A polyurethane super-hydrophobic compound and fluorine-free waterproofing agent and preparation method thereof

Abstract

The invention discloses a kind of polyurethane fluorine-free super-hydrophobic compound and its fluorine-free waterproofing agent and preparation method, and the polyurethane fluorine-free super-hydrophobic compound is obtained by diol compound, polyisocyanate and functional monomer through polycondensation reaction.The present invention is through the condensation reaction of polyurethane and long-chain hydroxyl compound, constructs super-hydrophobic polymer compound, and its arrangement on fabric surface can significantly reduce the surface energy of fabric, and meanwhile, the hard segment that polyurethane has effectively enhances the bonding fastness of product and fiber.The present invention is applied to the fluorine-free waterproof finishing of fabric, can give fabric efficient waterproof performance and excellent washability.

Description

Technical Field

[0001] The present invention belongs to the field of polymers and textile auxiliaries, and in particular relates to a composition of a polyurethane super-hydrophobic compound, a preparation method of the polyurethane super-hydrophobic compound, and a method for preparing a fluorine-free waterproofing agent using the polyurethane super-hydrophobic compound. The present invention is used as a fluorine-free waterproofing agent for water-repellent finishing of fiber fabrics. Background Art

[0002] Current technology already has a variety of compounds or compositions that can be used on various fibers to reduce surface energy and provide a waterproofing effect. The most widely used of these are fluorine-based water repellents based on perfluoroalkyl groups. Fluorine-based water repellents are usually obtained by polymerization or copolymerization of monomers with long-chain alkyl groups containing perfluoro groups. Due to the low surface energy characteristics of the fluorocarbon segments, fibers can obtain excellent water and oil repellency after being treated with fluorine-based additives. However, due to the environmental and ecological issues caused by the low biodegradability and cumulative effects of perfluorochemicals, which have attracted global attention, reducing the use of fluorine-based water repellents and replacing them with non-fluorine-based products with comparable performance has become a trend and necessity.

[0003] At present, as an alternative to fluorine compounds, the common ones are modified paraffins, polyacrylates, silicones, etc. Chinese patent CN106661303A discloses an emulsion polymer copolymerized by alkyl acrylate and functional free radical monomer, compounded with paraffin, blocked isocyanate, amino resin, modified siloxane, etc. to improve the durability and feel. Chinese patent CN11764159A reports the composition and implementation method of a fluorine-free silicon-containing waterproofing agent for cotton fibers, specifically, nano-silicon dioxide is modified with long-chain alkyl and reactive groups, and then used in combination with long-chain alkyl modified siloxane to produce a waterproof synergistic effect, and the process adopts a two-step method or a one-step method. However, although these existing compounding schemes can provide water-repellent properties for fabrics, their effectiveness is mostly lower than that of the corresponding fluorides. Summary of the Invention

[0004] The first object of the present invention is to provide a polyurethane fluorine-free super-hydrophobic compound that imparts high-efficiency waterproofing and washability to fabrics, which can be used as a substitute for fluorine-containing waterproofing agents.

[0005] The first object of the present invention is achieved through the following technical measures: a polyurethane fluorine-free super-hydrophobic compound, characterized in that it is obtained by a condensation reaction of a diol compound, a polyisocyanate and a functional monomer.

[0006] The polyurethane fluorine-free super-hydrophobic compound of the present invention is used as a fluorine-free waterproof agent after being emulsified and applied to water-repellent finishing of fiber fabrics, thereby imparting the fabrics with high-efficiency waterproof performance and washability.

[0007] The structural formula of the diol compound of the present invention is:

[0008]

[0009] R1: A saturated or unsaturated linear or branched long-chain alkyl group with 6 to 30 carbon atoms. Considering the hydrophobic effect, saturated linear alkyl groups are preferred, with linear saturated alkyl groups with 10 to 22 carbon atoms being most effective. R1 includes, but is not limited to, octyl, decyl, lauryl, tetradecyl, hexadecyl, and eicosyl.

[0010] R2: a linear or branched alkyl group with 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or a linear or branched alkyl group with two carbonyl groups;

[0011] R3: a straight-chain or branched alkyl group with 1 to 6 carbon atoms, including but not limited to methyl, ethyl, propyl, butyl and the like.

[0012] The diol compound of the present invention is obtained by catalytic reduction of the following first compound (Formula I), and suitable catalysts include sodium borohydride, lithium aluminum hydride, diborane, lithium isopropoxide, and the like.

