel, keep low temperature to be slowly dropped into above-mentioned reaction solution.Stirred after completion of dropping from cryogenic thermostat
Mix and three-necked flask is taken out in reactive bath technique, be placed under normal temperature and react 6 h.Then reaction solution is poured into 100 mL separatory funnel,
Washing 3 times（3×30 mL）, organic phase is taken out, 8 h are dried in anhydrous magnesium sulfate, suction filtration, vacuum rotary steam obtain 1.73 g oranges
Yellow solid, yield is 75.9%.
（3）The preparation of silk macromole evocating agent
10 g real silk fabrics are put into immersion and stirring and washing in tetrahydrofuran, the real silk fabric transfer after then cleaning up
Into vacuum drying chamber, the h of vacuum drying 4 under the conditions of 50 DEG C takes out dried real silk fabric, is placed in drier and balances
24h。
The real silk fabric after 1.1g cooling balances is weighed to add in single-necked flask.Weigh 0.22g DMAP
(DMAP) add in the single-necked flask equipped with 54 mL THF solutions, stirring and dissolving, 0.25g triethylamines (TEA) are then added dropwise molten
Liquid, 0.58g 2- bromine isobutyl acylbromides then be slowly added in single-necked flask and shaken up.
Reaction system is sealed, is put into water-bath constant temperature oscillator, at 50 DEG C after oscillating reactions 2h, real silk fabric is taken out simultaneously
Cleaned successively 3 times with 30ml water and 30ml ethanol.Then the real silk fabric after cleaning is put into vacuum drying chamber, 50 DEG C of conditions
The lower h of vacuum drying 4, finally places into and balance is cooled down in drier, obtain silk macromole evocating agent.
（4）Graft copolymerization
0.48 g silks macromole evocating agent, 0.07 g copper bromides and 0.66 g cuprous bromides is weighed to be added to equipped with 35 mL first
In the single-necked flask of benzole soln, rubber stopper seal is used.
Nitrogen is passed through after closed system is vacuumized, operation is repeated 3 times, makes to be full of nitrogen in single-necked flask.Then will
0.008g ligand pentamethyl-diethylenetriamines are dissolved in 8mL toluene solutions, and above-mentioned sealing system is added with disposable syringe
In.
Single-necked flask is put into water-bath constant temperature oscillator, solution colour in 40 min, closed system is vibrated at 45 DEG C and is become
To be blackish green and with there is floccule generation.Trifluoro hexyl-the p ' of 2.1 g p- ten-acrylate-based azobenzene is weighed, its is molten
Solution is equally added in closed system in 12 mL toluene solution with disposable syringe, temperature is increased into 75 DEG C, instead
Answer after 40min, take out real silk fabric.
15 min are embathed with 0.01 mol/L dilute HCl solution, then 15ml ethanol and 15ml acetone solns are successively to true
Silk fabrics carry out extraction embathe, repeatedly operate 4 times, fully remove autopolymer and no reaction monomer, finally gone with 20ml from
Sub- water washing 3 times.Grafting real silk fabric is put into vacuum drying oven, dries 6 hours, balances 24 hours at room temperature in 35 DEG C,
Surface hydrophilic-hydrophobic controllable intelligent real silk fabric is obtained, it is 14.64% to measure modified real silk fabric surface fluorine element content.Connect
As shown in Figure 3, in formula, R is isobutyric acid ester group to the chemical constitution schematic diagram on branch silk surface, and m is 4~8.
（5）Ultraviolet light-can be by light stimulus azo group isomery
Graft modification real silk fabric is irradiated under spectrum ultraviolet light entirely, makes grafted chain side base azo group isomerization, test silk is knitted
Thing surface contact angle；Then, by real silk fabric in a heated condition with radiation of visible light, azo group in its surface grafting chain is tested
It is transformed into fabric contact angle after anti-configuration.So isomery is irradiated through UV-Visible circulation and test real silk fabric surface
Contact angle.
Using the full-automatic microscopic droplets wetability measuring instrument of the types of OCAH 200 of dataphysics companies of the U.S. to silicon chip table
Face self-assembled film carries out wetability test, chooses water as test fluid, and droplet size is 3 μ L, and each sample test takes it 3 times
Average value.Measuring modified real silk fabric, the iterative cycles between 128.7 °/90.3 ° change to water contact angle.
