CN109610177B - Preparation method and application of cationic polyurethane acrylate water repellent agent - Google Patents
Preparation method and application of cationic polyurethane acrylate water repellent agent Download PDFInfo
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- CN109610177B CN109610177B CN201811517772.7A CN201811517772A CN109610177B CN 109610177 B CN109610177 B CN 109610177B CN 201811517772 A CN201811517772 A CN 201811517772A CN 109610177 B CN109610177 B CN 109610177B
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- China
- Prior art keywords
- water repellent
- acrylate
- polyurethane
- fabric
- cationic polyurethane
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 230000002940 repellent Effects 0.000 title claims abstract description 118
- 239000005871 repellent Substances 0.000 title claims abstract description 118
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 239000004814 polyurethane Substances 0.000 title claims abstract description 76
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 76
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 104
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- 238000000034 method Methods 0.000 claims description 39
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
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- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 125000000129 anionic group Chemical group 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- RIDLAELISSCOQY-UHFFFAOYSA-N 2-[ethyl(2-hydroxyethyl)amino]butan-1-ol Chemical compound CCC(CO)N(CC)CCO RIDLAELISSCOQY-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229940043237 diethanolamine Drugs 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- NHGQBOQYUPIPCD-UHFFFAOYSA-N 2-methyl-2-sulfanylbutanoic acid Chemical compound CCC(C)(S)C(O)=O NHGQBOQYUPIPCD-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
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- 238000009962 finishing (textile) Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 2
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
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- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
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Abstract
The invention discloses a preparation method and application of a cationic polyurethane acrylate water repellent agent, and belongs to the field of environment-friendly textiles. In the water repellent prepared by the invention, the polyurethane and the acrylate are connected by chemical bonds, and the polymer has excellent film forming property, flexibility and water repellency; the polymer self-emulsification is realized by introducing the cationizable monomer in the polymerization process, and the problems of water repellency effect reduction, environmental pollution and the like caused by emulsification of a conventional acrylate water repellent agent by an external low-molecular surfactant are avoided; meanwhile, the cationic water repellent avoids the problem that the conventional anionic product cannot be tightly adsorbed with the fabric, and is more beneficial to the uniform film formation of the water repellent on the surface of the fabric; the cationic polyurethane-acrylate water repellent agent prepared by the invention avoids the problems of environmental pollution and bioaccumulation toxicity caused by fluorine-containing water repellent agents, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method and an application method of a cationic polyurethane acrylate water repellent agent, and belongs to the field of textiles.
Background
The development of science and technology promotes the continuous development of textile industry, the demand of consumers for functional textiles is gradually increased, and various functional textiles are widely concerned and developed. Hydrophobic fabrics are used in large quantities due to their excellent water repellency, stain resistance, self-cleaning properties, etc. The water repellent history of the fabric is long, and the commonly used water repellent mainly comprises fluorine-containing compounds, organic silicon compounds and aliphatic hydrocarbon compounds. The fluorine-containing water repellent can endow the fabric with excellent water repellent effect, but the fluorine-containing water repellent has certain bioaccumulation and toxicity in the synthesis and use processes, so the problem of ecological pollution exists; at the same time, it is expensive, resulting in high production and use costs. The silicone-based water repellent can impart better water repellency and softness to the fabric, but has the disadvantage of increasing pilling and seam release properties on the surface of the fabric. The long-chain aliphatic hydrocarbon water repellent agent mainly comprises an acrylate compound, and can endow the fabric with better hydrophobic property. But has the defects of hot sticking, cold brittleness, poor flexibility, solvent intolerance and the like when in use. Polyurethane is a high molecular compound containing a urethane repeating unit on a molecular main chain, has the advantages of low temperature resistance, good flexibility, high bonding strength and the like, but is lack of hydrophobic property. The complementation of the advantages and the disadvantages of the polyurethane and the acrylic ester polymer is beneficial to improving the service performance of the polyacrylate water repellent. Since the 80's of the last century, polyurethanes have been used to modify acrylate products to obtain new water repellents with complementary advantageous properties. The early polyurethane modified acrylate adopts a physical blending method and utilizes a mode of hydrogen bond combination of polyurethane and acrylate to improve the intersolubility of two molecules. But the stability of the polyurethane acrylate water repellent agent is poor due to weak intermolecular force of hydrogen bonds. In order to improve the compatibility of polyurethane and acrylate, chemical crosslinking can be adopted to generate chemical bonding between polyurethane and acrylate so as to improve the stability of the polyurethane and acrylate. The chemical crosslinking mostly adopts carbonyl-containing diacetone acryloyl monomer, and a crosslinking system is obtained by forming crosslinking through dehydration reaction, but because polyurethane and acrylic ester already form relatively stable macromolecules before crosslinking, the crosslinking between the two macromolecules has certain limitation. In the preparation process of the conventional acrylate water repellent agent, an additional low-molecular emulsifier is required. The added emulsifier can affect the water repellency of the water repellent agent, and meanwhile, the emulsifier is dissolved in water and causes harm to the environment, for example, the emulsifier polyoxyethylene octyl phenol ether has poor biodegradability, and the dosage of the emulsifier is limited in some countries and regions. And the added emulsifier causes certain pollution to the environment in the processes of waste liquid discharge, dissolution and washing in the preparation and use processes of the water repellent and the process of fabric treatment and taking. Self-emulsification is achieved by the introduction of hydrophilic moieties, such as groups that can be ionized as anions or cations. The self-emulsifying water repellent can effectively avoid the product defects caused by the addition of an emulsifier. The fabric is electronegative in water, so that an anionic product cannot be tightly adsorbed with the fabric, and the requirement of an anionic water repellent on water quality is high, so that the wider application of the anionic water repellent is limited. At present, most of waterborne polyurethane is anionic polyurethane, and no report of cationic polyurethane-acrylic acid type water repellent agent exists. In addition, the existing conventional non-fluorine water repellent agent also has the problem of poor fastness to washing, and the fastness to washing does not exceed 10 times of washing of a common household washing machine.