[0013]

[0014] R1: a saturated or unsaturated straight or branched long carbon chain alkyl group having 6 to 30 carbon atoms;

[0015] R2: a straight-chain or branched-chain alkyl group having 2 to 8 carbon atoms, or a straight-chain or branched-chain alkyl group having two carbonyl groups;

[0016] R3: a linear or branched alkyl group having 1 to 6 carbon atoms.

[0017] The first compound (Formula I) of the present invention is obtained by sequentially reacting the following second compound (Formula II) and third compound (Formula III) through condensation reaction, and then further adding the fourth compound (Formula IV):

[0018]

[0019] R0: independently a hydrogen atom;

[0020] R1: a saturated or unsaturated straight or branched long carbon chain alkyl group having 6 to 30 carbon atoms;

[0021] R3: a linear or branched alkyl group having 1 to 6 carbon atoms;

[0022] R4: a saturated or unsaturated carbon chain group with 1 to 6 carbon atoms;

[0023] R5: a linear, branched or cyclic alkane group having 2 to 8 carbon atoms;

[0024] X: is simultaneously a halogen atom such as Cl, Br, or I, or an α,β-unsaturated carbonyl group.

[0025] The second compound of the present invention is a series of derivatives of formate, including but not limited to methyl formate, ethyl formate or butyl formate.

[0026] The third compound of the present invention is one or a combination of two or more of a series of long-chain alkyl esters, including but not limited to methyl laurate, ethyl laurate, methyl cocoate, ethyl cocoate, methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, methyl oleate, butyl oleate, ethyl oleate, methyl arachidate, ethyl arachidate, methyl behenate, and ethyl behenate.

[0027] The fourth compound (Formula IV) of the present invention is a dihalogenated hydrocarbon substituted with a halogen atom such as Cl, Br, or I, or a compound having an α,β-unsaturated carbonyl group at the end, including but not limited to 1,2-dichloroethane, 1,2-dibromoethane, 1,4-dichlorobutane, 1,4-dibromobutane, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, or a combination of two or more thereof.

[0028] The first compound (Formula I) of the present invention is prepared by a stepwise reaction of a second compound (Formula II), a third compound (Formula III), and a fourth compound (Formula IV), wherein the molar ratio of the second compound (Formula II): the third compound (Formula III): the fourth compound (Formula IV) is 1-1.5:1:1-1.5. Specifically, the second compound (Formula II) and the third compound (Formula III) undergo a first condensation reaction at a reaction temperature of 0-50°C for 1-24 hours. The reaction catalyst includes, but is not limited to, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like. The molar ratio of the catalyst to the second compound (Formula II) is 2-1:1.

[0029] The first compound (Formula I) of the present invention is prepared by a step-by-step reaction of a second compound (Formula II), a third compound (Formula III) and a fourth compound (Formula IV), specifically a condensation reaction of the second compound (Formula II) and the third compound (Formula III) and a second step reaction with the fourth compound (Formula IV). The reaction catalyst includes but is not limited to sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc. The molar ratio of the reaction catalyst to the fourth compound (Formula IV) is 2 to 1:1, the reaction temperature is 0 to 50° C., and the reaction time is 1 to 24 hours.

[0030] The polyisocyanate described in the present invention is one or a combination of two or more substances having two or more isocyanate groups. It includes but is not limited to one or a combination of two or more of the aromatic or aliphatic isocyanates selected from toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), tetramethyl-m-xylylene diisocyanate (TMXDI), and trimethyl-1,6-hexamethylene diisocyanate (TMHDI), as well as one or a combination of two or more of derivatives of the aforementioned diisocyanates, such as dimers, trimers, biuret, carbodiimide-modified derivatives, reaction products with propylene glycol, and reaction products with trimethylolpropane. Preferred are one or a combination of two or more of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and their derivatives.

[0031] The functional monomers of the present invention are small molecule compounds with active hydrogen, i.e., polyols or phenols with two or more hydroxyl groups, or polyamines with two or more amino groups, or compounds with a single active hydrogen functional group such as amides, oximes, imidazoles, etc., or a combination of two or more thereof. The functional monomers include, but are not limited to, polyhydroxy compounds such as 1,4-butanediol, ethylene glycol, diethylene glycol, 1,6-hexanediol, glycerol, trimethylolpropane, ditrimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, diethanolamine, triethanolamine, methyldiethanolamine, or ethylenediamine, hexamethylenediamine, isophoronediamine, diamine, diethylenetriamine, or compounds containing a single active hydrogen atom such as phenols, caprolactam, ethyl acetoacetate, diethyl malonate, acetone oxime, methyl ethyl ketone oxime, 3,5-dimethylpyrazole, or a combination of two or more thereof.

