CN109988264B - Fluorine-free waterproof agent and preparation method and application thereof - Google Patents
Fluorine-free waterproof agent and preparation method and application thereof Download PDFInfo
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a fluorine-free waterproof agent and a preparation method and application thereof. The fluorine-free waterproof agent comprises the following components in percentage by mass: 10-20% of fluorine-free copolymer, 1-5% of surfactant, 2-10% of cosolvent, 5-15% of paraffin and the balance of water. The comonomers of the fluorine-free copolymer include: acrylate monomer a, carbon-carbon double bond-containing end-capped isocyanate monomer b, vinyl silane coupling agent monomer c and other functional monomers d. The fluorine-free waterproof agent has an excellent waterproof effect, can endow the fabric with good hand feeling, and improves the washing resistance of the fabric.
Description
Technical Field
The invention relates to the field of textile auxiliaries, and particularly relates to a fluorine-free waterproof agent for textiles and a preparation method and application thereof.
Background
The water-repellent properties of textiles are usually obtained by finishing with water-repellent agents. The textile water repellent finishing is to reduce the surface energy of the textile by a physical or chemical method, thereby achieving the purpose that the surface of the textile is not easy to be wetted by water molecules. The chemical method usually adopts a water repellent finishing agent, wherein the fluorocarbon has the best water repellent effect. However, the fluorocarbon water repellent finishing agent monomers perfluorooctanoic acid (PFOA) and perfluorooctane sulfonyl compounds (PFOS) are potential carcinogenic substances, and toxic fluoride is released during and after finishing, thus harming human bodies and environment. On 27.6.2008, the european union formally implemented instructions to limit the use of perfluorooctanesulfonyl compounds (PFOS). The instruction will affect the export of textiles, leather, paper, packaging, printing and dyeing auxiliaries, cosmetics, etc. in our country. Therefore, finding a substitute of a fluorine-containing finishing agent and adopting a new finishing technology are hot research hotspots of water repellent finishing, and adopting a fluorine-free waterproof agent is a development trend.
Chinese patent CN102333915B discloses a water repellent comprising an acrylate based copolymer, a paraffin wax and a dispersant. This patent uses paraffin wax having a melting point of less than 80 degrees as a key component, so that the water-repellent agent is limited in water repellency and washing resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fluorine-free waterproof agent and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides a fluorine-free waterproof agent, which comprises the following components in percentage by mass: 10-20% of fluorine-free copolymer, 1-5% of surfactant, 2-10% of cosolvent, 5-15% of paraffin and the balance of water; the comonomers of the fluorine-free copolymer include: acrylate monomer a, carbon-carbon double bond-containing end-capped isocyanate monomer b, vinyl silane coupling agent monomer c and other functional monomers d.
Further, the carbon-carbon double bond-containing blocked isocyanate monomer b is obtained by reacting a blocking agent with alpha olefinic bond and isocyanate.
Further, the blocking agent with alpha-olefinic bond is hydroxyl-terminated acrylate with alpha-olefinic bond.
Further, the hydroxyl-terminated acrylate having an alpha-olefinic bond is selected from one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
Further, the isocyanate is selected from a mono-isocyanate, a di-isocyanate or a polyisocyanate.
Specifically, the isocyanate is selected from one or a combination of at least two of isocyano ethyl methacrylate, isocyano ethyl acrylate, toluene diisocyanate, diphenylmethane-4, 4-diisocyanate, hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, cyclohexyl diisocyanate ester, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and isophorone diisocyanate.
Further, the structure of the vinyl silane coupling agent monomer c is shown as the formula (I): CH (CH)2＝CH(CH2)nSiX3(I) Wherein n is 1-5, and X is selected from chlorine, methoxy, ethoxy, methoxyethoxy, acetoxy or tert-butoxy.
Further, the vinyl silane coupling agent monomer c is selected from one or a combination of at least two of vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl tri-tert-butoxy silane and vinyl triacetoxy silane.
Further, the other functional monomer d is selected from one or a combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, vinyl chloride, polycaprolactone of hydroxyethyl acrylate and polycaprolactone of hydroxyethyl methacrylate.
Further, the fluorine-free copolymer has a content of a constituent unit based on the monomer a of 30 to 70% by mass, a content of a constituent unit based on the monomer b of 10 to 50% by mass, a content of a constituent unit based on the monomer c of 1 to 50% by mass, and a content of a constituent unit based on the monomer d of 1 to 30% by mass.
