Bio-based polyurethane-acrylate fluoride-free waterproof agent as well as preparation method and application thereof

Abstract

The invention discloses a bio-based polyurethane-acrylate fluoride-free waterproof agent as well as a preparation method and application thereof. The bio-based polyurethane-acrylate fluoride-free waterproof agent is prepared from the following raw materials in parts by mass based on the total amount of 100 parts: 6-16 parts of bio-based polyurethane monomer; 2-10 parts of a crosslinking monomer; 15-35 parts of a bio-based acrylic monomer; 5 to 10 parts of a bio-based surfactant; 0.1 to 0.5 part of an initiator; the balance is a bio-based cosolvent; wherein the bio-based polyurethane monomer is prepared from the following raw materials in parts by mass based on the total amount of 100 parts: 40 to 70 parts of bio-based polyol; 25 to 55 parts of diisocyanate; 0.1 to 0.5 part of a catalyst; 2-7 parts of a chain extender; and 1-7 parts of a bio-based end-capping reagent. The fluorine-free waterproof agent is obtained through free radical polymerization of the bio-based polyurethane monomer, the cross-linking monomer and the bio-based acrylate, a group with a hydrophobic function is introduced to a side group of a long chain of the bio-based acrylate, so that the emulsion keeps high bio-based content, and excellent spraying waterproof and washing-resistant effects are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of textile auxiliaries and relates to a bio-based polyurethane-acrylate fluorine-free waterproofing agent and a preparation method and application thereof. Background Art

[0002] As the concept of "Healthy China" becomes more and more popular, the enthusiasm for national fitness continues to rise, and the public's demand for high-quality, green and environmentally friendly outdoor sports textiles with special functions has increased significantly. In particular, textile fabrics with waterproof properties have been widely used in outdoor sports equipment such as jackets, casual jackets, tents, outdoor trousers, sweatshirts, protective workwear and bags because they can effectively cope with the changing outdoor climate conditions.

[0003] The waterproof property of outdoor textiles is mainly achieved by applying waterproofing agents in the subsequent printing, dyeing and finishing processes. Currently, textile waterproofing agents on the market are mainly divided into two categories: fluorine-based waterproofing agents and fluorine-free waterproofing agents. With the increasing emphasis on safety and environmental protection, fluorine-free waterproofing agents are gradually winning the favor and choice of more brands and consumers due to their environmentally friendly and harmless characteristics.

[0004] Fluorine-free waterproofing agents are currently widely used in the field of post-printing and dyeing waterproofing as environmentally friendly additives to replace fluorine-containing waterproofing agents. Therefore, there is an urgent need to develop a fluorine-free waterproofing agent. Summary of the invention

[0005] The purpose of the present invention is to provide a bio-based polyurethane-acrylate fluorine-free waterproofing agent and a preparation method and application thereof.

[0006] The present invention utilizes bio-based polyurethane monomers and functional cross-linking monomers to polymerize with bio-based acrylates through free radicals to obtain a fluorine-free water repellent. By introducing hydrophobic groups into the side groups of the long chains of bio-based acrylates, the emulsion maintains a high bio-based content while also having excellent spray waterproofing and washability effects.

[0007] The present invention provides a bio-based polyurethane-acrylate fluorine-free waterproofing agent, which includes the following raw materials in parts by weight, with the total amount being 100 parts: 6-16 parts of bio-based polyurethane monomer; 2-10 parts of cross-linking monomer; 15-35 parts of bio-based acrylic monomer; 5-10 parts of bio-based surfactant; 0.1-0.5 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer is prepared by the following raw materials in parts by weight, with the total amount being 100 parts: 40-70 parts of bio-based polyol; 25-55 parts of diisocyanate; 0.1-0.5 parts of catalyst; 2-7 parts of chain extender; and 1-7 parts of bio-based end-capping agent.

