CN107129556A - Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof - Google Patents
Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof Download PDFInfo
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- CN107129556A CN107129556A CN201710254855.0A CN201710254855A CN107129556A CN 107129556 A CN107129556 A CN 107129556A CN 201710254855 A CN201710254855 A CN 201710254855A CN 107129556 A CN107129556 A CN 107129556A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—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
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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Abstract
The invention discloses convertible smart fabric finishing agent of the close and distant property in a kind of surface and preparation method thereof there is provided finishing agent active ingredient be 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 during emulsion polymerization, obtained copolymer polymerization degree is low, and copolymer molecule main chain is small compared with short, strand winding degree, therefore the molecule isomerism ability of side base azobenzene is strong, is conducive to the close and distant property conversion in surface.The intelligent water repellent finishing agent that the present invention is provided prepares reaction condition gently, and preparation technology is easy, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of fabric face finishing agent；Specifically related 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 technology
Azobenzene structure unit is mainly incorporated into polymer chain by azobenzene polymer by way of chemical bond is connected
On.Up to the present, researcher has synthesized substantial amounts of azobenzene polymer, and 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
Thing.Azobenzene group has two kinds of isomer configurations：Bar-shaped anti-configuration（trans）With the cis-configuration (cis) for turning shape, instead
Formula configuration is presented plane, and chondritic is presented in cis-configuration.Analyzed from the angle of structural chemistry, azobenzene compound
Two kinds of isomers are to be mostly derived from azo group（-N=N-）The pi bond of middle double bond limits rotating freely for two nitrogen-atoms so that even
C-N singly-bounds and N=N double bonds not point-blank, form certain angle in pyridine molecule.The anti-configuration base of azobenzene
State energy level is relatively low, thermal stability preferably, the ground state level of cis-configuration is higher relative to anti-configuration, thermal stability compared with
Difference.Therefore, generally azobenzene molecule is all stabilized with anti-configuration at room temperature, and the common chemistry of cis-configuration
Means are unavailable.
The content of the invention
It is an object of the invention to provide a kind of convertible smart fabric finishing agent of the close and distant property in surface and its preparation side
Method, obtained product has light isomery characteristic, and connects the perfluoroalkyl of different chain length in its end, and is integrally bonded to olefin(e) acid
Ester monomer；Obtained function monomer is used to prepare fabric water repellent finishing agent, because finishing agent is under environmental stimuli, can pass through azo
Phenyl isomery situation controls the end perfluoroalkyl in the enrichment degree on fabric fibre surface, and obtained fabric finishing agent has table
The characteristic of the close and distant controllable conversion of property in face.
To achieve the above object of the invention, the technical solution adopted in the present invention is：
A kind of convertible smart fabric finishing agent of close and distant property in surface, its chemical structural formula is as follows：
Wherein, x=2~8；Y=6~20；Z=1~4；N=2~8.
The invention also discloses the preparation method 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, preparep- Perfluoroalkylanilin；
（2）Withp- Perfluoroalkylanilin, natrium nitrosum, sodium phenate are raw material, are preparedp- perfluoroalkyl-p′- azophenol；
（3）Withp- perfluoroalkyl-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, breast
Liquid polymerize, and prepares the described convertible smart fabric finishing agent of the close and distant property in surface.
In above-mentioned technical proposal,
Step（1）In, perfluoroalkyl iodides, para-bromoaniline, the mass ratio of copper powder are 2~5: 1: 1~2；
Step（2）In,p- Perfluoroalkylanilin, natrium nitrosum, the mass ratio of sodium phenate are 1~2: 4~8: 0.35~1.2；
Step（3）In,p- perfluoroalkyl-p′- azophenol, acryloyl chloride, the mass ratio of triethylamine are 1~3: 0.2~1: 0.4
~1；
Step（4）In, perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, the matter of 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
Consumption, obtained oligomer can effectively be enriched in fabric face, so as to realize the characteristic of the close and distant controllable conversion of property in surface.
In above-mentioned technical proposal,
Step（1）In, at 40~70 DEG C, perfluoroalkyl iodine solution is added dropwise to the mixing of para-bromoaniline, copper powder, organic solvent
In liquid；Then react 2~24 hours, obtain in 100~140 DEG Cp- Perfluoroalkylanilin；
Step（2）In, 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 obtainedp- perfluoroalkyl-p′- azophenol；
Step（3）In, at -20~0 DEG C, acryloyl chloride alkane solution is added dropwise top- perfluoroalkyl-p′- azophenol, three
In ethamine, alkane mixed liquor；Then react 2~10 hours at room temperature, obtain perfluoroalkyl azobenzene acrylate monomer；
Step（4）In, by perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate with
Emulsifying agent, nonionic surfactant mixing；Then in inert gas, at 60~95 DEG C, initiator solution is added dropwise；Enter again
Row emulsion polymerization 1~10 hour, obtains the convertible smart fabric finishing agent of the close and distant property in surface.
