CN110172122A - A kind of preparation method of the convertible smart fabric finishing agent of the close and distant property in surface - Google Patents
A kind of preparation method of the convertible smart fabric finishing agent of the close and distant property in surface Download PDFInfo
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- CN110172122A CN110172122A CN201910563322.XA CN201910563322A CN110172122A CN 110172122 A CN110172122 A CN 110172122A CN 201910563322 A CN201910563322 A CN 201910563322A CN 110172122 A CN110172122 A CN 110172122A
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a kind of preparation method of the convertible smart fabric finishing agent of the close and distant property in surface, the finishing agent effective component provided is perfluoroalkyl azobenzene acrylate copolymer.Using perfluoroalkyl azophenol as initial feed, by obtaining the acrylate monomer of the azobenzene containing perfluoroalkyl with acryloyl chloride esterification, the acrylate copolymer emulsion of the azobenzene containing perfluoroalkyl is then made by emulsion polymerization with hydroxyethyl methacrylate, butyl acrylate.By increasing initiator amount when emulsion polymerization, obtained copolymer polymerization degree is low, and copolymer molecule main chain is compared with short, strand winding degree is small, therefore the molecule isomerism ability of side group azobenzene is strong, is conducive to the close and distant property conversion in surface.It is mild that intelligent water repellent finishing agent provided by the invention prepares reaction condition, and preparation process is easy, is suitble to industrialized production.
Description
The present invention be convertible smart fabric finishing agent of entitled a kind of close and distant property in surface and preparation method thereof,
The applying date is on April 18th, 2017, application No. is the divisional applications of 2017102548550 patent applications, belongs to product preparation side
Method part.
Technical field
The present invention relates to a kind of fabric surface finishing agents；More particularly to a kind of close and distant convertible smart fabric of property in surface
Finishing agent and preparation method thereof belongs to Polymer Synthesizing and weaving auxiliary chemicals field.
Background technique
Azobenzene structure unit is mainly introduced into polymer chain by way of chemistry key connection by azobenzene polymer
On.Up to the present, researcher has synthesized a large amount of azobenzene polymer, these polymer are broadly divided into following four
Type: end group azobenzene polymer, side chain type azobenzene polymer, backbone chain type azobenzene polymer and the polymerization of doping type azobenzene
Object.Azobenzene group tool is there are two types of isomer configuration: rodlike anti-configuration (trans) and the cis-configuration (cis) for turning shape, instead
The presentation of formula configuration is planar, and chondritic is presented in cis-configuration.It is analyzed from the angle of structural chemistry, azobenzene compound
Two kinds of isomers are to be mostly derived from the pi bond of double bond in azo group (- N=N-) to limit rotating freely for two nitrogen-atoms, so that even
C-N singly-bound and N=N double bond not point-blank, form certain angle in pyridine molecule.The anti-configuration base of azobenzene
State energy level is lower, and thermal stability is preferable, and the ground state level of cis-configuration is higher relative to anti-configuration, thermal stability compared with
Difference.Therefore, usually azobenzene molecule is stabilized with anti-configuration at room temperature, and the common chemistry of cis-configuration
Means are unavailable.
Summary of the invention
The purpose of the present invention is to provide a kind of convertible smart fabric finishing agent of the close and distant property in surface and its preparation sides
Method, obtained product have light isomery characteristic, and connect the perfluoroalkyl of different chain length at its end, and be integrally bonded to olefin(e) acid
Ester monomer；Obtained function monomer is used to prepare fabric water repellent finishing agent, since finishing agent is under environmental stimuli, can pass through azo
Phenyl isomery situation controls end perfluoroalkyl in the enrichment degree on fabric fibre surface, and obtained fabric finishing agent has table
The characteristic that the close and distant property in face is controllably converted.
To achieve the above object of the invention, the technical scheme adopted by the invention is that:
A kind of convertible smart fabric finishing agent of close and distant property in surface, chemical structural formula are as follows:
Wherein, x=2~8；Y=6~20；Z=1~4；N=2~8.
The invention also discloses the preparation methods of the convertible smart fabric finishing agent of the close and distant property in above-mentioned surface, including such as
Lower step:
(1) using perfluoroalkyl iodides, para-bromoaniline as raw material, in the presence of copper powder, preparationpPerfluoroalkylanilin；
(2) withpPerfluoroalkylanilin, sodium nitrite, sodium phenate are raw material, preparationpPerfluoroalkyl-p′Azophenol；
(3) withpPerfluoroalkyl-p′Azophenol, acryloyl chloride, triethylamine are raw material, prepare perfluoroalkyl azobenzene third
Olefin(e) acid ester monomer；
(4) using perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate as raw material, cream
Liquid polymerization, prepares the convertible smart fabric finishing agent of the close and distant property in surface.
In above-mentioned technical proposal,
In step (1), perfluoroalkyl iodides, para-bromoaniline, copper powder mass ratio be 2~5: 1: 1~2；
In step (2),pPerfluoroalkylanilin, sodium nitrite, sodium phenate mass ratio be 1~2: 4~8: 0.35~1.2；
In step (3),pPerfluoroalkyl-p′Azophenol, acryloyl chloride, triethylamine mass ratio be 1~3: 0.2~1: 0.4
~1；
In step (4), the matter of perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate
Amount is than being 0.5~2: 1~2: 0.05~0.1；Initiator amount is the 10%~40% of monomer gross mass.The present invention limits initiator
Dosage, obtained oligomer can effectively be enriched in fabric surface, to realize the characteristic that the close and distant property in surface is controllably converted.
In above-mentioned technical proposal,
In step (1), at 40~70 DEG C, perfluoroalkyl iodine solution is added dropwise to the mixing of para-bromoaniline, copper powder, organic solvent
In liquid；Then it reacts 2~24 hours, obtains in 100~140 DEG CpPerfluoroalkylanilin；
In step (2), at 5~10 DEG C, sodium nitrite in aqueous solution is added dropwise topIn Perfluoroalkylanilin acid solution, reaction 2
~5 hours；Then at 5~10 DEG C, phenol sodium solution is added dropwise；Then regulation system pH is 6~7, is obtainedpPerfluoroalkyl-p′Azophenol；
In step (3), at -20~0 DEG C, acryloyl chloride alkane solution is added dropwise topPerfluoroalkyl-p′Azophenol, three
In ethamine, alkane mixed liquor；Then it reacts 2~10 hours at room temperature, obtains perfluoroalkyl azobenzene acrylate monomer；
In step (4), by perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate with
Emulsifier, nonionic surfactant mixing；Then in inert gas, at 60~95 DEG C, initiator solution is added dropwise；Again into
Row emulsion polymerization 1~10 hour, obtain the convertible smart fabric finishing agent of the close and distant property in surface.