[0008] In the present invention, 1) the bio-based polyurethane-acrylate fluorine-free waterproofing agent is specifically prepared from the following raw materials in parts by weight, with the total amount being 100 parts: 16 parts of bio-based polyurethane monomer; 2 parts of cross-linking monomer; 35 parts of bio-based acrylic monomer; 5 parts of bio-based surfactant; 0.5 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer specifically includes the following raw materials in parts by weight, based on a total of 100 parts: 59.6 parts of bio-based polyol; 35.4 parts of diisocyanate; 0.25 parts of catalyst; 3.75 parts of chain extender; 1 part of bio-based end-capping agent; 2) The bio-based polyurethane-acrylate fluorine-free waterproofing agent is specifically prepared from the following raw materials in parts by weight, with the total amount being 100 parts: 10 parts of bio-based polyurethane monomer; 10 parts of cross-linking monomer; 30 parts of bio-based acrylic monomer; 10 parts of bio-based surfactant; 0.5 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer specifically includes the following raw materials in parts by weight, with a total amount of 100 parts: 54 parts of bio-based polyol; 35.5 parts of diisocyanate; 0.2 parts of catalyst; 4 parts of chain extender; 6.3 parts of bio-based end-capping agent; 3) The bio-based polyurethane-acrylate fluorine-free waterproofing agent specifically includes the following raw materials in parts by weight, with the total amount being 100 parts: 12 parts of bio-based polyurethane monomer; 8.2 parts of cross-linking monomer; 24.5 parts of bio-based acrylic monomer; 10 parts of bio-based surfactant; 0.35 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer is prepared by the following raw materials in parts by weight, with the total amount being 100 parts: 42 parts of bio-based polyol; 50.75 parts of diisocyanate; 0.25 parts of catalyst; 6 parts of chain extender; 1 part of bio-based end-capping agent; 4) The bio-based polyurethane-acrylate fluorine-free waterproofing agent specifically comprises the following raw materials in parts by weight, with the total amount being 100 parts: 12 parts of bio-based polyurethane monomer; 8.2 parts of cross-linking monomer; 24.5 parts of bio-based acrylic monomer; 10 parts of bio-based surfactant; 0.35 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer is prepared by the following raw materials in parts by weight, with the total amount being 100 parts: 69.7 parts of bio-based polyol; 25.55 parts of diisocyanate; 0.25 parts of catalyst; 3.5 parts of chain extender; and 1 part of bio-based end-capping agent.

