CN109400798B - Environment-friendly super-hydrophobic/oleophobic textile finishing agent, preparation method and application thereof - Google Patents

Environment-friendly super-hydrophobic/oleophobic textile finishing agent, preparation method and application thereof Download PDF

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CN109400798B
CN109400798B CN201710702447.7A CN201710702447A CN109400798B CN 109400798 B CN109400798 B CN 109400798B CN 201710702447 A CN201710702447 A CN 201710702447A CN 109400798 B CN109400798 B CN 109400798B
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monomer
finishing agent
acrylate
hydrophobic
oleophobic
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CN109400798A (en
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张丹
郑君红
郑磊
黄婵娟
龙柱
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Jiangnan University
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Jiangnan University
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
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    • 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
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    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
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    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses an environment-friendly super-hydrophobic/oleophobic textile finishing agent, and a preparation method and application thereof. The preparation method comprises the following steps: dispersing the composite emulsifier in deionized water, stirring and heating, mixing with acrylate monomer, styrene monomer, uvioresistant polymerizable monomer, etc. to perform pre-emulsification reaction, heating in nitrogen gas, adding fluoric monomer and initiator to initiate polymerization reaction, and adding inorganic uvioresistant finishing agent after polymerization reaction. The preparation process is simple and easy to implement, convenient for large-scale production, safe, environment-friendly and low in cost, and meanwhile, the environment-friendly super-hydrophobic/oleophobic textile finishing agent is simple and convenient to use, can endow the fabric with excellent wear resistance, washing resistance and hydrophobic and oleophobic properties, can also greatly improve the ultraviolet resistance and rupture strength of the fabric, keeps the soft hand feeling and good air permeability of the fabric, and does not influence the wearability of the fabric at all.

Description

Environment-friendly super-hydrophobic/oleophobic textile finishing agent, preparation method and application thereof
Technical Field
The invention relates to a fabric finishing agent, in particular to an environment-friendly super-hydrophobic/oleophobic textile finishing agent, a preparation method and application thereof, and belongs to the technical field of textile finishing.
Background
In recent years, the super-hydrophobic/oleophobic material has important application in daily life and has extremely wide application prospect in many fields such as national defense industry, medical health and the like. Super hydrophobic/oleophobic fabrics are becoming popular because of their special wettability properties, as well as their water, oil, stain, corrosion, icing and self-cleaning properties. Research shows that the micro-nano composite rough structure and low surface energy are key factors for forming the super-hydrophobic/oleophobic surface.
Based on this, many methods for preparing superhydrophobic/oleophobic surfaces have been proposed, such as layer-by-layer self-assembly, sol-gel, plasma techniques, electrochemical deposition, etching, phase separation, and templating. However, most of the methods have complicated processes, difficult process control, and need special equipment, and some of the methods are also only suitable for flat surfaces made of special materials, which is difficult to be widely applied.
On the other hand, in the field of fabric finishing, the traditional fluorine-containing acrylate finishing agent is mostly prepared by a solution polymerization method, wherein most of organic solvents are toxic, harmful and volatile, and although the effect is good, the finishing agent is unhealthy, not environment-friendly and has higher cost. Further, perfluorooctylsulfonyl derivatives (PFOS) having 8 carbon atoms and perfluorooctanoic acid compounds (PFOA) are often used as conventional fluorine-containing finishing agents, and they are considered to have excellent water-and-oil-repellent properties and good surface activity. However, PFOS is a perfluorocarbon compound which is chemically stable, environmentally durable, bioaccumulating and toxic, not easily degradable, and hazardous and potentially carcinogenic to organisms, and has been banned for use and import in european union countries.
