Bio-based fluoride-free waterproof agent, and preparation method therefor and use thereof

Abstract

Provided in the present application are a bio-based fluoride-free waterproof agent, and a preparation method therefor and the use thereof. In the present application, firstly, a bio-based monomer is added into a reaction; secondly, a rosin-based amino acid surfactant is introduced, which is a bio-based ampholytic surfactant, has the advantages of good decontamination, resistance to hard water and being stable to an acid and an alkali and has the performances of sterilization, corrosion prevention, static electricity resistance, etc.; and finally, a lignin-furfural bio-based resin is added after the reaction, which resin is a new furfural bio-based resin, can be uniformly cross-linked on the surface layer of a yarn to adhere fiber ends to the yarn, and has a relatively strong adhesive force, such that the resin can bond the fibers, thereby limiting the movement of the fibers. The raw materials of the fluoride-free waterproof agent prepared in the present application are derived from bio-based products and are completely biodegradable in the natural environment, such that the fluoride-free waterproof agent is environmentally friendly and safe, thereby increasing the regenerative and environmentally friendly values of the product and having significant social benefits and wide market prospects.

Description

A bio-based fluorine-free waterproofing agent and its preparation method and application Technical Field

[0001] The present application belongs to the field of textile printing and dyeing technology in the printing and dyeing production of the textile industry, and in particular relates to a bio-based fluorine-free waterproofing agent and its preparation method and application. Background Art

[0002] With the continuous improvement of living standards and consumption levels, people's requirements for clothing comfort and special functions are becoming higher and higher. In addition, the popularity of outdoor sports such as climbing, skiing, surfing, cycling, and camping has increased both domestically and internationally. The application of waterproof finishing is becoming more and more extensive, and the requirements are becoming increasingly higher, especially for outdoor sports equipment. When climbing, a complete equipment set includes at least a jacket, tent, thermal clothing, waterproof shoes, waterproof raincoat, etc., and all of these equipment have been waterproofed.

[0003] The so-called waterproof means that after the fabric has been specially treated, water droplets will fall on the fabric, form round beads and slide off. The water droplets will not spread or even penetrate the fabric and wet the fabric.

[0004] Fabrics become roughened after repeated processing and washing during processing and daily use, and synthetic fabrics generally experience this worsening. To make fabrics soft, cool, smooth, and comfortable, as well as waterproof, they require finishing. Currently, the most widely used method is the use of a water-repellent agent. Therefore, finishing is an essential process in textile printing and dyeing, improving product quality and increasing product value.

[0005] There are many types of waterproofing agents, mainly quaternary ammonium salts of pyridinium, hydroxymethyl melamine derivatives, silicone waterproofing agents, etc., which have good waterproofing effects but average feel; fluorocarbon waterproof and oil-proof agents have good spinning effects, good feel, and are resistant to washing, but perfluorocarbon compounds contain PFOA, PFOS and APEO, which are currently difficult to degrade in the environment, are bioaccumulative and have multiple toxicities, and have common characteristics of persistent organic pollutants. They are considered to be new persistent environmental pollutants that are the focus of research in the 21st century and do not conform to the development trends and requirements of the textile industry.

[0006] Currently common waterproofing agents have a strong odor when processed in the production workshop, which is not friendly to the working environment and operators; the waterproofing effect decreases after washing, affecting the future use of textiles.

[0007] Summary of the Invention

[0008] This application provides a bio-based fluorine-free waterproofing agent, its preparation method, and its application. The fluorine-free waterproofing agent provided in this application is stable and odorless. After treatment, the fabric discoloration is minimal, the yarn binding is strong, the hand feels tough, and there are no creases. Furthermore, the fluorine-free waterproofing agent is naturally derived, biodegradable, and environmentally friendly. The treated fabric can directly contact the human body, is non-cytotoxic, and is non-irritating to the skin, making it suitable for a wide range of applications.