Therefore, there is an urgent market demand for a high-performance cationic polyurethane-acrylate water repellent.
Disclosure of Invention
In order to solve the problems and widen the application range of the polyurethane-acrylate water repellent, the invention constructs the polyurethane-acrylate water repellent with a cationic structure. The polyurethane-acrylate water repellent agent, namely the self-emulsifying cationic high-fastness water-based emulsion, is prepared by introducing an unsaturated monomer end-capping monomer, a cationizable monomer and a crosslinkable monomer.
The first object of the invention is to provide a preparation method of a cationic polyurethane-acrylate water repellent, which comprises the following steps:
(1) preparing a polyurethane prepolymer by using polymer polyol, partial alcohol amine and diisocyanate;
(2) the polyurethane prepolymer and the residual alcohol amine and unsaturated alcohol obtain a double-bond end-capped polyurethane molecular main chain;
(3) adding water for self-emulsification to obtain an aqueous cationic polyurethane self-emulsion;
(4) and polymerizing the polyurethane self-emulsion and an acrylate monomer to construct a graft copolymer to obtain the cationic polyurethane-acrylate water repellent.
In one embodiment of the present invention, the molar ratio of the isocyanate group (diisocyanate monomer) to the hydroxyl group (polymer polyol, alcohol amine, unsaturated alcohol) in the step (1) is 1.2 to 2.2.
In one embodiment of the present invention, the polymer polyol accounts for 84 to 90% of the total mass of the hydroxyl group-containing monomers (polymer polyol, alcohol amine, unsaturated alcohol).
In one embodiment of the invention, the alcohol amine is 2-8% of the total mass of the hydroxyl group-containing monomers (polymer polyol, alcohol amine, unsaturated alcohol).
In one embodiment of the present invention, the unsaturated alcohol accounts for 2 to 8% of the total mass of the hydroxyl group-containing monomers (polymer polyol, alcohol amine, unsaturated alcohol).
In one embodiment of the present invention, the self-emulsification in step (3) is obtained by adding a neutralizing agent and water, and stirring according to a solid content of 15% to 40%.
In one embodiment of the invention, in the step (4), the mass ratio of the acrylate monomer to the solid content of the polyurethane self-emulsion is (1-2): 1.
In one embodiment of the present invention, the step (4) of introducing the acrylate monomer by the pre-swelling method is to add the acrylate monomer into the self-emulsifying cationic polyurethane emulsion, fully stir the mixture for a certain time to obtain a swelling solution, and then perform polymerization initiated by the initiator.
In one embodiment of the present invention, the diisocyanate comprises one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
In one embodiment of the invention, the polymer polyol comprises one or more of polyether diol and polyester diol with molecular weight of 200-1000.
In one embodiment of the present invention, the alcohol amine comprises one or more of diethanolamine, triethanolamine, N-methyldiethanolamine, t-butyldiethanolamine, dimethyldiethanolamine, N-ethyldiethanolamine.
In one embodiment of the present invention, the unsaturated alcohol comprises one or both of hydroxyethyl acrylate and hydroxyethyl methacrylate.
In one embodiment of the present invention, the neutralizing agent comprises one or more of glacial acetic acid, hydrochloric acid, lactic acid, and dimethylmercaptopropionic acid.
In one embodiment of the present invention, the acrylate alkane monomer comprises one or more of methyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, and octadecyl methacrylate.
In one embodiment of the present invention, the acrylate functional monomer comprises one or more of glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate.
In one embodiment of the present invention, the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, potassium persulfate, ammonium persulfate, dibenzoyl peroxide.
In an embodiment of the present invention, the preparation method of the aqueous cationic polyurethane self-emulsion in the step (3) specifically includes:
according to the ratio of isocyanic acid radical to hydroxyl group being 1.2-2.2, carrying out vacuum drying and water removal on polymer polyol (accounting for 84% -90% of the total mass of the polymer polyol, the alcohol amine and the unsaturated alcohol), alcohol amine (accounting for 2% -8% of the total mass of the polymer polyol, the alcohol amine and the unsaturated alcohol) and unsaturated alcohol (accounting for 2% -8% of the total mass of the polymer polyol, the alcohol amine and the unsaturated alcohol) at 50-60 ℃; adding polymer polyol into partial alcohol amine, adding dibutyltin dilaurate (accounting for 0.2 percent of the mass of the total monomers participating in the reaction), slowly dropwise adding diisocyanate at the temperature of 50-70 ℃ under the protection of nitrogen, measuring the-NCO value in a reaction system by adopting a di-n-butylamine method, raising the temperature to 60-80 ℃ when the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent) is reached, adding residual alcohol amine, measuring the-NCO content in the reaction system to reach the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), adding unsaturated alcohol until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and realizing the blocking. And (3) reducing the temperature of the reaction system to room temperature, adding a neutralizing agent (the neutralization degree is 100-120%) to adjust the pH (the pH is 6-7), adding deionized water according to 15-40% of the solid content of the product mass, and stirring at a high speed for self-emulsification to obtain the water-based cationic polyurethane self-emulsion.