Disclosure of Invention
The invention mainly aims to provide an environment-friendly super-hydrophobic/oleophobic textile finishing agent, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the embodiment of the invention provides a preparation method of an environment-friendly super-hydrophobic/oleophobic textile finishing agent, which comprises the following steps:
(1) uniformly dispersing the composite emulsifier in deionized water, continuously stirring at the speed of 100-900 r/min, heating to 40-60 ℃, adding an acrylate monomer, a styrene monomer and an anti-ultraviolet polymerizable monomer, and carrying out pre-emulsification reaction for 30-120 min;
(2) continuously heating the pre-emulsified reaction mixture obtained in the step (1) to 65-85 ℃ under a protective atmosphere, and slowly adding a fluorine-containing monomer;
(3) and (3) adding an initiator into the mixed reaction system obtained in the step (2), carrying out polymerization reaction for 8-24 hours, and then adding an inorganic anti-ultraviolet finishing agent to prepare the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
In some preferred embodiments, step (3) comprises: and (3) slowly dripping an aqueous solution of an initiator into the mixed reaction system obtained in the step (2) at a constant speed to initiate polymerization, wherein the dripping time is 30-120 min, continuing to perform polymerization reaction for 8-24 h, and adding an inorganic anti-ultraviolet finishing agent after the polymerization reaction is finished to obtain the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
The embodiment of the invention also provides the environment-friendly super-hydrophobic/oleophobic textile finishing agent prepared by the method.
The embodiment of the invention also provides application of the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
Compared with the prior art, the invention has the advantages that:
(1) the preparation process of the environment-friendly super-hydrophobic/oleophobic textile finishing agent provided by the invention is realized by adopting an emulsion polymerization method, and water is used as a disperse phase, so that the preparation process is simple and easy, is convenient for large-scale production, and is low in cost and environment-friendly; the fabric can be endowed with super-hydrophobic, oleophobic and antifouling properties; b, carrying out the following steps of;
(2) the environment-friendly super-hydrophobic/oleophobic textile finishing agent provided by the invention is safe and environment-friendly, does not contain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) compounds, is simple and convenient to use, can be suitable for finishing textiles in spraying, dipping, brushing and other modes, and is suitable for fabrics including various textiles such as cotton, hemp, silk, wool, velvet, fiber, leather and the like.
(3) The environment-friendly super-hydrophobic/oleophobic textile finishing agent provided by the invention can endow the fabric with excellent wear resistance and washability and excellent hydrophobic and oleophobic properties, can also greatly improve the ultraviolet resistance of the fabric and greatly enhance the breaking strength of the fabric, and the fabric finished by the finishing agent has soft hand feeling and good air permeability which are equal to those of a fibril material, and the wearability of the fabric is not influenced at all.
Drawings
FIGS. 1 a-1 b are test plots of the contact angles (160 ℃ and 130 ℃ respectively) of water and n-dodecane on a textile after finishing with a typical environmentally friendly superhydrophobic/oleophobic textile finish according to the invention.
FIG. 2 is a graph of wettability testing of 10 μ L to 30 μ L water droplets on a textile finished with a typical environmentally friendly superhydrophobic/oleophobic textile finish of the invention.
FIG. 3 is a graph showing the wettability of water, olive oil, n-hexadecane, and n-dodecane on a textile finished with a typical environmentally friendly superhydrophobic/oleophobic textile finish of the invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. One aspect of the embodiments of the present invention provides a method for preparing an environment-friendly superhydrophobic/oleophobic textile finishing agent, comprising:
(1) uniformly dispersing the composite emulsifier in deionized water, continuously stirring at the speed of 100-900 r/min, heating to 40-60 ℃, adding an acrylate monomer, a styrene monomer and an anti-ultraviolet polymerizable monomer, and carrying out pre-emulsification reaction for 30-120 min;
(2) continuously heating the pre-emulsified reaction mixture obtained in the step (1) to 65-85 ℃ under a protective atmosphere, and slowly adding a fluorine-containing monomer;
(3) and (3) adding an initiator into the mixed reaction system obtained in the step (2), carrying out polymerization reaction for 8-24 hours, and then adding an inorganic anti-ultraviolet finishing agent to prepare the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
In some preferred embodiments, the step (3) comprises: and (3) slowly dripping an aqueous solution of an initiator into the mixed reaction system obtained in the step (2) at a constant speed to initiate polymerization, wherein the dripping time is 30-120 min, continuing to perform polymerization reaction for 8-24 h, and adding an inorganic anti-ultraviolet finishing agent after the polymerization reaction is finished to obtain the environment-friendly super-hydrophobic/oleophobic textile finishing agent. In some more specific embodiments, the method for preparing the environmentally friendly superhydrophobic/oleophobic textile finish comprises:
(1) uniformly dispersing the composite emulsifier in deionized water, stirring and heating to 40-60 ℃, wherein the stirring speed is 100-900 r/min, adding an acrylate monomer, a styrene monomer and an anti-ultraviolet polymerizable monomer into a reaction system, and carrying out pre-emulsification reaction for 30-120 min;
(2) then introducing protective gas such as nitrogen and the like, continuously heating to 65-85 ℃, and slowly adding a fluorine-containing monomer;
(3) and then slowly dripping aqueous solution of an initiator into the system at a constant speed to initiate polymerization, wherein the dripping time is 30-120 min, continuing the polymerization reaction for 8-24 h, and adding an inorganic anti-ultraviolet finishing agent after the polymerization is finished to obtain the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
Further, the compound emulsifier comprises an anionic surfactant and a nonionic surfactant; the anionic surfactant includes one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, sodium didodecylphenyl ether disulfonate, sodium dodecyl sulfate, sodium oleate, sodium stearate, sodium abietate, and sodium laurate, but is not limited thereto.