[0032] The second object of the present invention is to provide a method for preparing the above-mentioned polyurethane super-hydrophobic compound.

[0033] The second object of the present invention is achieved by the following technical measures: a method for preparing the above-mentioned polyurethane super-hydrophobic compound, characterized in that a diol compound is reacted with a polyisocyanate to synthesize a prepolymer, and then a functional monomer is added to the prepolymer to obtain the super-hydrophobic polyurethane compound through a condensation reaction.

[0034] In the polycondensation reaction of the present invention, the reaction temperature is 50-100 DEG C, the reaction time is 2-8 hours, and the solvent is acetone, butanone, methyl isobutyl ketone, benzene, toluene, ethyl acetate or butyl acetate.

[0035] The third object of the present invention is to provide a method for preparing a fluorine-free waterproofing agent using the above-mentioned polyurethane super-hydrophobic compound.

[0036] The third object of the present invention is achieved by the following technical measures: a method for preparing a fluorine-free waterproofing agent using the above-mentioned polyurethane super-hydrophobic compound, characterized in that the polyurethane super-hydrophobic compound is mixed with an emulsifier and deionized water and then homogenized and emulsified to obtain the obtained product.

[0037] Compared with the prior art, the present invention has the following significant effects:

[0038] This invention creates a super-hydrophobic polymer compound through a condensation reaction between polyurethane and a long-chain hydroxyl compound. Applying this compound to a fabric surface significantly reduces the fabric's surface energy. The hard segments of the polyurethane effectively enhance the bond between the product and the fiber. This method, when applied to a fluorine-free waterproof finish on fabrics, imparts effective waterproofing and excellent washability. DETAILED DESCRIPTION

[0039] Example 1

[0040] In a three-necked flask equipped with a stirring system and a reflux condenser, 51.2 g of methyl formate, 213 g of methyl laurate, and 55.3 g of a methanol solution of sodium methoxide were added and reacted at 30-40 ° C for 8 h. After the reaction, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0041] Then take 192 g of the above product, add 22.7 g of methanol solution of sodium methoxide, add 35.2 g of 1,4-dibromobutane dropwise at 0-5°C, react at 0-5°C for 5 hours, add 22 g of methanol solution of sodium borohydride, react at 0-5°C for 4 hours, evaporate part of the methanol, add water to split, wash the organic phase with water until neutral, dry it with anhydrous sodium sulfate, then transfer it to a rotary evaporator and distill under reduced pressure to obtain a waxy intermediate.

[0042] Take 176 g of the above intermediate, add 198.1 g of methyl isobutyl ketone, 63.6 g of hexamethylene diisocyanate (HDI), 18.3 g of N-methylethanolamine, and 0.06 g of dibutyltin dilaurate, and react at 70 ° C for 6 hours. After the system is determined to have no residual isocyanate by the di-n-butylamine method, the reaction is completed, and the solvent is removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0043] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 1.23 g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.83 g of TWEEN 80 (Croda, UK), 0.68 g of isomeric tridecyl polyoxyethylene 10 ether, 0.5 g of acetic acid, and 71.3 g of water, and homogenize twice at a pressure of 300 bar to obtain a polyurethane hydrophobic compound waterproofing agent product with a uniform appearance and a bluish glow.

[0044] Example 2

[0045] In a three-necked flask equipped with a stirring system and a reflux condenser, 63.1 g of ethyl formate, 303.3 g of methyl oleate, and 53.8 g of a methanol solution of sodium methoxide were added and reacted at 30-40 ° C for 8 h. After the reaction was completed, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0046] Then take 253 g of the above product, add 27 g of methanol solution of sodium methoxide, add 36 g of 1,4-dibromobutane dropwise at 0-5°C, react at 0-5°C for 5 hours, add 19.4 g of methanol solution of sodium borohydride, react at 0-5°C for 4 hours, evaporate part of the methanol, add water to separate, wash the organic phase with water until neutral, dry it with anhydrous sodium sulfate, then transfer it to a rotary evaporator and distill under reduced pressure to obtain a waxy intermediate.