[0009] In a first aspect, the present application provides a bio-based fluorine-free waterproofing agent, wherein the raw materials of the fluorine-free waterproofing agent include a bio-based monomer, a base monomer, a functional monomer, an initiator, a bio-based emulsifier, a natural oil sulfonated oil, a rosin-based amino acid surfactant, a lignin-furfural bio-based resin, a pH regulator, a defoamer and deionized water;

[0010] Wherein, taking the total mass of the raw materials of the fluorine-free waterproofing agent as 100%, the mass percentage of each component is:

[0011] Bio-based monomers 15%-25%;

[0012] Base monomer 2%-5%;

[0013] Functional monomer 1%-3%;

[0014] Initiator 0.01%-0.4%;

[0015] Bio-based emulsifier 1%-5%;

[0016] Natural oil sulfonated oil 1%-5%;

[0017] Rosin-based amino acid surfactant 1%-5%;

[0018] Lignin-furfural bio-based resin 5%-15%;

[0019] pH adjuster 0.01%-1%;

[0020] Defoaming agent 0.01%-0.5%; and

[0021] The balance was deionized water.

[0022] In the present application, the bio-based monomer is at least one of bio-based octadecyl methacrylate or bio-based octadecyl acrylate;

[0023] The monomer is at least one of butyl methacrylate, methyl methacrylate, alkyl ketene dimer or dodecyl acrylate;

[0024] The functional monomer is at least one of methacrylamide, hydroxyethyl methacrylate, methacryloylmorpholine or hydroxyethyl acrylate;

[0025] The initiator is at least one of azobisisobutylamidine hydrochloride, ammonium persulfate or potassium persulfate;

[0026] The bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS 1305, NSS 1305A, NSS 1308 or octadecyltrimethylammonium bromide;

[0027] The natural sulfonated oil is at least one of natural sulfonated rapeseed oil, natural sulfonated castor oil or sulfated natural neatsfoot oil;

[0028] The pH regulator is at least one of ammonia water, liquid alkali or sodium carbonate;

[0029] The defoaming agent is at least one of polyoxypropyl polyoxyethyl glycerol ether and polyether-modified polysiloxanes.

[0030] In a second aspect, the present application provides a method for preparing a bio-based fluorine-free waterproofing agent, which comprises the following steps:

[0031] (1) mixing 20% ​​to 30% by weight of deionized water, 55% to 70% by weight of a bio-based emulsifier, 55% to 65% by weight of a natural oil sulfonated oil, a bio-based monomer, a base monomer, and a functional monomer to obtain a mixture A;

[0032] (2) dissolving 70% to 85% of the initiator by mass in deionized water to prepare an initiator aqueous solution with a mass concentration of 20%;

[0033] (3) Add the remaining deionized water, bio-based emulsifier and natural oil sulfonated oil to the reactor, stir evenly, heat to 40-45°C, add the remaining initiator and 1 / 20-1 / 15 of the mass of mixture A, then heat to 75-82°C and stabilize for 20-30 minutes;

[0034] (4) adding the remaining portion of the mixture A obtained in step (1) and the initiator aqueous solution in step (2) dropwise to the reactor described in step (2) simultaneously;

[0035] (5) After the reaction system is cooled to 60-65° C., the rosin-based amino acid surfactant and the lignin-furfural bio-based resin are added to the reactor, mixed and stirred evenly; and

[0036] (6) After the reaction system is cooled to below 45° C., a pH regulator and a defoaming agent are added to the reactor, mixed and stirred, and filtered to obtain a bio-based fluorine-free waterproofing agent.

[0037] In the step (1), the stirring speed is 800-1500 rpm, and the stirring time is 45-60 min.

[0038] In this application, the monomers are uniformly dispersed in water using an emulsifier. The more uniform and stable the dispersion, the smoother the subsequent polymerization reaction. If the emulsion shows stratification or precipitation, the subsequent polymerization temperature will be unstable, potentially exceeding the reaction limit and producing a large amount of filter residue.

[0039] In the step (3), the stirring speed is 50-200 rpm.

[0040] In the step (4), the dropwise addition time is 120-180 min, and the mixture is kept at 78-82° C. for 150-200 min.