In an embodiment of the present invention, the method for preparing the cationic polyurethane-acrylate water repellent in step (4) specifically includes:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of the total mass of the acrylate monomer to the solid content of the polyurethane self-emulsion is (1-2): 1) at 40-50 ℃, stirring at the rotating speed of 3000-5000 r/min for 15-20 min, and stirring at the rotating speed of 500-1000 r/min for 12 hours to obtain the acrylate monomer pre-swelling solution of the cationic polyurethane. Adding a certain amount of initiator (the amount of the initiator is 0.1-1% of the amount of the acrylate monomer), and preserving the heat for 2-3 h at 70-80 ℃ under the protection of nitrogen atmosphere. And naturally cooling to 30-40 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent agent.
The second purpose of the invention is to provide a cationic polyurethane-acrylate water repellent prepared by the method.
The third purpose of the invention is to provide a cationic polyurethane-acrylate water repellent agent, the structure of which comprises the structure shown in formula (I):
Aa-Bb-C-Dd-E-Dm-C-Bn-Ai
formula (1)
Wherein a, B, D, m, n and i are natural numbers of 1-100, the chemical structural general formula of A is (2), the chemical structural general formula of B is (3), C is an alkyl part of unsaturated alcohol, the chemical structural general formula of D is (4), and the chemical structural general formula of E is (5); B. c, D, E is not fixed;
wherein R is1Is a carbon chain with the number of carbon atoms of 1-18; r2Is H or-CH3；R3Is H or-CH3；R4Is epoxypropyl ester or hydroxyethyl ester; wherein R is5Is a non-isocyanato group of a diisocyanate monomer; r6Is a non-hydroxyl group of a polyol organic compound; wherein R is7，R8，R9Is an alkane group.
The fourth purpose of the invention is to provide a method for hydrophobic treatment of fabric, which comprises the steps of dipping the fabric into a treatment solution for treatment, and then rolling and baking the fabric; the treatment comprises the cationic polyurethane-acrylate water repellent agent
The fifth purpose of the invention is to provide a hydrophobic fabric, wherein the fabric contains the cationic polyurethane-acrylate water repellent agent or is prepared by the hydrophobic treatment method.
The invention has the following beneficial effects:
1. the method of the invention adopts unsaturated double-bond terminated cationic polyurethane and acrylate to prepare the water repellent agent through copolymerization. The polyurethane and the acrylate are connected by chemical bonds, so that the compatibility of polymer molecular chain segments is improved, the polymer cannot be separated in the using process, and the film forming effect is better.
2. In the method, hydrophilic alcohol amine is introduced during prepolymerization to generate competitive polymerization, diisocyanate reacts with the alcohol amine firstly and then reacts with polymer dihydric alcohol, so that the chain segment between amphiphilic water bases is short in length, and cationic hydrophilic groups are relatively uniformly distributed in the prepolymer.
3. The method of the invention adopts a mode of introducing cationizable monomers in the polyurethane polymerization process to implement polymer self-emulsification, thereby avoiding the problems of water repellency effect reduction, environmental pollution and the like caused by emulsification of conventional acrylate water repellent agents by external low molecular surfactants. The cationic water repellent avoids the problem that the conventional anionic product can not be tightly adsorbed with the fabric (showing electronegativity), and is more beneficial to the uniform film formation of the water repellent on the surface of the fabric.
4. The polymer polyol monomer in the cationic polyurethane-acrylate water repellent agent prepared by the method can provide product flexibility, the diisocyanate unit can provide strength, the alcohol amine can provide product self-emulsifying hydrophilicity, and soft and hard molecular chain segments in a polyurethane main chain structure can endow the fabric with good low temperature resistance, flexibility and bonding strength. The acrylate alkane monomer can effectively reduce the surface energy and has the function of water repellency. The introduction of the acrylate monomer containing the crosslinking functional group in the molecular structure of the water repellent can establish the crosslinking among polymer molecules and the chemical bond between the polymer molecules and the fabric, and endow the product with higher fastness. Overcomes the defects that the conventional water repellent product has poor fastness and a cross-linking agent needs to be added into the fabric finishing liquid to improve the fastness.
5. The cationic polyurethane-acrylate water repellent agent prepared by the invention avoids the problems of environmental pollution and biological accumulated toxicity caused by using a fluorine-containing water repellent agent, and simultaneously overcomes the defects of hot sticking, cold brittleness, poor flexibility and solvent intolerance of acrylate monomers to a certain extent. The advantages of the polyurethane and the acrylate are complementary, and the physical mechanical property, the water-soluble resistance and the thermodynamic property of the finished fabric are improved.
6. The water repellent agent has simple operation for water repellent finishing of the fabric and saves more energy. The prepared water repellent agent is nearly neutral, the damage of the finished fabric is small, the product has good uniformity, a layer of water repellent film can be formed on the surface of the fabric, and the water repellency of the fabric is greatly improved. And the addition of the polyurethane can endow the fabric with soft and full hand feeling. In addition, the VOC emission is extremely low, and the method is suitable for environmental protection requirements. In general, the finished fabric has the characteristics of good water repellency, softness, air permeability, stain resistance and water washing resistance.