The every step reaction of the present invention further includes purification step, specifically:
In step (1), after reaction, ether solvent is added, then organic layer is washed, is dry, removed by isolated organic layer
Solvent obtainspPerfluoroalkylanilin；
In step (2), after reaction, natural filtration obtains solid；Then dry after solid being recrystallized, it obtainspPerfluor alkane
Base-p′Azophenol；
In step (3), after reaction, washed reaction liquid takes organic phase drying, except solvent, obtains perfluoroalkyl azobenzene
Acrylate monomer.
In above-mentioned technical proposal, the perfluoroalkyl is pentafluoroethyl group, and nona-fluoro butyl group, ten trifluoro hexyls or 17 fluorine are pungent
Base；The organic solvent is dimethyl sulfoxide；The acid is hydrochloric acid；The reagent of the regulation system pH is that sodium bicarbonate saturation is molten
Liquid；The alkane is methylene chloride, dichloroethanes or tetrachloroethanes；The nonionic surfactant is AEO-6 or AEO-9；
The emulsifier is lauryl sodium sulfate；The initiator is ammonium persulfate or potassium peroxydisulfate.
In above-mentioned technical proposal,
In step (1), the time that perfluoroalkyl iodine solution is added dropwise is 0.5~2 hour；
In step (2), phenol is dissolved in sodium hydrate aqueous solution, phenol sodium solution is made；
In step (3), at -10~-5 DEG C, acryloyl chloride alkane solution is added dropwise topPerfluoroalkyl-p′Azophenol, three
In ethamine, alkane mixed liquor；
In step (4), the time that initiator solution is added dropwise is 0.5~2 hour.
In above-mentioned technical proposal, in step (1), solvent is dimethyl sulfoxide in perfluoroalkyl iodine solution；Alkane in step (3)
Hydrocarbon is dry alkane；In step (4), solvent is water in initiator solution.
The invention also discloses the above-mentioned surface convertible smart fabric finishing agents of close and distant property to prepare fabric finishing agent
In application in textile finishing of application and the above-mentioned surface convertible smart fabric finishing agent of close and distant property.
Perfluoroalkyl key is successfully connected in azobenzene by the present invention by single Electron Transfer Reactions and diazonium, coupling reaction,
Synthesize the azobenzene acrylate monomer containing perfluoroalkyl, and intelligent fluorine-containing textile finishing agent obtained by emulsion polymerization,
With good smooth isomery performance and thermal mobility energy；Specific preparation can be divided into following steps:
1、pPerfluoroalkylanilin synthesis
Para-bromoaniline, copper powder, dimethyl sulfoxide are mixed, under agitating and heating, perfluoroalkyl iodides is slowly added dropwise and are dissolved in dimethyl sulfoxide
Middle be configured to solution.After a certain period of time by reaction mixture heating reflux reaction, it is cooled to room temperature, pours into container to go
Ionized water quenching reaction.It is extracted again with ether, removes copper powder.Organic layer is washed with deionized, dry, removes solvent, obtainsp-
Perfluoroalkylanilin.
2、pPerfluoroalkyl-p′Azophenol synthesis
It willpPerfluoroalkylanilin is suspended in dilute hydrochloric acid solution, cooling after heating for dissolving, and the water-soluble of sodium nitrite is slowly added dropwise
Diazo-reaction is completed in liquid, heat preservation.Be added dropwise sodium phenate aqueous solution, with saturated solution of sodium bicarbonate adjust reaction solution pH to 6 ~
7, natural filtration obtains crude product.Finally, being recrystallized product with the mixed solvent of methanol/water (1:1), filters, dries, obtain
PurificationpPerfluoroalkyl-p′Azophenol product.
3, perfluoroalkyl azobenzene acrylate monomer synthesizes
It willpPerfluoroalkyl-p′Azophenol is dissolved in dry chlorinated paraffin solvent, and triethylamine is added, stirs evenly, and is cooled down
Acryloyl chloride is slowly added dropwise afterwards and is dissolved in the acryloyl chloride solution that dry chlorinated paraffin solvent is configured to.After being added dropwise, make anti-
It answers object to be warming up to room temperature, continues to be stirred to react.After stopping reaction, reaction solution washing, organic anhydrous magnesium sulfate that is added to is dry, removes
Desiccant is removed, solvent is steamed and obtains perfluoroalkyl azobenzene acrylate monomer.
4, emulsion copolymerization
Emulsifier sodium lauryl sulfate and nonionic surfactant are compounded, deionized water, stirring and dissolving is added.It is added complete
Fluoroalkyl azobenzene acrylate monomer, acrylate butyl ester and hydroxyethyl methacrylate.With mulser high-speed stirred, obtain
To finely dispersed pre-emulsion.
Pre-emulsion is added in reactor, N2Under protection, it is heated to certain temperature, the aqueous solution of initiator is slowly added dropwise.
After adding, insulation reaction.Reaction solution is cooled to room temperature, pH to 6 ~ 7 is adjusted with ammonium hydroxide, obtains fluorine-contaninig polyacrylate lotion.
Obtained perfluoroalkyl azobenzene acrylate copolymer emulsion is opened with deionized water dilute, is configured to finishing fluid.
Cotton fabric is immersed in prepared finishing fluid, after second dipping and rolling, through preliminary drying, is baked, the close and distant type fabric of intelligence is obtained.Utilize purple
After outer light irradiation finish fabric, its contact angle is tested；By fabric after ultraviolet lighting in a heated condition by radiation of visible light, test
Its contact angle；Test recycles the fabric surface contact angle of irradiation front and back through UV-visible light.Under ultraviolet light, azo
The anti-configuration of benzene occurs photo-isomerisable and is changed into cis-configuration, and under the action of visible light or heat, azobenzene is by cis- structure
Type is returned to anti-configuration, which is known as the cis-trans isomerism of azobenzene compound.