On the other hand, the invention also provides a preparation method of the fluorine-free waterproof agent, which comprises the following steps: and adding the monomer a, the monomer b, the monomer c, the monomer d, a surfactant, a cosolvent and paraffin into deionized water in the presence of a polymerization initiator, mixing, and emulsifying to obtain the fluorine-free waterproof agent.
Furthermore, the invention also provides a textile processed by the fluorine-free waterproof agent.
Detailed description of the invention
1. Fluorine-free water-proofing agent
(1) Fluorine-free copolymer
In the fluorine-free water repellent, the mass percent of the fluorine-free copolymer is 10-20%, preferably 15-20%.
(i) Acrylate monomer a
The acrylate monomer a is a fluorine-free acrylate compound.
Preferably, the acrylic monomer a is an acrylate or methacrylate containing 1 to 22 carbon atoms.
Specifically, non-limiting examples of the acrylate monomer a include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 3-ethoxypropyl acrylate, methoxybutyl acrylate, 2-ethylbutyl acrylate, 1, 3-dimethylbutyl acrylate, 2-methylpentyl acrylate, and the like.
In the fluorine-free copolymer, the constituent unit based on the monomer a accounts for 30 to 70% by mass, preferably 30 to 60% by mass, more preferably 35 to 50% by mass.
(ii) Carbon-carbon double bond end-capped isocyanate monomer b
The double-carbon-bond-containing blocked isocyanate monomer b is obtained by reacting a blocking agent with alpha olefinic bond and isocyanate.
The blocking agent with alpha-olefinic bond is hydroxyl-terminated acrylate with alpha-olefinic bond.
Specifically, non-limiting examples of the hydroxyl-terminated acrylate having an alpha olefinic bond include: hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and the like.
The isocyanate is selected from a monoisocyanate, a diisocyanate or a polyisocyanate.
The polyisocyanate is a substance having three or more isocyanate groups.
Specifically, non-limiting examples of the isocyanate include: isocyanoethyl methacrylate (IEMA), isocyanoethyl acrylate, Toluene Diisocyanate (TDI), diphenylmethane-4, 4-diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), 1, 6-Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), cyclohexyl diisocyanate ester (HTDI), dicyclohexylmethane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), and the like.
In some embodiments, the double carbon-carbon bond-containing blocked isocyanate monomer b is selected from one or a combination of at least two of hydroxyethyl methacrylate-blocked isocyanoethyl methacrylate, hydroxyethyl acrylate-blocked isocyanoethyl methacrylate, hydroxypropyl acrylate-blocked isocyanoethyl acrylate monomer, hydroxyethyl methacrylate-blocked hexamethylene diisocyanate, hydroxypropyl methacrylate-blocked toluene diisocyanate, hydroxypropyl methacrylate-blocked tetramethylxylylene diisocyanate, hydroxyethyl acrylate-blocked tetramethylxylylene diisocyanate, hydroxypropyl methacrylate-blocked tetramethylxylylene diisocyanate monomer, hydroxypropyl acrylate-blocked hexamethylene diisocyanate.
In the fluorine-free copolymer, the constituent unit based on the monomer b accounts for 10 to 50% by mass, preferably 15 to 50% by mass, more preferably 15 to 30% by mass.
(iii) Vinyl silane coupling agent monomer c
The structure of the vinyl silane coupling agent monomer c is shown as the formula (I): CH (CH)2＝CH(CH2)nSiX3(I) Wherein n is 1-5, and X is selected from chlorine, methoxy, ethoxy, methoxyethoxy, acetoxy or tert-butoxy.
Specifically, non-limiting examples of the vinyl silane coupling agent monomer c include: vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, vinyltri-t-butoxysilane, vinyltriacetoxysilane, and the like.
In some embodiments, the vinyl silane coupling agent monomer c is selected from one or a combination of at least two of vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (. beta. -methoxyethoxy) silane, vinyl tri-t-butoxysilane, vinyl triacetoxysilane.
In the fluorine-free copolymer, the constituent unit based on the monomer c accounts for 1 to 50% by mass, preferably 10 to 30% by mass, more preferably 15 to 30% by mass.
(iiii) other functional monomers d
The other functional monomer d is a crosslinkable fluorine-free monomer other than the monomer a, the monomer b and the monomer c.
In particular, non-limiting examples of the other functional monomer d include: hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, vinyl chloride, polycaprolactone of hydroxyethyl acrylate, polycaprolactone of hydroxyethyl methacrylate, and the like.