[0009] In the above-mentioned bio-based polyurethane-acrylate fluorine-free waterproofing agent, the bio-based polyol is selected from at least one of cashew nut shell oil diol, cashew nut shell oil polyester diol, cashew nut shell oil polyol, soybean oil polyol, palm oil polyol and castor oil polyol; preferably, cashew nut shell oil branched diol, cashew nut shell oil polyester polyol or / and soybean oil polyol; The diisocyanate is bio-based 1,5-pentyl diisocyanate (PDI for short) and / or 1,5-pentyl diisocyanate trimer and its derivatives; The catalyst is selected from at least one of bis(2-dimethylaminoethyl) ether, triethylenediamine, bismuth isooctanoate and bismuth neodecanoate; The chain extender is selected from at least one of trimethylolpropane, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-methyl-1,3-propanediol, 1,4-butanediol and 2-ethylhexanol; The bio-based capping agent is selected from 4-hydroxybutenolide or a mixture of 4-hydroxybutenolide and cashew nut shell oil phenolic resin, 4-hydroxybutenolide has biological activities such as antioxidant and antibacterial, and the cashew nut shell oil phenolic resin can be specifically NX-2026 of Cardolite Company; In the above-mentioned bio-based polyurethane-acrylate fluorine-free waterproofing agent, the cross-linking monomer is selected from at least one of N-hydroxymethyl acrylamide, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, 2-hydroxyethyl methacrylate, hydroxyethyl methacrylate, dimethyldiethoxysilane and trimethylolpropane monoallyl ether; The bio-based acrylic acid monomer is any one of bio-based octadecyl acrylate, bio-based octadecyl methacrylate, bio-based behenyl acrylate, bio-based 2-ethylhexyl acrylate, bio-based isobornyl acrylate and bio-based 2-octyl acrylate; preferably, the bio-based acrylic acid monomer is bio-based octadecyl methacrylate, specifically VISIOMER from Evonik ® Terra series products; The bio-based surfactant includes a nonionic surfactant, an amphoteric surfactant and / or a combination of a nonionic surfactant and a cationic surfactant; the nonionic surfactant is selected from at least one of decyl glucoside, polyglycerol ricinoleate, sorbitan monooleate and cardanol ethoxylate (ethoxy addition number EO=9); the amphoteric surfactant is selected from cocamidopropyl betaine and / or sulfobetaine; the cationic surfactant is selected from hexadecyl ammonium bromide and / or octadecyl ammonium bromide; preferably, the bio-based surfactant is a composition in which the mass ratio of decyl glucoside to hexadecyl ammonium bromide is 1:1-3, a composition in which the mass ratio of polyglycerol ricinoleate to hexadecyl ammonium bromide is 1:1-3, a composition in which the mass ratio of sorbitan monooleate to hexadecyl ammonium bromide is 1:1-3, and a composition in which the mass ratio of cardanol ethoxylate (ethoxy addition number EO=9) to octadecyl ammonium bromide is 1.5-2:1-3; The initiator is selected from at least one of benzoyl peroxide, ammonium persulfate, potassium persulfate, 2-azobisisobutyronitrile and azobisisobutyramidine hydrochloride; preferably, the initiator is a composition in which the mass ratio of potassium persulfate to 2-azobisisobutyronitrile and azobisisobutyramidine hydrochloride is 1:1 and 1:2; The bio-based co-solvent is at least one of bio-based acetone, bio-based ethyl acetate, bio-based diethylene glycol dimethyl ether, bio-based propylene glycol, bio-based ethylene glycol, bio-based dipropylene glycol, bio-based tripropylene glycol, bio-based tetrapropylene glycol, citrus peel extract D-limonene, cellulose hydrolyzate levulinate and deionized water; preferably, the bio-based co-solvent can be bio-based acetone, a mixed solvent of bio-based acetone, bio-based ethylene glycol or bio-based propylene glycol and bio-based D-limonene in a mass ratio of 1 to 3:1, and a mixed solvent of bio-based acetone and deionized water in a mass ratio of 30:11.5.

[0010] The present invention also provides a method for preparing the above-mentioned bio-based polyurethane-acrylate fluorine-free waterproofing agent, comprising the following steps: 1) In an inert atmosphere, the bio-based polyol, diisocyanate and catalyst are mixed for polymerization reaction, and then a chain extender, a cross-linking monomer and a solvent are added for chain extension reaction, and after the reaction, a bio-based end-capping agent is added for end-capping, and after the end-capping reaction, the bio-based polyurethane monomer is obtained through post-treatment; 2) The bio-based polyurethane monomer, the cross-linking monomer, the bio-based acrylic acid monomer, the bio-based surfactant, the bio-based cosolvent and deionized water are mixed, and then an initiator is added to carry out a polymerization reaction to obtain the bio-based polyurethane-acrylate fluorine-free waterproofing agent.

[0011] In the above preparation method, in step 1), the inert atmosphere includes a nitrogen atmosphere or a helium atmosphere; The polymerization conditions are as follows: heating to 70-90°C during mixing, reacting at 70-90°C for 2-4h, and then cooling to 45-50°C. The conditions of the chain extension reaction are as follows: react at 45-50°C for 2-4h; The post-treatment conditions after the end-capping reaction are as follows: cooling to 20-30° C., adding glacial acetic acid to adjust the pH to 5-7, and removing the solvent in the reaction system under reduced pressure at an ambient temperature of 40-45° C.