Mechanism of the invention is: using bromaniline and perfluoroiodoalkyl as reactant, sending out under conditions of copper powder is as catalyst
Raw single Electron Transfer Reactions are madepPerfluoroalkylanilin, then willpPerfluoroalkylanilin diazotising, coupling, are madepPerfluor alkane
Base-p'-azophenol, reaction route such as formula 1.
(formula 1)
Then perfluoroalkyl azophenol and acryloyl chloride esterification are obtained into the azo bezene acrylic acid list containing perfluoroalkyl
Body (formula 2).
(formula 2)
Finally, perfluoroalkyl azobenzene acrylate monomer and hydroxyethyl methacrylate and butyl acrylate are passed through cream
Liquid copolymerization obtains the lower fluorinated copolymer of the degree of polymerization, polymerization reaction formula is shown in formula 3 by increasing initiator amount.
(formula 3)
Specific preparation can be exemplified below:
(1)pPerfluoroalkylanilin synthesis
By weight, 2 ~ 5 parts of perfluoroalkyl iodides are dissolved in 5 ~ 10 parts of dimethyl sulfoxides, are configured to solution, it is spare.By weight
1 part of para-bromoaniline, 1 ~ 2 part of copper powder, 10 ~ 50 parts of dimethyl sulfoxides are mixed, are heated with stirring to 40 ~ 70 DEG C by meter.It is slowly added dropwise
Above-mentioned perfluoroalkyl iodine solution, time for adding control are 0.5 ~ 2 hour.
Reaction system is warming up to 100 ~ 140 DEG C, back flow reaction 2 ~ 24 hours.Reaction mixture is cooled to room temperature,
It pours into container, 20 ~ 100 parts of deionized water quenching reactions is added, 40 ~ 100 parts of ether are added, stirring layering removes copper powder.Point
It separates out organic layer and is washed × 3 times with 5 ~ 10 parts of deionized waters.
By weight, it is 1 ~ 8 hour dry that 1 ~ 3 part of anhydrous magnesium sulfate is added, removes desiccant, vacuum rotary steam removes solvent,
?pPerfluoroalkylanilin, temperature is 40 ~ 60 DEG C when distillation, vacuum degree is 0.5 ~ 2mmHg.
(2)pPerfluoroalkyl-p′Azophenol synthesis
By weight, 0.3 ~ 1 part of phenol is dissolved in the sodium hydrate aqueous solution that 20 ~ 50 parts of concentration are 1mol/L, benzene is made
Sodium phenolate solution, it is spare.By weight, 1 ~ 2 part of Perfluoroalkylanilin is suspended in 5 ~ 20 parts of dilute hydrochloric acid that concentration is 2 mol/L
In solution, 40 ~ 50 DEG C are heated to, Perfluoroalkylanilin is completely dissolved.Perfluoroalkylanilin solution is cooled to 5 ~ 10 DEG C,
4 ~ 8 parts of sodium nitrites are slowly added dropwise and are dissolved in the aqueous solution that 8 ~ 12 parts of deionized waters are made into, insulation reaction 2 ~ 5 hours.
Above-mentioned phenol sodium solution is added dropwise, control drop rate makes reaction temperature be maintained at 5 ~ 10 DEG C.It is saturated with sodium bicarbonate
Solution adjusts the pH to 6 ~ 7 of reaction solution, and natural filtration goes out solid product.
By weight, solid product is recrystallized with the mixed solvent of 3 ~ 20 parts of methanol/waters (volume ratio is 1:0.5 ~ 2),
Filtering, drying, obtain powdered purificationpPerfluoroalkyl-p′Azophenol product.
(3) perfluoroalkyl azobenzene acrylate monomer synthesizes
By weight, 0.2 ~ 1 part of acryloyl chloride is dissolved in 5 ~ 20 parts of dry chlorinated paraffin solvents, it is molten is configured to acryloyl chloride
Liquid, it is spare.By weight, by 1 ~ 3 partpPerfluoroalkyl-p′Azophenol is dissolved in 10 ~ 30 parts of dry chlorinated paraffin solvents
In, 0.4 ~ 1 part of triethylamine is added.It stirs evenly, is cooled to -10 ~ 0 DEG C.Above-mentioned prepared acryloyl chloride solution is slowly added dropwise,
Control is added dropwise under cryogenic.
After being added dropwise, reactant is made to be warming up to room temperature, continues to be stirred to react 2 ~ 10 hours.After stopping reaction, reaction solution
It is washed × 3 times with 5 ~ 20 parts of water, separates organic phase, dry 1 ~ 8 h of 0.2 ~ 0.5 part of anhydrous magnesium sulfate is added, removes desiccant,
Solvent is evaporated off and obtains perfluoroalkyl azobenzene acrylate monomer.
(4) emulsion copolymerization
By weight, 0.01 ~ 0.05 part of lauryl sodium sulfate of emulsifier, 0.01 ~ 0.05 portion of nonionic surfactant is multiple
Match, 50 ~ 100 parts of deionized waters, stirring and dissolving is added.By weight, 0.5 ~ 2 part of perfluoroalkyl azobenzene acrylate is added
Monomer, 1 ~ 2 part of acrylate butyl ester and 0.05 ~ 0.1 part of hydroxyethyl methacrylate.It is stirred with mulser high speed (8000r/min)
It mixes 15 ~ 60 minutes, obtains finely dispersed pre-emulsion.
By weight, 10% ~ 40% initiator of monomer gross mass is dissolved in 2 ~ 10 parts of deionized waters, is configured to initiator
Solution.Above-mentioned pre-emulsion is added in reactor, N2Under protection, 60 ~ 95 DEG C are heated to, in above-mentioned draw is added dropwise in 0.5 ~ 2 hour
Send out agent solution.
After adding, insulation reaction 1 ~ 10 hour.Reaction solution is cooled to room temperature, pH to 6 ~ 7 is adjusted with ammonium hydroxide, obtains fluorine-containing
Acrylate copolymer emulsion.
Obtained perfluoroalkyl azobenzene acrylate copolymer emulsion is opened with deionized water dilute, it is configured to 10 ~
The finishing fluid of 100g/L.Cotton fabric is immersed in prepared finishing fluid 15 minutes ~ 2 hours, (is rolled using second dipping and rolling technique
Remaining rate 90% ~ 100%, room temperature) → preliminary drying (100 DEG C × 10 minutes) → (160 DEG C × 3 minutes) are baked, the close and distant type of intelligence is obtained and knits
Object.
