CN109134746B - Intelligent fabric and application thereof - Google Patents

Intelligent fabric and application thereof Download PDF

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CN109134746B
CN109134746B CN201810956975.XA CN201810956975A CN109134746B CN 109134746 B CN109134746 B CN 109134746B CN 201810956975 A CN201810956975 A CN 201810956975A CN 109134746 B CN109134746 B CN 109134746B
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perfluoroalkyl
fabric
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CN109134746A (en
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李战雄
刘群
戴礼
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Suzhou University
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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
    • 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
    • D06M2101/16—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
    • 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 Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses an intelligent fabric and application thereof. The acrylate copolymer emulsion containing perfluoroalkyl azophenyl is prepared by emulsion polymerization of azo-phenyl acrylate containing perfluoroalkyl, hydroxyethyl methacrylate and butyl acrylate. The finishing agent is applied to aramid fabric finishing, and the surface hydrophobicity of the obtained water-repellent fabric is reduced after the surface of the water-repellent fabric is irradiated by ultraviolet light; after the composite material is subjected to high-temperature baking/visible light stimulation again, the hydrophobicity is improved, and the surface affinity and hydrophobicity can be circularly converted for many times. Because the surface of the aramid fiber is smooth, the finishing agent forms a film on the surface of the fiber to be smooth; meanwhile, the aramid fiber fabric has very excellent high-temperature stability, the aramid fiber structure cannot be damaged after the finishing fabric is repeatedly baked at high temperature/stimulated by visible light, so that good affinity-hydrophobicity reversible recovery can be shown, and the provided intelligent fabric is simple and convenient in preparation process and suitable for industrial production.

Description

Intelligent fabric and application thereof
The invention belongs to an intelligent fabric and a preparation method thereof, and divisional application of invention application with application date of 2017, 4 and 18 months and application number of 201710254844.2, and belongs to the technical field of products and application thereof.
Technical Field
The invention relates to an intelligent fabric and a preparation method thereof, belonging to the field of textile chemical auxiliary agents and intelligent textile manufacturing.
Background
The modification of the hydrophilicity and hydrophobicity of the material is always a great research hotspot in the field of material application, and the hydrophilicity and hydrophobicity can directly influence the interaction between the surface of the material and a contact object, thereby influencing the application performance of the material. Through years of research, the hydrophilic and hydrophobic modification of the material surface is greatly developed from theory to practice, and the application technology is mature. However, with the development and development of research, researchers are no longer satisfied with a single wettability surface in many application fields such as controlled drug release, microfluidic devices, sensors, etc., and thus the integration of different wettability on the same substrate surface has become a hot research spot.
It is known that the wettability of a solid surface is determined by both the surface morphology and the surface chemical composition, and that reversible conversion of the surface wettability can be achieved by changing the surface structure or the surface chemical composition. At present, research on reversible conversion of surface wettability by directly changing the structure of a solid surface is less, and reversible conversion of surface wettability is mostly realized by controlling external conditions such as light, temperature, PH and the like.
However, most intelligent surfaces with controllable wettability are generally realized on metal surfaces, and the research on the fabric as a common material in this respect is rare.
Disclosure of Invention
The invention aims to provide an intelligent fabric and a preparation method thereof; the polyacrylate type fabric finishing agent with the photo-isomerism characteristic is prepared, the finishing agent is applied to finishing of fabrics such as aramid fabrics, and the spatial conformation of side group perfluoroalkyl is controlled by controlling the azobenzene photo-isomerism state of the surface of the aramid fabrics through external stimulation, so that the surface affinity and hydrophobicity of the aramid fabrics are controlled, and the intelligent fabric with surface affinity and hydrophobicity capable of being converted repeatedly is provided.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of an intelligent fabric comprises the following steps:
(1) prepared by taking perfluoroalkyl iodide and p-bromoaniline as raw materials in the presence of copper powderp-a perfluoroalkylaniline;
(2) to be provided withpPreparation of perfluoroalkyl aniline, sodium nitrite and sodium phenolate as raw materialpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
(3) to be provided withpPerfluoroalkyl-substituted carboxylic acidsp′Preparing perfluoroalkyl azo phenyl acrylate monomer by using azophenol, acryloyl chloride and triethylamine as raw materials;
(4) carrying out emulsion polymerization on a perfluoroalkyl azo phenyl acrylate monomer, butyl acrylate and hydroxyethyl methacrylate serving as raw materials to prepare a perfluoroalkyl azo acrylate copolymer emulsion;
(5) mixing the perfluoroalkyl azo acrylate copolymer emulsion with water to prepare a finishing liquid; and then soaking the fabric into the finishing liquid for finishing to obtain the intelligent fabric.
In the technical proposal, the device comprises a base,
in the step (1), the mass ratio of perfluoroalkyl iodide to p-bromoaniline to copper powder is 2-5: 1-2;
in the step (2),pthe mass ratio of the perfluoroalkyl aniline to the sodium nitrite to the sodium phenolate is 1-2: 4-8: 0.35-1.2;
in the step (3), the step (c),pperfluoroalkyl-substituted carboxylic acidsp′The mass ratio of the azophenol to the acryloyl chloride to the triethylamine is 1-3: 0.2-1: 0.4-1;
in the step (4), the mass ratio of the perfluoroalkyl azo phenyl acrylate monomer to the butyl acrylate to the hydroxyethyl methacrylate is 0.5-2: 1-2: 0.05-0.1; the using amount of the initiator is 10 to 40 percent of the total mass of the monomers; the invention limits the dosage of the initiator, and the obtained oligomer can be effectively enriched on the surface of the fabric, thereby realizing the characteristic of controllable conversion of surface affinity and hydrophobicity.
In the step (5), the concentration of the finishing liquid is 10-100 g/L.
In the technical proposal, the device comprises a base,
in the step (1), dropwise adding a perfluoroalkyl iodide solution into a mixed solution of p-bromoaniline, copper powder and an organic solvent at 40-70 ℃; then reacting for 2-24 hours at 100-140 ℃ to obtainp-a perfluoroalkylaniline;
in the step (2), dropwise adding a sodium nitrite aqueous solution at the temperature of 5-10 DEG CpReacting for 2-5 hours in perfluoroalkyl aniline acid solution; then dropwise adding a sodium phenolate solution at 5-10 ℃; then adjusting the pH value of the system to 6-7 to obtainpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
in the step (3), at the temperature of minus 20 to 0 ℃, dripping acryloyl chloralkane solution into the mixturepPerfluoroalkyl-substituted carboxylic acidsp′-azophenol, triethylamine, alkane mixed liquor; then reacting for 2-10 hours at room temperature to obtain a perfluoroalkyl azophenyl acrylate monomer;
in the step (4), a perfluoroalkyl azo phenyl acrylate monomer, butyl acrylate, hydroxyethyl methacrylate, an emulsifier and a nonionic surfactant are mixed; then, dropwise adding an initiator solution in inert gas at the temperature of 60-95 ℃; then carrying out emulsion polymerization for 1-10 hours to obtain perfluoroalkyl azo acrylate copolymer emulsion;
and (5) padding the fabric with the finishing liquid for 15 minutes to 2 hours, and then pre-drying and baking to obtain the intelligent fabric.