[0041] In the present application, the dropping speed of the polymerization reaction cannot be too fast. If it is too fast, the polymerization reaction temperature may rise instantly and exceed the upper limit, and then the temperature will fall back. The temperature fluctuation will produce filter residue.

[0042] In the step (5), stirring is performed during mixing, and the stirring time is 15-30 minutes;

[0043] In the step (6), stirring is performed during mixing, the stirring speed is 20-50 rpm, and the stirring time is 10-30 min.

[0044] Preferably, the bio-based monomer is at least one of bio-based octadecyl methacrylate or bio-based octadecyl acrylate;

[0045] The bio-based monomer is selected to be 15%-25%. When the bio-based monomer is less than 15%, the film-forming fluorine-free waterproofing agent is too soft and does not meet the use requirements; when the bio-based monomer is greater than 25%, the film-forming fluorine-free waterproofing agent is too brittle and easily forms a crust and slag.

[0046] In this application, bio-based octadecyl methacrylate and bio-based octadecyl acrylate are obtained by the chemical esterification of bio-based acrylic acid or bio-based methacrylic acid with bio-based octadecyl alcohol. Bio-based octadecyl alcohol is produced by hydrogenation of bio-based stearic acid under the catalysis of copper chromate. Therefore, the raw materials for bio-based octadecyl methacrylate and bio-based octadecyl acrylate are derived from bio-based raw materials.

[0047] Preferably, the functional monomer is at least one or any combination of methacrylamide, hydroxyethyl methacrylate, methacryloylmorpholine or hydroxyethyl acrylate;

[0048] Among them, methacrylamide has excellent cross-linking performance, and the fluorine-free waterproofing agent produced has good waterproof performance, poor product permeability, and average hydrophilicity; hydroxyethyl methacrylate has average cross-linking performance, but good hydrophilicity and average waterproof performance; when the two are used together, the product can obtain suitable hydrophilicity and waterproof effect.

[0049] Preferably, the initiator is at least one of azobisisobutylamidine hydrochloride, ammonium persulfate or potassium persulfate, preferably azobisisobutylamidine hydrochloride;

[0050] Azobisisobutylamidine hydrochloride is a low-temperature initiator that decomposes at around 45°C to generate free radicals, which promote polymerization. The initiator dosage ranges from 0.01% to 0.4%. When the initiator dosage is less than 0.01%, the reaction speed is slow, and the heating and holding time is prolonged. When the initiator dosage is greater than 0.4%, the reaction speed is too fast, making it difficult to control and prone to implosion during the reaction.

[0051] Preferably, the bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS 1305, NSS 1305A, NSS 1308 or octadecyltrimethylammonium bromide;

[0052] Among them, cardanol polyoxyethylene ether is a good bio-based non-ionic emulsifier, and octadecyltrimethylammonium bromide is a bio-based anionic emulsifier. The combined effect of anionic and non-ionic emulsifiers is beneficial to the stability of the monomer emulsion.

[0053] Preferably, the natural oil sulfonated oil is at least one of natural sulfonated rapeseed oil, natural sulfonated castor oil or sulfated natural neatsfoot oil, preferably natural sulfonated rapeseed oil;

[0054] Among them, the natural sulfonated rapeseed oil is an anionic surfactant, which works synergistically with the above-mentioned bio-based emulsifier non-ionic surfactant cardanol polyoxyethylene ether to make the monomer uniformly and stably dispersed in the emulsion. The mass ratio of natural sulfonated rapeseed oil to NSS 1305 is 1: (1.1-1.3).

[0055] Preferably, the pH regulator is at least one of aqueous ammonia, liquid caustic soda or sodium carbonate, preferably liquid caustic soda;

[0056] The liquid caustic soda does not generate ammonia smell during high-temperature setting in the preparation process to pollute the working environment. The mass percentage of NaOH in the liquid caustic soda is 32.5%.