[0047] Take 192.3 g of the above intermediate, add 214 g of methyl isobutyl ketone, 55.6 g of toluene diisocyanate (TDI), 13.3 g of N-methylethanolamine, and 0.09 g of bismuth neodecanoate, react at 70 ° C for 4 hours, add 2.8 g of butanone oxime, and react at 70 ° C for 2 hours. After determining that there is no residual isocyanate in the system by the di-n-butylamine method, the reaction is completed, and the solvent is removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0048] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 1.23 g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.83 g of TWEEN 80, 0.68 g of isomeric tridecyl polyoxyethylene 9 ether, 0.5 g of acetic acid, and 71.3 g of water, and homogenize twice under a pressure of 300 bar to obtain a polyurethane hydrophobic compound-based waterproofing agent product with a uniform appearance and a bluish glow.

[0049] Example 3

[0050] In a three-necked flask equipped with a stirring system and a reflux condenser, 63.2 g of ethyl formate, 276.7 g of methyl palmitate, and 54.3 g of a methanol solution of sodium methoxide were added and reacted at 30-40 ° C for 8 h. After the reaction was completed, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0051] Then take 231.2 g of the above product, add 26.7 g of methanol solution of sodium methoxide, add 36 g of 1,4-dibromobutane dropwise at 0-5°C, react at 0-5°C for 5 hours, add 19 g of methanol solution of sodium borohydride, react at 0-5°C for 4 hours, evaporate part of the methanol, add water to separate, wash the organic phase with water until neutral, dry it with anhydrous sodium sulfate, then transfer it to a rotary evaporator and distill under reduced pressure to obtain a waxy intermediate.

[0052] Take 168 g of the above intermediate, add 188.4 g of methyl isobutyl ketone, 53.7 g of hexamethylene diisocyanate (HDI), 19.3 g of N-methylethanolamine, and 0.06 g of dibutyltin dilaurate, and react at 70 ° C for 6 hours. After the system is determined to have no residual isocyanate by the di-n-butylamine method, the reaction is completed, and the solvent is removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0053] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 1.23 g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.83 g of TWEEN 80, 0.68 g of isomeric tridecyl polyoxyethylene 10 ether, 0.5 g of acetic acid, and 71.3 g of water, and homogenize twice under a pressure of 300 bar to obtain a waterproofing agent product based on a polyurethane hydrophobic compound.

[0054] Example 4

[0055] In a three-necked flask equipped with a stirring system and a reflux condenser, 68.2 g of methyl formate, 219.3 g of methyl laurate, and 56.3 g of a methanol solution of sodium methoxide were added and reacted at 30-40 ° C for 8 h. After the reaction, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0056] Then, 202 g of the above product was taken, 22.7 g of a methanol solution of sodium methoxide was added, 58.9 g of 1,6-hexanediol diacrylate was added dropwise at 30 ° C, and the reaction was carried out at 30 ° C for 5 h. Then, 21 g of a methanol solution of sodium borohydride was added, the temperature was lowered to 0-5 ° C and the reaction was carried out for 4 h. A 50% acetic acid solution was added to adjust the entire system to a weak acidity, and water was added to separate the organic phase. The organic phase was washed with water until neutral and then dried with anhydrous sodium sulfate. Then, it was transferred to a rotary evaporator and distilled under reduced pressure to obtain a waxy intermediate.

[0057] Take 178 g of the above intermediate, add 199.8 g of methyl isobutyl ketone, 53.8 g of hexamethylene diisocyanate (HDI), 22.4 g of dihydroxymethylpropionic acid, and 0.06 g of dibutyltin dilaurate, and react at 70 ° C for 6 hours. After the system is determined to have no residual isocyanate by the di-n-butylamine method, the reaction is completed, and the solvent is removed by vacuum distillation to obtain a polyurethane hydrophobic compound product.

[0058] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 1.87 g of TWEEN 80, 0.68 g of castor oil polyoxyethylene ether, 0.55 g of triethylamine, and 71.8 g of water, and homogenize twice under a pressure of 300 bar to obtain a waterproofing agent product based on the polyurethane hydrophobic compound.