In the technical proposal, the device comprises a base,
in the step (1), after the reaction is finished, an ether solvent is added, an organic layer is obtained by separation, and then the organic layer is washed, dried and desolventized to obtainp-a perfluoroalkylaniline;
in the step (2), after the reaction is finished, filtering at normal pressure to obtain a solid; then recrystallizing the solid and drying to obtainpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
in the step (3), after the reaction is finished, washing the reaction solution with water, taking an organic phase, drying and removing a solvent to obtain a perfluoroalkyl azophenyl acrylate monomer;
in the step (4), after the reaction is finished, ammonia water is used for adjusting the pH value of the system to 6-7, and perfluoroalkyl azo acrylate copolymer emulsion is obtained.
In the above technical scheme, the perfluoroalkyl group is pentafluoroethyl, nonafluorobutyl, tridecafluorohexyl or heptadecafluorooctyl; the organic solvent is dimethyl sulfoxide; the acid is hydrochloric acid; the reagent for adjusting the pH of the system is a saturated solution of sodium bicarbonate; the alkane is dichloromethane, dichloroethane or tetrachloroethane; the nonionic surfactant is AEO-6 or AEO-9; the emulsifier is sodium dodecyl sulfate; the initiator is ammonium persulfate or potassium persulfate; the padding is two-padding and two-rolling; the fabric is aramid fiber fabric.
In the technical proposal, the device comprises a base,
in the step (1), the time for dripping the perfluoroalkyl iodide solution is 0.5-2 hours;
in the step (2), phenol is dissolved in a sodium hydroxide aqueous solution to prepare a sodium phenolate solution;
in the step (3), the acryloyl chloroalkane solution is dripped into the mixture at the temperature of between 10 ℃ below zero and 5 ℃ below zeropPerfluoroalkyl-substituted carboxylic acidsp′-azophenol, triethylamine, alkane mixed liquor;
in the step (4), the time for dripping the initiator solution is 0.5-2 hours;
in the step (5), the pre-drying is carried out for 10 minutes at 100 ℃; the baking is carried out for 3 minutes at 160 ℃.
In the technical scheme, in the step (1), the solvent in the perfluoroalkyl iodide solution is dimethyl sulfoxide; in the step (3), the alkane is dry alkane; in the step (4), the solvent in the initiator solution is water; in the step (5), padding is carried out at room temperature, wherein the padding allowance rate of padding is 90-100%.
The invention also discloses the intelligent fabric prepared by the preparation method of the intelligent fabric.
The invention further discloses a textile with convertible surface affinity and hydrophobicity, which is prepared from the intelligent fabric.
Meanwhile, the invention also discloses application of the intelligent fabric in preparing textile with convertible surface affinity and hydrophobicity.
The perfluoroalkyl is successfully bonded into azobenzene through single electron transfer reaction and diazo and coupling reaction to synthesize an azophenyl acrylate monomer containing perfluoroalkyl, and the intelligent fluorine-containing fabric finishing agent is obtained through emulsion polymerization and has good photoisomerization performance and thermal migration performance; the preparation of the intelligent fabric can be divided into the following steps:
1. preparation of emulsions
（1）p-perfluoroalkyl radical-p' -azophenol Synthesis
Will be provided withpSuspending perfluoroalkyl aniline in a dilute hydrochloric acid solution, heating for dissolving, cooling, slowly dropwise adding an aqueous solution of sodium nitrite, and preserving heat to finish diazotization. And dropwise adding a sodium phenolate aqueous solution to perform coupling reaction. And (3) adjusting the pH value of the reaction mixture to 6-7 by using a saturated solution of sodium bicarbonate, and filtering at normal pressure to obtain a crude product. Finally, recrystallizing the product with a mixed solvent of methanol/water (1: 1), filtering, and drying to obtain the refined productpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol product.
(2) Synthesis of perfluoroalkyl azo phenyl acrylate monomer
Will be provided withpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol was dissolved in dry chloroalkane solvent and triethylamine was added. Stirring uniformly, and cooling to-10-0 ℃. Slowly dripping acryloyl chloride solution prepared by dissolving acryloyl chloride in dry chloralkane solvent. After the addition, the reaction is controlled to be carried out for a certain time under the condition of low temperature, then the temperature of the reactant is raised to the room temperature, and the reaction is continuously stirred. And after the reaction is stopped, washing the reaction liquid with water, adding anhydrous magnesium sulfate into the organic phase for drying, removing the drying agent, and evaporating the solvent to obtain the perfluoroalkyl azophenyl acrylate.
(3) Emulsion copolymerization
Compounding emulsifier sodium dodecyl sulfate and non-ionic surfactant, adding into deionized water, stirring and dissolving. Adding perfluoroalkyl azo phenyl acrylate monomer, butyl acrylate and hydroxyethyl methacrylate. Stirring at high speed by an emulsifying machine to obtain the pre-emulsion with uniform dispersion. Adding the pre-emulsion to a reactor, N2Under protection, heating to a certain temperature, slowly dropping and initiatingAn aqueous solution of the agent. After the addition, the reaction is carried out for a certain time under the condition of heat preservation. And cooling the reaction liquid to room temperature, and adjusting the pH value to 6-7 by using ammonia water to obtain the perfluoroalkyl azo acrylate copolymer emulsion.
The chemical structural formula of the perfluoroalkyl azo acrylate copolymer is as follows:
Figure 157849DEST_PATH_IMAGE001
wherein x = 2-8; y = 6-20; z = 1-4; n = 2~ 8.
2. Finishing of textiles
Diluting the obtained perfluoroalkyl azobenzene acrylate copolymer emulsion with deionized water to prepare finishing liquid. Soaking the cotton fabric into the prepared finishing liquid, soaking twice, rolling twice, pre-drying and baking to obtain the intelligent hydrophilic-hydrophobic fabric. Irradiating the finished fabric under ultraviolet light for a certain time, and testing the contact angle of the finished fabric; heating and baking the fabric irradiated by the ultraviolet light under the condition of visible light, and testing the contact angle of the fabric; the fabric surface contact angle before and after visible light cyclic irradiation under the ultraviolet light-heating condition was tested.
3. Performance testing
Irradiating the finished aramid fabric under full-spectrum ultraviolet light to isomerize the azo group of the polymer side group into a cis-configuration, and testing the reduction degree of the contact angle. Then, the fabric was again irradiated with visible light under heating conditions, and the fabric contact angle after the azo group was converted into the trans configuration was tested. The fabric surface contact angle before and after visible light cyclic irradiation under the ultraviolet light-heating condition was tested.
The mechanism of the invention is as follows: perfluoroalkyl azo phenyl acrylate monomers, hydroxyethyl methacrylate and butyl acrylate are subjected to emulsion polymerization to prepare acrylate copolymer emulsion containing perfluoroalkyl azo benzene, and the polymer emulsion is applied to aramid fabric finishing to enable the polymer to form a film on the surface of aramid fibers. Under the stimulation of ultraviolet light, the side group azo group of the perfluoroalkyl group azobenzene acrylate copolymer on the surface of the aramid fiber is isomerized into a cis-configuration, the enrichment degree of the perfluoroalkyl group on the surface is weakened, and the surface contact angle is reduced; and irradiating the aramid fiber fabric with visible light under the heating condition again to convert the azo group from cis configuration to trans configuration, so that the enrichment degree of the perfluoroalkyl group on the surface is increased, and the surface contact angle is increased (see formula 1). The configuration of the azo group is converted in such a circulating way, so that the conversion control of the surface affinity and hydrophobicity of the aramid fabric can be realized for many times.