[0057] Preferably, the defoaming agent is at least one of polyoxypropyl polyoxyethyl glycerol ether or polyether-modified polysiloxane, preferably polyether-modified polysiloxane CD-1116M;

[0058] The polyether-modified polysiloxane CD-1116M can quickly penetrate into the foam in a high-temperature foaming system, destroying the stability of the foam and thus achieving a defoaming effect.

[0059] In a third aspect, the present application provides an application of a bio-based fluorine-free waterproofing agent, wherein the bio-based fluorine-free waterproofing agent is applied to the finishing of fabrics, which comprises the following steps:

[0060] S1: mixing a bio-based fluorine-free waterproofing agent with water to obtain a working solution, wherein the concentration of the working solution is 50-100 g / L;

[0061] S2: The fabric is padded in the working solution obtained in step S1, with the liquid rate being 60-80%, and then dried and shaped.

[0062] Preferably, in S2, the padding treatment is one dip and one padding, the roller pressure is 0.15-0.25 MPa, the drying and shaping temperature is 150-180° C., and the drying and shaping time is 60-120 s;

[0063] Preferably, the fabric is at least one of pure cotton fabric, blended fabric of cotton and polyamide fiber, blended fabric of cotton and polyester fiber, or Tencel, preferably pure cotton woven fabric.

[0064] In a fourth aspect, the present application provides a bio-based fluorine-free waterproofing agent, which is prepared using the raw materials and preparation method described in the present application.

[0065] In a fifth aspect, the present application provides an application of a bio-based fluorine-free waterproofing agent, wherein the bio-based fluorine-free waterproofing agent described in the present application or the bio-based fluorine-free waterproofing agent prepared by any method of the present application is used for finishing of textiles.

[0066] Compared with the prior art, this application has the following beneficial effects:

[0067] (1) This application incorporates bio-based monomers to replace traditional fossil carbon-based acrylic compounds. Bio-based monomers are produced using plant carbon, thereby increasing the renewable carbon content. The product has excellent properties such as ultra-low odor, low VOC (volatile organic compounds), and environmental safety.

[0068] (2) This application introduces a rosin-based amino acid surfactant, which is a bio-based amphoteric surfactant. Rosin is a renewable resource abundant in nature. Its main component is resin acid. The large non-polar tricyclic structure in its molecular structure has good hydrophobicity, while the polar carboxyl part has hydrophilicity. A series of rosin acid-N-acyl amino acid surfactants are synthesized by chemical, enzymatic, and chemoenzymatic methods by embedding natural glutamic acid, sarcosine, and polypeptides. They have good stain resistance, hard water resistance, acid and alkali stability, and have bactericidal, antiseptic, and antistatic properties.

[0069] (3) The present application adds natural oil sulfonated oil, which is an anionic sulfonated oil fatliquor made from natural oil as the main raw material, modified by sulfur trioxide gas sulfonation process, and then compounded with other necessary components. It is an excellent anionic surfactant with excellent penetration performance, improved hydrophilicity and antistatic properties; it can reduce the friction between fabrics and between fibers, and at the same time improve the feel of the cloth.

[0070] (4) This application incorporates lignin-furfural bio-based resin, which is a furfural-based bio-based resin. Furfural is an important chemical raw material that can be prepared by biomass conversion. Lignin is a biopolymer obtained from agricultural or forestry residues or paper pulping wastewater, and is the only aromatic natural biopolymer. Through enzymatic hydrolysis of lignin, the methoxy groups in lignin are demethylated and converted into phenolic hydroxyl products, resulting in highly reactive nano-lignin. Furfural is used to completely replace formaldehyde, and reacts with highly reactive nano-lignin to synthesize lignin-furfural bio-based resin. This resin can cross-link the network film-forming function on the fiber surface, wrapping the fiber surface with a wear-resistant resin film, reducing the slippage between fibers, and achieving a good yarn binding effect; at the same time, the resin is evenly cross-linked and condensed on the surface of the yarn, causing the fiber ends to adhere to the yarn, making it less likely to pill during friction. It helps acrylic resin form a film on the fabric surface, improving the fabric's wrinkle resistance, anti-static properties, and waterproof properties.

