CN109180857A - A kind of close and distant convertible fabric finishing liquor of property in intelligent surface - Google Patents

A kind of close and distant convertible fabric finishing liquor of property in intelligent surface Download PDF

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Publication number
CN109180857A
CN109180857A CN201810963389.8A CN201810963389A CN109180857A CN 109180857 A CN109180857 A CN 109180857A CN 201810963389 A CN201810963389 A CN 201810963389A CN 109180857 A CN109180857 A CN 109180857A
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perfluoroalkyl
solution
distant
property
azobenzene
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CN109180857B (en
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李战雄
孙弋
戴礼
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Nantong Textile and Silk Industrial Technology Research Institute
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Nantong Textile and Silk Industrial Technology Research Institute
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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
    • 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
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • 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
    • 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
    • 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
    • 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
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a kind of intelligent close and distant convertible fabric finishing liquor of property in surface, the finishing fluid 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

A kind of close and distant convertible fabric finishing liquor of property in intelligent surface
The invention belongs to a kind of convertible fabric finishing liquor of the entitled intelligent close and distant property in surface and its preparation sides Method, the applying date are on April 18th, 2017, the divisional application that application number 2017102548616 is patent application, belong to product technology Part.
Technical field
The present invention relates to a kind of fabric surface finishing fluids；More particularly to a kind of intelligent close and distant convertible fabric of property in surface Finishing fluid 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 fabric finishing liquor of intelligent 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:
The invention also discloses the preparation methods of the above-mentioned intelligent close and distant convertible fabric finishing liquor of property in surface, including walk 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, obtains perfluoroalkyl azo group acrylate copolymer emulsion；
(5) perfluoroalkyl azo group acrylate is total to after adjusting perfluoroalkyl azo group acrylate copolymer emulsion pH-value Copolymer emulsion is mixed with water, prepares the close and distant convertible fabric finishing liquor of property in intelligent surface.
The chemical structural formula of the perfluoroalkyl azo group acrylate copolymer is as follows:
Wherein, x=2~8；Y=6~20；Z=1~4；N=2~8.
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；It is poly- that the present invention limits lotion The dosage of initiator is closed, available oligomer is conducive to finishing agent and is enriched with and converts in fabric surface；It is close and distant to be conducive to surface The convertible embodiment of property.
In step (5), the concentration of finishing fluid is 10~100g/L.
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 perfluoroalkyl azo group acrylate copolymer emulsion.
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；The adjusting perfluoroalkyl is even The reagent of nitrogen base acrylate copolymer emulsion pH-value is ammonium hydroxide.
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 preparations of the preparation method of the above-mentioned intelligent close and distant convertible fabric finishing liquor of property in surface The close and distant convertible fabric finishing liquor of property of the intelligent convertible fabric finishing liquor of the close and distant property in surface and above-mentioned intelligent surface Application 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 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.The sodium hydrate aqueous solution of phenol is added dropwise, adjusts reaction solution with saturated solution of sodium bicarbonate PH to 6 ~ 7, natural filtration obtains crude product.Finally, being recrystallized product with the mixed solvent of methanol/water (1:1), filters, dries It is dry, it is refinedpPerfluoroalkyl-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, perfluoroalkyl azo group acrylate copolymer emulsion is obtained.
Obtained perfluoroalkyl azobenzene acrylate copolymer emulsion ammonium hydroxide is adjusted into pH to 6 ~ 7, with deionized water It opens dilute, is configured to finishing fluid.Cotton fabric is immersed in prepared finishing fluid, after second dipping and rolling, through preliminary drying, bakes, obtains intelligence It can close and distant type fabric.After ultraviolet light finish fabric, its contact angle is tested；By fabric after ultraviolet lighting in heating condition Under 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, the anti-configuration of azobenzene occurs photo-isomerisable and is changed into cis-configuration, in visible light or the work of heat Under, azobenzene is returned to anti-configuration by cis-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 The aqueous solution of phenol sodium, it is spare.By weight, 1 ~ 2 part of Perfluoroalkylanilin is suspended in concentration is 5 ~ 20 parts of 2 mol/L dilute In hydrochloric acid 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, the initiator of monomer gross mass 10%-40% is dissolved in 2 ~ 10 parts of deionized waters, is configured to cause Agent solution.Above-mentioned pre-emulsion is added in reactor, N2Under protection, 60 ~ 95 DEG C are heated to, it is above-mentioned in being added dropwise in 0.5 ~ 2 hour Initiator solution.
After adding, insulation reaction 1 ~ 10 hour.Reaction solution is cooled to room temperature, pH to 6 ~ 7 is adjusted with ammonium hydroxide, with deionization Water is opened dilute, is configured to the finishing fluid of 10 ~ 100g/L.Cotton fabric is immersed in prepared finishing fluid 15 minutes ~ 2 hours, is used Second dipping and rolling technique (pick-up 90% ~ 100%, room temperature) → preliminary drying (100 DEG C × 10 minutes) → (160 DEG C × 3 minutes) are baked, are obtained To the close and distant type fabric of intelligence.
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 effectively realize turning for the close and distant property in surface It changes.