Figure 402885DEST_PATH_IMAGE002
(formula 1)
The invention discloses an intelligent fabric with convertible surface affinity and hydrophobicity, which is formed by crosslinking a perfluoroalkyl azophenyl acrylate copolymer finishing agent on the surface of a fiber, taking aramid fiber as an example, and has the following structure:
Figure 651464DEST_PATH_IMAGE003
wherein x = 2-8; y = 6-20; z = 1-4; n = 2~ 8.
Specific examples of the method for preparing the intelligent fabric include the following:
（1）p-perfluoroalkyl radical-p' -azophenol Synthesis
0.3-1 part of phenol is dissolved in 20-50 parts of 1mol/L sodium hydroxide aqueous solution by weight to prepare a sodium phenolate solution for later use.
According to the weight, 1-2 parts of perfluoroalkyl aniline is suspended in 5-20 parts of dilute hydrochloric acid solution with the concentration of 2 mol/L, and the solution is heated to 40-50 ℃ so that the perfluoroalkyl aniline is completely dissolved.
And cooling the perfluoroalkyl aniline solution to 5-10 ℃, slowly dropwise adding an aqueous solution prepared by dissolving 4-8 parts of sodium nitrite in 8-12 parts of deionized water, and reacting for 2-5 hours in a heat preservation manner.
And dropwise adding the sodium phenolate solution, controlling the dropwise adding speed to keep the temperature of the reaction liquid at 5-10 ℃, and gradually separating out a solid product.
And (3) adjusting the pH value of the reaction solution to 6-7 by using a saturated sodium bicarbonate solution, and filtering at normal pressure to obtain a product.
By weightRecrystallizing the product with 3-20 parts of mixed solvent of methanol/water (volume ratio of 1: 0.5-2), filtering, and drying to obtain powdered refined productpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol product.
(2) Synthesis of perfluoroalkyl azo phenyl acrylate monomer
0.2-1 part by weight of acryloyl chloride is dissolved in 5-20 parts by weight of dry chloralkane solvent to prepare acryloyl chloride solution for later use.
1 to 3 portions by weight ofpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol is dissolved in 10-30 parts of dry chloroalkane solvent, and 0.4-1 part of triethylamine is added. Stirring uniformly, and cooling to-10-0 ℃.
Slowly dripping the acryloyl chloride solution, and controlling the dripping and the reaction under the low temperature condition.
After the dropwise addition, the temperature of the reactant is raised to room temperature, and the reaction is continued to be stirred for 2-10 hours.
And after the reaction is stopped, washing the reaction solution with 5-20 parts of water for 3 times, adding 0.2-0.5 part of anhydrous magnesium sulfate into an organic phase, drying for 1-8 hours, removing a drying agent, and evaporating the solvent to obtain the perfluoroalkyl azophenyl acrylate monomer.
(3) Emulsion copolymerization
According to the weight, 0.01-0.05 part of sodium dodecyl sulfate and 0.01-0.05 part of nonionic surfactant AEO-9 are compounded, 50-100 parts of deionized water is added, and the mixture is stirred and dissolved.
0.5-2 parts by weight of perfluoroalkyl azophenyl acrylate monomer, 1-2 parts by weight of butyl acrylate and 0.05-0.1 part by weight of hydroxyethyl methacrylate are added. Stirring the mixture for 15 minutes at a high speed (8000 r/min) by an emulsifying machine to obtain a pre-emulsion with uniform dispersion.
According to the weight, 10% -40% of the total amount of the monomers of the initiator is dissolved in 2-10 parts of deionized water to prepare an initiator solution.
Adding the above pre-emulsion into a reactor, N2Under protection, heating to 60-95 ℃, and dripping the initiator solution within 0.5-2 hours.
And after the addition is finished, carrying out heat preservation reaction for 1-10 hours.
And cooling the reaction liquid to room temperature, and adjusting the pH value to 6-7 by using ammonia water to obtain the fluorine-containing acrylate copolymer emulsion.
(4) Finishing of textiles
Diluting the obtained perfluoroalkyl azobenzene acrylate copolymer emulsion with deionized water to prepare 10-100 g/L finishing liquid. Soaking the aramid fiber fabric into the prepared finishing liquid for 15 minutes to 2 hours, and performing a two-dip and two-roll process (the rolling residual rate is 90% to 100%, and the room temperature) → pre-drying (100 ℃ multiplied by 10 minutes) → baking (160 ℃ multiplied by 3 minutes), so as to obtain the finished aramid fiber fabric.
(5) Performance testing
And (3) irradiating the finished aramid fabric for 10-30 minutes under full-spectrum ultraviolet light, and then testing the contact angle of the aramid fabric. And (3) irradiating the fabric subjected to ultraviolet irradiation by visible light for 10-30 minutes under the heating condition of 160 ℃, and then testing the contact angle of the fabric. And testing the contact angle of the surface of the fabric before and after the cyclic irradiation of the ultraviolet light and the visible light.
In the invention, the aramid fabric is any one of Kevlar aramid fabric or Nomex aramid fabric.
The technical scheme provided by the invention has the beneficial effects that:
1. according to the invention, perfluoroalkyl azophenyl polyacrylate is arranged on the surface of aramid fabric, azo groups on the side group of molecules of the finishing agent can be isomerized into cis-configuration under the irradiation of ultraviolet light, and then converted into trans-configuration after receiving visible light/thermal stimulation again, and can be circularly converted for many times, and the terminal perfluoroalkyl conformation is induced to be converted simultaneously each time.
2. According to the invention, the perfluoroalkyl azophenyl polyacrylate is arranged on the surface of the aramid fiber fabric, and the aramid fiber has a smooth surface, so that the finishing agent can form a flat film on the surface of the fiber, and the finishing agent is beneficial to receiving photo-thermal stimulation and generating response. Meanwhile, the aramid fiber fabric has very excellent high-temperature stability, and the aramid fiber structure cannot be damaged after the thermal stimulation of repeated high-temperature baking treatment is carried out on the finished fabric, so that good affinity and hydrophobicity reversible recovery can be still shown after multiple high-temperature baking treatment cycles, and the intelligent fabric finishing application with surface affinity and hydrophobicity for multiple cycle conversion is provided.
3. When the fluorine-containing acrylate copolymer emulsion for the fabric finishing agent is prepared, the technical bias that the using amount of an initiator is not suitable to be large (generally 1-2%) in the prior art is overcome, the copolymer with lower polymerization degree is obtained by increasing the using amount of the initiator by 10-40%, preferably 15-25%, and when the emulsion is used as the finishing agent for finishing the surface of a fabric, the azo-group photoisomerization function can be fully exerted and recovered due to the fact that the molecular chain of the copolymer is shorter, the winding degree of the main chain is small, and the molecular isomerism of the azo-group is small, so that the conversion of surface affinity and hydrophobicity can be effectively realized.
4. The invention adopts emulsion polymerization to prepare perfluoroalkyl azobenzene acrylate polymer type fabric water repellent finishing agent, and carries out fabric finishing application, and the prepared intelligent affinity-hydrophobicity conversion fabric is suitable for industrial production and popularization and application.