[0012] In the above preparation method, in step 1), the final value of the polyurethane prepolymer R in the bio-based polyurethane monomer is controlled to be 1.0-1.5; The solvent is at least one of bio-based acetone, bio-based ethyl acetate, bio-based diethylene glycol dimethyl ether, bio-based propylene glycol, bio-based ethylene glycol, bio-based dipropylene glycol, bio-based tripropylene glycol, bio-based tetrapropylene glycol, citrus peel extract D-limonene and cellulose hydrolyzate levulinate; The amount of the solvent added is 20-50% of the total mass percentage of the bio-based polyurethane monomer raw material for preparing the bio-based polyurethane, and can be specifically 25%, 40%, or 50%.

[0013] In the above preparation method, in step 2), the polymerization reaction temperature can be 70-90° C. and the time can be 4-6 hours.

[0014] The bio-based polyurethane-acrylate fluorine-free waterproofing agent of the present invention is applied to the padding liquid for preparing waterproof textile fabrics.

[0015] The present invention also provides a padding solution for waterproof textile fabrics, which is an aqueous solution prepared from the bio-based polyurethane-acrylate fluorine-free waterproofing agent with a mass-volume concentration of 40-80 g / L.

[0016] The present invention further provides a method for preparing a waterproof textile fabric, comprising the following steps: applying the padding liquid of the waterproof textile fabric to the textile fabric through a padding-setting treatment to obtain the waterproof textile fabric.

[0017] In the above method, the temperature of the qualitative treatment may be 150-200°C.

[0018] The present invention has the following beneficial effects: 1. This invention uses bio-based materials as the main raw materials, which have lower carbon emissions and higher renewability compared to traditional petrochemical-based materials.

[0019] 2. Using bio-based polyurethane monomers, bio-based acrylates, bio-based cosolvents and surfactants as the main raw materials, a polymerizable bio-based urethane monomer with a double bond structure is formed by a condensation reaction of bio-based polyols and polyisocyanates, and a high-biobased content polyurethane-acrylate fluorine-free waterproofing agent with a network interpenetrating structure is obtained by free radical emulsion polymerization technology. By adjusting the types and amounts of bio-based polyurethane monomers, bio-based acrylates, bio-based cosolvents and surfactants, reaction temperature and reaction time and other factors, a bio-based fluorine-free waterproofing agent with high biobased content, good waterproof performance and excellent washing resistance is obtained.

[0020] 3. This bio-based fluorine-free waterproofing agent can be used in the waterproofing finishing of various textile fabrics, meeting the market demand for environmentally friendly and green upgrades of textile fabrics. Its high bio-based content and excellent performance indicators give it a significant advantage in the highly competitive market.

[0021] 4. The method of the present invention is simple and the reaction conditions are mild. DETAILED DESCRIPTION

[0022] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0024] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0025] Embodiment 1: Preparation method of bio-based polyurethane-acrylate fluorine-free waterproofing agent for ordinary textiles: 1. Preparation of bio-based polyurethane monomer M1 (raw material ratio is based on 100 parts by mass): Cashew nut shell oil branched diol (59.6 parts) was added to the reactor after dehydration at 120℃ for 2h. 2 Under protective conditions, pentamethylene pentamethylene diisocyanate (35.4 parts), hydrophilic chain extender N-methyl-diethanolamine (3 parts), catalyst bis(2-dimethylaminoethyl) ether (0.25 parts) were added, the temperature was controlled at 80°C, and the reaction was carried out for 3 hours. The temperature was lowered to 45°C, trimethylolpropane (0.75 parts) was added, and 40% of the total mass of the raw materials, bio-based acetone, was added to adjust the viscosity of the reaction product, and the reaction was continued for 1 hour. The temperature was raised to 55°C, 4-hydroxybutene lactone (1 part) was added for end-capping, the reaction was carried out for 2 hours, and then the temperature was lowered to 35°C, and the low-boiling point solvent was removed under reduced pressure to obtain the bio-based polyurethane monomer M1.