In some embodiments, the other functional monomer d is selected from two or three of hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, and vinyl chloride.
In the fluorine-free copolymer, the mass percentage of the constituent unit based on the monomer d is 1 to 30%.
From the viewpoint of abrasion resistance, the ratio of the constituent unit based on the monomer d is preferably 1 to 20% by mass, more preferably 10 to 20% by mass.
(2) Surface active agent
The surfactant may, for example, be a hydrocarbon surfactant, and each may, for example, be a nonionic surfactant, a cationic surfactant or an amphoteric surfactant.
The surfactant is preferably a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone, and more preferably a combination of a nonionic surfactant and a cationic surfactant, from the viewpoint of dispersion stability.
The ratio of the nonionic surfactant to the cationic surfactant expressed as nonionic surfactant/cationic surfactant is preferably 97:3 to 4:60 in terms of mass ratio.
The specific combination of the nonionic surfactant and the cationic surfactant may be 1 to 5% by mass based on the mass of the fluorine-free water repellent emulsion, and the adverse effect on the water repellency of the article can be reduced.
Non-limiting examples of nonionic surfactants include: sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, and the like.
Examples of the nonionic surfactant include an epoxide adduct of a linear and/or branched saturated and/or unsaturated aliphatic group, a polyalkylene glycol ester of a linear and/or branched saturated and/or unsaturated fatty acid, a Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (a random copolymer or a block copolymer), and an epoxide adduct of acetylene glycol. Among them, it is preferable that the structures of the epoxide addition moiety and the polyalkylene glycol moiety are Polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP copolymer (random copolymer or block copolymer).
Cationic surfactants are quaternary ammonium salts, non-limiting examples of which include: dodecyl trimethyl ammonium acetate, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, docosyl trimethyl ammonium chloride, (dodecyl methyl) trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, benzyl tetradecyl dimethyl ammonium chloride, benzyl octadecyl dimethyl ammonium chloride, and the like.
Non-limiting examples of amphoteric surfactants include: alkyl betaines, alkyl thiobetaines, fatty acid amide propyl betaines, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaines, alkyl (or dialkyl) diethylene triamine acetic acids, alkyl amide oxides, and the like.
The dosage of the surfactant accounts for 1 to 5 percent of the mass of the whole fluorine-free waterproof agent, and preferably 2 to 5 percent.
(3) Cosolvent
The cosolvent is preferably a water-soluble organic solvent, such as ketones, alcohols, ethers, and the like.
In particular, non-limiting examples of the co-solvent include: acetone, methyl ethyl ketone, ethanol, propanol, isopropanol, n-butanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 2-t-butoxyethanol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 800, and the like.
The using amount of the cosolvent accounts for 2-10% of the mass of the whole fluorine-free waterproof agent, and preferably 6-8%.
(4) Paraffin wax
The paraffin wax is preferably a paraffin wax having a melting range of 35 to 105 ℃, more preferably a paraffin wax having a melting range of 45 to 85 ℃, and particularly preferably a paraffin wax having a melting range of 55 to 65 ℃.
The dosage of the paraffin accounts for 5-15 percent of the total mass of the fluorine-free waterproof agent, preferably 10-15 percent.
2. Preparation of fluoride-free water-proofing agent
The preparation method of the fluorine-free waterproof agent comprises the following steps:
and adding the monomer a, the monomer b, the monomer c, the monomer d, a surfactant, a cosolvent and paraffin into deionized water in the presence of a polymerization initiator, mixing, and emulsifying to obtain the fluorine-free waterproof agent.
The initiator is an oil-soluble polymerization initiator or a water-soluble polymerization initiator.
In some embodiments, the initiator is selected from 2, 2-azobisisobutyronitrile, benzamide peroxide, di-t-butyl peroxide, ammonium persulfate, potassium persulfate, or azobisisobutyramidine hydrochloride.
The average molecular weight of the fluorine-free polymer of the present invention is 10000-250000. The water and oil repellent compositions containing the fluorine-free polymer obtained by emulsion polymerization and having an average molecular weight in the range of 10000-250000 all showed very excellent water and oil repellent properties.
In order to obtain a polymer dispersed in water excellent in storage stability, it is desirable that monomers are finely emulsified in water by using an emulsifier capable of applying strong shear energy (for example, a high-pressure homogenizer and an ultrasonic homogenizer), followed by polymerization using a water-soluble polymerization initiator.