Drawings
FIG. 1 is an infrared spectrum of an intelligent aramid fabric prepared in an example;
fig. 2 is a graph of the contact angle cyclic conversion result of the intelligent aramid fabric prepared in the first example after being cyclically irradiated by visible light under the ultraviolet-heating condition;
FIG. 3 is a scanning electron microscope image of a nonafluorobutyl azophenyl acrylate copolymer emulsion prepared in the first example before and after finishing an aramid fabric;
FIG. 4 is a graph showing the cyclic conversion result of the contact angle of the intelligent cotton fabric prepared in the first example after the intelligent cotton fabric is subjected to the cyclic irradiation of visible light under the ultraviolet light-heating condition;
FIG. 5 is a scanning electron microscope image before and after finishing a cotton fabric by the nonafluorobutyl azophenyl acrylate copolymer emulsion prepared in the first example.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example one
（1）p-nonafluorobutylaniline
A250 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 3.44 g of p-bromoaniline, 5g of copper powder (catalyst) and 100ml of dimethyl sulfoxide (DMSO), and stirredHeating to 60 ℃, then dissolving 9g of nonafluoroiodobutane in 25ml of DMSO, adding the mixture into a constant-pressure dropping funnel, slowly dropping the mixture into a three-neck flask, heating the reaction system to 120 ℃ after the dropwise addition of the nonafluoroiodobutane solution is finished, condensing and refluxing the reaction system for 24 h, cooling the reaction system to room temperature, pouring the reaction system into a 500 ml beaker, simultaneously adding 100ml of deionized water and 200ml of anhydrous diethyl ether, stirring and layering the mixture, filtering out copper powder, pouring the filtrate into a 500 ml separating funnel, separating an organic layer, washing the organic layer with deionized water (30 ml × 3 times), drying the anhydrous magnesium sulfate for 8 h, filtering out a drying agent, decompressing and carrying out rotary evaporation to remove the diethyl ether to obtain 3.39g of dark brown liquid 1a with the yield of 54.5% of the 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) 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) -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-nonafluorobutyl-p′-azophenol
0.93 g of 4-nonafluorobutylaniline and 10 ml of a dilute hydrochloric acid solution (2 mol/L) were placed in a 100ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, and the mixture was stirred and heated until the 4-perfluoroalkylaniline was completely dissolved. Then the mixed solution is put in an ice bath to be cooled to 10 ℃, 4.5 g of sodium nitrite aqueous solution is slowly dripped by using a constant pressure dropping funnel, and the reaction solution turns into light yellow after 2 hours of reaction at 10 ℃. 0.42 g of phenol was dissolved in 20 ml of an aqueous sodium hydroxide solution (1 mol/L) to prepare an aqueous solution of sodium phenolate. Then, the sodium phenolate solution was slowly dropped into the previous reaction using a constant pressure dropping funnel, and the temperature was kept below 10 ℃, so that orange-red solids were gradually precipitated. Adjusting pH of the reaction solution to 6-7 with saturated solution of sodium bicarbonate, filtering under normal pressure to obtain crude product, and dissolving in mixed solution of methanol/water (1: 1)Recrystallization to give 0.74 g of a pure orange-red solid, which is dried to a powder. The yield thereof was found to be 59.3%. The product FT-IR was 3419.5, 1595.2, 1354.6, 1231.7,1198.8, 1136.8, 1096.5 cm-1.1H NMR (400 MHz, CDCl3) 7.96 (dd,J= 19.1, 8.6Hz, 4H), 7.74 (d,J= 8.4 Hz, 2H), 6.99 (d,J= 8.7 Hz, 2H), 5.32 (s, 1H, -OH)。
(3) 4-nonafluorobutyl-4' -acrylate azobenzene
A100 mL three-necked flask equipped with a magnetic stirrer and a thermometer was charged with 4-nonafluorobutyl-4' -azophenol 1.66 g, methylene chloride solution (30 mL) with water removed, and triethylamine solution 0.83 g. Then the three-neck flask is fixed in a low-temperature constant-temperature stirring reaction bath and stirred for 30min, and the temperature is controlled to be-5 ℃. 0.54 g of acryloyl chloride was dissolved in 15 mL of dehydrated dichloromethane, and poured into a dropping funnel having a constant pressure, and slowly dropped into the above reaction solution while maintaining a low temperature. After the dropwise addition, the three-neck flask is taken out of the low-temperature constant-temperature stirring reaction bath and placed at the normal temperature for reaction for 6 hours. The reaction mixture was poured into a 100mL separatory funnel, washed 3 times with water (3X 30 mL), the organic phase was taken out, dried over anhydrous magnesium sulfate for 8 hours, filtered under suction, and rotary evaporated under reduced pressure to give 1.42 g of an orange solid with a yield of 77.4%.
(4) Emulsion polymerization
90g of deionized water was added to a beaker, followed by 0.3g of the emulsifiers Sodium Dodecyl Sulfate (SDS) and 0.3g of AEO-9, as well as 8.3g of nonafluorobutylazophenylacrylate, 11.6g of butyl acrylate and 0.7g of hydroxyethyl methacrylate. All monomers and emulsifiers were pre-emulsified for 15 min on an emulsifier with 8000 rps and transferred to a 100mL three-neck flask under N2Heating to 75 ℃ under the protection of gas, adding 4.12g of ammonium persulfate dissolved in 10 mL of deionized water, dropwise adding into the pre-emulsion, and continuing the reaction for 3 h after the dropwise addition is finished. After the reaction is finished, filtering to remove gel substances to obtain perfluoroalkyl azobenzene acrylate copolymer emulsion, wherein the fluorine content of the product is 15.0%, and x = 2-7; y = 12-20; z = 1~ 3.
(5) Textile finishing applications
Diluting the obtained nonafluorobutylazobenzene acrylate copolymer emulsion with deionized water to prepare 20 g/L finishing liquid. Soaking the aramid fiber fabric into the prepared finishing liquid for 15 min, soaking twice and rolling twice, wherein the rolling residual rate is 90%. Then pre-baking at 100 deg.C for 10 min, and baking at 160 deg.C for 3 min. And preparing the intelligent hydrophilic and hydrophobic fabric.
(6) Performance testing
FIG. 1 is an infrared spectrum of an intelligent aramid fabric prepared in an example; wherein curve a is the finish prepared in example one, it can be seen that the finish is 1731cm-1And a-C = O stretching vibration absorption peak appears nearby, and corresponds to a characteristic absorption peak presented by a fluorinated acrylate copolymer finishing agent forming a film on the surface of aramid fiber.
And (3) irradiating the finished aramid fabric for 20 minutes under full-spectrum ultraviolet light, and then testing the contact angle of the aramid fabric. The fabric after UV irradiation was irradiated with visible light under heating at 160 ℃ for 20 minutes, and then the contact angle was measured. Testing the contact angle of the surface of the fabric before and after the ultraviolet-visible light cyclic irradiation; fig. 2 shows that after the intelligent aramid fiber fabric prepared by the method is subjected to cyclic irradiation of visible light under an ultraviolet light-heating condition, the contact angle of the intelligent aramid fiber fabric can be repeatedly and cyclically changed between 132 degrees and 127 degrees for more than 40 times.
Fig. 3 is a scanning electron microscope image of a nonafluorobutylazo phenyl acrylate copolymer emulsion prepared in this example before and after finishing an aramid fabric, fig. 3a is before finishing, and fig. 3b is after finishing. Wherein, the fiber surface in the aramid fiber fabric is smooth and flat before finishing, and a polymer film is formed after finishing.