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, 4.12g 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
It is 6 that obtained nona-fluoro butyl group azobenzene acrylate copolymer emulsion ammonium hydroxide, which is adjusted pH value, is opened with deionized water It is dilute, it is configured to the finishing fluid of 20 g/L.Cotton fabric is immersed into 15 min, second dipping and rolling, pick-up in prepared finishing fluid 90%.Then 10 min of preliminary drying at 100 DEG C, bakes 3 min at 160 DEG C.The close and distant type fabric of intelligence is made.
Fig. 1 is the infrared spectrogram of the perfluoroalkyl azobenzene acrylate copolymer of preparation of the embodiment of the present invention.Wherein, Curve a is perfluoroalkyl azobenzene acrylate copolymer prepared by embodiment one, in 1731cm-1The neighbouring flexible vibration of appearance-C=O Dynamic absorption peak, corresponds to the characteristic absorption peak of ester group in acrylate.
Fabric after arrangement is irradiated after twenty minutes under spectrum ultraviolet light entirely, tests its contact angle.By fabric after ultraviolet lighting Under 160 DEG C of heating conditions after twenty minutes by radiation of visible light, its contact angle is tested.Test is recycled through UV-visible light shines Penetrate the fabric surface contact angle of front and back；Fig. 2 is that the nona-fluoro butyl group azobenzene acrylate copolymer emulsion of above-mentioned preparation arranges After cotton fabric, fabric recycles the surface contact angle figure of irradiation front and back through UV-visible light, and contact angle is between 124 ° ~ 131 ° It can convert repeatedly, up to 17 times or more.
Cotton fabric is changed to kevlar fabric, after visible light circulation irradiation under the conditions of ultraviolet-heating, contact angle exists Iterative cycles transformation is shown in Fig. 3 up to 40 times or more between 132 °/127 °.
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 arranging kevlar fabric by nona-fluoro butyl group azobenzene acrylate copolymer emulsion manufactured in the present embodiment 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 3.39g 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
It is 7 that ten obtained trifluoro hexyl azobenzene acrylate copolymer emulsion ammonium hydroxide, which are adjusted pH value, with deionized water It opens dilute, is configured to the finishing fluid of 20 g/L.Cotton fabric is immersed into 15 min, second dipping and rolling, pick-up in prepared finishing fluid 90%.Then 10 min of preliminary drying at 100 DEG C, bakes 3 min at 160 DEG C.
Fig. 1 is the infrared spectrogram of the perfluoroalkyl azobenzene acrylate copolymer of preparation of the embodiment of the present invention.Wherein, Curve b is perfluoroalkyl azobenzene acrylate copolymer prepared by embodiment two, in 1731cm-1The neighbouring flexible vibration of appearance-C=O Dynamic absorption peak, corresponds to the characteristic absorption peak of ester group in acrylate.
Fabric after arrangement is irradiated after twenty minutes under spectrum ultraviolet light entirely, tests its contact angle.By fabric after ultraviolet lighting Under 160 DEG C of heating conditions after twenty minutes by radiation of visible light, its contact angle is tested.Test is recycled through UV-visible light shines Penetrate the fabric surface contact angle of front and back；Measuring contact angle can convert between 126 ° ~ 132 ° up to 16 times or more repeatedly.By cotton fabric Be changed to kevlar fabric, through under the conditions of ultraviolet-heating visible light circulation irradiation after, contact angle between 133 °/127 ° repeatedly Circulation transformation is up to 30 times or more.
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 from cryogenic thermostat stirring reactive bath after finishing, and is placed under room temperature and is reacted 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 5.48g 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, fluorine content 21.5%, x=1~4 are obtained；y =10~16；Z=1~2.
(5) textile finishing application
It is 6 that 17 obtained fluorine octyl azobenzene acrylate copolymer emulsion ammonium hydroxide, which are adjusted pH value, with deionized water It opens dilute, is configured to the finishing fluid of 15 g/L.Cotton fabric is immersed into 30min in prepared finishing fluid, second dipping and rolling, pick-up 100%.Then 10 min of preliminary drying at 100 DEG C, bakes 3 min at 160 DEG C.The close and distant type fabric of intelligence is made.
Fig. 1 is the infrared spectrogram of the perfluoroalkyl azobenzene acrylate copolymer of preparation of the embodiment of the present invention.Wherein, Curve c is perfluoroalkyl azobenzene acrylate copolymer prepared by embodiment three, in 1731cm-1Neighbouring appearance-C=O is flexible Vibration absorption peak corresponds to the characteristic absorption peak of ester group in acrylate.
Fabric after arrangement is irradiated after twenty minutes under spectrum ultraviolet light entirely, tests its contact angle.By fabric after ultraviolet lighting Under 160 DEG C of heating conditions after twenty minutes by radiation of visible light, its contact angle is tested.Test is recycled through UV-visible light shines Penetrate the fabric surface contact angle of front and back；Measuring contact angle can convert between 127 ° ~ 132 ° up to 17 times or more repeatedly.By cotton fabric Be changed to kevlar fabric, through under the conditions of ultraviolet-heating visible light circulation irradiation after, contact angle between 128 °/135 ° repeatedly Circulation transformation is up to 38 times or more.
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 Do into powder.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 0.23g 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=20~40；Y=100~200；Z=8~20.
(5) textile finishing application
It is 6.5 that ten obtained trifluoro hexyl azobenzene acrylate copolymer emulsion ammonium hydroxide, which are adjusted pH value, with deionization Water is opened dilute, is configured to the finishing fluid of 20 g/L.Cotton fabric is immersed into 15 min, second dipping and rolling in prepared finishing fluid, is rolled remaining Rate 90%.Then 10 min of preliminary drying at 100 DEG C, bakes 3 min at 160 DEG C.Measuring finish fabric contact angle is 123 °, warp After ultraviolet light, contact angle is 121 °, and contact angle does not decline substantially；Kevlar fabric also similar results, contact angle substantially not under Drop.Analysis arranges to fiber surface rear copolymer strand and winds, affect side group in the external world since copolymer polymerization is spent greatly Isomerization under Photic Stimulation, therefore cannot the close and distant surface of intelligence.