Further, the nonionic surfactant includes any one or a combination of two or more of lauryl alcohol polyoxyethylene ether, secondary alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether and isomeric tridecyl alcohol ether, but is not limited thereto.
Further, the acrylic ester monomer includes any one or a combination of two or more of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and butyl acrylate, but is not limited thereto.
Further, the fluorine-containing monomer includes any one or a combination of two or more of perfluorohexylethyl acrylate and tridecafluorooctyl methacrylate, but is not limited thereto.
Further, the initiator includes any one or a combination of two or more of ammonium persulfate, potassium persulfate, t-butyl peroxide, azobisisobutylamidine hydrochloride, dibenzoyl peroxide, 2' -azobis (2-methylpropionamide) dihydrochloride, but is not limited thereto.
Further, the ultraviolet ray-resistant polymerizable monomer includes any one or a combination of two or more of 2-ethyl-2' -cyano-3-biphenyl acrylate, acrylamide, γ - (methacryloyloxy) propyltrimethoxysilane, acrylate-based benzophenone compounds, 2-hydroxy-4-acryloxybenzophenone, 2,2,6, 6-tetramethylpiperidine acrylate, 2,2,6, 6-tetramethylpiperidine methacrylate, 1,2,2,6, 6-pentamethylpiperidine acrylate, and 1,2,2,6, 6-pentamethylpiperidine methacrylate, and is not limited thereto.
Further, the inorganic ultraviolet-resistant finishing agent comprises TiO2、ZnO、Al2O3Kaolin, talcum powder, carbon black and oxideIron, lead protoxide, pottery clay, CaCO3Any one or a combination of two or more of them, but not limited thereto.
Preferably, the volume ratio of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer, the fluorine-containing monomer and the deionized water is 1: 0.1-5: 0.01-0.1: 0.1-5: 20-200.
Preferably, the mass of the composite emulsifier is 1 wt% -10 wt% of the total mass of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer and the fluorine-containing monomer.
Preferably, the composite emulsifier comprises an anionic surfactant and a nonionic surfactant in a mass ratio of 1: 0.1-10.
Preferably, the mass of the initiator is 0.05 wt% -10 wt% of the total mass of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer and the fluorine-containing monomer.
Preferably, the mass of the inorganic ultraviolet-resistant finishing agent is 0.1 wt% -10 wt% of the total mass of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer and the fluorine-containing monomer.
Preferably, the concentration of the aqueous solution of the initiator is 0.1 wt% to 10 wt%.
In another aspect of the embodiments of the present invention, there is also provided an environmentally friendly superhydrophobic/oleophobic textile finish made by the foregoing method. Further, the environment-friendly super-hydrophobic/oleophobic textile finishing agent is an emulsion system, wherein the particle size of emulsion liquid drops is 5-200 nm.
In yet another aspect, the embodiments of the present invention further provide a use of the environmentally friendly superhydrophobic/oleophobic textile finish in the field of fabric finishing. Preferably, the fabric comprises cotton, hemp, silk, wool, velvet, fiber or leather textile; preferably, the finished fabric has at least superhydrophobic, oleophobic and stain resistant properties.