Drawings
FIG. 1: static water contact angle plot of treated fabric.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1:
preparing a cationic polyurethane-acrylate water repellent agent and finishing the fabric according to the following steps:
preparation of cationic polyurethane self-emulsion:
according to the isocyanate group-hydroxyl group ratio of 1.2:1, polytetrahydrofuran (Mn ═ 850) (accounting for 90% of the total mass of polytetrahydrofuran (Mn ═ 850), N-methyldiethanolamine and hydroxyethyl acrylate), N-methyldiethanolamine (accounting for 2% of the total mass of polytetrahydrofuran (Mn ═ 850), N-methyldiethanolamine and hydroxyethyl acrylate) and hydroxyethyl acrylate (accounting for 8% of the total mass of polytetrahydrofuran (Mn ═ 850), N-methyldiethanolamine and hydroxyethyl acrylate) are dried in vacuum at 50 ℃ to remove water;
adding 1/3N-methyldiethanolamine into polytetrahydrofuran, adding dibutyltin dilaurate (accounting for 0.2 percent of the total mass of monomers participating in the reaction), slowly dropwise adding isophorone diisocyanate at the temperature of 50 ℃ under the protection of nitrogen, measuring the-NCO content by adopting a di-N-butylamine method, raising the temperature to 60 ℃ when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanato is less than or equal to 32 percent), adding the residual N-methyldiethanolamine, measuring the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanato is less than or equal to 7 percent), adding hydroxyethyl acrylate until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanato is less than or equal to 0.5 percent), and. And (3) reducing the temperature of the reaction system to room temperature, adding neutralizing agent acetic acid (neutralization degree is 100%) to adjust the reaction pH (pH is 6-7), adding deionized water according to 15% of the mass solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
Preparing a water repellent agent by the self-emulsion reaction of an acrylate monomer and waterborne polyurethane:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of octadecyl acrylate to epoxypropyl acrylate is 95:5, and the mass ratio of the total mass of the acrylate monomer to the solid content of the polyurethane self-emulsion is 1: 1) at 40 ℃, stirring at the rotating speed of 3000r/min for 15min, and stirring at the rotating speed of 500r/min for 12 hours to obtain the acrylic ester monomer pre-swelling solution of cationic polyurethane. Adding initiator ammonium persulfate (the initiator amount is 0.1 percent of the acrylate monomer amount), and preserving heat for 3 hours at 70 ℃ under the protection of nitrogen atmosphere. Naturally cooling to 30 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent.
Treating the fabric with the cationic polyurethane-acrylate water repellent agent:
the content of the cationic polyurethane-acrylate water repellent agent is 100g/L, and after the fabric is soaked, padding liquor with the padding rate of 100% is used for pre-baking at 100 ℃ for 2min and then baking at 140 ℃ for 3 min. The parameters of the treated fabric are shown in table 1.
Example 2:
referring to the conditions of example 1, an aqueous cationic polyurethane self-emulsion was obtained, and the mass ratio of the total mass of acrylate monomers to the solid content in the polyurethane self-emulsion was adjusted from 1:1 is replaced by 2: 1. 1.5:1, other conditions are not changed, and the cationic polyurethane-acrylate water repellent agent is prepared.
The fabric is treated by the obtained cationic polyurethane-acrylate water repellent agent according to the fabric treatment conditions of example 1, and the related parameters of the treated fabric are shown in table 1.
TABLE 1 relevant parameters of the treated Fabric
Note: the fabric before treatment had a CIE whiteness value of 75.8, a softness of 66.19, a warp break strength of 720N, a weft break strength of 480N, and a wash resistance Test according to the 2A Test standard in AATCC Test Method 61-2010 color fastness to washing, one soaping of the AATCC 2A standard being equivalent to 5 washes with a common household washing machine.
The product has the following hydrophobic effect: as can be seen from Table 1, the water repellent effect of the fabric finished by the cationic polyurethane-acrylate water repellent prepared according to the mass ratio of the total mass of the acrylate monomers to the solid content of the polyurethane self-emulsion is good, the static water pressure resistance is high, the fuzzing and pilling resistance is good, the whiteness of the fabric is good, and the breaking strength is high.
And fastness to washing of the product: from table 1, it can be seen that after fabrics finished by the cationic polyurethane-acrylate water repellent prepared under the condition of different mass ratios of the total mass of the acrylate monomers to the solid content of the polyurethane self-emulsion are washed by 25 times of household washing machine, the static water contact angles (hydrophobicity) of the fabrics are all higher than 125 degrees, and the fabrics have higher hydrophobicity, which indicates that the fabrics finished by the water repellent prepared by the method have higher fastness to washing.
And (3) repeatability of hydrophobic effect of the product: according to the cationic polyurethane-acrylate water repellent agent prepared from acrylate monomers in different proportions, after 10 times of batch finishing, the range error of the static water contact angle of each finished fabric is +/-2 degrees, and the contact angle data shows that the hydrophobic effect repeatability of the treated fabric is good.
Example 3:
the cationic polyurethane-acrylate water repellent agent is prepared according to the conditions of example 1, the content of the water repellent agent in the fabric finishing process is replaced from 100g/L to 80g/L, 60g/L, 40g/L and 20g/L, and the fabric is respectively treated under the same other conditions. The parameters of the treated fabric are shown in table 2.