[0026] 2. Preparation of fluorine-free waterproofing agent (raw material ratio is based on 100 parts by mass): Bio-based polyurethane monomer M1 (16 parts), bio-based octadecyl methacrylate (35 parts), N-hydroxymethyl acrylamide (2 parts), a mixture of non-ionic surfactant decyl glucoside and cationic surfactant hexadecyl ammonium bromide in a mass ratio of 1:1 (5 parts), bio-based acetone (30 parts) and deionized water (11.5 parts), stirred evenly and dispersed evenly through a homogenizer, and an initiator (potassium persulfate and AIBN mixed in a mass ratio of 1:1, 0.5 parts) was added. The temperature was raised to 70°C and reacted for 4 hours to obtain a polyurethane-acrylate fluorine-free waterproofing agent emulsion with a high bio-based content.

[0027] 3. Preparation of padding solution: The fluorine-free waterproofing agent emulsion was diluted with tap water to an aqueous solution with a mass-volume concentration of 40 g / L, 60 g / L and 80 g / L.

[0028] Embodiment 2: Preparation method of bio-based polyurethane-acrylate fluorine-free waterproofing agent for outdoor clothing: 1. Preparation of bio-based polyurethane monomer M2 (raw material ratio is based on 100 parts by mass): Cashew nut shell oil polyester diol (54 parts) was added to the reactor after dehydration at 120°C for 2 hours. 2 Under protective conditions, pentamethylene pentamethylene diisocyanate (35.5 parts), chain extender 2-methyl-1,3-propanediol (2 parts), catalyst triethylenediamine: bismuth isooctanoate mass ratio of 1:1 (0.2 parts), temperature control at 75°C, react for 3 hours. Cool down to 45°C, add N-methyldiethanolamine (2 parts), add 40% solvent bio-based acetone of the total mass of the raw materials to adjust the viscosity of the reaction product, and continue to react for 1 hour. Heat up to 55°C, first add end-capping agent cashew nut shell oil phenolic resin (5.3 parts), then add end-capping agent 4-hydroxybutene lactone (1 part) for end-capping, react for 2 hours, then cool down to 45°C, remove low boiling point solvent under reduced pressure, and obtain bio-based polyurethane monomer.

[0029] 2. Preparation of fluorine-free waterproofing agent (raw material ratio is based on 100 parts by mass): Bio-based polyurethane monomer M2 (10 parts), bio-based octadecyl acrylate (30 parts), hydroxyethyl methacrylate (10 parts), a mixture of non-ionic surfactant sorbitol ester and cationic surfactant sulfobetaine in a mass ratio of 1:2 (10 parts), a mixture of bio-based ethylene glycol and D-limonene in a mass ratio of 1:1 (30 parts) and deionized water (9.5 parts), stirred evenly and dispersed evenly through a homogenizer, and an initiator (ammonium persulfate and VA-044 mixed in a mass ratio of 1:2, 0.5 parts) was added. The temperature was raised to 90°C and reacted for 6 hours to obtain a polyurethane-acrylate fluorine-free waterproofing agent emulsion with a high bio-based content. 3. Preparation of padding solution: The fluorine-free waterproofing agent emulsion was diluted with tap water to aqueous solutions with mass-volume concentrations of 40 g / L, 60 g / L and 80 g / L, respectively.