[0059] Example 5

[0060] In a three-necked flask equipped with a stirring system and a reflux condenser, 63.2 g of ethyl formate, 303.3 g of methyl oleate, and 66.3 g of an ethanol solution of sodium ethoxide were added and reacted at 30-40 ° C for 8 h. After the reaction, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0061] Then, 252 g of the above product was taken, 27.7 g of a methanol solution of sodium methoxide was added, 57.9 g of 1,6-hexanediol diacrylate was added dropwise at 30 ° C, and the reaction was carried out at 30 ° C for 5 h. Then, 20.4 g of a methanol solution of sodium borohydride was added, the temperature was lowered to 0-5 ° C and the reaction was carried out for 4 h. A 50% acetic acid solution was added to adjust the entire system to a weak acidity, and water was added to separate the organic phase. The organic phase was washed with water until neutral and dried with anhydrous sodium sulfate. Then, it was transferred to a rotary evaporator and distilled under reduced pressure to obtain a waxy intermediate.

[0062] Take 177 g of the above intermediate, add 238 g of methyl isobutyl ketone, 48.3 g of hexamethylene diisocyanate (HDI), 1.68 g of 1,4-butanediol, and 0.06 g of dibutyltin dilaurate, react at 70 ° C for 4 hours, cool to 50 ° C, add 11.86 g of diethylenetriamine, and react at 50 ° C for 2 hours. After determining that there is no residual isocyanate in the system by the di-n-butylamine method, the reaction is completed, and the solvent is removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0063] Homogenize 25.5g of the aforementioned polyurethane hydrophobic compound, 1.3g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.76g of castor oil polyoxyethylene ether, 0.78g of isomeric tridecyl alcohol polyoxyethylene 10 ether, 0.5g of acetic acid, and 71.2g of water twice at 300 bar to obtain a polyurethane hydrophobic compound-based waterproofing agent.

[0064] Example 6

[0065] In a three-necked flask equipped with a stirring system and a reflux condenser, 63.2 g of ethyl formate, 303.3 g of palm methyl ester, and 67 g of an ethanol solution of sodium ethoxide were added and reacted at 30-40°C for 8 h. After the reaction was completed, 50% acetic acid solution was added to the flask to adjust the pH of the entire system to weak acidity. An equal volume of saturated sodium chloride solution was added and the mixture was vigorously shaken. The organic layer was separated, and the aqueous layer was extracted with 15 mL of toluene. The extract and the organic phase were combined and dried over anhydrous sodium sulfate. The dried organic layer was transferred to a rotary evaporator and distilled under reduced pressure to obtain the intermediate product.

[0066] Then, 237.1 g of the above product was taken, 28.5 g of a methanol solution of sodium methoxide was added, 63.1 g of 1,6-hexanediol diacrylate was added dropwise at 30°C, and the mixture was reacted at 30°C for 5 h. Then, 18.3 g of a methanol solution of sodium borohydride was added, the temperature was lowered to 0-5°C, and the reaction was carried out for 4 h. A 50% acetic acid solution was added to adjust the entire system to be weakly acidic, and water was added to separate the mixture. The organic phase was washed with water until neutral, dried with anhydrous sodium sulfate, and then transferred to a rotary evaporator and distilled under reduced pressure to obtain a waxy intermediate.

[0067] Take 188 g of the above intermediate, add 211 g of methyl isobutyl ketone, 57.7 g of isophorone diisocyanate (IPDI), 12.3 g of N-methylethanolamine, and 0.06 g of dibutyltin dilaurate, and react at 70 ° C for 6 hours. After the system is determined to have no residual isocyanate by the di-n-butylamine method, the reaction is completed, and the solvent is removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0068] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 0.9 g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.8 g of isomeric tridecyl polyoxyethylene 10 ether, 1.25 g of lauryl polyoxyethylene 7 ether, 0.5 g of acetic acid, and 72 g of water, and homogenize twice under a pressure of 300 bar to obtain a waterproofing agent product based on a polyurethane hydrophobic compound.

[0069] Comparative Example 1

[0070] In a three-necked flask equipped with a stirring system and a reflux condenser, 197.5 g of 1,12-dodecanediol, 193 g of hexamethylene diisocyanate (HDI), 41 g of N-methylethanolamine, and 0.06 g of dibutyltin dilaurate were added and reacted at 70 ° C for 6 h. After the system was determined to have no residual isocyanate by the di-n-butylamine method, the reaction was terminated and the solvent was removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0071] Take 25.5 g of the above-mentioned polyurethane hydrophobic compound product, 1.23 g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.83 g of TWEEN 80, 0.68 g of isomeric tridecyl polyoxyethylene 10 ether, 0.5 g of acetic acid, and 71.3 g of water, and homogenize twice at a pressure of 300 bar to obtain a waterproofing agent product with a uniform appearance and a bluish glow.