The present invention often step reaction also includes purification step, is specially：
Step（1）In, after reaction terminates, ether solvent is added, then organic layer is washed, dried, removed by isolated organic layer
Solvent, is obtainedp- Perfluoroalkylanilin；
Step（2）In, after reaction terminates, natural filtration obtains solid；Then dry, obtain after solid is recrystallizedp- perfluor alkane
Base-p′- azophenol；
Step（3）In, after reaction terminates, washed reaction liquid takes organic phase to dry, except solvent, obtains perfluoroalkyl azobenzene
Acrylate monomer.
In above-mentioned technical proposal, the perfluoroalkyl is pentafluoroethyl group, and nine fluorine butyl, 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 acid carbonate saturation is molten
Liquid；The alkane is dichloromethane, dichloroethanes or tetrachloroethanes；The nonionic surfactant is AEO-6 or AEO-9；
The emulsifying agent is lauryl sodium sulfate；The initiator is ammonium persulfate or potassium peroxydisulfate.
In above-mentioned technical proposal,
Step（1）In, the time that perfluoroalkyl iodine solution is added dropwise is 0.5~2 hour；
Step（2）In, phenol is dissolved in sodium hydrate aqueous solution, phenol sodium solution is made；
Step（3）In, at -10~-5 DEG C, acryloyl chloride alkane solution is added dropwise top- perfluoroalkyl-p′- azophenol, three
In ethamine, alkane mixed liquor；
Step（4）In, the time that initiator solution is added dropwise is 0.5~2 hour.
In above-mentioned technical proposal, step（1）In, solvent is dimethyl sulfoxide (DMSO) in perfluoroalkyl iodine solution；Step（3）Middle alkane
Hydrocarbon is dry alkane；Step（4）In, solvent is water in initiator solution.
Fabric finishing agent is being prepared the invention also discloses the above-mentioned surface convertible smart fabric finishing agent of close and distant property
In application of the convertible smart fabric finishing agent of the close and distant property of application and above-mentioned surface in textile finishing.
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 light isomery performance and thermal mobility energy；Specific prepare can be divided into following steps：
1、p- Perfluoroalkylanilin is synthesized
Para-bromoaniline, copper powder, dimethyl sulfoxide (DMSO) are mixed, under agitating and heating, perfluoroalkyl iodides is slowly added dropwise and are dissolved in dimethyl sulfoxide
Middle be configured to solution.After reactant mixture heating reflux reaction certain time, room temperature is cooled to, pours into container to go
Ionized water quenching reaction.Extracted again with ether, remove copper powder.Organic layer is washed with deionized, and dries, and removes solvent, obtainsp-
Perfluoroalkylanilin.
2、p- perfluoroalkyl-p′- azophenol is synthesized
Willp- Perfluoroalkylanilin is suspended in dilute hydrochloric acid solution, after heating for dissolving, cooling, and the water-soluble of natrium nitrosum is slowly added dropwise
Liquid, insulation completes diazo-reaction.Be added dropwise sodium phenate the aqueous solution, with saturated solution of sodium bicarbonate adjust reaction solution pH to 6 ~
7, natural filtration obtains crude product.Finally, methanol/water is used（1：1）Mixed solvent product is recrystallized, filter, dry, obtain
Refinedp- perfluoroalkyl-p′- azophenol product.
3rd, perfluoroalkyl azobenzene acrylate monomer is synthesized
Willp- perfluoroalkyl-p′- azophenol is dissolved in dry chlorinated paraffin solvent, is added triethylamine, is stirred, and is cooled
Acryloyl chloride is slowly added dropwise afterwards and is dissolved in the acryloyl chloride solution that dry chlorinated paraffin solvent is configured to.After completion of dropping, make anti-
Answer thing to be warming up to room temperature, continue stirring reaction.Stop after reaction, reaction solution washing is organic to be added to anhydrous magnesium sulfate drying, removes
Drier is removed, solvent is steamed and obtains perfluoroalkyl azobenzene acrylate monomer.
4th, emulsion copolymerization
Emulsifier sodium lauryl sulfate and nonionic surfactant are compounded, deionized water, stirring and dissolving is added.Add 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, certain temperature is heated to, the aqueous solution of initiator is slowly added dropwise.