Technical solution provided by the invention the beneficial effect is that:
1, the functional fluoropolymer monomer of fabric finishing agent is perfluoroalkyl azobenzene acrylate, azo in side group in the present invention
Phenyl can be changed into cis-configuration by anti-configuration by photo-isomerisable under ultraviolet light, in visible light or the work of heat
Under, azobenzene is returned to anti-configuration by cis-configuration again.Transformation can induce the perfluor alkane that its end is bonded repeatedly
The transformation of base occurred conformation intelligent is knitted thus to obtain the close and distant property in surface is reversible to change the fluorine element content of material surface
Object finishing agent.
2, when fabric finishing agent of the invention preparation, overcome prior art initiator amount should not greatly (generally 1% ~ 2%)
Technology prejudice, by increase initiator amount, 10% ~ 40%, preferably 15% ~ 25%, obtain the lower copolymer of the degree of polymerization, as
When finishing agent is arranged to fabric surface, since copolymer molecule chain is compared with short, main chain winding degree is small, to the molecule of side group azo group
Isomery obstruction is small, so as to give full play to azo group light isomery function and reply, thus can realize the conversion of the close and distant property in surface.
3, the present invention prepares perfluoroalkyl azobenzene acrylate copolymer type fabric finishing agent using emulsion polymerization, instead
Mild condition is answered, the advantage of be easy to get, be suitble to simple process, raw material industrialized production and popularization and application.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the smart fabric finishing agent of preparation of the embodiment of the present invention；
Fig. 2 is fabric warp after nona-fluoro butyl group azobenzene acrylate copolymer emulsion finishing of cotton textiles prepared by embodiment one
The surface contact angle figure of UV-visible light circulation irradiation front and back；
Fig. 3 is fabric after nona-fluoro butyl group azobenzene acrylate copolymer emulsion prepared by embodiment one arranges kevlar fabric
The surface contact angle figure of irradiation front and back is recycled through UV-visible light；
Fig. 4 is nona-fluoro butyl group azobenzene acrylate copolymer emulsion finishing of cotton textiles traversing of probe electricity prepared by embodiment one
Mirror figure；
Fig. 5 is that nona-fluoro butyl group azobenzene acrylate copolymer emulsion prepared by embodiment one arranges kevlar fabric traversing of probe
Electron microscope.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment one
(1)pNona-fluoro butyl group aniline
3.44 g para-bromoaniline, 5 g are added in the 250 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dimethyl sulfoxide (DMSO) of copper powder (catalyst) and 100 ml, is heated with stirring to 60 DEG C.Then 9 g, nine fluorine iodobutane is molten
It in the DMSO of 25 ml and is added in constant pressure funnel, is slowly dropped into three-necked flask.When nine fluorine iodobutane solution are added dropwise
After, reaction system is warming up to 120 DEG C of 24 h of condensing reflux.Reaction system is cooled to room temperature, and 500 ml are poured into reaction
Beaker in, while the deionized water of 100ml and the anhydrous ether of 200ml is added, stirring layering filters out copper powder.By filtrate
It pours into the separatory funnel of 500 ml and isolates organic layer and be washed with deionized (30 ml × 3 time), anhydrous magnesium sulfate is dry
8 h, filter out desiccant, and vacuum rotary steam removes ether, obtains the dark-brown liquid 1a of 3.39 g, yield 54.5%.Product FT-IR:
3405.42, 3046.5, 1522.0, 1351.0, 1235.9, 1204.7, 1132.6, 1086.4 cm-1. 1H NMR
(400 MHz, CDCl3) δ 7.41 (d, J = 8.7 Hz, 1H), 6.71 (d, J = 8.5 Hz, 1H), 4.16
(d, J = 7.0 Hz, 1H), 19F NMR (376 MHz, CDCl3) δ -80.93 – -81.20 (m, 3F, CF 3),
-109.71 (td, J = 13.3, 2.6 Hz, 2F, CF3CF 2), -122.84 – -123.07 (m, 2F,
CF3CF2CF 2), -125.54 – -125.74 (m, 2F, CF3(CF2)2CF 2)。
(2)pNona-fluoro butyl group- p′Azophenol
0.93 g4- nona-fluoro butyl group benzene is added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dilute hydrochloric acid solution (2 mol/L) of amine and 10 ml is heated with stirring to 4- Perfluoroalkylanilin and all dissolves.It then will mixing
Solution is placed on the aqueous solution for being cooled to 10 DEG C in ice bath and 4.5 g sodium nitrites being slowly added dropwise using constant pressure funnel, 10
Reaction solution becomes faint yellow after reacting 2 h at DEG C.0.42 g phenol is dissolved in sodium hydrate aqueous solution (1 mol/ of 20 ml
L phenol sodium solution is formed in).Then in the reaction before phenol sodium solution being slowly dropped into using constant pressure funnel, temperature
10 DEG C are maintained at hereinafter, gradually there is orange-red solid to be precipitated.The PH to 6-7 of reaction solution is adjusted with saturated solution of sodium bicarbonate,
Natural filtration obtains crude product, and pure orange red solid of 0.74 g is recrystallized to give in the mixed solution of methanol/water (1:1)
Body is dried into powder.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)。
(3) 4- nona-fluoro butyl group -4 '-acrylate-based azobenzene
1.66-4 '-azobenzenes of g4- nona-fluoro butyl group are added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer
The dichloromethane solution and 0.83 g triethylamine solution that phenol, 30 mL are removed water.Then three-necked flask cryogenic thermostat is fixed on to stir
It mixes and stirs 30 min in reactive bath technique, temperature control is -5 DEG C.0.54 g acryloyl chloride is dissolved in the methylene chloride of 15 mL water removal
In, and pour into constant pressure funnel, keep low temperature to be slowly dropped into above-mentioned reaction solution.It is stirred after being added dropwise from cryogenic thermostat
Three-necked flask is taken out in reactive bath technique, is placed under room temperature and is reacted 6 h.Then reaction solution is poured into the separatory funnel of 100 mL, water
It washes 3 times (3 × 30 mL), takes out organic phase, dry 8 h in anhydrous magnesium sulfate are filtered, vacuum rotary steam obtains orange/yellow solid
1.42 g, yield 77.4%.