TABLE 2 correlation parameters of the fabrics after dip treatment with different water repellent contents
Note: the fabric before treatment had a CIE whiteness value of 75.8, a softness of 66.19, a warp break strength of 720N, a weft break strength of 480N, and a wash resistance Test according to the 2A Test standard in AATCC Test Method 61-2010 color fastness to washing, one soaping of the AATCC 2A standard being equivalent to 5 washes with a common household washing machine.
The product has the following hydrophobic effect: as can be seen from table 2, the cationic polyurethane-acrylate water repellent prepared under the same conditions uses different water repellent dosages when finishing the fabric, and the obtained fabric has good water repellent effect, high hydrostatic pressure resistance, excellent fuzzing and pilling resistance, good fabric whiteness and high breaking strength.
And fastness to washing of the product: as can be seen from Table 2, the cationic polyurethane-acrylate water repellent agent prepared under the same conditions adopts different water repellent agent dosages when finishing the fabric, the static water contact angles (hydrophobicity) of the fabric after the fabric is washed by 25 times of household washing machine are all higher than 125 degrees, and the fabric has higher hydrophobicity, which shows that the fabric has higher washing fastness after the fabric is finished by the water repellent agent prepared by the invention.
And (3) repeatability of hydrophobic effect of the product: according to the polyurethane-acrylate water repellent agent prepared from acrylate monomers in different proportions, after 10 times of batch finishing, the range error of the static water contact angle of each finished fabric is +/-2 degrees, and the contact angle data shows that the hydrophobic effect repeatability of the treated fabric is good.
Example 4:
preparation of cationic polyurethane self-emulsion:
drying polyester diol (Mn 1000) (84% of the total mass of polyester diol (Mn 1000), triethanolamine and hydroxyethyl methacrylate), triethanolamine (8% of the total mass of polyester diol (Mn 1000), triethanolamine and hydroxyethyl methacrylate), and hydroxyethyl methacrylate (8% of the total mass of polyester diol (Mn 1000), triethanolamine and hydroxyethyl methacrylate) in vacuum at 60 ℃ according to the ratio of isocyanate group to hydroxyl group of 2.2:1 to remove water;
adding 1/3 triethanolamine into polyester diol, adding dibutyltin dilaurate (accounting for 0.2 percent of the total monomer mass participating in the reaction), slowly dripping toluene diisocyanate at the temperature of 70 ℃ under the protection of nitrogen, measuring the-NCO content by adopting a di-n-butylamine method, raising the temperature to 80 ℃ when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent), adding the rest triethanolamine, measuring the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), adding hydroxyethyl methacrylate until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and realizing the blocking of unsaturated double bonds. And (3) reducing the temperature of the reaction system to room temperature, adding a neutralizing agent hydrochloric acid (the neutralization degree is 120%) to adjust the reaction pH (the pH is 6-7), adding deionized water according to 40% of the mass solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
Preparing a water repellent agent by the self-emulsion reaction of an acrylate monomer and waterborne polyurethane:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of cetyl acrylate to methyl methacrylate to hydroxyethyl acrylate is 100:120:10, and the mass ratio of the total mass of the acrylate monomer to the solid content of the polyurethane self-emulsion is 2: 1) at 50 ℃, stirring at the rotating speed of 5000r/min for 20min, and stirring at the rotating speed of 1000r/min for 12 hours to obtain the acrylate monomer pre-swelling solution of the cationic polyurethane. Adding initiator potassium persulfate (the initiator amount is 1 percent of the acrylate monomer amount), and preserving the heat for 2 hours at 80 ℃ under the protection of nitrogen atmosphere. Naturally cooling to 40 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent.
Treating the fabric with the cationic polyurethane-acrylate water repellent agent:
the content of the cationic polyurethane-acrylate water repellent agent is 40g/L, and after the fabric is soaked, the fabric is pre-dried at 105 ℃ for 2min and then is baked at 150 ℃ for 2min by using padding liquor with a padding residual rate of 80%. The parameters of the treated fabric are shown in Table 3.
Example 5:
preparation of cationic polyurethane self-emulsion:
drying polyoxyethylene glycol (Mn 400) (88% of the total mass of polyoxyethylene glycol (Mn 400), diethyl diethanolamine and hydroxyethyl acrylate), diethyl diethanolamine (6% of the total mass of polyoxyethylene glycol (Mn 400), diethyl diethanolamine and hydroxyethyl acrylate), and hydroxyethyl acrylate (6% of the total mass of polyoxyethylene glycol (Mn 400), diethyl diethanolamine and hydroxyethyl acrylate) in vacuum at 60 ℃ according to the isocyanate group-to-hydroxyl group ratio of 1.4:1 to remove water;
adding 1/3 diethyl diethanol amine into polyoxyethylene glycol, adding dibutyltin dilaurate (accounting for 0.2 percent of the total monomer mass participating in the reaction), slowly dropwise adding 1, 6-hexamethylene diisocyanate at the temperature of 70 ℃ under the protection of nitrogen, measuring the-NCO content by adopting a di-n-butylamine method, raising the temperature to 80 ℃ when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent), adding the residual diethyl diethanol amine, measuring the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), adding hydroxyethyl acrylate until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and realizing the blocking of unsaturated. And (3) reducing the temperature of the reaction system to room temperature, adding lactic acid (neutralization degree is 110%) serving as a neutralizing agent to adjust the pH (pH is 6-7), adding deionized water according to 30% of the solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
Preparing a water repellent agent by the self-emulsion reaction of an acrylate monomer and waterborne polyurethane:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of tetradecyl acrylate to octadecyl acrylate to butyl methacrylate to hydroxyethyl methacrylate is 100:100:120:2, and the mass ratio of the total mass of the acrylate monomer to the solid content of the polyurethane self-emulsion is 1.5:1) at 40 ℃, stirring at the rotating speed of 5000r/min for 20min, and stirring at the rotating speed of 1000r/min for 12 hours to obtain the acrylate monomer pre-swelling solution of the cationic polyurethane. Adding an initiator azobisisobutyronitrile (the amount of the initiator is 0.5 percent of the amount of the acrylate monomer), and preserving heat for 3 hours at 75 ℃ under the protection of nitrogen atmosphere. Naturally cooling to 30 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent.