After adding, insulation reaction.Reaction solution is cooled to room temperature, pH is adjusted to 6 ~ 7 with ammoniacal liquor, obtains fluorine-contaninig polyacrylate emulsion.
Obtained perfluoroalkyl azobenzene acrylate copolymer emulsion is opened dilute with deionized water, dressing liquid is configured to.
Bafta is immersed in the dressing liquid prepared, after two leachings two are rolled, through preliminary drying, 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；The fabric face contact angle tested after circulating pre-irradiation through UV-Visible.Under ultraviolet light, azo
The anti-configuration of benzene occurs photo-isomerisable and is changed into cis-configuration, and in the presence of visible ray or heat, azobenzene is by cis structure
Type is returned to anti-configuration, and the transformation is referred to as the cis-trans isomerism of azobenzene compound.
The present invention mechanism be：Using bromaniline and perfluoroiodoalkyl as reactant, sent out under conditions of copper powder is as catalyst
Raw single Electron Transfer Reactions are madep- Perfluoroalkylanilin, then willp- Perfluoroalkylanilin diazotising, coupling, are madep- perfluor alkane
Base-p'-azophenol, reaction scheme 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 into breast
Liquid copolymerization, by increasing initiator amount, obtains the relatively low fluorinated copolymer of the degree of polymerization, polymerisation formula is shown in formula 3.
（Formula 3）
Specific prepare can be exemplified below：
（1）p- Perfluoroalkylanilin is synthesized
By weight, 2 ~ 5 parts of perfluoroalkyl iodides are dissolved in 5 ~ 10 parts of dimethyl sulfoxide (DMSO)s, are configured to solution, it is standby.By weight
Meter, 1 part of para-bromoaniline, 1 ~ 2 part of copper powder, 10 ~ 50 parts of dimethyl sulfoxide (DMSO)s are mixed, 40 ~ 70 DEG C are heated with stirring to.It is slowly added dropwise
Above-mentioned perfluoroalkyl iodine solution, time for adding control is 0.5 ~ 2 hour.
Reaction system is warming up to 100 ~ 140 DEG C, back flow reaction 2 ~ 24 hours.Reactant mixture is cooled to room temperature,
Pour into container, add 20 ~ 100 parts of deionized water quenching reactions, add 40 ~ 100 parts of ether, stirring layering removes copper powder.Point
Separate out organic layer and washed × 3 times with 5 ~ 10 parts of deionized waters.
By weight, add 1 ~ 3 part of anhydrous magnesium sulfate to dry 1 ~ 8 hour, remove drier, vacuum rotary steam removes solvent,
p- Perfluoroalkylanilin, during distillation temperature be 40 ~ 60 DEG C, vacuum be 0.5 ~ 2mmHg.
（2）p- perfluoroalkyl-p′- azophenol is synthesized
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 standby.By weight, 1 ~ 2 part of Perfluoroalkylanilin is suspended in 5 ~ 20 parts of watery 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 natrium nitrosums 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.Use sodium acid carbonate saturation
Solution adjusts the pH to 6 ~ 7 of reaction solution, and natural filtration goes out solid product.
By weight, with 3 ~ 20 parts of methanol/waters（Volume ratio is 1：0.5~2）Mixed solvent solid product is recrystallized,
Filtering, drying, obtain powdered refinedp- perfluoroalkyl-p′- azophenol product.
（3）Perfluoroalkyl azobenzene acrylate monomer is synthesized
By weight, 0.2 ~ 1 part of acryloyl chloride is dissolved in 5 ~ 20 parts of dry chlorinated paraffin solvents, is configured to acryloyl chloride molten
Liquid, it is standby.By weight, by 1 ~ 3 partp- perfluoroalkyl-p′- azophenol is dissolved in 10 ~ 30 parts of dry chlorinated paraffin solvents
In, add 0.4 ~ 1 part of triethylamine.Stir, be cooled to -10 ~ 0 DEG C.The above-mentioned acryloyl chloride solution prepared is slowly added dropwise,
Control is added dropwise under cryogenic.
After completion of dropping, reactant is warming up to room temperature, continue stirring reaction 2 ~ 10 hours.Stop after reaction, reaction solution
Washed × 3 times with 5 ~ 20 parts of water, separate organic phase, added 0.2 ~ 0.5 part of anhydrous magnesium sulfate and dry 1 ~ 8 h, remove drier,
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 emulsifying agent, 0.01 ~ 0.05 portion of nonionic surfactant are answered
Match somebody with somebody, add 50 ~ 100 parts of deionized waters, stirring and dissolving.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.With mulser at a high speed（8000r/min）Stir
Mix 15 ~ 60 minutes, obtain finely dispersed pre-emulsion.