[0071] (5) The bio-based monomers, bio-based emulsifiers, natural oil sulfonated oils, rosin-based amino acid surfactants and lignin-furfural bio-based resins used in this application are all derived from nature, are non-toxic and harmless, and biodegrade rapidly and thoroughly, without polluting the environment; at the same time, the products are mild in effect, and textiles are less damaged after treatment, thus achieving green and sustainable development of the industry.

[0072] (6) The raw materials of the fluorine-free waterproofing agent prepared in this application are derived from bio-based products, which can be completely biodegraded in the natural environment, are environmentally friendly and safe, and enhance the renewable and environmentally friendly value of the product, with significant social benefits and broad market prospects. DETAILED DESCRIPTION

[0073] To make the technical solutions and advantages of this application clearer and more specific, the following examples are given to further illustrate this application in detail. It should be understood that the specific examples described herein are only used to explain this application and are not intended to limit this application.

[0074] The present application is described in detail below through specific embodiments.

[0075] Example 1

[0076] This embodiment provides a fluorine-free waterproofing agent, and its preparation method is as follows:

[0077] (1) 114 g of deionized water, 21 g of NSS 1305, 6 g of octadecyltrimethylammonium bromide, 18 g of natural sulfonated rapeseed oil, 120 g of bio-based octadecyl methacrylate, 120 g of bio-based octadecyl acrylate, 20 g of butyl methacrylate, 30 g of alkyl ketene dimer, 10 g of methacrylamide, and 10 g of hydroxyethyl methacrylate were sequentially added into a high-level mixing tank 1 and stirred at high speed to obtain an opaque stable emulsion mixture A;

[0078] (2) Weigh 1.6 g of azobisisobutylamidine hydrochloride and dissolve it in 6.4 g of deionized water to prepare an initiator aqueous solution B with a mass concentration of 20%;

[0079] (3) Add 345.6 g of deionized water, 14 g of NSS 1305, 4 g of octadecyltrimethylammonium bromide, and 12 g of natural sulfonated rapeseed oil to reactor 1, stir and heat to 40°C, add 0.4 g of azobisisobutylamidine hydrochloride and 25 g of mixture A, quickly heat to 75-82°C, and keep the temperature for 20-30 min;

[0080] (4) After the solution in the reactor 1 becomes a clear solution, that is, after the polymerization reaction is initiated, the remaining mixture A and the initiator aqueous solution B are added dropwise, and the addition is continued for 120 minutes, and then kept at 80°C for 150 minutes;

[0081] (5) After the reaction system is cooled to 60°C, 40g of rosin-based amino acid surfactant and 100g of lignin-furfural bio-based resin are added to the reactor 1, stirred for 30min, and cooled to 40°C;

[0082] (6) Add 5 g of liquid alkali and 2 g of CD-1116M into the reaction kettle 1, stir for 15 min, and filter to obtain the fluorine-free waterproofing agent 1.

[0083] Example 2

[0084] This embodiment provides a fluorine-free waterproofing agent, and its preparation method is as follows:

[0085] (1) 114 g of water, 21 g of NSS 1305, 6 g of octadecyltrimethylammonium bromide, 18 g of natural sulfonated rapeseed oil, 150 g of bio-based octadecyl methacrylate, 100 g of bio-based octadecyl acrylate, 20 g of butyl methacrylate, 30 g of methyl methacrylate, 10 g of methacrylamide, and 10 g of hydroxyethyl methacrylate were sequentially added into a high-level mixing tank 1 and stirred at high speed to obtain an opaque stable emulsion mixture A;

[0086] (2) Weigh 1.6 g of azobisisobutylamidine hydrochloride and dissolve it in 6.4 g of deionized water to prepare an initiator aqueous solution B with a mass concentration of 20%;

[0087] (3) Add 335.6 g of deionized water, 14 g of NSS 1305, 4 g of octadecyltrimethylammonium bromide, and 12 g of natural sulfonated rapeseed oil to reactor 1, stir and heat to 40°C, add 0.4 g of azobisisobutylamidine hydrochloride and 25 g of mixture A, quickly heat to 75-82°C, and keep the temperature for 20-30 min;