FIG. 4 is a surface contact angle diagram of the prepared nonafluorobutyl azophenyl acrylate copolymer emulsion after finishing cotton fabric, before and after the fabric is circularly irradiated by ultraviolet light-visible light, wherein the contact angle can be repeatedly converted between 124 degrees and 131 degrees and can be more than 17 times.
Fig. 5 is a scanning electron microscope image before and after finishing a cotton fabric by the nonafluorobutyl azophenyl acrylate copolymer emulsion prepared in the embodiment, fig. 5a is before finishing, and fig. 5b is after finishing. Wherein, the surface of the fiber in the cotton fabric has natural wrinkles before finishing, and the polymer forms a film after finishing.
Example two
（1）pSynthesis of (tridecafluorohexylaniline)
Adding 3.44 g of para-bromoaniline, 5g of copper powder (catalyst) and 100ml of dimethyl sulfoxide (DMSO) into a 250 ml three-neck flask provided with a magnetic stirrer, a thermometer and a condenser, stirring and heating to 60 ℃, then dissolving 11.6g of tridecafluoriodohexane into 25ml of DMSO, adding the DMSO into a constant pressure dropping funnel, slowly dropping the mixture into the three-neck flask, after dropping the tridecafluoriodohexane solution, heating the reaction system to 120 ℃ to condense and reflux for 24 h, cooling the reaction system to room temperature, pouring the reaction into a 500 ml beaker, simultaneously adding 100ml of deionized water and 200ml of anhydrous diethyl ether, stirring and layering to filter out the copper powder, pouring the filtrate into a 500 ml separating funnel to separate out an organic layer, washing the organic layer with deionized water (30 ml of × times), drying the anhydrous magnesium sulfate for 8 h, filtering out a drying agent, removing the diethyl ether by rotary evaporation under reduced pressure to obtain 4.32 g of dark brown liquid, wherein the yield is 52.6%, FT-IR 3405.2, 3051.0, 1523.6, 1362.2, 3892, 3875, 1145.0,1088.1 cm, 3875, 64 cm, 3 cm and 64-1.1H NMR (400 MHz, CDCl3) 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) -80.97 – -81.26 (m, 3F,C 3F), -116.08 – -116.52 (m, 2F, CF3C 2F), -122.17 (d, J = 11.4 Hz, 2F,CF3CF2CF2), -123.11 (d, J = 2.9 Hz, m, 2F, CF3(CF2)2C 2F), -123.40–-123.89 (m,2F, CF3(CF2)3C 2F), -126.22–-126.58 (m, 2F, CF3(CF2)4C 2F)。
（2）p-tridecafluorohexyl-p′Synthesis of azophenol
In a 100ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser were placed 1.23 g of 4-tridecafluorohexylaniline and 10 ml of a dilute hydrochloric acid solution (2 mol/L), and the reaction mixture was heated with stirring to dissolve the whole amount. Then the mixed solution is put in an ice bath to be cooled to 10 ℃, 4.5 g of sodium nitrite aqueous solution is slowly dripped by using a constant pressure dropping funnel, and the reaction solution turns into light yellow after 2 hours of reaction at 10 ℃. 0.42 g of phenol was dissolved in 20 mL sodium hydroxide aqueous solution (1 mol/L) to form a sodium phenolate solution, thereby obtaining an aqueous sodium phenolate solution. Then, the sodium phenolate solution was slowly dropped into the previous reaction using a constant pressure dropping funnel, and the temperature was kept below 10 ℃, so that orange-red solids were gradually precipitated. The pH of the reaction solution was adjusted to 6-7 with a saturated solution of sodium bicarbonate, filtered at normal pressure to give a crude product, recrystallized in a mixed solution of methanol/water (1: 1) to give 0.81g of a pure orange-red solid, and dried to give a powder. The yield thereof was found to be 52.3%. Products FT-IR 3448.0, 1596.6, 1391.68,1248.1, 1205.0, 1143.8, 1104.7, 1010.0 cm-1。
(3) Synthesis of 4-tridecafluorohexyl-4' -acrylate azobenzene
In a 100mL three-necked flask equipped with a magnetic stirrer and a thermometer, 2.06 g of 4-tridecafluorohexyl-4' -azophenol, 30mL of a methylene chloride solution with water removed and 0.83 g of a triethylamine solution were placed. Then the three-neck flask is fixed in a low-temperature constant-temperature stirring reaction bath and stirred for 30min, and the temperature is controlled to be-5 ℃. 0.54 g of acryloyl chloride was dissolved in 15 mL of dehydrated dichloromethane, and poured into a dropping funnel having a constant pressure, and slowly dropped into the above reaction solution while maintaining a low temperature. After the dropwise addition, the three-neck flask is taken out of the low-temperature constant-temperature stirring reaction bath and placed at the normal temperature for reaction for 6 hours. The reaction mixture was then poured into a 100mL separatory funnel, washed 3 times with water (3X 30 mL), the organic phase was taken out, dried over anhydrous magnesium sulfate for 8 h, filtered with suction, and rotary evaporated under reduced pressure to give 1.73 g of an orange-yellow solid with a yield of 75.9%.
(4) Emulsion polymerization
95g of deionized water was added to a beaker, followed by 0.3g of the emulsifiers Sodium Dodecyl Sulfate (SDS) and 0.3g of AEO-9, as well as 10.3g of tridecafluorohexylazobenzene acrylate, 11.6g of butyl acrylate and 0.7g of hydroxyethyl methacrylate. All monomers and emulsifiers were pre-emulsified for 15 min on an emulsifier with 8000 rps and transferred to a 100mL three-neck flask under N2Heating to 75 ℃ under the protection of gas, adding 3.39g of ammonium persulfate dissolved in 10 mL of deionized water, dropwise adding into the pre-emulsion, and continuing the reaction for 3 h after the dropwise addition is finished. Filtering to remove gel after the reaction is finished to obtain perfluoroalkyl azobenzene acrylate copolymer emulsion with fluorine content21.6%，x=2～5；y=10～18；z=1～3。
(5) Textile finishing applications
Diluting the obtained tridecafluorohexylazobenzene acrylate copolymer emulsion with deionized water to prepare 20 g/L finishing liquid. Soaking the aramid fiber fabric into the prepared finishing liquid for 15 min, soaking twice and rolling twice, wherein the rolling residual rate is 90%. Then pre-baking at 100 deg.C for 10 min, and baking at 160 deg.C for 3 min.
(6) Performance testing
After the finished aramid fabric is irradiated by ultraviolet light-visible light in a circulating way, the measured contact angle can be repeatedly and circularly changed between 135 degrees and 130 degrees for more than 32 times; the contact angle of the treated cotton fabric can be repeatedly converted between 124 degrees and 131 degrees and can reach more than 16 times.
FIG. 1 is an infrared spectrum of an intelligent aramid fabric prepared in an example; wherein curve b is the finish prepared in example two at 1731cm-1And a-C = O stretching vibration absorption peak appears nearby, and corresponds to a characteristic absorption peak presented by a fluorinated acrylate copolymer finishing agent forming a film on the surface of aramid fiber.