Yet another aspect of an embodiment of the present invention also provides a textile finishing method, including: the environment-friendly super-hydrophobic/oleophobic textile finishing agent is applied to the fabric at least in a spraying, dipping or brushing mode, and then the fabric is pre-dried and baked, preferably at 70-90 ℃ for 5-30 min, and at 120-150 ℃ for 20-60 min.
Further, the fabric comprises cotton, hemp, silk, wool, velvet, fiber or leather textiles.
The environment-friendly super-hydrophobic/oleophobic textile finishing agent has the characteristics of good waterproof and oilproof effects, environment friendliness and the like, and can endow textiles with super-hydrophobic, oleophobic, antifouling, high-efficiency and durable ultraviolet resistance.
The preparation method of the environment-friendly super-hydrophobic/oleophobic textile finishing agent has the advantages of simple and feasible preparation process, convenience for large-scale production and the like.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1: uniformly dispersing a composite emulsifier (containing 0.35g of sodium dodecyl benzene sulfonate and 0.65g of polyoxyethylene lauryl ether) in 200mL of deionized water, stirring and heating to 60 ℃, wherein the stirring speed is 300r/min, adding 5mL of methyl methacrylate monomer, 5mL of styrene monomer and 0.5mL of 2-ethyl-2' -cyano-3-biphenyl acrylate into a reaction system, and carrying out pre-emulsification reaction for 60 min; then introducing nitrogen, continuing to heat to 70 ℃, and slowly adding 15mL of perfluorohexyl ethyl acrylate; dissolving 0.2g of ammonium persulfate in 25mL of deionized water, then slowly dropwise adding an aqueous solution of ammonium persulfate into the system at a constant speed to initiate polymerization, wherein the dropwise adding time is 60min, continuing the polymerization reaction for 10h, and adding 0.25g of TiO after the polymerization is finished2And obtaining the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
Example 2: uniformly dispersing a composite emulsifier (containing 0.65g of sodium dodecyl sulfate and 0.35g of secondary alcohol polyoxyethylene ether) in 300mL of deionized water, stirring and heating to 40 ℃, wherein the stirring speed is 200r/min, adding 5mL of butyl acrylate monomer, 5mL of styrene monomer and 0.25mL of acrylamide into a reaction system, and carrying out pre-emulsification reaction for 30 min; then introducing nitrogen, continuing to heat to 65 ℃, and slowly adding 10mL of tridecafluorooctyl methacrylate; dissolving 0.1g of potassium persulfate in 30mL of deionized water, then slowly dropwise adding an aqueous solution of potassium persulfate into the system at a constant speed to initiate polymerization, wherein the dropwise adding time is 90min, continuing the polymerization reaction for 8h, and adding 0.1g of ZnO after the polymerization is finished to obtain the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
Example 3: uniformly dispersing a composite emulsifier (containing 0.5g of sodium didodecylphenyl ether disulfonate and 0.5g of alkylphenol polyoxyethylene) in 100mL of deionized water, stirring and heating to 50 ℃, wherein the stirring speed is 400r/min, adding 5mL of methyl acrylate monomer, 5mL of styrene monomer and 0.2mL of gamma- (methacryloyloxy) propyl trimethoxy silane into a reaction system, and carrying out pre-emulsification reaction for 90 min; then introducing nitrogen, continuing to heat to 75 ℃, and slowly adding 5mL of perfluorohexyl ethyl acrylate; dissolving 0.1g of tert-butyl peroxide in 10mL of deionized water, then slowly dropwise adding an aqueous solution of tert-butyl peroxide into the system at a constant speed to initiate polymerization, wherein the dropwise adding time is 30min, continuing the polymerization reaction for 12h, and adding 0.15g of Al after the polymerization is finished2O3And obtaining the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
Example 4: uniformly dispersing a composite emulsifier (containing 0.2g of lauryl sodium sulfate and 0.6g of fatty acid methyl ester polyoxyethylene ether) in 250mL of deionized water, stirring and heating to 55 ℃, wherein the stirring speed is 500r/min, adding 10mL of ethyl acrylate monomer, 5mL of styrene monomer and 0.1mL of 2-hydroxy-4-propenyloxybenzophenone into a reaction system, and carrying out pre-emulsification reaction for 120 min; then introducing nitrogen, continuing to heat to 80 ℃, and slowly adding 5mL of tridecafluorooctyl methacrylate; dissolving 0.2g of azobisisobutylamidine hydrochloride in 40mL of deionized water, then slowly dropwise adding an aqueous solution of the azobisisobutylamidine hydrochloride into the system at a constant speed to initiate polymerization, wherein the dropwise adding time is 120min, continuing the polymerization reaction for 15h, and adding 1g of kaolin after the polymerization is finished to obtain the environment-friendly superhydrophobic/oleophobic textile finishing agent.