Embodiment 4
（1）p- ten seven fluorine octyl groups- p′- azophenol
1.13 g are added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe p- ten seven fluorine are pungent
Base aniline and the ml of dilute hydrochloric acid solution 10 that concentration is 2 mol/L, are heated with stirring top- ten seven fluorine octyl group aniline all dissolve.
Then mixed solution is placed on to the water that 8 DEG C are cooled in ice bath and 4.6 g natrium nitrosums are slowly added dropwise using constant pressure funnel
Solution, reacts 2 h at 10 DEG C.0.43 g phenol is dissolved in 20 ml sodium hydrate aqueous solution（1 mol/L）It is middle to be formed
Phenol sodium solution.Then in the reaction before the phenol sodium solution configured is slowly dropped into using constant pressure funnel, temperature
Less than 8 DEG C are maintained at, gradually has orange-red solid to separate out.With the PH of saturated solution of sodium bicarbonate regulation reaction solution to 6-7,
Natural filtration obtains crude product, in methanol/water（1：1）Mixed solution in be recrystallized to give pure orange red solid of 0.76 g
Body, is dried into powder.Yield is 61.1%.
（2）p- ten seven fluorine octyl groups- p′- acrylate-based azobenzene
Fluorine octyl group-the p ' of 1.71 g p- 17-azo is added in equipped with magnetic stir bar, 100 ml three-necked flasks of thermometer
Phenol, the dichloromethane solution and 0.85 g triethylamines of 30 mL water removals.Then three-necked flask is fixed on cryogenic thermostat stirring
30 min are stirred in reactive bath technique, temperature control is -8 DEG C.In the dichloromethane that 0.56 g acryloyl chlorides are dissolved in 18 mL water removals,
And pour into constant pressure funnel, it is slowly dropped into above-mentioned reaction solution, dropping temperature is advisable with being kept for less than -8 DEG C.Drip
Three-necked flask is taken out from cryogenic thermostat stirring reactive bath after finishing, is placed under normal temperature and reacts 8 h.Then reaction solution is poured into 100
In mL separatory funnel, wash 3 times, 30 mL deionized waters are used every time.Organic phase is taken out, adds and 6 is dried in anhydrous magnesium sulfate
H, suction filtration, vacuum rotary steam obtain the g of orange/yellow solid 1.56, and yield is 79.1%.
（3）The preparation of silk macromole evocating agent
10 g real silk fabrics are put into immersion and stirring and washing in tetrahydrofuran, the real silk fabric transfer after then cleaning up
Into vacuum drying chamber, the h of vacuum drying 4 under the conditions of 50 DEG C takes out dried real silk fabric, is placed in drier and balances
24h。
The real silk fabric after 1.2g cooling balances is weighed to add in single-necked flask.Weigh 0.25g DMAP
(DMAP) add in the single-necked flask equipped with 58 mL THF solutions, stirring and dissolving, 0.25g triethylamines (TEA) are then added dropwise molten
Liquid, 0.60g 2- bromine isobutyl acylbromides then be slowly added in single-necked flask and shaken up.
Reaction system is sealed, is put into water-bath constant temperature oscillator, at 50 DEG C after oscillating reactions 2h, real silk fabric is taken out simultaneously
Cleaned successively 3 times with 35ml water and 35ml ethanol.Then the real silk fabric after cleaning is put into vacuum drying chamber, 50 DEG C of conditions
Lower vacuum drying 6h, finally places into and balance is cooled down in drier, obtain silk macromole evocating agent.
（4）Graft copolymerization
0.55 g silks macromole evocating agent, 0.08 g copper bromides and 0.68 g cuprous bromides is weighed to be added to equipped with 40 mL first
In the single-necked flask of benzole soln, rubber stopper seal is used.
Nitrogen is passed through after closed system is vacuumized, operation is repeated 3 times, makes to be full of nitrogen in single-necked flask.Then will
0.01g ligand pentamethyl-diethylenetriamines are dissolved in 10mL toluene solutions, and above-mentioned sealing system is added with disposable syringe
In.
Single-necked flask is put into water-bath constant temperature oscillator, solution colour in 30 min, closed system is vibrated at 45 DEG C and is become
To be blackish green and with there is floccule generation.Weigh 2.3 gp- ten seven fluorine octyl groups- p′- acrylate-based azobenzene, its is molten
Solution is equally added in closed system in 15 mL toluene solution with disposable syringe, and temperature is increased into 75 ~ 78
DEG C, after reaction 50min, take out real silk fabric.