[0030] Embodiment 3: Preparation method of bio-based polyurethane-acrylate fluorine-free waterproofing agent for protective workwear fabrics: 1. Preparation of bio-based polyurethane monomer M3 (raw material ratio is based on 100 parts by mass): Cashew nut shell oil polyester diol (42 parts) was dehydrated under reduced pressure at 120°C for 2 hours. 2 Under protective conditions, pentamethylene pentamethylene diisocyanate trimer (50.75 parts), N,N-dimethylethanolamine (5 parts), and catalyst bismuth isooctanoate (0.25 parts) were added, and the temperature was controlled at 75°C for 3 hours. The reaction was continued for 1 hour after cooling to 45°C, 1,4-butanediol (1 part) was added, and 50% of the total mass of the raw materials, bio-based acetone, was added to adjust the viscosity of the reaction product, and the reaction was continued for 1 hour. The temperature was raised to 55°C, and the end-capping agent 4-hydroxybutene lactone (1 part) was added for end-capping, and the reaction was continued for 2 hours, and then the temperature was lowered to 35°C, and the low-boiling point solvent was removed under reduced pressure to obtain the bio-based polyurethane monomer M3.

[0031] 2. Preparation of fluorine-free waterproofing agent (raw material ratio is based on 100 parts by mass): Bio-based polyurethane monomer M3 (12 parts), bio-based isobornyl acrylate (24.5 parts), dimethyl diethoxysilane (8.2 parts), a mixture of non-ionic surfactant cardanol polyoxyethylene ether and cationic surfactant cocamidopropyl betaine in a mass ratio of 1:2 (10 parts), a mixture of bio-based propylene glycol and D-limonene in a mass ratio of 1:1 (35 parts) and deionized water (9.95 parts), stirred evenly and dispersed evenly through a homogenizer, and an initiator (benzoyl peroxide and VA-044 mixed in a ratio of 1:1, 0.35 parts) was added. The temperature was raised to 80°C and reacted for 5 hours to obtain a polyurethane-acrylate fluorine-free waterproofing agent emulsion with a high bio-based content.

[0032] 3. Preparation of padding solution: The fluorine-free waterproofing agent emulsion was diluted with tap water to aqueous solutions with mass-volume concentrations of 40 g / L, 60 g / L and 80 g / L, respectively.

[0033] Embodiment 4: Preparation method of bio-based polyurethane-acrylate fluorine-free waterproofing agent for luggage fabrics: 1. Preparation of bio-based polyurethane monomer M4 (raw material ratio is based on 100 parts by mass): Soybean oil diol (69.7 parts) was dehydrated under reduced pressure at 120°C for 2 hours. 2 Under protective conditions, add pentamethylene pentamethylene diisocyanate trimer (25.55 parts), add N,N-dimethylethanolamine (2.5 parts), add catalyst bismuth isooctanoate (0.25 parts), control the temperature at 75°C, and react for 3 hours. Cool down to 45°C, add 1,4-butanediol (1 part), add 25% of the total mass of the raw materials, solvent bio-based acetone to adjust the viscosity of the reaction product, and continue to react for 1 hour. Heat up to 55°C, add end-capping agent 4-hydroxybutene lactone (1 part) for end-capping, react for 2 hours, then cool to 35°C, remove the low boiling point solvent under reduced pressure, and obtain a bio-based polyurethane monomer.

[0034] 2. Preparation of fluorine-free waterproofing agent (raw material ratio is based on 100 parts by mass): Bio-based polyurethane monomer M4 (14 parts), bio-based isobornyl acrylate (25.5 parts), dimethyl diethoxysilane (7.5 parts), a mixture of non-ionic surfactant cardanol polyoxyethylene ether and cationic surfactant cocamidopropyl betaine in a mass ratio of 1:2 (10 parts), a mixture of bio-based propylene glycol and D-limonene in a mass ratio of 1:1 (35 parts) and deionized water (7.65 parts), stirred evenly and dispersed evenly through a homogenizer, and an initiator (benzoyl peroxide and VA-044 mixed in a ratio of 1:1, 0.35 parts) was added. The temperature was raised to 80°C and reacted for 5 hours to obtain a polyurethane-acrylate fluorine-free waterproofing agent emulsion with a high bio-based content.

[0035] 3. Preparation of padding solution: The fluorine-free waterproofing agent emulsion was diluted with tap water to aqueous solutions with mass-volume concentrations of 40 g / L, 60 g / L and 80 g / L, respectively.