Example 5: uniformly dispersing a composite emulsifier (containing 0.6g of sodium abietate and 0.2g of isomeric tridecanol ether) in 200mL of deionized water, stirring and heating to 60 ℃, wherein the stirring speed is 900r/min, adding 5mL of ethyl methacrylate monomer, 10mL of styrene monomer and 0.5mL of acrylic acid-2, 2,6, 6-tetramethyl piperidine ester into a reaction system, and carrying out pre-emulsification reaction for 70 min; then introducing nitrogen, continuing to heat to 85 ℃, and slowly adding 10mL of perfluorohexyl ethyl acrylate; dissolving 0.5g of dibenzoyl peroxide in 50mL of deionized water, then slowly dropwise adding an aqueous solution of dibenzoyl peroxide into the system at a constant speed to initiate polymerization, wherein the dropwise adding time is 60min, continuing the polymerization reaction for 10h, and adding 0.15g of talcum powder after the polymerization is finished to obtain the environment-friendly super-hydrophobic/oleophobic textile finishing agent.
The environment-friendly super-hydrophobic/oleophobic textile finishing agent prepared in the embodiment 1-5 (hereinafter referred to as the product of the invention) is sprayed, dipped or brushed on the textile, and then the textile is pre-baked and baked for a period of time. Through test detection, the water contact angles of the product after finishing the fabric are all larger than 150 degrees, the vegetable oil contact angles are all larger than 130 degrees, the product has excellent hydrophobic, oleophobic and self-cleaning performances, and the finished fabric still has good hydrophobic and oleophobic performances after 30 times of conventional washing or 1000 times of rubbing, and also has excellent washing fastness and wear resistance. Furthermore, the product of the invention can greatly improve the ultraviolet resistance of the fabric and enhance the breaking strength of the fabric while endowing the fabric with excellent hydrophobic and oleophobic properties, and the fabric after finishing has soft hand feeling and good air permeability which are equal to those of a fibril material, and the wearability of the fabric is not influenced at all. The environment-friendly super-hydrophobic/oleophobic textile finishing agent product is suitable for various textiles such as cotton, hemp, silk, wool, velvet, fiber, leather and the like.
Referring to fig. 1 a-1 b, the contact angles (160 ° and 130 °, respectively) of water and n-dodecane on a finished textile of a typical environmentally friendly superhydrophobic/oleophobic textile finish of the invention are shown. FIG. 2 shows the wettability of 10 μ L to 30 μ L of water droplets on a textile finished with a typical environmentally friendly superhydrophobic/oleophobic textile finish of the invention. FIG. 3 shows the wettability of water, olive oil, n-hexadecane, n-dodecane on a textile finished with a typical environmentally friendly superhydrophobic/oleophobic textile finish of the invention.