(4) emulsion polymerization
90g deionized water is added in beaker in tall form, adds 0.3g emulsifier sodium lauryl sulfate (SDS) and 0.3gAEO-9,
And 8.3g nona-fluoro butyl group azo bezene acrylic acid, 11.6g butyl acrylate, 0.7g hydroxyethyl methacrylate.All monomers
And emulsifier is transferred in the three-necked flask of 100 mL after 15 min of pre-emulsification on the mulser of 8000 rps, in N2Gas shielded
Under be heated to 75 DEG C, 4.33g ammonium persulfate be added be dissolved in 10 mL deionized waters and is added dropwise in pre-emulsion, after being added dropwise to complete
The reaction was continued 3 h.It is filtered to remove jello after reaction, obtains perfluoroalkyl azobenzene acrylate copolymer emulsion, produces
Object fluorine content 15.0%, x=2~7；Y=12~20；Z=1~3.
(5) textile finishing application
Obtained nona-fluoro butyl group azobenzene acrylate copolymer emulsion is opened with deionized water dilute, is configured to the arrangement of 20 g/L
Liquid.Cotton fabric is immersed into 15 min in prepared finishing fluid, second dipping and rolling, pick-up 90%.Then the preliminary drying 10 at 100 DEG C
Min bakes 3 min at 160 DEG C.The close and distant type fabric of intelligence is made.Kevlar fabric after arrangement is irradiated under spectrum ultraviolet light entirely
After twenty minutes, its contact angle is tested.By fabric after ultraviolet lighting under 160 DEG C of heating conditions by radiation of visible light after twenty minutes,
Test its contact angle.Test recycles the fabric surface contact angle of irradiation front and back through UV-visible light.
Fig. 1 is the infrared spectrogram of the smart fabric finishing agent of preparation of the embodiment of the present invention.Wherein, curve a is to implement
Finishing agent infrared spectroscopy prepared by example one, it is seen that finishing agent appearance-C=O stretching vibration absworption peak near 1731cm-1 is right
Should in acrylate ester group characteristic absorption peak.
Fig. 2 is fabric warp after the nona-fluoro butyl group azobenzene acrylate copolymer emulsion finishing of cotton textiles of above-mentioned preparation
The surface contact angle figure of UV-visible light circulation irradiation front and back, contact angle can be converted repeatedly between 124 ° ~ 131 °, reachable
17 times or more.
Cotton fabric is changed to kevlar fabric, finish fabric connects after visible light circulation irradiation under the conditions of ultraviolet-heating
Feeler iterative cycles transformation between 132 °/127 ° is shown in Fig. 3 up to 40 times or more.
Before Fig. 4 is the nona-fluoro butyl group azobenzene acrylate copolymer emulsion finishing of cotton textiles as prepared by the present embodiment
Scanning electron microscope (SEM) photograph afterwards, Fig. 4 a are before arranging, and Fig. 4 b is after arranging.Wherein, fiber surface has natural gauffer in cotton fabric before arranging,
Then there is polymer film forming after arrangement.
Fig. 5 is before the nona-fluoro butyl group azobenzene acrylate copolymer emulsion prepared by embodiment one arranges kevlar fabric
Scanning electron microscope (SEM) photograph afterwards, Fig. 5 a are before arranging, and Fig. 5 b is after arranging.Wherein, fiber surface is smooth in kevlar fabric before arranging,
Then there is polymer film forming after arrangement.
Embodiment two
(1)pThe synthesis of-ten trifluoro hexyl aniline
3.44 g para-bromoaniline, 5 g are added in the 250 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dimethyl sulfoxide (DMSO) of copper powder (catalyst) and 100 ml, is heated with stirring to 60 DEG C.Then by 11.6 g, ten trifluoro iodine oneself
Alkane is dissolved in the DMSO of 25 ml and is added in constant pressure funnel, is slowly dropped into three-necked flask.When the ten own solution of trifluoro iodine
After being added dropwise, reaction system is warming up to 120 DEG C of 24 h of condensing reflux.Reaction system is cooled to room temperature, and reaction is poured into
In the beaker of 500 ml, while the deionized water of 100 ml and the anhydrous ether of 200 ml is added, stirring layering filters out copper
Powder.Filtrate is poured into the separatory funnel of 500 ml and isolates organic layer and be washed with deionized (30 ml × 3 time), it is anhydrous
Magnesium sulfate dries 8 h, filters out desiccant, and vacuum rotary steam removes ether, obtains the dark-brown liquid of 4.32 g, yield 52.6%.It produces
Object FT-IR:3405.2,3051.0,1523.6,1362.2,1291.0,1240.1,1200.4,1 145.0,
1088.1 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz, 1H), 6.75 (d, J =
8.4 Hz, 1H), 3.75 (s, 1H), 19F NMR (376 MHz, CDCl3) δ -80.97 – -81.26 (m, 3F,
CF3 ), -116.08 – -116.52 (m, 2F, CF3CF2 ), -122.17 (d, J = 11.4 Hz, 2F,
CF3CF2CF2), -123.11 (d, J = 2.9 Hz, m, 2F, CF3(CF2)2CF2 ), -123.40–-123.89 (m,
2F, CF3(CF2)3CF2 ), -126.22–-126.58 (m, 2F, CF3(CF2)4CF2 )。
(2)p- ten trifluoro hexyls-p′Azophenol synthesis
1.23 g4-, ten trifluoro hexyl is added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe
The dilute hydrochloric acid solution (2 mol/L) of aniline and 10 ml, agitating and heating reactant all dissolve.Then mixed solution is placed on
It is cooled to 10 DEG C in ice bath and the aqueous solution of 4.5 g sodium nitrites 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 shape in the sodium hydrate aqueous solution (1 mol/L) of 20 ml
At phenol sodium solution.Then in the reaction before phenol sodium solution being slowly dropped into using constant pressure funnel, temperature is maintained at
10 DEG C hereinafter, gradually there is orange-red solid to be precipitated.The PH to 6-7 of reaction solution, normal pressure mistake are adjusted with saturated solution of sodium bicarbonate
Filter obtains crude product, and the pure Orange red solid of 0.81 g is recrystallized to give in the mixed solution of methanol/water (1:1), dries
At 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。
(3) ten trifluoro hexyl -4 of 4- '-acrylate-based azobenzene synthesis
2.06 g 4-, ten -4 '-azo of trifluoro hexyl is added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer
The dichloromethane solution and 0.83 g triethylamine solution that phenol, 30mL are removed water.Then three-necked flask is fixed on cryogenic thermostat
It is stirred to react in bath and stirs 30 min, temperature control is -5 DEG C.0.54 g acryloyl chloride is dissolved in the dichloromethane of 15 mL water removal
It in alkane, and pours into constant pressure funnel, low temperature is kept to be slowly dropped into above-mentioned reaction solution.It is stirred after being added dropwise from cryogenic thermostat
It mixes and takes out three-necked flask in reactive bath technique, be placed under room temperature and react 6 h.Then reaction solution is poured into the separatory funnel of 100 mL,
3 times (3 × 30 mL) is washed, organic phase is taken out, dry 8 h in anhydrous magnesium sulfate are filtered, vacuum rotary steam obtains 1.73 g orange
Yellow solid, yield 75.9%.