Treating the fabric with the cationic polyurethane-acrylate water repellent agent:
the content of the cationic polyurethane-acrylate water repellent agent is 60g/L, and after the fabric is soaked, padding liquor with the padding rate of 150% is used for pre-baking at 110 ℃ for 2min and then baking at 150 ℃ for 2 min. The parameters of the treated fabric are shown in Table 3.
Example 6:
preparation of cationic polyurethane self-emulsion:
according to the isocyanate group-hydroxyl ratio of 1.5:1, polypropylene glycol (Mn 400) (accounting for 85 percent of the total mass of the polypropylene glycol (Mn 400), N-methyldiethanolamine and hydroxyethyl methacrylate), N-methyldiethanolamine (accounting for 8 percent of the total mass of the polypropylene glycol (Mn 400), N-methyldiethanolamine and hydroxyethyl methacrylate), and hydroxyethyl methacrylate (accounting for 7 percent of the total mass of the polypropylene glycol (Mn 400), N-methyldiethanolamine and hydroxyethyl methacrylate) are dried in vacuum at 50 ℃ to remove water;
adding 1/3N-methyldiethanolamine into polypropylene glycol, adding dibutyltin dilaurate (accounting for 0.2 percent of the total mass of monomers participating in the reaction), slowly dropwise adding isophorone diisocyanate at the temperature of 70 ℃ under the protection of nitrogen, measuring the-NCO content by adopting a di-N-butylamine method, raising the temperature to 75 ℃ when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent), adding the residual N-methyldiethanolamine, measuring the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), adding hydroxyethyl methacrylate until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and realizing the blocking of unsaturated double bonds. And (3) reducing the temperature of the reaction system to room temperature, adding lactic acid (neutralization degree is 100%) serving as a neutralizing agent to adjust the pH (pH is 6-7), adding deionized water according to 20% of the solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
Preparing a water repellent agent by the self-emulsion reaction of an acrylate monomer and waterborne polyurethane:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of octadecyl methacrylate to lauryl acrylate to epoxypropyl methacrylate is 100:150:10, and the mass ratio of the total mass of the acrylate monomer to the solid content in the polyurethane self-emulsion is 1: 1) at 40 ℃, stirring at the rotating speed of 3000r/min for 20min, and stirring at the rotating speed of 500r/min for 12 hours to obtain the acrylate monomer pre-swelling solution of the cationic polyurethane. Adding initiator potassium persulfate (the amount of the initiator is 0.5 percent of that of the acrylate monomer), and preserving the temperature for 2 hours at 80 ℃ under the protection of nitrogen atmosphere. Naturally cooling to 30 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent.
Treating the fabric with the cationic polyurethane-acrylate water repellent agent:
the content of the cationic polyurethane-acrylate water repellent agent is 20g/L, and after the fabric is soaked, padding liquor with the padding rate of 100% is used for pre-baking at 100 ℃ for 2min and then baking at 140 ℃ for 5 min. The parameters of the treated fabric are shown in Table 3.
Example 7:
preparation of cationic polyurethane self-emulsion:
according to the isocyanate group-hydroxyl group ratio of 1.8:1, poly-epsilon-caprolactone diol (Mn 1000) (accounting for 90 percent of the total mass of the poly-epsilon-caprolactone diol (Mn 1000), the tert-butyl diethanolamine and the hydroxyethyl methacrylate), tert-butyl diethanolamine (accounting for 7 percent of the total mass of the poly-epsilon-caprolactone diol (Mn 1000), the tert-butyl diethanolamine and the hydroxyethyl methacrylate), and hydroxyethyl methacrylate (accounting for 3 percent of the total mass of the poly-epsilon-caprolactone diol (Mn 1000), the tert-butyl diethanolamine and the hydroxyethyl methacrylate) are dried in vacuum at 50 ℃ to remove water;
adding 1/3 tert-butyldiethanolamine into poly-epsilon-caprolactone diol, adding dibutyltin dilaurate (accounting for 0.2 percent of the total monomer mass participating in the reaction), slowly dropwise adding 1, 4-benzene diisocyanate at the temperature of 70 ℃ under the protection of nitrogen, measuring the-NCO content by adopting a di-N-butylamine method, raising the temperature to 75 ℃ when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent), adding the residual N-methyldiethanolamine, measuring the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), adding hydroxyethyl methacrylate until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and realizing the blocking of unsaturated double bonds. And (3) reducing the temperature of the reaction system to room temperature, adding a neutralizing agent dimethylmercaptopropionic acid (the neutralization degree is 120%) to adjust the reaction pH (the pH is 6-7), adding deionized water according to 30% of the solid content of the product mass, and self-emulsifying by high-speed stirring (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
Preparing a water repellent agent by the self-emulsion reaction of an acrylate monomer and waterborne polyurethane:
dropwise adding the self-emulsifying cationic polyurethane emulsion into an acrylate monomer (the mass ratio of tetradecyl methacrylate to octyl methacrylate to hydroxyethyl methacrylate is 100:110:5, and the mass ratio of the total mass of the acrylate monomer to the solid content in the polyurethane self-emulsion is 1.2: 1) at 50 ℃, stirring at 3000r/min for 20min, and stirring at 500r/min for 12 hours to obtain the acrylate monomer pre-swelling solution of the cationic polyurethane. Adding initiator potassium persulfate (the amount of the initiator is 0.5 percent of that of the acrylate monomer), and preserving the temperature for 2 hours at 80 ℃ under the protection of nitrogen atmosphere. Naturally cooling to 30 ℃, preserving heat and discharging to obtain the cationic polyurethane-acrylate water repellent.