3. Fabric aftertreatment
The fluorine-free waterproof agent can be applied to the surfaces of various fiber surface base materials, including the surfaces of various cotton fibers, nylon, terylene and non-woven fabrics.
The fabric post-treatment may be carried out using conventional methods known in the art.
In some embodiments, the method of post-treatment of the fabric is as follows:
diluting the prepared fluorine-free waterproof agent to 30g/L by using deionized water, soaking cotton cloth in the diluted solution for 15 minutes, rolling the cotton cloth once by using a padder, wherein the liquid carrying rate is 100%, and drying the cotton cloth at 170 ℃ for 5 minutes respectively after the process of one-soaking-one-rolling.
The invention has the beneficial effects that:
(1) the fluorine-free polymer uses a double-bond-containing blocked isocyanate monomer, can be polymerized with fluorine-free acrylate to form a copolymer containing blocked isocyanate groups, can be crosslinked with fiber fabrics to form stable chemical bonds, and is favorable for improving the washing resistance of the fabrics;
(2) the fluorine-free polymer uses the vinyl silane coupling agent, can be polymerized with fluorine-free acrylate to form a material containing silicon-oxygen bonds and silicon-carbon bonds, can reduce the hardness of the fabric, and enables the fabric to be softer;
(3) the fluorine-free waterproof agent provided by the invention is environment-friendly and has good industrial prospect.
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that, for those skilled in the art, on the basis of the inventive concept herein, several variations and modifications are possible which fall within the scope of the invention, and for further description of the invention, reference is made to the following description of specific embodiments.
Example 1
5g of methyl methacrylate, 2g of hydroxyethyl methacrylate-terminated hexamethylene diisocyanate monomer, 2g of vinyl trichlorosilane, 1g of glycidyl methacrylate, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide are added into 40g of deionized water and emulsified at a high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 0.5g of glycidyl acrylate was added while passing nitrogen through for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 2
Taking 5g of octadecyl methacrylate, 2g of hydroxypropyl methacrylate blocked toluene diisocyanate monomer, 2g of vinyl triethoxysilane, 1g of glycidyl methacrylate, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the materials into 40g of deionized water, and emulsifying at high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 0.5g of glycidyl acrylate was added while passing nitrogen through for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 3
5g of butyl methacrylate, 2g of hydroxypropyl methacrylate-terminated tetramethylxylylene diisocyanate monomer, 2g of vinyltris (. beta. -methoxyethoxy) silane, 1g of glycidyl methacrylate, 10g of paraffin wax, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid, and 1g of cetyltrimethylammonium bromide were taken, added to 40g of deionized water, and emulsified at high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 0.5g of glycidyl acrylate was added while passing nitrogen through for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 4
Taking 5g of lauryl acrylate, 2g of hydroxypropyl methacrylate end-capped tetramethylxylylene diisocyanate monomer, 1g of glycidyl methacrylate, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the mixture into 40g of deionized water, and emulsifying at high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 0.5g of hydroxyethyl methacrylate, 2g of vinyltris (. beta. -methoxyethoxy) silane and 2g of hydroxypropyl methacrylate-capped tetramethylxylylene diisocyanate monomer were added while passing nitrogen gas for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 5
Taking 5g of lauryl methacrylate, 2g of hydroxyethyl acrylate-terminated tetramethylxylylene diisocyanate monomer, 1g of glycidyl methacrylate, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the materials into 40g of deionized water, and emulsifying at high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 0.5g of hydroxyethyl methacrylate, 2g of vinyltris (. beta. -methoxyethoxy) silane and 2g of hydroxypropyl methacrylate-capped tetramethylxylylene diisocyanate monomer were added while passing nitrogen gas for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 6
Taking 5g of behenyl acrylate, 2g of hydroxypropyl acrylate-terminated isocyano ethyl methacrylate monomer, 1g of 3-chloro-2-hydroxypropyl methacrylate, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the materials into 40g of deionized water, and carrying out high-speed emulsification for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ and 2g of vinyltris (. beta. -methoxyethoxy) silane and 2g of hydroxypropyl methacrylate-terminated tetramethylxylylene diisocyanate monomer were added while introducing nitrogen gas for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 7