EXAMPLE III
（1）p-heptadecafluorooctylaniline
A250 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 3.45 g of p-bromoaniline, 5.15 g of copper powder (catalyst) and 100ml of dimethyl sulfoxide, and heated to 60 ℃ with stirring. Then, 9.21 g of heptadecafluoroiodooctane was dissolved in 25ml of dimethyl sulfoxide and charged into a constant pressure dropping funnel, and slowly dropped into a three-necked flask. After the dropwise addition of the nonafluoroiodobutane solution is finished, the reaction system is heated to 115 ℃ and condensed and refluxed for 12 hours. The reaction system is cooled to room temperature, the reaction is poured into a 500 ml beaker, 100ml of deionized water and 200ml of anhydrous ether are added at the same time, the mixture is stirred and layered, and copper powder is filtered. The filtrate was poured into a 500 ml separatory funnel to separate the organic layer and washed with deionized water (30 ml. times.3 times), dried over anhydrous magnesium sulfate for 6 hours, the desiccant was filtered off, and the ether was removed by rotary evaporation under reduced pressure to give 3.51 g of a dark brown liquid product with a yield of 55.1%.
（2）p-heptadecafluorooctyl-p′-azophenol
A100 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 1.13 g of waterp10 ml of (E) -heptadecafluorooctylaniline and 2 mol/L diluted hydrochloric acid solution, stirring and heating to obtain a solutionp-heptadecafluorooctylaniline was completely dissolved. Then the mixed solution was cooled to 8 ℃ in an ice bath and 4.6 g of an aqueous solution of sodium nitrite was slowly dropped using a constant pressure dropping funnel, followed by reaction at 10 ℃ for 2 hours. An aqueous solution of sodium phenolate was prepared by dissolving 0.43 g of phenol in 20 ml of an aqueous sodium hydroxide solution (1 mol/L) to prepare a sodium phenolate solution. Then, the sodium phenolate solution was slowly dropped into the previous reaction using a constant pressure dropping funnel, and the temperature was kept below 8 ℃, so that orange-red solids were gradually precipitated. The pH of the reaction solution was adjusted to 6-7 with a saturated solution of sodium bicarbonate, filtered at normal pressure to give a crude product, recrystallized in a mixed solution of methanol/water (1: 1) to give 0.76 g of a pure orange-red solid, and dried to give a powder. The yield thereof was found to be 61.1%.
（3））p-heptadecafluorooctyl-p′-acrylic ester based azobenzene
A100 mL three-necked flask equipped with a magnetic stirrer and a thermometer was charged with 1.71 g p-heptadecafluorooctyl-p' -azophenol, 30mL of a methylene chloride solution with water removed, and 0.85 g of triethylamine. Then the three-neck flask is fixed in a low-temperature constant-temperature stirring reaction bath and stirred for 30min, and the temperature is controlled to be-8 ℃. 0.56 g of acryloyl chloride was dissolved in 18 mL of dehydrated dichloromethane, and poured into a constant pressure dropping funnel, and slowly dropped into the above reaction solution at a temperature preferably kept at-8 ℃ or lower. After the dropwise addition, the three-neck flask is taken out of the low-temperature constant-temperature stirring reaction bath and placed at the normal temperature for reaction for 8 hours. The reaction was then poured into a 100mL separatory funnel and washed 3 times with 30mL portions of deionized water. The organic phase is taken out, added into anhydrous magnesium sulfate for drying for 6 hours, filtered, decompressed and rotary evaporated to obtain 1.56 g of orange solid with the yield of 79.1 percent.
(4) Emulsion polymerization
90g of deionized water was added to a beaker, followed by 0.3g of Sodium Dodecyl Sulfate (SDS) as an emulsifier, 0.3g of AEO-9, and 10.2g of heptadecafluorooctylazophenylacrylate,11.1g of butyl acrylate and 1g of hydroxyethyl methacrylate. All monomers and emulsifiers were pre-emulsified for 30min on an emulsifier with 8000 rps and transferred to a 100mL three-neck flask under N2Heating to 75 ℃ under the protection of gas, adding 5.48g of potassium persulfate, dissolving in 10 mL of deionized water, dropwise adding into the pre-emulsion, and continuing to react for 3 hours after the dropwise adding is finished to obtain a heptadecafluoroazobenzene acrylate copolymer emulsion, wherein the fluorine content of the product is 18.5%, and x = 1-3; y = 8-15; z = 1~ 2.
(5) Textile finishing applications
Diluting the obtained heptadecafluorooctyl azobenzene acrylate copolymer emulsion with deionized water to prepare 15 g/L finishing liquid. And soaking the aramid fiber fabric into the prepared finishing liquid for 30min, and soaking and rolling twice, wherein the rolling residual rate is 100%. Then pre-baking at 100 deg.C for 10 min, and baking at 160 deg.C for 3 min. And preparing the intelligent hydrophilic and hydrophobic fabric.
(6) Performance testing
After the finished fabric is irradiated by ultraviolet light-visible light circularly, the contact angle is measured to be between 136 DEG and 130 DEG, and the repeated cyclic conversion can reach more than 38 times; the contact angle of the treated cotton fabric can be repeatedly converted between 124 degrees and 131 degrees and can reach more than 17 times.
FIG. 1 is an infrared spectrum of an intelligent aramid fabric prepared in an example; wherein curve c is the finish prepared in example three at 1731cm-1And a-C = O stretching vibration absorption peak appears nearby, and corresponds to a characteristic absorption peak presented by a fluorinated acrylate copolymer finishing agent forming a film on the surface of aramid fiber.
Example four
（1）pSynthesis of (tridecafluorohexylaniline)
A250 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 3.45 g of p-bromoaniline, 5.11 g of copper powder and 100ml of DMSO, and heated to 60 ℃ with stirring. Then, 11.5g of tridecafluoriodohexane was dissolved in 25ml of DMSO and charged into a constant pressure dropping funnel, and slowly dropped into the three-necked flask. After the dropwise addition of the hexane tridecafluoriodoiodide solution is finished, the reaction system is heated to 120 ℃ and condensed and refluxed for 24 hours. The reaction system is cooled to room temperature, the reaction is poured into a 500 ml beaker, 100ml of deionized water and 200ml of anhydrous ether are added at the same time, the mixture is stirred and layered, and copper powder is filtered. The filtrate was poured into a 500 ml separatory funnel to separate the organic layer and washed 3 times with 30ml deionized water, dried over anhydrous magnesium sulfate for 8 h, filtered to remove the drying agent, and evaporated under reduced pressure to remove ether, yielding 4.54 g of dark brown liquid with a yield of 53.3%.
（2）p-tridecafluorohexyl-p′Synthesis of azophenol
In a 100ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser were charged 1.21 g of 4-tridecafluorohexylaniline and 10 ml of a dilute hydrochloric acid solution (2 mol/L), and the reaction mixture was heated with stirring to dissolve the whole amount. Then the mixed solution is put in an ice bath to be cooled to 10 ℃, 4.6 g of sodium nitrite aqueous solution is slowly dripped by using a constant pressure dropping funnel, and the reaction solution turns into light yellow after 2 hours of reaction at 10 ℃. An aqueous solution of sodium phenolate was prepared by dissolving 0.41 g of phenol in 20 ml of an aqueous sodium hydroxide solution (1 mol/L) to prepare a sodium phenolate solution. Then, the sodium phenolate solution was slowly dropped into the previous reaction using a constant pressure dropping funnel, and the temperature was kept below 10 ℃, so that orange-red solids were gradually precipitated. The pH of the reaction solution was adjusted to 6-7 with a saturated solution of sodium bicarbonate, filtered at normal pressure to give a crude product, recrystallized in a mixed solution of methanol/water (1: 1) to give 0.84 g of a pure orange-red solid, and dried to give a powder. The yield thereof was found to be 53.5%.