Treating the fabric with the cationic polyurethane-acrylate water repellent agent:
the content of the cationic polyurethane-acrylate water repellent agent is 80g/L, and after the fabric is soaked, padding liquor with the padding rate of 100% is used for pre-baking for 2min at 100 ℃, and then the fabric is baked for 5min at 150 ℃. The parameters of the treated fabric are shown in Table 3.
Comparative example 1:
the acrylate water repellent is prepared by the following steps:
emulsifying agents, namely Sodium Dodecyl Sulfate (SDS) and polyoxyethylene stearate (AEO-18), are dissolved in deionized water to prepare an emulsion (the mass ratio of SDS: AEO-18 is 1:4, and the dosage is 10% of the total mass of the monomers). Stearyl acrylate and methyl methacrylate (the mass ratio of the monomers is 1:1, and the total mass of the monomers is 20% of the mass of the emulsion) are added into the emulsion system under high-speed stirring (5000r/min) for pre-emulsification. Adding 50% of the pre-emulsion into a reaction vessel, heating to 75 ℃, dropwise adding an initiator potassium persulfate (the initiator amount is 0.6%) under the protection of a nitrogen environment, continuously reacting for 2h, adding the rest of the pre-emulsion, preserving heat for 2h, cooling to room temperature, cooling and discharging.
The method for preparing the water repellent agent finished fabric comprises the following steps:
the water repellent agent content is 80g/L, the fabric is soaked and then is pre-dried at 105 ℃ for 2min and then is baked at 140 ℃ for 5min by padding with a padding rate of 100%. The parameters of the treated fabric are shown in Table 3.
Comparative example 2:
the anionic polyurethane modified acrylate water repellent agent is prepared according to the following steps:
referring to example 1, an anionic urethane-modified acrylate water repellent agent was prepared by replacing only cationizable alcohol amine (N-methyldiethanolamine) with anionizable dimethylolbutyric acid and adding triethylamine as a neutralizing agent.
The method for preparing the water repellent agent finished fabric comprises the following steps:
the finishing method of the fabric is the same as that of the example 1, and the relevant parameters of the fabric after treatment are shown in a table 3.
Comparative example 3:
referring to example 1, the addition mode of N-methyldiethanolamine is changed, alcohol amine is not added during prepolymerization, and only the addition is completely carried out during the second chain extension:
polytetrahydrofuran and dibutyltin dilaurate (accounting for 0.2 percent of the total mass of monomers participating in the reaction) are slowly dripped into isophorone diisocyanate at the temperature of 50 ℃ under the protection of nitrogen, the-NCO content is determined by adopting a dibutylamine method, when the-NCO value in a reaction system reaches a theoretical value (the theoretical residual content of the isocyanate is less than or equal to 32 percent), the temperature is raised to 60 ℃, N-methyldiethanolamine is added, the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 7 percent), hydroxyethyl acrylate is added until the-NCO content in the reaction system reaches the theoretical value (the theoretical residual content of the isocyanate is less than or equal to 0.5 percent), and the end capping of. And (3) reducing the temperature of the reaction system to room temperature, adding neutralizing agent acetic acid (neutralization degree is 100%) to adjust the reaction pH (pH is 6-7), adding deionized water according to 15% of the mass solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
The polyurethane-acrylate water repellent agent is obtained according to the preparation conditions of the water repellent agent in example 1 and is used for fabric treatment, and the related parameters of the treated fabric are shown in table 3.
Comparative example 4:
referring to example 1, only changing the adding mode of N-methyldiethanolamine, alcohol amine is completely added at one time during prepolymerization:
under the protection of nitrogen, slowly dripping isophorone diisocyanate at the temperature of 50 ℃, raising the temperature to 60 ℃, and adding hydroxyethyl acrylate to realize the end capping of unsaturated double bonds. And (3) reducing the temperature of the reaction system to room temperature, adding neutralizing agent acetic acid (neutralization degree is 100%) to adjust the reaction pH (pH is 6-7), adding deionized water according to 15% of the mass solid content of the product, and self-emulsifying at a high speed (1000r/min) to obtain the water-based cationic polyurethane self-emulsion.