[0088] (4) After the solution in the reactor 1 becomes a clear solution, that is, after the polymerization reaction is initiated, the remaining mixture A and the initiator aqueous solution B are added dropwise, and the addition is continued for 120 minutes, and then kept at 80°C for 150 minutes;

[0089] (5) After the reaction system is cooled to 60°C, 40g of rosin-based amino acid surfactant and 100g of lignin-furfural bio-based resin are added to the reactor 1, stirred for 30min, and cooled to 40°C;

[0090] (6) Add 5 g of liquid alkali and 2 g of CD-1116M into the reaction kettle 1, stir for 15 min, and filter to obtain the fluorine-free waterproofing agent 2.

[0091] Example 3

[0092] This embodiment provides a fluorine-free waterproofing agent, and its preparation method is as follows:

[0093] (1) 114 g of water, 21 g of NSS 1305, 6 g of octadecyltrimethylammonium bromide, 18 g of natural sulfonated rapeseed oil, 100 g of bio-based octadecyl methacrylate, 150 g of bio-based octadecyl acrylate, 20 g of methyl methacrylate, 30 g of alkyl ketene dimer, 10 g of methacrylamide, and 10 g of hydroxyethyl methacrylate were sequentially added into a high-position mixing tank 1 and stirred at high speed to obtain an opaque stable emulsion mixture A;

[0094] (2) Weigh 1.6 g of azobisisobutylamidine hydrochloride and dissolve it in 6.4 g of deionized water to prepare an initiator aqueous solution B with a mass concentration of 20%;

[0095] (3) Add 335.6 g of deionized water, 14 g of NSS 1305, 4 g of octadecyltrimethylammonium bromide, and 12 g of natural sulfonated rapeseed oil to reactor 1, stir and heat to 40°C, add 0.4 g of azobisisobutylamidine hydrochloride and 25 g of mixture A, quickly heat to 75-82°C, and keep the temperature for 20-30 min;

[0096] (4) After the solution in the reactor 1 becomes a clear solution, that is, after the polymerization reaction is initiated, the remaining mixture A and the initiator aqueous solution B are added dropwise, and the addition is continued for 120 minutes, and then kept at 80°C for 150 minutes;

[0097] (5) After the reaction system is cooled to 60°C, 40g of rosin-based amino acid surfactant and 100g of lignin-furfural bio-based resin are added to the reactor 1, stirred for 30min, and cooled to 40°C;

[0098] (6) Add 5 g of liquid alkali and 2 g of CD-1116M into the reaction kettle 1, stir for 15 min, and filter to obtain the fluorine-free waterproofing agent 3.

[0099] The evaluation of the quality of fluorine-free waterproofing agents mainly focuses on the waterproof performance and wash fastness of the fabric. A comprehensive evaluation of product stability, impact on fabric color and anti-yellowing performance is also required.

[0100] The present application will be further described below in conjunction with comparative examples. The embodiments and comparative examples are only intended to help understand the present application and should not be regarded as specific limitations of the present application.

[0101] Comparative Example 1

[0102] Commercially available No. 3 waterproofing agent is a commonly used waterproofing agent on the market.

[0103] 1. Physical properties test

[0104] The physical properties of the bio-based fluorine-free waterproofing agents prepared by Examples 1-3 of the present application were tested, and the results are shown in Table 1:

[0105] Table 1

[0106] As can be seen from Table 1, the bio-based fluorine-free waterproofing agent product prepared by this application is stable, high in content, and safe. It is a finishing agent that can be used for textile processing, has high safety, and has good application prospects.

[0107] 2. Fluorine-free waterproofing agent application performance test

[0108] The bio-based fluorine-free waterproofing agents prepared in the above Examples 1-3 were compared with the commercially available waterproofing agent Comparative Example 1.