By weight, the initiator of monomer gross mass 10% ~ 40% 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 is adjusted to 6 ~ 7 with ammoniacal liquor, obtains fluorine-containing
Acrylate copolymer emulsion.
Obtained perfluoroalkyl azobenzene acrylate copolymer emulsion is opened dilute with deionized water, it is configured to 10 ~
100g/L dressing liquid.Bafta is immersed in the dressing liquid prepared 15 minutes ~ 2 hours, using two two roll process of leaching（Roll
Remaining rate 90% ~ 100%, room temperature）→ preliminary drying（100 DEG C × 10 minutes）→ (160 DEG C × 3 minutes) are baked, obtain the close and distant type of intelligence and knit
Thing.
Technical scheme its advantage that the present invention is provided is：
1st, the functional fluoropolymer monomer of fabric finishing agent is azo in perfluoroalkyl azobenzene acrylate, its side base in the present invention
Phenyl by anti-configuration can be changed into cis-configuration under ultraviolet light by photo-isomerisable, in visible ray or the work of heat
Under, azobenzene is returned to anti-configuration by cis-configuration again.So changing repeatedly can induce the perfluor alkane that its end is bonded
Base occurred conformation changes, so as to change the fluorine cellulose content of material surface, is derived from that the close and distant property in surface is reversible intelligent to knit
Thing finishing agent.
2nd, when prepared by fabric finishing agent of the invention, overcome prior art initiator amount big（Generally 1% ~ 2%）
Technology prejudice, by increasing initiator amount, 10% ~ 40%, preferably 15% ~ 25%, obtain the relatively low copolymer of the degree of polymerization, as
When finishing agent is arranged to fabric face, because copolymer molecule chain is small compared with short, main chain winding degree, to the molecule of side base azo group
Isomery hinders 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.
3rd, the present invention prepares perfluoroalkyl azobenzene acrylate copolymer type fabric finishing agent using emulsion polymerization, instead
Mild condition is answered, with technique is easy, raw material are easy to get, be adapted to industrialized production and the advantage of popularization and application.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of smart fabric finishing agent prepared by the embodiment of the present invention；
Fig. 2 be embodiment one prepare nine fluorine butyl azobenzene acrylate copolymer emulsion finishing of cotton textiles after, fabric warp
Surface contact angle figure after UV-Visible circulation pre-irradiation；
Fig. 3 is that nine fluorine butyl azobenzene acrylate copolymer emulsions prepared by embodiment one are arranged after kevlar fabric, fabric
Surface contact angle figure after circulating pre-irradiation through UV-Visible；
Fig. 4 is nine fluorine butyl azobenzene acrylate copolymer emulsion finishing of cotton textiles traversing of probe electricity prepared by embodiment one
Mirror figure；
Fig. 5 is that nine fluorine butyl azobenzene acrylate copolymer emulsions prepared by embodiment one arrange kevlar fabric traversing of probe
Electron microscope.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment one
（1）p- nine fluorine butylanilines
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
Copper powder（Catalyst）And 100 ml dimethyl sulfoxide（DMSO）, it is heated with stirring to 60 DEG C.Then it is the fluorine iodobutanes of 9 g nine is molten
In 25 ml DMSO and it is added in constant pressure funnel, is slowly dropped into three-necked flask.When nine fluorine iodobutane solution are added dropwise
After finishing, reaction system is warming up to 120 DEG C of h of condensing reflux 24.Reaction system is cooled to room temperature, and reaction is poured into 500 ml
Beaker in, while add 100ml deionized water and 200ml absolute ether, stirring layering, filter out copper powder.By filtrate
Organic layer is isolated in the separatory funnel for pouring into 500 ml and is washed with deionized（30 ml × 3 time）, anhydrous magnesium sulfate drying
8 h, filter out drier, and vacuum rotary steam removes ether, obtains the dark-brown liquid 1a of 3.39 g, yield is 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）p- 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 in the reaction before phenol sodium solution is slowly dropped into using constant pressure funnel, temperature
Less than 10 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 0.74 g
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）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%.