(4) emulsion polymerization
90g deionized water is added in beaker in tall form, adds 0.3g emulsifier sodium lauryl sulfate (SDS) and 0.3gAEO-9,
And ten trifluoro hexyl azo bezene acrylic acid of 10.3g, 11.6g butyl acrylate, 0.7g hydroxyethyl methacrylate.All lists
Body and emulsifier are transferred in the three-necked flask of 100 mL after 15 min of pre-emulsification on the mulser of 8000 rps, in N2Gas is protected
75 DEG C are heated under shield, addition 3.41g ammonium persulfate, which is dissolved in 10 mL deionized waters, to be added dropwise in pre-emulsion, is added dropwise to complete
The reaction was continued afterwards 3 h.It is filtered to remove jello after reaction, obtains perfluoroalkyl azobenzene acrylate copolymer emulsion,
Product fluorine content 21.6%, x=2~5；Y=10~18；Z=1~3.
(5) textile finishing application
Ten obtained trifluoro hexyl azobenzene acrylate copolymer emulsions are opened with deionized water dilute, is configured to the whole of 20 g/L
Manage liquid.Cotton fabric is immersed into 15 min in prepared finishing fluid, second dipping and rolling, pick-up 90%.Then the preliminary drying at 100 DEG C
10 min bake 3 min at 160 DEG C.
Fig. 1 is the infrared spectrogram of the smart fabric finishing agent of preparation of the embodiment of the present invention.Wherein, curve b is to implement
Finishing agent infrared spectroscopy prepared by example two, it is seen that finishing agent appearance-C=O stretching vibration absworption peak near 1731cm-1 is right
Should in acrylate ester group characteristic absorption peak.
Cotton fabric recycles the surface contact angle figure of irradiation front and back through UV-visible light, and contact angle is between 126 ° ~ 131 °
It can convert repeatedly, up to 18 times or more.
Cotton fabric is changed to kevlar fabric, after arrangement after visible light circulation irradiation under the conditions of ultraviolet-heating, contact
Angle iterative cycles transformation between 127 °/131 ° is 31 times reachable.
Embodiment three
(1)p- ten seven fluorine octyl aniline
3.45 g para-bromoaniline are added in the 250 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe,
The dimethyl sulfoxide of 5.15 g copper powders (catalyst) and 100 ml, is heated with stirring to 60 DEG C.Then 9.21 g, 17 fluorine iodine is pungent
Alkane is dissolved in the dimethyl sulfoxide of 25 ml and is added in constant pressure funnel, is slowly dropped into three-necked flask.When nine fluorine iodobutanes
After solution is added dropwise, reaction system is warming up to 115 DEG C of condensing reflux 12h.Reaction system is cooled to room temperature, and reaction is fallen
In the beaker for entering 500 ml, while the deionized water of 100ml and the anhydrous ether of 200ml is added, stirring layering filters out copper
Powder.Filtrate is poured into the separatory funnel of 500 ml and isolates organic layer and be washed with deionized (30 ml × 3 time), it is anhydrous
Magnesium sulfate dries 6 h, filters out desiccant, and vacuum rotary steam removes ether, obtains the dark-brown liquid 1a of 3.51 g, yield 55.1%.
(2)p- ten seven fluorine octyls- 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
10 ml of dilute hydrochloric acid solution that base aniline and concentration are 2 mol/L, is heated with stirring top- ten seven fluorine octyl aniline all dissolve.
Then mixed solution is placed on to the water for being cooled to 8 DEG C in ice bath and 4.6 g sodium nitrites being slowly added dropwise using constant pressure funnel
Solution reacts 2 h at 10 DEG C.0.43 g phenol is dissolved in the sodium hydrate aqueous solution (1 mol/L) of 20 ml and is formed
Phenol sodium solution.Then in the reaction before phenol sodium solution being slowly dropped into using constant pressure funnel, temperature is maintained at 8
DEG C hereinafter, gradually there is orange-red solid to be precipitated.The PH to 6-7 of reaction solution, natural filtration are adjusted with saturated solution of sodium bicarbonate
Crude product is obtained, the pure Orange red solid of 0.76 g is recrystallized to give in the mixed solution of methanol/water (1:1), is dried into
Powder.Yield is 61.1%.
(3))p- ten seven fluorine octyls- p′Acrylate-based azobenzene
1.71 g p-, 17 fluorine octyl-p '-azo is added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer
The dichloromethane solution and 0.85 g triethylamine that phenol, 30 mL are removed water.Then three-necked flask is fixed on cryogenic thermostat stirring
30 min are stirred in reactive bath technique, temperature control is -8 DEG C.0.56 g acryloyl chloride is dissolved in the methylene chloride of 18 mL water removal,
And pour into constant pressure funnel, it is slowly dropped into above-mentioned reaction solution, dropping temperature is advisable with being kept for -8 DEG C or less.It drips
Three-necked flask is taken out in Bi Houcong cryogenic thermostat stirring reactive bath, is placed under room temperature and reacts 8 h.Then reaction solution is poured into 100
It in the separatory funnel of mL, washes 3 times, uses 30 mL deionized waters every time.Organic phase is taken out, is added dry 6 in anhydrous magnesium sulfate
H is filtered, vacuum rotary steam obtains 1.56 g of orange/yellow solid, yield 79.1%.