18 min are embathed with 0.01 mol/L dilute HCl solution, then 25ml ethanol and 25ml acetone solns are successively to true
Silk fabrics carry out extraction embathe, repeatedly operate 4 times, fully remove autopolymer and no reaction monomer, finally gone with 25ml from
Sub- water washing 3 times.Grafting real silk fabric is put into vacuum drying oven, dries 6 hours, balances 24 hours at room temperature in 35 DEG C,
Surface hydrophilic-hydrophobic controllable intelligent real silk fabric is obtained, it is 16.72% to measure modified real silk fabric surface fluorine element content.Connect
The chemical constitution schematic diagram on branch silk surface is as shown in Figure 3：In formula, R is isobutyric acid ester group, and m is 5~10.
（5）Ultraviolet light-can be by light stimulus azo group isomery
Graft modification real silk fabric is irradiated under spectrum ultraviolet light entirely, makes grafted chain side base azo group isomerization, test silk is knitted
Thing surface contact angle；Then, by real silk fabric in a heated condition with radiation of visible light, azo group in its surface grafting chain is tested
It is transformed into fabric contact angle after anti-configuration.So isomery is irradiated through UV-Visible circulation and test real silk fabric surface
Contact angle.
Using the full-automatic microscopic droplets wetability measuring instrument of the types of OCAH 200 of dataphysics companies of the U.S. to silicon chip table
Face self-assembled film carries out wetability test, chooses water as test fluid, and droplet size is 3 μ L, and each sample test takes it 3 times
Average value.Measuring modified real silk fabric, the iterative cycles between 130.4 °/104.7 ° change to water contact angle.
Embodiment 5
（1）p- ten trifluoro hexyls-p′- azophenol is synthesized
Added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe 1.21 g the trifluoros of 4- ten oneself
The dilute hydrochloric acid solution of base aniline and 10 ml（2 mol/L）, all dissolvings of agitating and heating reactant.Then mixed solution is put
10 DEG C are cooled in ice bath and the aqueous solution of 4.6 g natrium nitrosums is slowly added dropwise using constant pressure funnel, at 10 DEG C
React reaction solution after 2 h and become faint yellow.0.41 g phenol is dissolved in 20 ml sodium hydrate aqueous solution（1 mol/L）In
Form phenol sodium solution.Then in the reaction before the phenol sodium solution configured is slowly dropped into using constant pressure funnel,
Temperature is maintained at less than 10 DEG C, gradually has orange-red solid to separate out.With saturated solution of sodium bicarbonate adjust reaction solution PH to
6-7, natural filtration obtains Orange red solid product, and yield is 53.5%.
（2）Trifluoro hexyl-the p ' of p- ten-acrylate-based azobenzene synthesis
Trifluoro hexyl-the p ' of 2.12 g p- ten-azo is added in equipped with magnetic stir bar, 100 ml three-necked flasks of thermometer
Phenol, the dichloroethane solution and 0.85 g triethylamines of 30mL water removals.Then three-necked flask is fixed on cryogenic thermostat stirring
30 min are stirred in reactive bath technique, temperature control is -10 DEG C.0.52 g acryloyl chlorides are dissolved in the dichloroethanes of 15 mL water removals
In, and pour into constant pressure funnel, keep low temperature to be slowly dropped into above-mentioned reaction solution.Stirred after completion of dropping from cryogenic thermostat
Three-necked flask is taken out in reactive bath technique, is placed under normal temperature and reacts 6 h.Then reaction solution is poured into 100 mL separatory funnel, water
Wash 3 times（3×30 mL）, organic phase is taken out, 8 h are dried in anhydrous magnesium sulfate, suction filtration, vacuum rotary steam obtain 1.75 g orange
Color solid product, yield is 76.3%.Using n-hexane as eluent, refined products can be made using the method for chromatographic column.
（3）The preparation of silk macromole evocating agent
The real silk fabric after 1.1g cooling balances is weighed to add in single-necked flask.Weigh 0.20g DMAP
(DMAP) add in the single-necked flask equipped with 50 mL THF solutions, stirring and dissolving, 0.25g triethylamines (TEA) are then added dropwise molten
Liquid, 0.62g 2- bromine isobutyl acylbromides then be slowly added in single-necked flask and shaken up.
Reaction system is sealed, is put into water-bath constant temperature oscillator, at 50 DEG C after oscillating reactions 2h, real silk fabric is taken out simultaneously
Cleaned successively 3 times with 30ml water and 35ml ethanol.Then the real silk fabric after cleaning is put into vacuum drying chamber, 45 DEG C of conditions
Lower vacuum drying 6h, finally places into and balance is cooled down in drier, obtain silk macromole evocating agent.