[0109] 2.1 Finishing agent application process:

[0110] Fabric: 100% cotton woven fabric

[0111] Process: Padding and baking

[0112] Application of bio-based fluorine-free waterproofing agent examples 1-3, padding and baking process:

[0113] S1. The bio-based fluorine-free water repellent prepared in Examples 1-3 and a commercially available water repellent were mixed with water to obtain a working solution having a concentration of 80 g / L;

[0114] S2. The fabric is dipped in the working solution obtained in step S1 and padded, with a liquid rate of 60-80%, and then dried at 160 ℃ for 90s;

[0115] S3. Moisture resurgence to evaluate waterproof performance.

[0116] 2.2 The yellowing and waterproof performance of the examples and comparative examples were tested respectively:

[0117] (1) Softness performance evaluation method

[0118] Hand feel evaluation: The two fabric samples were evaluated by hand touch, with the original fabric hand feel rated as level 1 and the best hand feel rated as level 5. The larger the value, the better the hand feel. The test results are shown in Table 2.

[0119] (2) Whiteness and color evaluation methods

[0120] The test was conducted using a Datacolor colorimeter. The whiteness of the treated fabric was compared with that of the untreated fabric. The greater the change in whiteness, the greater the yellowing. The test results are shown in Table 2.

[0121] (3) Waterproof test

[0122] Use a round iron ring to tighten the cloth and make it 45 degrees to the water outlet. ° At an angle of 15 cm from the center of the fabric, 100 mL of water was sprayed vertically at a constant speed. After the water was sprayed, the floating water was knocked off the fabric. The number and size of the water marks and spots on the fabric were observed and scored. 100 points means no water marks or spots. Lower scores indicate poorer waterproofing.

[0123] Table 2

[0124] As can be seen from Table 2, the products of Examples 1, 2, and 3 are superior to or close to conventional products on the market, are not prone to color change, and have good anti-yellowing effects. In addition, the treated fabrics also have excellent hand feel and waterproof properties.

[0125] In summary, the present application provides a bio-based fluorine-free waterproofing agent and a preparation method thereof. First, a bio-based monomer is added to the reaction to replace the traditional fossil carbon-based acrylic compound; secondly, a rosin-based amino acid surfactant is introduced, which is a bio-based amphoteric surfactant with good stain resistance, hard water resistance, acid and alkali stability, and bactericidal, antiseptic, antistatic and other properties; finally, a lignin-furfural bio-based resin is added after the reaction. This is a new type of furfural bio-based resin. The resin will be evenly cross-linked on the surface of the yarn, so that the fiber tips adhere to the yarn, and the strong adhesive force of the resin can bond the fibers to restrict their movement. After washing, the fabric does not fall off or break. The fabric treated with the waterproofing agent will have less yellowing, good waterproof performance, and a soft and non-rough feel. The raw materials of the fluorine-free waterproofing agent made in this application are derived from bio-based products, which can be completely biodegraded in the natural environment, are environmentally friendly and safe, and enhance the renewable and environmentally friendly value of the product.

[0126] The applicant declares that this application uses the above-mentioned embodiments to illustrate the bio-based fluorine-free waterproofing agent, preparation method, and application of this application, but this application is not limited to the above-mentioned detailed method, that is, it does not mean that this application must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent replacement of various raw materials of the product of this application, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the scope of protection and disclosure of this application.

Claims

1. A bio-based fluorine-free waterproofing agent, the raw materials of which include: Bio-based monomers, base monomers, functional monomers, initiators, bio-based emulsifiers, natural oil sulfonated oils, rosin-based amino acid surfactants, lignin-furfural bio-based resins, pH regulators, defoamers and deionized water; Taking the total mass of the raw materials of the bio-based fluorine-free waterproofing agent as 100%, the mass percentage of each component is: Bio-based monomers 15%-25%; Base monomer 2%-5%; Functional monomer 1%-3%; Initiator 0.01%-0.4%; Bio-based emulsifier 1%-5%; Natural oil sulfonated oil 1%-5%; Rosin-based amino acid surfactant 1%-5%; Lignin-furfural bio-based resin 5%-15%; pH adjuster 0.01%-1%; Defoaming agent 0.01%-0.5%; and The balance was deionized water.