(4) emulsion polymerization
90g deionized water is added in beaker in tall form, adds 0.3g emulsifier sodium lauryl sulfate (SDS) and 0.3gAEO-9,
And 17 fluorine octyl azobenzene acrylate of 10.2g, 11.2g butyl acrylate, 0.9g hydroxyethyl methacrylate.It is all
Monomer and emulsifier are transferred in the three-necked flask of 100 mL after 30 min of pre-emulsification on the mulser of 8000 rps, in N2Gas
75 DEG C are heated under protection, addition 5.352g potassium peroxydisulfate, which is dissolved in 10 mL deionized waters, to be added dropwise in pre-emulsion, is dripped
At rear the reaction was continued 3 h, ten sevoflurane base azobenzene acrylate copolymer emulsions are obtained, product fluorine content 21.5%, x=1~
4；Y=10~16；Z=1~2.
(5) textile finishing application
17 obtained fluorine octyl azobenzene acrylate copolymer emulsions are opened with deionized water dilute, is configured to the whole of 15 g/L
Manage liquid.Cotton fabric is immersed into 30min in prepared finishing fluid, second dipping and rolling, pick-up 100%.Then the preliminary drying at 100 DEG C
10 min bake 3 min at 160 DEG C.The close and distant type fabric of intelligence is made.
Fig. 1 is the infrared spectrogram of the smart fabric finishing agent of preparation of the embodiment of the present invention.Wherein, curve c is to implement
Finishing agent infrared spectroscopy prepared by example three, it is seen that finishing agent is in 1731cm-1Neighbouring appearance-C=O stretching vibration absworption peak, corresponds to
The characteristic absorption peak of ester group in acrylate.
Cotton fabric recycles the surface contact angle figure of irradiation front and back through UV-visible light, and contact angle is between 126 ° ~ 131 °
It can convert repeatedly, up to 20 times or more.Cotton fabric is changed to kevlar fabric, through visible under the conditions of ultraviolet-heating after arrangement
After light circulation irradiation, contact angle iterative cycles transformation between 127 °/131 ° is 35 times reachable.
Comparative example one
(1)pThe synthesis of-ten trifluoro hexyl aniline
3.45 g para-bromoaniline are added in the 250 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe,
The DMSO of 5.11 g copper powders and 100 ml, is heated with stirring to 60 DEG C.Then 11.5 g, ten trifluoro iodohexane is dissolved in 25 ml
DMSO in and be added in constant pressure funnel, be slowly dropped into three-necked flask.After the ten own solution of trifluoro iodine are added dropwise,
Reaction system is warming up to 120 DEG C of 24 h of condensing reflux.Reaction system is cooled to room temperature, and reaction is poured into the beaker of 500 ml
In, while the deionized water of 100 ml and the anhydrous ether of 200 ml is added, stirring layering filters out copper powder.Filtrate is poured into
Organic layer is isolated in the separatory funnel of 500 ml and is washed 3 times with 30 ml deionized waters, and dry 8 h of anhydrous magnesium sulfate are filtered out
Desiccant, vacuum rotary steam remove ether, obtain the dark-brown liquid of 4.54 g, yield 53.3%.
(2)p- ten trifluoro hexyls-p′Azophenol synthesis
Equipped with magnetic stir bar, thermometer and condenser pipe 100 ml three-necked flasks in be added 1.21 g ten trifluoro of 4- oneself
The dilute hydrochloric acid solution (2 mol/L) of base aniline and 10 ml, agitating and heating reactant all dissolve.Then mixed solution is put
It is cooled to 10 DEG C in ice bath and the aqueous solution of 4.6 g sodium nitrites is slowly added dropwise using constant pressure funnel, at 10 DEG C
Reaction solution becomes faint yellow after reacting 2 h.0.41 g phenol is dissolved in the sodium hydrate aqueous solution (1 mol/L) of 20 ml
Form phenol sodium solution.Then in the reaction before phenol sodium solution being slowly dropped into using constant pressure funnel, temperature is kept
At 10 DEG C hereinafter, gradually there is orange-red solid to be precipitated.The PH to 6-7 of reaction solution, normal pressure are adjusted with saturated solution of sodium bicarbonate
Crude product is obtained by filtration, the pure Orange red solid of 0.84 g is recrystallized to give in the mixed solution of methanol/water (1:1), dries
Dry Cheng Fenmo.Yield is 53.5%.
(3) ten trifluoro hexyl -4 of 4- '-acrylate-based azobenzene synthesis
2.12 g 4-, ten -4 '-azo of trifluoro hexyl is added in the 100 ml three-necked flasks equipped with magnetic stir bar, thermometer
The dichloroethane solution and 0.85 g triethylamine that phenol, 30mL are removed water.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 chloride is dissolved in the dichloroethanes of 15 mL water removal
In, and pour into constant pressure funnel, keep low temperature to be slowly dropped into above-mentioned reaction solution.It is stirred after being added dropwise from cryogenic thermostat
Three-necked flask is taken out in reactive bath technique, is placed under room temperature and is reacted 6 h.Then reaction solution is poured into the separatory funnel of 100 mL, water
It washes 3 times (3 × 30 mL), takes out organic phase, dry 8 h, filter, vacuum rotary steam, it is orange to obtain 1.75 g in anhydrous magnesium sulfate
Color solid product, yield 76.3%.Using n-hexane as eluent, refined products can be made using the method for chromatographic column.
(4) emulsion polymerization
100g deionized water is added in beaker in tall form, adds 0.3g emulsifier sodium lauryl sulfate (SDS) and 0.3gAEO-
9 and 10.5g, ten trifluoro hexyl azo bezene acrylic acid, 11.5g butyl acrylate, 0.9g hydroxyethyl methacrylate.It is all
Monomer and emulsifier are transferred in the three-necked flask of 100 mL after 30 min of pre-emulsification on the mulser of 8000 rps, in N2Gas
75 DEG C are heated under protection, addition 0.34g potassium peroxydisulfate, which is dissolved in 5 mL deionized waters, to be added dropwise in pre-emulsion, is added dropwise to complete
The reaction was continued afterwards 3 h.It is generated in reaction process without jello, reaction mixture is drained, perfluoroalkyl azo propenyl benzene is obtained
Acid ester copolymer lotion, product fluorine content 20.5%, x=15~35；Y=90~180；Z=8~18.