Claims (8)

1. a kind of close and distant convertible fabric finishing liquor of property in intelligent surface, which is characterized in that the intelligent close and distant property in surface The preparation method of convertible fabric finishing liquor includes the following steps:
(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, In the presence of initiator, emulsion polymerization obtains perfluoroalkyl azo group acrylate copolymer emulsion；
(5) perfluoroalkyl azo group acrylate is total to after adjusting perfluoroalkyl azo group acrylate copolymer emulsion pH-value Copolymer emulsion is mixed with water, prepares the close and distant convertible fabric finishing liquor of property in intelligent surface.
2. the intelligent close and distant convertible fabric finishing liquor of property in surface as described in claim 1, which is characterized in that the perfluor The chemical structural formula of alkyl azo group acrylate copolymer is as follows:
Wherein, x=2~8；Y=6~20；Z=1~4；N=2~8.
3. the intelligent close and distant convertible fabric finishing liquor of property in surface as described in claim 1, which is characterized in that
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；
In step (5), the concentration of finishing fluid is 10~100g/L.
4. the intelligent close and distant convertible fabric finishing liquor of property in surface as described in claim 1, which is characterized in that
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 perfluoroalkyl azo group acrylate copolymer emulsion.
5. the intelligent close and distant convertible fabric finishing liquor of property in surface as claimed in claim 4, which is characterized in that every step reaction It further include 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.
6. the intelligent close and distant convertible fabric finishing liquor of property in surface as claimed in claim 4, which is characterized in that the perfluor Alkyl is pentafluoroethyl group, nona-fluoro butyl group, ten trifluoro hexyls or 17 fluorine octyls；The organic solvent is dimethyl sulfoxide；The acid For hydrochloric acid；The reagent of the regulation system pH is saturated solution of sodium bicarbonate；The alkane is methylene chloride, dichloroethanes or four Chloroethanes；The nonionic surfactant is AEO-6 or AEO-9；The emulsifier is lauryl sodium sulfate；The initiation Agent is ammonium persulfate or potassium peroxydisulfate；It is described adjust perfluoroalkyl azo group acrylate copolymer emulsion pH-value reagent be Ammonium hydroxide.
7. the intelligent close and distant convertible fabric finishing liquor of property in surface as claimed in claim 4, which is characterized in that
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, the aqueous solution of sodium phenate 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.
8. the intelligent close and distant convertible fabric finishing liquor of property in surface as claimed in claim 4, which is characterized in that step (1) In, solvent is dimethyl sulfoxide in perfluoroalkyl iodine solution；Alkane is dry alkane in step (3)；In step (4), cause Solvent is water in agent solution.
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