2. The bio-based fluorine-free waterproofing agent according to claim 1, wherein: The bio-based monomer is at least one of bio-based octadecyl methacrylate or bio-based octadecyl acrylate; The matrix monomer is at least one of butyl methacrylate, methyl methacrylate, alkyl ketene dimer or dodecyl acrylate; The functional monomer is at least one of methacrylamide, hydroxyethyl methacrylate, methacryl morpholine or hydroxyethyl acrylate; The initiator is at least one of azobisisobutylamidine hydrochloride, ammonium persulfate or potassium persulfate; The bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS1305, NSS1305A, NSS1308 or octadecyl trimethyl ammonium bromide; The natural sulphonated oil is at least one of natural sulphonated rapeseed oil, natural sulphonated castor oil or sulphated natural neatsfoot oil; The pH regulator is at least one of ammonia water, liquid alkali or sodium carbonate; The defoaming agent is at least one of polyoxypropyl polyoxyethyl glycerol ether and polyether modified polysiloxane.

3. A method for preparing a bio-based fluorine-free waterproofing agent, comprising: (1) 20% to 30% by weight of deionized water, 55% to 70% by weight of a bio-based emulsifier, 55% to 65% by weight of a natural oil sulfonated oil, a bio-based monomer, a base monomer, and a functional monomer are mixed to obtain a mixture A; (2) dissolving 70% to 85% of the mass of the initiator in deionized water to prepare an initiator aqueous solution with a mass concentration of 20%; (3) Add the remaining deionized water, bio-based emulsifier and natural oil sulfonated oil into the reactor, stir evenly, heat to 40-45° C., add the remaining initiator and 1 / 20-1 / 15 of the mass of mixture A, then heat to 75-82° C. and stabilize for 20-30 minutes; (4) adding the remaining portion of the mixture A obtained in step (1) and the initiator aqueous solution in step (2) dropwise to the reaction kettle described in step (2) respectively; (5) After the reaction system is cooled to 60-65° C., the rosin-based amino acid surfactant and the lignin-furfural bio-based resin are added to the reaction kettle, and mixed and stirred evenly; and (6) After the reaction system is cooled to below 45° C., a pH regulator and a defoaming agent are added to the reaction kettle, mixed and stirred, and filtered to obtain a bio-based fluorine-free waterproofing agent.

4. The preparation method according to claim 3, wherein In the step (1), the stirring speed is 800-1500 rpm, and the stirring time is 45-60 min.

5. The preparation method according to claim 4, wherein: In the step (3), the stirring speed is 50-200 rpm; In the step (4), the dropping time is 120-180 min, and the temperature is kept at 78-82° C. for 150-200 min; In the step (5), stirring is performed during mixing, and the stirring time is 15-30 minutes; In the step (6), stirring is performed during mixing, the stirring speed is 20-50 rpm, and the stirring time is 10-30 min.

6. An application of a bio-based fluorine-free waterproofing agent, comprising applying the bio-based fluorine-free waterproofing agent to the finishing of fabrics, the application comprising the following steps: S1. Mixing the bio-based fluorine-free waterproofing agent according to claim 1 or 2 or the bio-based fluorine-free waterproofing agent prepared by the preparation method according to any one of claims 3 to 5 with water to obtain a working solution, The concentration of the working solution is 50-100g / L; S2. The fabric is padded in the working solution obtained in step S1, with the liquid rate being 60%-80%, and then dried and shaped.

7. The use of the bio-based fluorine-free waterproofing agent according to claim 6, wherein: In the step S2, the padding treatment is one dip and one padding, the roller pressure is 0.15-0.25Mpa, the drying and shaping temperature is 150-180°C, and the drying and shaping time is 60-120s.

8. The use of the bio-based fluorine-free waterproofing agent according to claim 6, wherein: In the step S2, the fabric is at least one of pure cotton fabric, blended fabric of cotton and polyamide fiber, blended fabric of cotton and polyester fiber, or Tencel.

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