[0036] The fluorine-free waterproofing agent prepared in the above embodiment was prepared into 40g / L, 60g / L and 80g / L padding solutions respectively, and applied to a 135g / m 2 Pure cotton yarn, weight 210g / m 2 Polyester cotton T / C65 / 35, weight 98g / m 2240T polyester pongee and weight 47g / m 2 On the 400T nylon spunlace fabric, the liquid carrying rates of the above fabrics are 55%, 50%, 68% and 37% respectively, which means that the waterproof finishing of the above fabrics is completed.

[0037] The bio-based carbon content of the fluorine-free waterproofing agent prepared above was tested according to ASTM D6866-22 "Biological-based content test" method B, the fabric performance was tested after the waterproof finishing was placed in a room temperature environment for 24 hours, the waterproof performance was tested according to the method of GB / T 4745-2012 "Testing and evaluating the waterproof performance of textiles by water dipping method", the washing and washing procedures were washed according to the 4N procedure of GB / T 8629-2017 "Household washing and drying procedures for textile testing", and the waterproof effect was tested after washing 10 times and 20 times according to 10.2.1 procedure F of GB / T 8629-2017. It can be seen from the values ​​measured in Table 1-2 that the fluorine-free waterproofing agent prepared by the present invention has a high bio-based content, outstanding waterproof performance, and excellent waterproof performance after washing.

[0038] Table 1 Results of biobased carbon content

[0039] Table 2 Waterproof performance test results

[0040] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. A bio-based polyurethane-acrylate fluorine-free waterproofing agent, characterized in that: The preparation includes the following raw materials in parts by weight, with the total amount being 100 parts: 6-16 parts of bio-based polyurethane monomer; 2-10 parts of cross-linking monomer; 15-35 parts of bio-based acrylic monomer; 5-10 parts of bio-based surfactant; 0.1-0.5 parts of initiator; the balance is bio-based cosolvent; The bio-based polyurethane monomer is prepared by the following raw materials in parts by weight, with the total amount being 100 parts: 40-70 parts of bio-based polyol; 25-55 parts of diisocyanate; 0.1-0.5 parts of catalyst; 2-7 parts of chain extender; and 1-7 parts of bio-based end-capping agent.

2. The bio-based polyurethane-acrylate fluorine-free waterproofing agent according to claim 1, characterized in that: The bio-based polyol is selected from at least one of cashew nut shell oil diol, cashew nut shell oil polyester diol, cashew nut shell oil polyol, soybean oil polyol, palm oil polyol and castor oil polyol; The diisocyanate is bio-based 1,5-pentyl diisocyanate and / or 1,5-pentyl diisocyanate trimer and its derivatives; The catalyst is selected from at least one of bis(2-dimethylaminoethyl) ether, triethylenediamine, bismuth isooctanoate and bismuth neodecanoate; The chain extender is selected from at least one of trimethylolpropane, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-methyl-1,3-propanediol, 1,4-butanediol and 2-ethylhexanol; The bio-based capping agent is selected from 4-hydroxybutenolide or a mixture of 4-hydroxybutenolide and cashew nut shell oil phenolic resin.