Although the various reaction participants and process conditions adopted in the foregoing embodiments are typical examples, a great deal of experiments by the inventors of the present invention prove that the reaction participants and other process conditions listed in the present specification are all applicable and all the claimed technical effects of the present invention can be achieved, for example, a uniform and dense film can be formed on the surface of the fabric fiber treated by the environment-friendly superhydrophobic/oleophobic textile finishing agent provided by the present invention, and the film not only provides the fabric with excellent superhydrophobic performance, but also significantly increases the breaking strength of the fabric.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A preparation method of an environment-friendly super-hydrophobic/oleophobic textile finishing agent is characterized by comprising the following steps:
(1) uniformly dispersing the composite emulsifier in deionized water, continuously stirring at the speed of 100-900 r/min, heating to 40-60 ℃, adding an acrylate monomer, a styrene monomer and an anti-ultraviolet polymerizable monomer, and carrying out pre-emulsification reaction for 30-120 min;
(2) continuously heating the pre-emulsified reaction mixture obtained in the step (1) to 65-85 ℃ under a protective atmosphere, and slowly adding a fluorine-containing monomer;
(3) slowly dripping aqueous solution of an initiator into the mixed reaction system obtained in the step (2) at a constant speed to initiate polymerization, wherein the dripping time is 30-120 min, continuing to perform polymerization reaction for 8-24 h, and adding an inorganic anti-ultraviolet finishing agent after the polymerization reaction is finished to obtain an environment-friendly super-hydrophobic/oleophobic textile finishing agent;
wherein the volume ratio of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer, the fluorine-containing monomer and the deionized water is 1: 0.1-5: 0.01-0.1: 0.1-5: 20 to 200 parts of a first resin composition, the composite emulsifier comprises the following components in a mass ratio of 1:0.1 to 10 parts of an anionic surfactant and a nonionic surfactant, the composite emulsifier accounts for 1-10 wt% of the total mass of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer and the fluorine-containing monomer, the mass of the initiator is 0.05 to 10 percent of the total mass of the acrylate monomer, the styrene monomer, the ultraviolet-resistant polymerizable monomer and the fluorine-containing monomer, the inorganic anti-ultraviolet finishing agent accounts for 0.1-10 wt% of the total mass of the acrylate monomer, the styrene monomer, the anti-ultraviolet polymerizable monomer and the fluorine-containing monomer;
the acrylate monomer comprises any one or more than two of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and butyl acrylate, the ultraviolet-resistant polymerizable monomer comprises any one or more than two of 2-ethyl-2' -cyano-3-biphenyl acrylate, acrylamide, gamma- (methacryloyloxy) propyl trimethoxy silane, acrylate benzophenone compound, 2-hydroxy-4-acryloxy benzophenone, 2,2,6, 6-tetramethylpiperidine acrylate, 2,2,6, 6-tetramethylpiperidine methacrylate, 1,2,2,6, 6-pentamethylpiperidine acrylate and 1,2,2,6, 6-pentamethylpiperidine methacrylate, the fluorine-containing monomer comprises one or a composition of more than two of perfluorohexyl ethyl acrylate and tridecafluorooctyl methacrylate.
2. The method of claim 1, wherein: the anionic surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium didodecyl phenyl ether disulfonate, sodium dodecyl sulfate, sodium oleate, sodium stearate, sodium abietate and sodium laurate.
3. The method of claim 1, wherein: the nonionic surfactant comprises one or a composition of more than two of lauryl alcohol polyoxyethylene ether, secondary alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether and isomeric tridecanol ether.
4. The method of claim 1, wherein: the initiator comprises any one or a composition of more than two of ammonium persulfate, potassium persulfate, tert-butyl peroxide, azo diisobutyl amidine hydrochloride, dibenzoyl peroxide and 2,2' -azo bis (2-methylpropionamide) dihydrochloride.
5. The method of claim 1, wherein: the inorganic ultraviolet-resistant finishing agent comprises TiO2、ZnO、Al2O3Kaolin, talcum powder, carbon black, iron oxide, lead protoxide, pottery clay and CaCO3Any one or a combination of two or more of them.
6. The method of claim 1, wherein: the concentration of the initiator aqueous solution is 0.1 wt% -10 wt%.
7. The environment-friendly super-hydrophobic/oleophobic textile finishing agent prepared by the method of any one of claims 1-6, which is an emulsion system in which the emulsion droplets have a particle size of 5-200 nm.
8. Use of the environmentally friendly superhydrophobic/oleophobic textile finish according to claim 7 in the field of textile finishing, said textile comprising cotton, hemp, silk, wool, down, fiber or leather-like textiles, and said finished textile having at least superhydrophobic, oleophobic and antifouling properties.
9. A method of finishing a fabric, comprising: the environment-friendly super-hydrophobic/oleophobic textile finishing agent of claim 7 is applied to a fabric at least by spraying, dipping or brushing, and then the fabric is pre-dried at 70-90 ℃ for 5-30 min and is baked at 120-150 ℃ for 20-60 min.
10. A method of finishing a fabric according to claim 9, characterized in that: the fabric comprises cotton, hemp, silk, wool, velvet, fiber or leather textiles.
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