（4）Emulsion polymerization
90g deionized waters are added in beaker in tall form, 0.3g emulsifier sodium lauryl sulfates are added（SDS）And 0.3gAEO-9,
And the fluorine butyl azo bezene acrylic acids of 8.3g nine, 11.6g butyl acrylates, 0.7g hydroxyethyl methacrylates.All monomers
And emulsifying agent is transferred in 100 mL three-necked flask on 8000 rps mulser after the min of pre-emulsification 15, in N2Gas shielded
Under be heated to 75 DEG C, add 4.33g ammonium persulfates and be dissolved in 10 mL deionized waters and is added dropwise in pre-emulsion, after being added dropwise to complete
Continue to react 3 h.Reaction is filtered to remove jello after terminating, and obtains perfluoroalkyl azobenzene acrylate copolymer emulsion, produces
Thing Oil repellent 15.0%, x=2~7；Y=12~20；Z=1~3.
（5）Textile finishing application
Nine obtained fluorine butyl azobenzene acrylate copolymer emulsions are opened dilute with deionized water, 20 g/L arrangement is configured to
Liquid.Bafta is immersed into 15 min in the dressing liquid prepared, two leachings two are rolled, 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 irradiates under spectrum ultraviolet light entirely after arranging
After 20 minutes, its contact angle is tested.By fabric after ultraviolet lighting under 160 DEG C of heating conditions after radiation of visible light 20 minutes,
Test its contact angle.The fabric face contact angle tested after circulating pre-irradiation through UV-Visible.
Fig. 1 is the infrared spectrogram of smart fabric finishing agent prepared by the embodiment of the present invention.Wherein, curve a is implementation
Finishing agent infrared spectrum prepared by example one, it is seen that finishing agent appearance-C=O stretching vibration absworption peaks near 1731cm-1, its is right
Should in acrylate ester group characteristic absorption peak.
After Fig. 2 is nine fluorine butyl azobenzene acrylate copolymer emulsion finishing of cotton textiles of above-mentioned preparation, fabric warp
Surface contact angle figure after UV-Visible circulation pre-irradiation, contact angle can be changed repeatedly between 124 ° ~ 131 °, reachable
More than 17 times.
Bafta is replaced by kevlar fabric, finish fabric connects after visible ray circulation irradiation under the conditions of ultraviolet-heating
Feeler iterative cycles transformation between 132 °/127 °, up to more than 40 times, is shown in Fig. 3.
Fig. 4 is as before nine fluorine butyl azobenzene acrylate copolymer emulsion finishing of cotton textiles prepared by the present embodiment
Scanning electron microscope (SEM) photograph afterwards, before Fig. 4 a is arrange, after Fig. 4 b is arrange.Wherein, fiber surface has natural gauffer in bafta before arranging,
Then there is polymer film forming after arrangement.
Fig. 5 is that the nine fluorine butyl azobenzene acrylate copolymer emulsions prepared by embodiment one are arranged before kevlar fabric
Scanning electron microscope (SEM) photograph afterwards, before Fig. 5 a is arrange, after Fig. 5 b is arrange.Wherein, fiber surface is smooth in kevlar fabric before arranging,
Then there is polymer film forming after arrangement.
Embodiment two
（1）p- ten trifluoro hexyl aniline are synthesized
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
Copper powder（Catalyst）And 100 ml dimethyl sulfoxide（DMSO）, it is heated with stirring to 60 DEG C.Then by the trifluoro iodine of 11.6 g ten oneself
Alkane is dissolved in 25 ml DMSO and is added in constant pressure funnel, is slowly dropped into three-necked flask.When the ten own solution of trifluoro iodine
After completion of dropping, reaction system is warming up to 120 DEG C of h of condensing reflux 24.Reaction system is cooled to room temperature, and reaction is poured into
In 500 ml beaker, while adding 100 ml deionized water and 200 ml absolute ether, stirring layering filters out copper
Powder.Filtrate is poured into organic layer is isolated in 500 ml separatory funnel and is washed with deionized（30 ml × 3 time）, it is anhydrous
Magnesium sulfate dries 8 h, filters out drier, and vacuum rotary steam removes ether, obtains the dark-brown liquid of 4.32 g, yield is 52.6%.Production
Thing FT-IR: 3405.2, 3051.0, 1523.6, 1362.2, 1291.0, 1240.1, 1200.4, 1145.0,
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 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 phenol sodium solution is slowly dropped into using constant pressure funnel, temperature is maintained at
Less than 10 DEG C, gradually there is orange-red solid to separate out.The PH to 6-7 of reaction solution, normal pressure mistake are adjusted with saturated solution of sodium bicarbonate
Filter obtains crude product, in methanol/water（1：1）Mixed solution in be recrystallized to give the pure Orange red solids of 0.81 g, dry
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。
（3）The trifluoro hexyls -4 of 4- 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%.