3. The bio-based polyurethane-acrylate fluorine-free waterproofing agent according to claim 1 or 2, characterized in that: The crosslinking monomer is selected from at least one of N-hydroxymethyl acrylamide, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, 2-hydroxyethyl methacrylate, hydroxyethyl methacrylate, dimethyl diethoxy silane and trimethylolpropane monoallyl ether; The bio-based acrylic acid monomer is any one of bio-based octadecyl acrylate, bio-based octadecyl methacrylate, bio-based behenyl acrylate, bio-based 2-ethylhexyl acrylate, bio-based isobornyl acrylate and bio-based 2-octyl acrylate; The bio-based surfactant includes a nonionic surfactant, an amphoteric surfactant and / or a combination of a nonionic surfactant and a cationic surfactant; the nonionic surfactant is selected from at least one of decyl glucoside, polyglycerol ricinoleate, sorbitan monooleate and cardanol ethoxylate; the amphoteric surfactant is selected from cocamidopropyl betaine and / or sulfobetaine; the cationic surfactant is selected from hexadecyl ammonium bromide and / or octadecyl ammonium bromide; The initiator is at least one selected from benzoyl peroxide, ammonium persulfate, potassium persulfate, 2-azobisisobutyronitrile and azobisisobutyramidine hydrochloride; The bio-based co-solvent is at least one of bio-based acetone, bio-based ethyl acetate, bio-based diethylene glycol dimethyl ether, bio-based propylene glycol, bio-based ethylene glycol, bio-based dipropylene glycol, bio-based tripropylene glycol, bio-based tetrapropylene glycol, citrus peel extract D-limonene, cellulose hydrolyzate levulinate and deionized water.

4. The method for preparing the bio-based polyurethane-acrylate fluorine-free waterproofing agent according to any one of claims 1 to 3, comprising the following steps: 1) In an inert atmosphere, the bio-based polyol, diisocyanate and catalyst are mixed for polymerization reaction, and then a chain extender, a cross-linking monomer and a solvent are added for chain extension reaction, and after the reaction, a bio-based end-capping agent is added for end-capping, and after the end-capping reaction, the bio-based polyurethane monomer is obtained through post-treatment; 2) The bio-based polyurethane monomer, the cross-linking monomer, the bio-based acrylic acid monomer, the bio-based surfactant, the bio-based cosolvent and deionized water are mixed, and then an initiator is added to carry out a polymerization reaction to obtain the bio-based polyurethane-acrylate fluorine-free waterproofing agent.

5. The preparation method according to claim 4, characterized in that: In step 1), the inert atmosphere includes a nitrogen atmosphere or a helium atmosphere; The polymerization conditions are as follows: heating to 70-90°C during mixing, reacting at 70-90°C for 2-4h, and then cooling to 45-50°C. The conditions of the chain extension reaction are as follows: react at 45-50°C for 2-4h; The post-treatment conditions after the end-capping reaction are as follows: cooling to 20-30° C., adding glacial acetic acid to adjust the pH to 5-7, and removing the solvent in the reaction system under reduced pressure at an ambient temperature of 40-45° C.

6. The preparation method according to claim 4 or 5, characterized in that: In step 1), the final value of the polyurethane prepolymer R in the bio-based polyurethane monomer is controlled to be 1.0-1.5; The solvent is at least one of bio-based acetone, bio-based ethyl acetate, bio-based diethylene glycol dimethyl ether, bio-based propylene glycol, bio-based ethylene glycol, bio-based dipropylene glycol, bio-based tripropylene glycol, bio-based tetrapropylene glycol, citrus peel extract D-limonene and cellulose hydrolyzate levulinate; The amount of the solvent added is 20-50% of the total mass percentage of the monomer raw material for preparing the bio-based polyurethane.

7. The preparation method according to claims 4-8, characterized in that: In step 2), the polymerization reaction temperature is 70-90° C. and the time is 4-6 hours.

8. Use of the bio-based polyurethane-acrylate fluorine-free waterproofing agent according to any one of claims 1 to 3 in the preparation of a padding solution for waterproof textile fabrics.

9. A padding solution for waterproof textile fabrics, characterized in that: The bio-based polyurethane-acrylate fluorine-free waterproofing agent according to any one of claims 1 to 3 is configured into an aqueous solution with a mass-volume concentration of 40 to 80 g / L.

10. A method for preparing a waterproof textile fabric, characterized in that: The method comprises the following steps: applying the padding liquid of the waterproof textile fabric according to claim 9 to the textile fabric through a padding-setting process to obtain the waterproof textile fabric.

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