(3) Synthesis of 4-tridecafluorohexyl-4' -acrylate azobenzene
A100 mL three-necked flask equipped with a magnetic stirrer and a thermometer was charged with 2.12 g of 4-tridecafluorohexyl-4' -azophenol, 30mL of a water-removed dichloroethane solution and 0.85 g of triethylamine. Then the three-neck flask is fixed in a low-temperature constant-temperature stirring reaction bath and stirred for 30min, and the temperature is controlled to be-10 ℃. 0.52 g of acryloyl chloride was dissolved in 15 mL of dehydrated dichloroethane, and poured into a constant pressure dropping funnel, and slowly dropped into the above reaction solution while maintaining a low temperature. After the dropwise addition, the three-neck flask is taken out of the low-temperature constant-temperature stirring reaction bath and placed at the normal temperature for reaction for 6 hours. The reaction mixture was then poured into a 100mL separatory funnel, washed 3 times with water (3X 30 mL), the organic phase was taken out, dried over anhydrous magnesium sulfate for 8 h, filtered with suction and rotary evaporated under reduced pressure to give 1.75 g of a product as an orange-yellow solid with a yield of 76.3%. The refined product can be prepared by using n-hexane as eluent and adopting a chromatographic column method.
(4) Emulsion polymerization
100g of deionized water was added to a beaker, followed by 0.3g of the emulsifiers Sodium Dodecyl Sulfate (SDS) and 0.3g of AEO-9, as well as 10.5g of tridecafluorohexylazobenzene acrylate, 11.5g of butyl acrylate and 0.9g of hydroxyethyl methacrylate. All monomers and emulsifiers were pre-emulsified for 30min on an emulsifier with 8000 rps and transferred to a 100mL three-neck flask under N2Heating to 75 ℃ under the protection of gas, adding 2.29g of potassium persulfate dissolved in 5mL of deionized water, dropwise adding into the pre-emulsion, and continuing the reaction for 3 hours after the dropwise addition is finished. No gel is generated in the reaction process, the reaction mixture is decanted to obtain perfluoroalkyl azobenzene acrylate copolymer emulsion, the fluorine content of the product is 21.7%, and x = 2-4; y = 9-16; z = 1~ 3.
(5) Textile finishing applications
Diluting the obtained tridecafluorohexylazobenzene acrylate copolymer emulsion with deionized water to prepare 20 g/L finishing liquid. Soaking the aramid fiber fabric into the prepared finishing liquid for 15 min, soaking twice and rolling twice, wherein the rolling residual rate is 90%. Then pre-baking at 100 deg.C for 10 min, and baking at 160 deg.C for 3 min.
(6) Performance testing
After the finished aramid fabric is irradiated by ultraviolet light-visible light in a circulating way, the measured contact angle can be repeatedly and circularly changed between 135 degrees and 131 degrees for more than 28 times; the contact angle of the treated cotton fabric can be repeatedly converted between 124 degrees and 131 degrees and can reach more than 14 times.
Comparative example 1
（1）pSynthesis of (tridecafluorohexylaniline)
A250 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 3.45 g of p-bromoaniline, 5.11 g of copper powder and 100ml of DMSO, and heated to 60 ℃ with stirring. Then, 11.5g of tridecafluoriodohexane was dissolved in 25ml of DMSO and charged into a constant pressure dropping funnel, and slowly dropped into the three-necked flask. After the dropwise addition of the hexane tridecafluoriodoiodide solution is finished, the reaction system is heated to 120 ℃ and condensed and refluxed for 24 hours. The reaction system is cooled to room temperature, the reaction is poured into a 500 ml beaker, 100ml of deionized water and 200ml of anhydrous ether are added at the same time, the mixture is stirred and layered, and copper powder is filtered. The filtrate was poured into a 500 ml separatory funnel to separate the organic layer and washed 3 times with 30ml deionized water, dried over anhydrous magnesium sulfate for 8 h, filtered to remove the drying agent, and evaporated under reduced pressure to remove ether, yielding 4.54 g of dark brown liquid with a yield of 53.3%.
（2）p-tridecafluorohexyl-p′Synthesis of azophenol
In a 100ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser were charged 1.21 g of 4-tridecafluorohexylaniline and 10 ml of a dilute hydrochloric acid solution (2 mol/L), and the reaction mixture was heated with stirring to dissolve the whole amount. Then the mixed solution is put in an ice bath to be cooled to 10 ℃, 4.6 g of sodium nitrite aqueous solution is slowly dripped by using a constant pressure dropping funnel, and the reaction solution turns into light yellow after 2 hours of reaction at 10 ℃. 0.41 g of phenol was dissolved in 20 ml of an aqueous sodium hydroxide solution (1 mol/L) to prepare a sodium phenolate solution. Then, the sodium phenolate solution was slowly dropped into the previous reaction using a constant pressure dropping funnel, and the temperature was kept below 10 ℃, so that orange-red solids were gradually precipitated. The pH of the reaction solution was adjusted to 6-7 with a saturated solution of sodium bicarbonate, filtered at normal pressure to give a crude product, recrystallized in a mixed solution of methanol/water (1: 1) to give 0.84 g of a pure orange-red solid, and dried to give a powder. The yield thereof was found to be 53.5%.
(3) Synthesis of 4-tridecafluorohexyl-4' -acrylate azobenzene
A100 mL three-necked flask equipped with a magnetic stirrer and a thermometer was charged with 2.12 g of 4-tridecafluorohexyl-4' -azophenol, 30mL of a water-removed dichloroethane solution and 0.85 g of triethylamine. Then the three-neck flask is fixed in a low-temperature constant-temperature stirring reaction bath and stirred for 30min, and the temperature is controlled to be-10 ℃. 0.52 g of acryloyl chloride was dissolved in 15 mL of dehydrated dichloroethane, and poured into a constant pressure dropping funnel, and slowly dropped into the above reaction solution while maintaining a low temperature. After the dropwise addition, the three-neck flask is taken out of the low-temperature constant-temperature stirring reaction bath and placed at the normal temperature for reaction for 6 hours. The reaction mixture was then poured into a 100mL separatory funnel, washed 3 times with water (3X 30 mL), the organic phase was taken out, dried over anhydrous magnesium sulfate for 8 h, filtered with suction and rotary evaporated under reduced pressure to give 1.75 g of a product as an orange-yellow solid with a yield of 76.3%. The refined product can be prepared by using n-hexane as eluent and adopting a chromatographic column method.