The polyurethane-acrylate water repellent agent is obtained according to the preparation conditions of the water repellent agent in example 1 and is used for fabric treatment, and the related parameters of the treated fabric are shown in table 3.
TABLE 3 parameters relating to the treated fabrics
Note: the fabric before treatment had a CIE whiteness value of 75.8, a softness of 66.19, a warp break strength of 720N, a weft break strength of 480N, and a wash resistance Test according to the 2A Test standard in AATCC Test Method 61-2010 color fastness to washing, one soaping of the AATCC 2A standard being equivalent to 5 washes with a common household washing machine.
The product has the following hydrophobic effect: the hydrophobic property data of the fabric after the water repellent agent treatment is shown in tables 1-3, and as can be seen from comparative examples 1-7 and comparative examples 1-4, the fabric treated by the cationic polyurethane modified acrylate water repellent agent designed by the invention has better water repellent effect (the contact angle is larger than 140 ℃) and better breaking strength (the strength loss is lower than 10%) than the fabric treated by the acrylate water repellent agent and the anionic polyurethane modified acrylate water repellent agent, and meanwhile, compared with the process of adding alcohol amine at one time, the water repellent agent prepared by adding alcohol amine in batches has better water repellent effect.
And (3) repeatability of hydrophobic effect of the product: the fabric finished according to the example 1 is finished by 10 times of batches, the range of the static water contact angle of the fabric finished each time is 146 +/-3 degrees, and the contact angle data shows that the hydrophobic effect repeatability of the fabric treated is good.
Water washing resistance: and (3) carrying out a washing fastness test on the fabric subjected to the finishing of the water repellent agent emulsion according to the standard of AATCC 61-2010 'washing fastness to light'. After the water wash was complete, the static water contact angle of the fabric was measured. After the fabrics finished in the examples 1 to 7 are washed by a household washing machine for 25 times, although the static contact angles are reduced compared with those before soaping, the fabric contact angles are all larger than 130 degrees, the fabrics still have higher hydrophobic performance, and the water repellent has better water washing resistance.
Breaking strength: and (3) performing a breaking strength test on the fabric before and after finishing the water repellent according to GB/T3923 and 2013 'determination strip sample method for tensile property, breaking strength and breaking elongation of fabric'. As can be seen from the data in table 3, the fabric finished with the cationic polyurethane-acrylate water repellent has less loss of breaking strength.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of a cationic polyurethane-acrylate water repellent agent is characterized by comprising the following steps:
(1) preparing a polyurethane prepolymer by using polymer polyol, partial alcohol amine and diisocyanate;
(2) the polyurethane prepolymer and the residual alcohol amine and unsaturated alcohol obtain a polyurethane molecular main chain containing terminal double bonds;
(3) adding water for self-emulsification to obtain a water-based cationic polyurethane self-emulsion;
(4) polymerizing the polyurethane self-emulsion and an acrylate monomer to construct a graft copolymer to obtain a cationic polyurethane-acrylate water repellent agent;
in the method, the molar ratio of isocyanic acid radicals to hydroxyl radicals in diisocyanate, polymer polyol, alcohol amine and unsaturated alcohol is 1.2-2.2;
in the step (4), the mass ratio of the acrylic ester monomer to the solid content in the polyurethane self-emulsion is (1-2) to 1;
the alcohol amine comprises one or more of diethanolamine, triethanolamine, N-methyldiethanolamine, tert-butyldiethanolamine, dimethyldiethanolamine, and N-ethyldiethanolamine.
2. The method of claim 1, wherein the polymer polyol is added in an amount of 84 to 90% by mass based on the total mass of the hydroxyl group-containing monomers, and the hydroxyl group-containing monomers are polymer polyol, alcohol amine and unsaturated alcohol.
3. The method according to claim 1, wherein the total amount of alcohol amine added in the method is 2-8% of the total mass of the hydroxyl group-containing monomers.
4. The method according to claim 1, wherein the unsaturated alcohol is added in an amount of 2 to 8% by mass based on the total mass of the hydroxyl group-containing monomers.
5. The cationic polyurethane-acrylate water repellent agent is characterized by being prepared by the method of any one of claims 1 to 4.
6. A cationic polyurethane-acrylate water repellent agent is characterized by having a structure shown in formula (1):
Aa-Bb-C-Dd-E-Dm-C-Bn-Ai
formula (1)
Wherein a, B, D, m, n and i are natural numbers of 1-100, the chemical structural general formula of A is formula (2), the chemical structural general formula of B is formula (3), C is an alkyl part of unsaturated alcohol, the chemical structural general formula of D is formula (4), and the chemical structural general formula of E is formula (5);
wherein R is1Is a carbon chain with the number of carbon atoms of 1-18; r2Is H or-CH3；R3Is H or-CH3；R4Is epoxypropyl ester or hydroxyethyl ester; wherein R is5Is a non-isocyanato group of a diisocyanate monomer; r6Is a non-hydroxyl group of a polyol organic compound; wherein R is7，R8，R9Is an alkane group.
7. A fabric hydrophobic treatment method is characterized in that the fabric is soaked in a treatment solution for treatment and then is rolled and baked to obtain the fabric hydrophobic treatment agent; the treatment comprising the cationic polyurethane-acrylate water repellent according to claim 5 or 6.
8. A hydrophobic fabric comprising the cationic polyurethane-acrylate water repellent of claim 5 or 6, or prepared by the method of claim 7.
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