[0072] Comparative Example 2

[0073] In a three-necked flask equipped with a stirring system and a reflux condenser, 183 g of 1,12-octadecanediol, 134.4 g of toluene diisocyanate (TDI), 28.6 g of N-methylethanolamine, 7.2 g of methyl ethyl ketone oxime, and 0.06 g of dibutyltin dilaurate were added, and the mixture was reacted at 70 ° C for 6 h. After the system was determined to have no residual isocyanate groups using the di-n-butylamine method, the reaction was terminated, and the solvent was removed by reduced pressure distillation to obtain a polyurethane hydrophobic compound product.

[0074] Take 25.5g of the above-mentioned polyurethane hydrophobic compound product, 0.9g of octadecyl polyoxyethylene ammonium chloride (Ethoquat HT25, AkzoNobel), 0.95g of isomeric tridecyl polyoxyethylene 10 ether, 1.05g of lauryl polyoxyethylene 7 ether, 0.5g of acetic acid, and 72g of water to obtain a waterproofing agent product with a uniform appearance and a bluish glow.

[0075] Test methods and results

[0076] The fluorine-free waterproofing agents of Examples 1-6 and the comparative example were diluted with deionized water to a concentration of 30 g / L, and the pH of the working solution was adjusted to 4-6 with acetic acid. The products were subjected to a one-dip and one-pad process, dried at 110°C, heat-treated at 170°C for 60 seconds, and left to stand for 2 hours. The water spray test was then conducted according to the AATCC 22-2010 standard to measure the waterproofing effect at the initial stage and after 10 home washes (10HL). The results are shown in FIG.

[0077] As shown in Table 1:

[0078]

[0079] The foregoing description is intended only to provide specific embodiments of the present disclosure, intended to enable those skilled in the art to understand and implement the present disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure is not intended to be limited to the embodiments described herein, but rather to be construed in the broadest manner consistent with the principles and novel features disclosed herein.

Claims

1. A polyurethane super-hydrophobic compound, characterized in that: It is obtained by polycondensation reaction of diol compound, polyisocyanate and functional monomer. The structural formula of the diol compound is: R1: a saturated or unsaturated straight or branched long-chain alkyl group with 6 to 30 carbon atoms; R2: a straight or branched long-chain alkyl group with 2 to 8 carbon atoms, or a straight or branched long-chain alkyl group with two carbonyl groups; R3: a straight or branched long-chain alkyl group with 1 to 6 carbon atoms; The functional monomer is one or a combination of two or more of a polyol or phenol having two or more hydroxyl groups, a polyamine having two or more amino groups, or a compound having a single active hydrogen functional group; A diol compound is reacted with polyisocyanate to synthesize a prepolymer, and then a functional monomer is added to the prepolymer to obtain the polyurethane super-hydrophobic compound through a condensation reaction.

2. The polyurethane super-hydrophobic compound according to claim 1, wherein: The diol compound is obtained by catalytic reduction of the following first compound (Formula I): R1: a saturated or unsaturated straight or branched long-chain alkyl group with 6 to 30 carbon atoms; R2: a straight or branched long-chain alkyl group with 2 to 8 carbon atoms, or a straight or branched long-chain alkyl group with two carbonyl groups; R3: a straight or branched long-chain alkyl group with 1 to 6 carbon atoms.

3. The polyurethane super-hydrophobic compound according to claim 2, wherein: The first compound is obtained by sequentially condensing the following second compound (Formula II) and third compound (Formula III), and then further adding the fourth compound (Formula IV): R0: independently a hydrogen atom; R1: a saturated or unsaturated straight or branched long carbon chain alkyl group with 6 to 30 carbon atoms; R3: a straight or branched long carbon chain alkyl group with 1 to 6 carbon atoms; R4: a saturated or unsaturated carbon chain group with 1 to 6 carbon atoms; R5: a straight, branched or cyclic alkane group with 2 to 8 carbon atoms; X: is simultaneously a halogen atom or an α, β-unsaturated carbonyl group.

4. The polyurethane super-hydrophobic compound according to claim 1, wherein: The polyisocyanate is one or a combination of two or more substances having two or more isocyanate groups.

5. A method for preparing a fluorine-free waterproofing agent using the polyurethane super-hydrophobic compound according to claim 1, characterized in that: The polyurethane super-hydrophobic compound is mixed with an emulsifier and deionized water and then homogenized and emulsified to obtain the super-hydrophobic compound.

Images