（4）Graft copolymerization
0.58 g silks macromole evocating agent, 0.09 g copper bromides and 0.70g cuprous bromides is weighed to be added to equipped with 45mL toluene
In the single-necked flask of solution, rubber stopper seal is used.
Nitrogen is passed through after closed system is vacuumized, operation is repeated 3 times, makes to be full of nitrogen in single-necked flask.Then will
0.009g ligand pentamethyl-diethylenetriamines are dissolved in 10mL toluene solutions, and above-mentioned sealing system is added with disposable syringe
In.
Single-necked flask is put into water-bath constant temperature oscillator, solution colour in 30 min, closed system is vibrated at 45 DEG C and is become
To be blackish green and with there is floccule generation.Trifluoro hexyl-the p ' of 2.3 g p- ten-acrylate-based azobenzene is weighed, its is molten
Solution is equally added in closed system in 15 mL toluene solution with disposable syringe, temperature is increased into 78 DEG C, instead
Answer after 60min, take out real silk fabric.
18 min are embathed with 0.01 mol/L dilute HCl solution, then 25ml ethanol and 25ml acetone solns are successively to true
Silk fabrics carry out extraction embathe, repeatedly operate 4 times, fully remove autopolymer and no reaction monomer, finally gone with 25ml from
Sub- water washing 3 times.Grafting real silk fabric is put into vacuum drying oven, dries 6 hours, balances 24 hours at room temperature in 35 DEG C,
Surface hydrophilic-hydrophobic controllable intelligent real silk fabric is obtained, it is 18.57% to measure modified real silk fabric surface fluorine element content.Connect
As shown in Figure 3, in formula, R is isobutyric acid ester group to the chemical constitution schematic diagram on branch silk surface, and m is 5~10.
（5）Ultraviolet light-can be by light stimulus azo group isomery
Graft modification real silk fabric is irradiated under spectrum ultraviolet light entirely, makes grafted chain side base azo group isomerization, test silk is knitted
Thing surface contact angle；Then, by real silk fabric in a heated condition with radiation of visible light, azo group in its surface grafting chain is tested
It is transformed into fabric contact angle after anti-configuration.So isomery is irradiated through UV-Visible circulation and test real silk fabric surface
Contact angle.
Using the full-automatic microscopic droplets wetability measuring instrument of the types of OCAH 200 of dataphysics companies of the U.S. to silicon chip table
Face self-assembled film carries out wetability test, chooses water as test fluid, and droplet size is 3 μ L, and each sample test takes it 3 times
Average value.Measure intelligent modified real silk fabric under environmental stimuli to the contact angle of water between 134.3 °/113.7 ° repeatedly
Circulation transformation.
Claims (5)
1. a kind of intelligent real silk fabric of hydrophilic and hydrophobic, it is characterised in that：The fiber surface of the real silk fabric is by perfluoroalkyl
The acrylic ester grafted modification by copolymerization of azobenzene；Perfluoroalkyl azobenzene polyacrylate grafting chain polymerization degree is 2~20；Entirely
Fluoroalkyl includes any one in pentafluoroethyl group, nine fluorine butyl, ten trifluoro hexyls or 17 fluorine octyl groups.