Taking 5g of behenyl methacrylate, 2g of hydroxypropyl acrylate-terminated isocyanoethyl acrylate monomer, 1g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyl tri-tert-butoxysilane, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the materials into 40g of deionized water, and emulsifying at a high speed for 30 minutes to obtain a pre-emulsion. The pre-emulsion temperature was adjusted to 62 ℃ while nitrogen was purged for 30 minutes. 0.1g of azobisisobutyramidine hydrochloride and 0.5g of vinyl chloride were added, and the reaction was carried out for 8 hours while maintaining the temperature. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 8
Taking 5g of octadecyl acrylate, 2g of hydroxypropyl acrylate-terminated hexamethylene diisocyanate monomer, 1g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyl tri-tert-butoxy silane, 10g of paraffin, 1g of sorbitan monolaurate, 5g of dipropylene glycol, 0.1g of acetic acid and 1g of hexadecyl trimethyl ammonium bromide, adding the mixture into 40g of deionized water, and emulsifying at a high speed for 30 minutes to obtain a pre-emulsion. Adding 2g of vinyltrimethoxysilane, stirring, adjusting the temperature of the pre-emulsion to 62 ℃, introducing nitrogen for 30 minutes, adding 0.1g of azodiisobutyramium hydrochloride and 0.5g of vinyl chloride, and keeping the temperature to react for 8 hours. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Example 9 Performance and applications
1. Performance test of fluorine-free waterproofing agent
The fluorine-free water repellent obtained in examples 1 to 8 was subjected to tests for molecular weight, average particle diameter, mechanical stability and storage stability, and the test results are shown in Table 1.
Mechanical stability: the mechanical stability is that a fluoride-free water-proofing agent is added into an l0mL centrifugal tube, the mixture is centrifuged for 30 minutes at 3000r/min in a centrifuge, and the existence of unstable phenomena such as floating, layering, precipitation and the like of the fluoride-free water-proofing agent is observed.
Storage stability: the aqueous dispersion was stored at 40 ℃ for 1 month, and the occurrence of sedimentation was observed.
O: no generation of agglomerates
And (delta): little generation of aggregates
X: generate a lot of aggregates
TABLE 1 Performance test results for fluorine-free water repellent
As can be seen from the test data in Table 1, the fluorine-free waterproofing agent prepared by the present invention has good mechanical stability and storage stability.
2. Fabric treatment and performance
The textile finishing process comprises the following steps: diluting the fluorine-free waterproof agent obtained in the examples 1-8 to a concentration of 30g/L with deionized water, soaking cotton cloth in the diluted solution for 15 minutes, rolling the cotton cloth once with a padder at a liquid carrying rate of 100%, and drying the cotton cloth at 170 ℃ for 5 minutes after a one-dip one-roll process to obtain the cotton cloth treated with the fluorine-free waterproof agent.
The following performance tests were carried out on the cotton cloth treated with the fluorine-free water repellent, and the test results are shown in Table 4.
(1) Water resistance testing method
Open spray water testing was performed according to AATCC-22. The spray resistance is expressed in water resistance rating. The suffix "+" attached to the data means that the performance is slightly better than the performance of the grade of the numerical characterization, and the suffix "-" means that the performance is slightly inferior to the performance of the grade of the numerical characterization. The evaluation criteria are shown in Table 2.
Table 2 description of water resistance rating
| Water resistance rating | Evaluation criteria |
| Level 1 | The drenched surface is totally wetted |
| Stage 2 | The surface of the drenched liquid is half wet |
| Grade 3 | The drenched surface is only discontinuously wetted in small areas |
| 4 stage | The surface of the drenched product is not wetted but is stained with water drops |
| Grade 5 | The surface of the shower is not wetted and is not stained with water drops |
(2) Method for testing washing fastness
Washing with 2g/L detergent at a bath ratio of 1:30 in a household washing machine at 40 deg.C for L0 min, discharging the washing solution, washing with clear water at 40 deg.C for 5 min, and dewatering. If washing is required multiple times, the above operation is repeated. And finally, naturally airing or baking at 80 ℃ for 30 minutes. The water and oil repellency was then tested. The test results are shown in table 4.
(3) Evaluation of hand feeling
The treated cotton cloth was evaluated for hand feeling according to the organoleptic evaluation method, and the evaluation criteria are shown in table 3.