(4) Emulsion polymerization
100g of deionized water was added to a beaker, followed by 0.3g of the emulsifiers Sodium Dodecyl Sulfate (SDS) and 0.3g of AEO-9, as well as 10.5g of tridecafluorohexylazobenzene acrylate, 11.5g of butyl acrylate and 0.9g of hydroxyethyl methacrylate. All monomers and emulsifiers were pre-emulsified for 30min on an emulsifier with 8000 rps and transferred to a 100mL three-neck flask under N2Heating to 75 ℃ under the protection of gas, adding 0.23g of potassium persulfate dissolved in 5mL of deionized water, dropwise adding into the pre-emulsion, and continuing the reaction for 3 hours after the dropwise addition is finished. No gel is generated in the reaction process, the reaction mixture is decanted to obtain perfluoroalkyl azobenzene acrylate copolymer emulsion, the fluorine content of the product is 20.5%, and x = 20-40; y =100 ~ 200; z = 8~ 20.
(5) Textile finishing applications
Regulating the pH value of the obtained tridecafluorohexylazobenzene acrylate copolymer emulsion to 6.5 by using ammonia water, diluting by using deionized water, and preparing into finishing liquid of 20 g/L. Soaking the cotton fabric into the prepared finishing liquid for 15 min, soaking twice and rolling twice, wherein the rolling residual rate is 90%. Then pre-baking at 100 deg.C for 10 min, and baking at 160 deg.C for 3 min. Measuring that the contact angle of the finished fabric is 123 degrees, after the fabric is irradiated by ultraviolet light, the contact angle is 121 degrees, and the contact angle is basically not reduced; similar results were obtained for aramid fabrics, with substantially no decrease in contact angle. Analysis shows that the intelligent hydrophilic and hydrophobic surface cannot be obtained because the polymerization degree of the copolymer is too large, the molecular chain of the copolymer is wound after the copolymer is finished to the surface of the fiber, and the isomerization of the side group under the stimulation of external light is influenced.

Claims (5)

1. An intelligent fabric, characterized in that the preparation method of the intelligent fabric comprises the following steps:
(1) prepared by taking perfluoroalkyl iodide and p-bromoaniline as raw materials in the presence of copper powderp-a perfluoroalkylaniline;
(2) to be provided withpPreparation of perfluoroalkyl aniline, sodium nitrite and sodium phenolate as raw materialpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
(3) to be provided withpPerfluoroalkyl-substituted carboxylic acidsp′Preparing perfluoroalkyl azo phenyl acrylate monomer by using azophenol, acryloyl chloride and triethylamine as raw materials;
(4) carrying out emulsion polymerization on a perfluoroalkyl azo phenyl acrylate monomer, butyl acrylate and hydroxyethyl methacrylate serving as raw materials to prepare a perfluoroalkyl azo phenyl acrylate copolymer emulsion;
(5) mixing the perfluoroalkyl azophenyl acrylate copolymer emulsion with water to prepare a finishing liquid; then soaking the fabric into finishing liquid for finishing to obtain intelligent fabric;
in the step (1), the mass ratio of perfluoroalkyl iodide to p-bromoaniline to copper powder is 2-5: 1-2;
in the step (2),pthe mass ratio of the perfluoroalkyl aniline to the sodium nitrite to the sodium phenolate is 1-2: 4-8: 0.35-1.2;
in the step (3), the step (c),pperfluoroalkyl-substituted carboxylic acidsp′The mass ratio of the azophenol to the acryloyl chloride to the triethylamine is 1-3: 0.2-1: 0.4-1;
in the step (4), the mass ratio of the perfluoroalkyl azo phenyl acrylate monomer to the butyl acrylate to the hydroxyethyl methacrylate is 0.5-2: 1-2: 0.05-0.1; the using amount of the initiator is 10 to 40 percent of the total mass of the monomers;
in the step (5), the concentration of the finishing liquid is 10-100 g/L.
2. The intelligent fabric of claim 1,
in the step (1), dropwise adding a perfluoroalkyl iodide solution into a mixed solution of p-bromoaniline, copper powder and an organic solvent at 40-70 ℃; then reacting for 2-24 hours at 100-140 ℃ to obtainp-a perfluoroalkylaniline;
in the step (2), dropwise adding a sodium nitrite aqueous solution at the temperature of 5-10 DEG CpIn perfluoroalkyl aniline acid solution, reaction2-5 hours; then dropwise adding a sodium phenolate solution at 5-10 ℃; then adjusting the pH value of the system to 6-7 to obtainpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
in the step (3), the acryloyl chloride chloralkane solution is dripped into the mixture at the temperature of minus 20 to 0 DEG CpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol, triethylamine, chloralkane mixed liquor; then reacting for 2-10 hours at room temperature to obtain a perfluoroalkyl azophenyl acrylate monomer;
in the step (4), a perfluoroalkyl azo phenyl acrylate monomer, butyl acrylate, hydroxyethyl methacrylate, an emulsifier and a nonionic surfactant are mixed; then, dropwise adding an initiator solution in inert gas at the temperature of 60-95 ℃; carrying out emulsion polymerization for 1-10 hours to obtain perfluoroalkyl azo phenyl acrylate copolymer emulsion;
in the step (5), padding the fabric with the finishing liquid for 15 minutes to 2 hours, and then pre-drying and baking to obtain an intelligent fabric;
the perfluoroalkyl group is pentafluoroethyl, nonafluorobutyl, tridecafluorohexyl or heptadecafluorooctyl; the organic solvent is dimethyl sulfoxide; the acid is hydrochloric acid; the reagent for adjusting the pH of the system is a saturated solution of sodium bicarbonate; the chloralkane is dichloromethane, dichloroethane or tetrachloroethane; the nonionic surfactant is AEO-6 or AEO-9; the emulsifier is sodium dodecyl sulfate; the initiator is ammonium persulfate or potassium persulfate; the padding is two-padding and two-rolling; the fabric is aramid fiber fabric.
3. The intelligent fabric of claim 2,
in the step (1), after the reaction is finished, an ether solvent is added, an organic layer is obtained by separation, and then the organic layer is washed, dried and desolventized to obtainp-a perfluoroalkylaniline;
in the step (2), after the reaction is finished, filtering at normal pressure to obtain a solid; then recrystallizing the solid and drying to obtainpPerfluoroalkyl-substituted carboxylic acidsp′-azophenol;
in the step (3), after the reaction is finished, washing the reaction solution with water, taking an organic phase, drying and removing a solvent to obtain a perfluoroalkyl azophenyl acrylate monomer;
in the step (4), after the reaction is finished, ammonia water is used for adjusting the pH value of the system to 6-7, and perfluoroalkyl azophenyl acrylate copolymer emulsion is obtained.
4. The intelligent fabric of claim 2,
in the step (1), the time for dripping the perfluoroalkyl iodide solution is 0.5-2 hours;
in the step (2), phenol is dissolved in a sodium hydroxide aqueous solution to prepare a sodium phenolate solution;
in the step (3), the acryloyl chloride chloralkane solution is dripped into the mixture at the temperature of between 10 ℃ below zero and 5 ℃ below zeropPerfluoroalkyl-substituted carboxylic acidsp′-azophenol, triethylamine, chloralkane mixed liquor;
in the step (4), the time for dripping the initiator solution is 0.5-2 hours;
in the step (5), the pre-drying is carried out for 10 minutes at 100 ℃; the baking is carried out for 3 minutes at 160 ℃.
5. The intelligent fabric according to claim 2, wherein in step (1), the solvent in the perfluoroalkyl iodide solution is dimethyl sulfoxide; the chloralkane in the step (3) is dry chloralkane; in the step (4), the solvent in the initiator solution is water; in the step (5), padding is carried out at room temperature, wherein the padding allowance rate of padding is 90-100%.
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