（4）Emulsion polymerization
90g deionized waters are added in beaker in tall form, 0.3g emulsifier sodium lauryl sulfates are added（SDS）And 0.3gAEO-9,
And the trifluoro hexyl azo bezene acrylic acids of 10.3g ten, 11.6g butyl acrylates, 0.7g hydroxyethyl methacrylates.All lists
Body and emulsifying agent are transferred in 100 mL three-necked flask on 8000 rps mulser after the min of pre-emulsification 15, in N2Gas is protected
75 DEG C are heated under shield, addition 3.41g ammonium persulfates, which are dissolved in 10 mL deionized waters, to be added dropwise in pre-emulsion, is added dropwise to complete
Continue to react 3 h afterwards.Reaction is filtered to remove jello after terminating, and obtains perfluoroalkyl azobenzene acrylate copolymer emulsion,
Product Oil repellent 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 dilute with deionized water, the whole of 20 g/L is configured to
Manage liquid.Bafta is immersed into 15 min in the dressing liquid prepared, two leachings two are rolled, 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 smart fabric finishing agent prepared by the embodiment of the present invention.Wherein, curve b is implementation
Finishing agent infrared spectrum prepared by example two, it is seen that finishing agent appearance-C=O stretching vibration absworption peaks near 1731cm-1, its is right
Should in acrylate ester group characteristic absorption peak.
Surface contact angle figure of the bafta after UV-Visible circulation pre-irradiation, contact angle is between 126 ° ~ 131 °
It can change repeatedly, up to more than 18 times.
Bafta is replaced by kevlar fabric, after arrangement after visible ray circulation irradiation under the conditions of ultraviolet-heating, contact
Angle iterative cycles transformation between 127 °/131 ° is reachable 31 times.
Embodiment three
（1）p- ten seven fluorine octyl group aniline
3.45 g para-bromoaniline are added in the 250 ml three-necked flasks equipped with magnetic stir bar, thermometer and condenser pipe,
5.15 g copper powders（Catalyst）And 100 ml dimethyl sulfoxide, be heated with stirring to 60 DEG C.Then it is the fluorine iodine of 9.21 g 17 is pungent
Alkane is dissolved in 25 ml dimethyl sulfoxide and is added in constant pressure funnel, is slowly dropped into three-necked flask.When nine fluorine iodobutanes
After solution completion of dropping, 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 adding 100ml deionized water and 200ml absolute ether, stirring layering filters out copper
Powder.Filtrate is poured into organic layer is isolated in 500 ml separatory funnel and is washed with deionized（30 ml × 3 time）, it is anhydrous
Magnesium sulfate dries 6 h, filters out drier, and vacuum rotary steam removes ether, obtains the dark-brown liquid 1a of 3.51 g, yield is 55.1%.
（2）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 phenol sodium solution is slowly dropped into using constant pressure funnel, temperature is maintained at 8
Below DEG C, gradually there is orange-red solid to separate out.The PH to 6-7 of reaction solution, natural filtration are adjusted with saturated solution of sodium bicarbonate
Crude product is obtained, in methanol/water（1：1）Mixed solution in be recrystallized to give the pure Orange red solids of 0.76 g, be dried into
Powder.Yield is 61.1%.
（3））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%.
（4）Emulsion polymerization
90g deionized waters are added in beaker in tall form, 0.3g emulsifier sodium lauryl sulfates are added（SDS）And 0.3gAEO-9,
And the fluorine octyl group azobenzene acrylate of 10.2g 17,11.2g butyl acrylates, 0.9g hydroxyethyl methacrylates.It is all
Monomer and emulsifying agent are transferred in 100 mL three-necked flask on 8000 rps mulser after the min of pre-emulsification 30, in N2Gas
75 DEG C are heated under protection, addition 5.352g potassium peroxydisulfates, which are dissolved in 10 mL deionized waters, to be added dropwise in pre-emulsion, is dripped
Continue to react 3 h into rear, obtain ten sevoflurane base azobenzene acrylate copolymer emulsions, product Oil repellent 21.5%, x=1~
4；Y=10~16；Z=1~2.
（5）Textile finishing application
17 obtained fluorine octyl group azobenzene acrylate copolymer emulsions are opened dilute with deionized water, the whole of 15 g/L is configured to
Manage liquid.Bafta is immersed into 30min in the dressing liquid prepared, two leachings two are rolled, 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 smart fabric finishing agent prepared by the embodiment of the present invention.Wherein, curve c is implementation
Finishing agent infrared spectrum prepared by example three, it is seen that finishing agent is in 1731cm-1Neighbouring appearance-C=O stretching vibration absworption peaks, its correspondence
The characteristic absorption peak of ester group in acrylate.