(5) textile finishing application
Ten obtained trifluoro hexyl azobenzene acrylate copolymer emulsions are opened with deionized water dilute, is configured to the whole of 20 g/L
Manage liquid.Cotton fabric is immersed into 15 min in prepared finishing fluid, second dipping and rolling, pick-up 90%.Then the preliminary drying at 100 DEG C
10 min bake 3 min at 160 DEG C.Measuring finish fabric contact angle is 123 °, and after ultraviolet light, contact angle is
121 °, contact angle does not decline substantially；Also similar results, contact angle do not decline kevlar fabric substantially.Analysis is due to copolymer polymerization
It spends greatly, arranges to fiber surface rear copolymer strand and wind, affect isomerization of the side group under extraneous Photic Stimulation,
It therefore cannot the close and distant surface of intelligence.
Claims (7)
1. a kind of preparation method of the convertible smart fabric finishing agent of close and distant property in surface, which is characterized in that including walking as follows
It is rapid:
(1) using perfluoroalkyl iodides, para-bromoaniline as raw material, in the presence of copper powder, preparationpPerfluoroalkylanilin；
(2) withpPerfluoroalkylanilin, sodium nitrite, sodium phenate are raw material, preparationpPerfluoroalkyl-p′Azophenol；
(3) withpPerfluoroalkyl-p′Azophenol, acryloyl chloride, triethylamine are raw material, prepare perfluoroalkyl azobenzene third
Olefin(e) acid ester monomer；
(4) using perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate as raw material, cream
Liquid polymerization, prepares the convertible smart fabric finishing agent of the close and distant property in surface；
The chemical structural formula of the convertible smart fabric finishing agent of the close and distant property in surface is as follows:
Wherein, x=2~8；Y=6~20；Z=1~4；N=2~8.
2. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as described in claim 1, feature exist
In,
In step (1), perfluoroalkyl iodides, para-bromoaniline, copper powder mass ratio be 2~5: 1: 1~2；
In step (2),pPerfluoroalkylanilin, sodium nitrite, sodium phenate mass ratio be 1~2: 4~8: 0.35~1.2；
In step (3),pPerfluoroalkyl-p′Azophenol, acryloyl chloride, triethylamine mass ratio be 1~3: 0.2~1: 0.4
~1；
In step (4), the matter of perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate
Amount is than being 0.5~2: 1~2: 0.05~0.1；Initiator amount is the 10%~40% of monomer gross mass.
3. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as described in claim 1, feature exist
In,
In step (1), at 40~70 DEG C, perfluoroalkyl iodine solution is added dropwise to the mixing of para-bromoaniline, copper powder, organic solvent
In liquid；Then it reacts 2~24 hours, obtains in 100~140 DEG CpPerfluoroalkylanilin；
In step (2), at 5~10 DEG C, sodium nitrite in aqueous solution is added dropwise topIn Perfluoroalkylanilin acid solution, reaction 2
~5 hours；Then at 5~10 DEG C, phenol sodium solution is added dropwise；Then regulation system pH is 6~7, is obtainedpPerfluoroalkyl-p′Azophenol；
In step (3), at -20~0 DEG C, acryloyl chloride alkane solution is added dropwise topPerfluoroalkyl-p′Azophenol, three
In ethamine, alkane mixed liquor；Then it reacts 2~10 hours at room temperature, obtains perfluoroalkyl azobenzene acrylate monomer；
In step (4), by perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate with
Emulsifier, nonionic surfactant mixing；Then in inert gas, at 60~95 DEG C, initiator solution is added dropwise；Again into
Row emulsion polymerization 1~10 hour, obtain the convertible smart fabric finishing agent of the close and distant property in surface.
4. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 3, feature exist
In, every step reaction further includes purification step, specifically:
In step (1), after reaction, ether solvent is added, then organic layer is washed, is dry, removed by isolated organic layer
Solvent obtainspPerfluoroalkylanilin；
In step (2), after reaction, natural filtration obtains solid；Then dry after solid being recrystallized, it obtainspPerfluor alkane
Base-p′Azophenol；
In step (3), after reaction, washed reaction liquid takes organic phase drying, except solvent, obtains perfluoroalkyl azobenzene
Acrylate monomer.
5. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 3, feature exist
In the perfluoroalkyl is pentafluoroethyl group, nona-fluoro butyl group, ten trifluoro hexyls or 17 fluorine octyls；The organic solvent is diformazan
Sulfoxide；The acid is hydrochloric acid；The reagent of the regulation system pH is saturated solution of sodium bicarbonate；The alkane be methylene chloride,
Dichloroethanes or tetrachloroethanes；The nonionic surfactant is AEO-6 or AEO-9；The emulsifier is dodecyl sulphur
Sour sodium；The initiator is ammonium persulfate or potassium peroxydisulfate.
6. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 3, feature exist
In,
In step (1), the time that perfluoroalkyl iodine solution is added dropwise is 0.5~2 hour；
In step (2), phenol is dissolved in sodium hydrate aqueous solution, phenol sodium solution is made；
In step (3), at -10~-5 DEG C, acryloyl chloride alkane solution is added dropwise topPerfluoroalkyl-p′Azophenol, three
In ethamine, alkane mixed liquor；
In step (4), the time that initiator solution is added dropwise is 0.5~2 hour.
7. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 3, feature exist
In in step (1), solvent is dimethyl sulfoxide in perfluoroalkyl iodine solution；Alkane is dry alkane in step (3)；Step
(4) in, solvent is water in initiator solution.
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| CN108640853A (en) * | 2018-06-13 | 2018-10-12 | 济南大学 | A kind of fluorine-containing azo surfactant and preparation method thereof |
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| WO2013107583A1 (en) * | 2012-01-19 | 2013-07-25 | Unilever Plc | Fabric treatment method and composition |
| CN104276975A (en) * | 2014-09-23 | 2015-01-14 | 东华大学 | Photoisomerized azobenzene fluorine-containing acrylate, and preparation method and application thereof |
| CN104594045A (en) * | 2015-01-29 | 2015-05-06 | 苏州大学 | Water and oil repellent finishing agent for fabrics and preparation method of finishing agent |
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| CN105924573B (en) * | 2016-06-13 | 2017-11-03 | 苏州大学 | A kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application |
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| WO2013107583A1 (en) * | 2012-01-19 | 2013-07-25 | Unilever Plc | Fabric treatment method and composition |
| CN104276975A (en) * | 2014-09-23 | 2015-01-14 | 东华大学 | Photoisomerized azobenzene fluorine-containing acrylate, and preparation method and application thereof |
| CN104594045A (en) * | 2015-01-29 | 2015-05-06 | 苏州大学 | Water and oil repellent finishing agent for fabrics and preparation method of finishing agent |
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