TABLE 3 hand feeling test Standard
TABLE 4 Performance test results of fabrics treated with fluorine-free water repellent
| Numbering | Water-proof property before washing | Water-proof performance after 10 times washing | Waterproof performance after 20 times of washing | Grade of hand feel |
| Example 1 | 5 | 5- | 4 | 4 |
| Example 2 | 5 | 5- | 4 | 4 |
| Example 3 | 5 | 5 | 4 | 4 |
| Example 4 | 5 | 5- | 4 | 3 |
| Example 5 | 5 | 4 | 4 | 4 |
| Example 6 | 5 | 5- | 3 | 3 |
| Example 7 | 4+ | 4 | 3 | 4 |
| Example 8 | 5 | 5- | 4 | 3 |
As can be seen from the test data in Table 4, the cotton cloth treated by the fluorine-free waterproof agent prepared by the invention has the optimal waterproof grade of 5, excellent washable effect, waterproof grade of more than 4 after 20 times of washing and good hand feeling.
Claims (9)
1. The fluorine-free waterproof agent is characterized by comprising the following components in percentage by mass: 10-20% of fluorine-free copolymer, 1-5% of surfactant, 2-10% of cosolvent, 5-15% of paraffin and the balance of water; the comonomers of the fluorine-free copolymer include: acrylate monomer a, carbon-carbon double bond-containing end-capped isocyanate monomer b, vinyl silane coupling agent monomer c and other functional monomers d; wherein, the other functional monomer d is selected from one or the combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, chloroethylene, polycaprolactone of hydroxyethyl acrylate and polycaprolactone of hydroxyethyl methacrylate.
2. The fluorine-free water repellent agent according to claim 1, wherein the carbon-carbon double bond-containing blocked isocyanate monomer b is obtained by reacting a blocking agent having an alpha-olefin bond with an isocyanate.
3. The fluorine-free water repellent agent according to claim 2, wherein the blocking agent having an alpha-olefin bond is a hydroxyl-terminated acrylate having an alpha-olefin bond.
4. The fluorine-free water repellent agent according to claim 3, wherein the hydroxyl terminated acrylate having an alpha-olefinic bond is one or a combination of at least two selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
5. The fluorine-free water repellent agent according to claim 2, wherein the isocyanate is one selected from the group consisting of isocyanoethyl methacrylate, isocyanoethyl acrylate, toluene diisocyanate, diphenylmethane-4, 4-diisocyanate, hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, or a combination of at least two thereof.
6. The fluorine-free water repellent agent according to claim 1, wherein the vinyl silane coupling agent monomer c has a structure represented by formula (I): CH (CH)2＝CH(CH2)nSiX3(I) Wherein n is 1-5, and X is selected from chlorine, methoxy, ethoxy, methoxyethoxy, acetoxy or tert-butoxy.
7. The fluorine-free water repellent according to claim 6, wherein the vinyl silane coupling agent monomer c is one or a combination of at least two selected from the group consisting of vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (β -methoxyethoxy) silane, vinyl tri-t-butoxysilane, and vinyl triacetoxysilane.
8. The fluorine-free water repellent agent according to claim 1, wherein the fluorine-free copolymer comprises 30 to 70% by mass of a constituent unit based on the monomer a, 10 to 50% by mass of a constituent unit based on the monomer b, 1 to 50% by mass of a constituent unit based on the monomer c, and 1 to 30% by mass of a constituent unit based on the monomer d.
9. A textile article formed from a fluorine-free water repellent agent as claimed in any one of claims 1 to 8.
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| CN110205818A (en) * | 2019-07-10 | 2019-09-06 | 广东湛丰精细化工有限公司 | A kind of fluorine-free ecological waterproofing agent and preparation method thereof of highly crosslinkable energy |
| CN110670359B (en) * | 2019-10-10 | 2022-02-11 | 广东中联邦精细化工有限公司 | Low-temperature type waterproof and oil-proof agent and preparation method thereof |
| CN110734518A (en) * | 2019-11-13 | 2020-01-31 | 福建华峰新材料有限公司 | non-silicon fluorine-free waterproof agent, preparation method thereof and waterproof fabric |
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| CN114933681B (en) * | 2022-05-16 | 2023-11-21 | 杭州美高华颐化工有限公司 | Isocyanate modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
| CN115926625A (en) * | 2022-12-06 | 2023-04-07 | 浙江氟信新材料科技有限公司 | Silicon dioxide fluoride-free waterproof agent and preparation method thereof |
| CN116289217A (en) * | 2023-02-24 | 2023-06-23 | 福可新材料(上海)有限公司 | Fluorine-free waterproof and oil-stain-resistant finishing agent for textiles, and preparation method and application thereof |
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