Surface contact angle figure of the bafta after UV-Visible circulation pre-irradiation, contact angle is between 126 ° ~ 131 °
It can change repeatedly, up to more than 20 times.Bafta is replaced by 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 reachable 35 times.
Comparative example one
（1）p- ten trifluoro hexyl aniline are synthesized
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 the trifluoro iodohexanes of 11.5 g ten are dissolved in 25 ml
DMSO in and be added in constant pressure funnel, be slowly dropped into three-necked flask.After ten trifluoro iodine own solution completion of dropping,
Reaction system is warming up to 120 DEG C of h of condensing reflux 24.Reaction system is cooled to room temperature, and reaction is poured into 500 ml beaker
In, while adding 100 ml deionized water and 200 ml absolute ether, stirring layering filters out copper powder.Filtrate is poured into
Organic layer is isolated in 500 ml separatory funnel and is washed 3 times with 30 ml deionized waters, anhydrous magnesium sulfate dries 8 h, filters out
Drier, vacuum rotary steam removes ether, obtains the dark-brown liquid of 4.54 g, yield is 53.3%.
（2）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 phenol sodium solution is slowly dropped into using constant pressure funnel, temperature is kept
Below 10 DEG C, gradually there is orange-red solid to separate out.The PH to 6-7 of reaction solution, normal pressure are adjusted with saturated solution of sodium bicarbonate
Crude product is filtrated to get, in methanol/water（1：1）Mixed solution in be recrystallized to give the pure Orange red solids of 0.84 g, dry
Do into powder.Yield is 53.5%.
（3）The trifluoro hexyls -4 of 4- ten '-acrylate-based azobenzene synthesis
- 4 '-azos of trifluoro hexyl of 2.12 g 4- ten are 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.
（4）Emulsion polymerization
100g deionized waters are added in beaker in tall form, 0.3g emulsifier sodium lauryl sulfates are added（SDS）And 0.3gAEO-
9, and the trifluoro hexyl azo bezene acrylic acids of 10.5g ten, 11.5g butyl acrylates, 0.9g hydroxyethyl methacrylates.It is all
Monomer and emulsifying agent are transferred in 100 mL three-necked flask on 8000 rps mulser after the min of pre-emulsification 30, in N2Gas
75 DEG C are heated under protection, addition 0.34g potassium peroxydisulfates, which are dissolved in 5 mL deionized waters, to be added dropwise in pre-emulsion, is added dropwise to complete
Continue to react 3 h afterwards.Produced in course of reaction without jello, reactant mixture is drained, perfluoroalkyl azo propenyl benzene is obtained
Acid ester copolymer emulsion, product Oil repellent 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 dilute with deionized water, the whole of 20 g/L is configured to
Manage liquid.Bafta is immersed into 15 min in the dressing liquid prepared, two leachings two are rolled, pick-up 90%.Then the preliminary drying at 100 DEG C
10 min, bake 3 min at 160 DEG C.Finish fabric contact angle is measured for 123 °, after ultraviolet light, contact angle is
121 °, contact angle does not decline substantially；Kevlar fabric also similar results, contact angle does not decline substantially.Analysis is due to copolymer polymerization
Spend greatly, arrange to the winding of fiber surface rear copolymer strand, have impact on isomerization of the side base under extraneous Photic Stimulation,
Therefore cannot the close and distant surface of intelligence.
Claims (10)
1. the convertible smart fabric finishing agent of a kind of close and distant property in surface, it is characterised in that the close and distant property in surface is convertible
Smart fabric finishing agent chemical structural formula it 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 claimed in claim 1, its feature exists
In comprising the following steps：
（1）Using perfluoroalkyl iodides, para-bromoaniline as raw material, in the presence of copper powder, preparep- Perfluoroalkylanilin；
（2）Withp- Perfluoroalkylanilin, natrium nitrosum, sodium phenate are raw material, are preparedp- perfluoroalkyl-p′- azophenol；
（3）Withp- perfluoroalkyl-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, breast
Liquid polymerize, and prepares the described convertible smart fabric finishing agent of the close and distant property in surface.
3. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 2, its feature exists
In,
Step（1）In, perfluoroalkyl iodides, para-bromoaniline, the mass ratio of copper powder are 2~5: 1: 1~2；
Step（2）In,p- Perfluoroalkylanilin, natrium nitrosum, the mass ratio of sodium phenate are 1~2: 4~8: 0.35~1.2；
Step（3）In,p- perfluoroalkyl-p′- azophenol, acryloyl chloride, the mass ratio of triethylamine are 1~3: 0.2~1: 0.4
~1；
Step（4）In, perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, the matter of 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.
4. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 2, its feature exists
In,
Step（1）In, at 40~70 DEG C, perfluoroalkyl iodine solution is added dropwise to the mixing of para-bromoaniline, copper powder, organic solvent
In liquid；Then react 2~24 hours, obtain in 100~140 DEG Cp- Perfluoroalkylanilin；
Step（2）In, 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 obtainedp- perfluoroalkyl-p′- azophenol；
Step（3）In, at -20~0 DEG C, acryloyl chloride alkane solution is added dropwise top- perfluoroalkyl-p′- azophenol, three
In ethamine, alkane mixed liquor；Then react 2~10 hours at room temperature, obtain perfluoroalkyl azobenzene acrylate monomer；
Step（4）In, by perfluoroalkyl azobenzene acrylate monomer, acrylate butyl ester, hydroxyethyl methacrylate with
Emulsifying agent, nonionic surfactant mixing；Then in inert gas, at 60~95 DEG C, initiator solution is added dropwise；Enter again
Row emulsion polymerization 1~10 hour, obtains the convertible smart fabric finishing agent of the close and distant property in surface.
5. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 4, its feature exists
In often step reaction also includes purification step, is specially：
Step（1）In, after reaction terminates, ether solvent is added, then organic layer is washed, dried, removed by isolated organic layer
Solvent, is obtainedp- Perfluoroalkylanilin；
Step（2）In, after reaction terminates, natural filtration obtains solid；Then dry, obtain after solid is recrystallizedp- perfluor alkane
Base-p′- azophenol；
Step（3）In, after reaction terminates, washed reaction liquid takes organic phase to dry, except solvent, obtains perfluoroalkyl azobenzene
Acrylate monomer.
6. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 4, its feature exists
In the perfluoroalkyl is pentafluoroethyl group, nine fluorine butyl, ten trifluoro hexyls or 17 fluorine octyl groups；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 dichloromethane,
Dichloroethanes or tetrachloroethanes；The nonionic surfactant is AEO-6 or AEO-9；The emulsifying agent is dodecyl sulphur
Sour sodium；The initiator is ammonium persulfate or potassium peroxydisulfate.
7. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 4, its feature exists
In,
Step（1）In, the time that perfluoroalkyl iodine solution is added dropwise is 0.5~2 hour；
Step（2）In, phenol is dissolved in sodium hydrate aqueous solution, phenol sodium solution is made；
Step（3）In, at -10~-5 DEG C, acryloyl chloride alkane solution is added dropwise top- perfluoroalkyl-p′- azophenol, three
In ethamine, alkane mixed liquor；
Step（4）In, the time that initiator solution is added dropwise is 0.5~2 hour.
8. the preparation method of the convertible smart fabric finishing agent of the close and distant property in surface as claimed in claim 4, its feature exists
In step（1）In, solvent is dimethyl sulfoxide (DMSO) in perfluoroalkyl iodine solution；Step（3）Middle alkane is dry alkane；Step
（4）In, solvent is water in initiator solution.
9. the convertible smart fabric finishing agent of close and distant property of surface described in claim 1 answering in fabric finishing agent is prepared
With.
10. application of the convertible smart fabric finishing agent of close and distant property of surface described in claim 1 in textile finishing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254855.0A CN107129556B (en) | 2017-04-18 | 2017-04-18 | Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof |
| CN201910563322.XA CN110172122B (en) | 2017-04-18 | 2017-04-18 | Preparation method of intelligent fabric finishing agent with switchable surface affinity and hydrophobicity |
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| CN201710254855.0A CN107129556B (en) | 2017-04-18 | 2017-04-18 | Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof |
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| CN201910563322.XA Division CN110172122B (en) | 2017-04-18 | 2017-04-18 | Preparation method of intelligent fabric finishing agent with switchable surface affinity and hydrophobicity |
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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 |
| CN110256623A (en) * | 2019-04-22 | 2019-09-20 | 苏州大学 | Perfluoroalkyl tetrafluoro sulphur methylene styrol copolymer and its application |
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| CN110256623B (en) * | 2019-04-22 | 2021-07-09 | 苏州大学 | Perfluoroalkyl tetrafluorothiomethylene styrene copolymer and application thereof |
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| CN110172122B (en) | 2021-07-09 |
| CN107129556B (en) | 2019-08-13 |
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