2. a kind of preparation method of the intelligent real silk fabric of hydrophilic and hydrophobic as claimed in claim 1, it is characterised in that including such as
Lower step：
（1）p- perfluoroalkyl-p′- azophenol is synthesized
By weight, 0.3~1 part of phenol is dissolved in the sodium hydrate aqueous solution that 10~40 parts of concentration are 1 mol/L, matched somebody with somebody
Phenol sodium solution is made；4~8 parts of natrium nitrosums are dissolved in 8~12 parts of deionized waters, sodium nitrite in aqueous solution is configured to；
Willp- Perfluoroalkylanilin is suspended in the dilute hydrochloric acid solution that concentration is 2mol/L, treats that Perfluoroalkylanilin is complete under heating condition
After dissolving, 5~10 DEG C are cooled to, sodium nitrite in aqueous solution, insulation reaction 2~5 hours is slowly added dropwise, then that sodium phenate is added dropwise is molten
Liquid, controlling reaction temperature is maintained at 5~10 DEG C；The pH for adjusting reaction solution with saturated solution of sodium bicarbonate is filtrated to get to 6~7p- perfluoroalkyl-p′- azophenol product；
（2）Perfluoroalkyl azobenzene acrylate monomer is synthesized
0.2~1 part of acryloyl chloride is dissolved in 5~20 parts of dry chlorinated paraffin solvents, acryloyl chloride solution is configured to；By 1
~3 partsp- perfluoroalkyl-p′- azophenol is dissolved in 10~30 parts of dry chlorinated paraffin solvents, adds 0.4~1 part of three second
Under amine, stirring condition, -10~0 DEG C is cooled to；Acryloyl chloride solution is slowly added dropwise under conditions of temperature is -20~0 DEG C again,
Time for adding is controlled in 30min~2h；After completion of dropping, reactant is warmed to room temperature, then reacts 2~10h under agitation；Stop
After only reacting, reaction solution separates organic phase after washing process, adds 0.2~0.5 part of anhydrous magnesium sulfate drying process 1~8
h；Drier is removed, is evaporated off after solvent, obtains perfluoroalkyl azobenzene acrylate monomer；
（3）The preparation of silk macromole evocating agent
1 part of real silk fabric is placed in tetrahydrofuran and soaks, stir, is cleaned up after taking-up, then real silk fabric is placed in vacuum
In drying box, vacuum drying handles 1~12 h under conditions of temperature is 30~70 DEG C, takes out dried real silk fabric, puts
It is placed in 2~24h of Balance Treatment in drier；
0.1~0.5 part of DMAP and 10~100 parts of ether solvents are added in reactor, stirring and dissolving；Add
After real silk fabric and 0.1~1.0 part of triethylamine, then 0.1~1.0 part of 2- bromine isobutyl acylbromide is slowly added dropwise, time for adding control is
30min~2h；After insulation reaction under conditions of temperature is 40~80 DEG C 1~24 hour, real silk fabric is taken out, with water and ethanol
Clean successively, then it is 1~12 h of vacuum drying processing under conditions of 30~70 DEG C that the real silk fabric after cleaning is placed in into temperature,
2~24h of Balance Treatment in drier is placed in, silk macromole evocating agent is prepared；
（4）Graft copolymerization
0.006 part of pentamethyl-diethylenetriamine is dissolved in 3~8 parts of aromatic hydrocarbon solvents, pentamethyl-diethylenetriamine is obtained molten
Liquid；By 1~3 part of step（2）The perfluoroalkyl azobenzene acrylate monomer of synthesis is dissolved in 5~30 parts of aromatic hydrocarbon solvents
In, obtain perfluoroalkyl azobenzene acrylate monomer solution；
By 1 part of step（3）Obtained silk macromole evocating agent, 0.01~0.05 part of copper bromide and 0.05~0.2 part of bromination
Cuprous, 30 parts of toluene are added in reactor, after vacuumizing under nitrogen protection, add pentamethyl-diethylenetriamine solution,
Temperature is 10~120 min of reaction under conditions of 25~65 DEG C；
Perfluoroalkyl azobenzene acrylate monomer solution is added, 50~105 DEG C are warming up to, 10~120 min are reacted；Take out
Real silk fabric, is embathed after 10~60 min with 0.01 mol/L dilute HCl solution, and real silk fabric is entered respectively with ethanol and acetone
Row extraction is embathed, then is washed with deionized, and is obtained being grafted real silk fabric, is placed in vacuum drying oven, is 20~85 DEG C in temperature
Under conditions of the h of drying and processing 1~12, then at 12~48 h are balanced at room temperature, obtain the intelligent real silk fabric of hydrophilic and hydrophobic.
3. a kind of preparation method of the intelligent real silk fabric of hydrophilic and hydrophobic according to claim 2, it is characterised in that：Step
（2）Described chlorinated paraffin solvent is any one in dichloromethane, dichloroethanes or tetrachloroethanes；Acryloyl chloride is added dropwise molten
The temperature of liquid is -10~-5 DEG C.
4. a kind of preparation method of the intelligent real silk fabric of hydrophilic and hydrophobic according to claim 2, it is characterised in that：Step
（3）Described ether solvent is any one in tetrahydrofuran, 1,4- dioxane, ether.
5. a kind of preparation method of the intelligent real silk fabric of hydrophilic and hydrophobic according to claim 2, it is characterised in that：Step
（4）Described aromatic hydrocarbon solvent is any one in toluene, dimethylbenzene.
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