WO2025092014A1 - Bio-based fluoride-free waterproof agent, and preparation method therefor and use thereof - Google Patents

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

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 a preparation method and application thereof.

Background Art

With the continuous improvement of the quality of life and consumption level, people have higher and higher requirements for the comfort and special functions of clothing. As outdoor sports such as climbing, skiing, surfing, cycling, camping, etc. are popular at home and abroad, the application of waterproof finishing is becoming more and more extensive, and the requirements are becoming higher and higher, especially for outdoor sports equipment. When climbing, the complete equipment includes at least assault jackets, tents, thermal insulation clothes, waterproof shoes, waterproof raincoats, etc., and these equipment have been waterproofed.

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

During processing or daily use, fabrics will become rough after multiple processing and washing, and synthetic fiber fabrics generally have a worse feel. In order to make the fabric soft, cool, smooth, comfortable, and waterproof, it needs to be finished. Currently, the most widely used method is to use waterproofing agents for finishing. Therefore, finishing is an important process in textile printing and dyeing to improve product quality and increase product added value.

There are many types of waterproofing agents, mainly quaternary ammonium pyridinium salts, hydroxymethyl melamine derivatives, silicone waterproofing agents, etc., which have good waterproofing effects but average hand feel; fluorocarbon waterproof and oil-proof agents have good spinning effects, good hand 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 the 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 meet the development trends and requirements of the textile industry.

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.

Summary of the invention

The present application provides a bio-based fluorine-free waterproofing agent and a preparation method and application thereof. Fluorine waterproofing agent has good stability and no odor. After the fabric is treated, the color change is small, the binding fastness is good, the hand feel is tough, and there is no crease. At the same time, the fluorine-free waterproofing agent is natural, degradable and pollution-free to the environment. The finished fabric can directly contact the human body, has no cytotoxicity, no irritation to the skin, and is suitable for a wide range of applications.

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;

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

Bio-based monomers 15%-25%;

Matrix monomer 2%-5%;

Functional monomers 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.

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

The 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 NSS 1305, NSS 1305A, NSS 1308 or octadecyl trimethyl ammonium bromide;

The natural oil sulfonated oil is natural sulfonated rapeseed oil, natural sulfonated castor oil or sulfated natural At least one of 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.

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

(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.

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

In the present application, the monomer is uniformly dispersed in water with the help of the emulsifying effect of the emulsifier. The more uniform and stable the dispersion is, the smoother the subsequent polymerization reaction will be. If the emulsion has stratification or precipitation, the temperature of the subsequent polymerization reaction will be unstable, which may break through the reaction upper limit and produce a lot of filter residue.

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 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 drops back. The temperature fluctuation will produce filter residue.

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.

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

The bio-based monomer is selected to be 15%-25%. When the bio-based monomer is lower 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.

In the present application, bio-based octadecyl methacrylate and bio-based octadecyl acrylate are obtained by chemical esterification of bio-based acrylic acid or bio-based methacrylic acid and bio-based octadecyl alcohol, and bio-based octadecyl alcohol is obtained by hydrogenation of bio-based stearic acid under the catalysis of copper chromate. Therefore, the raw materials of bio-based octadecyl methacrylate and bio-based octadecyl acrylate are derived from bio-based raw materials.

Preferably, the functional monomer is at least one or any combination of methacrylamide, hydroxyethyl methacrylate, methacryl morpholine or hydroxyethyl acrylate;

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

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

The azobisisobutylamidine hydrochloride is a low-temperature initiator, which can decompose at about 45°C to generate free radicals and promote polymerization. The dosage of the initiator is 0.01%-0.4%. When the initiator is less than 0.01%, the reaction speed is slow and the heating and insulation time is prolonged; when the initiator is greater than 0.4%, the reaction speed is too fast and difficult to control, and implosion is easy to occur during the reaction.

Preferably, the bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS 1305, NSS 1305A, NSS 1308 or octadecyl trimethyl ammonium bromide;

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.

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;

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 evenly and stably dispersed in the emulsion. The mass ratio of natural sulfonated rapeseed oil to NSS 1305 is 1: (1.1-1.3).

Preferably, the pH regulator is at least one of aqueous ammonia, liquid alkali or sodium carbonate, preferably liquid alkali;

The liquid caustic soda will 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%.

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

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

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:

S1: mixing the 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;

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

Preferably, in 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;

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.

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.

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.

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

(1) This application adds 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), environmental protection and safety.

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

(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 fabric.

(4) The present 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 to obtain highly reactive nano-lignin. Furfural is used to completely replace formaldehyde and react with highly reactive nano-lignin to synthesize lignin-furfural bio-based resin. This resin resin can cross-link the network film-forming function on the fiber surface, so that the fiber surface is wrapped with a wear-resistant resin film, which reduces the slippage between fibers and has a good yarn binding effect; at the same time, the resin is evenly cross-linked and condensed on the surface of the yarn, so that the fiber ends adhere to the yarn and are not easy to pilling during friction. It helps acrylic resin to form a film on the surface of the fabric, improving the fabric's wrinkle resistance, anti-static and waterproof properties.

(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 quickly 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.

(6) The raw materials of the fluorine-free waterproofing agent prepared in the present 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, thus having significant social benefits and broad market prospects.

DETAILED DESCRIPTION

In order to make the technical solutions and advantages of the present application clearer and more explicit, the following examples are listed to further illustrate the present application in detail. It should be understood that the specific examples described here are only used to explain the present application and are not intended to be construed as examples. It is not intended to limit this application.

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

Example 1

This embodiment provides a fluorine-free waterproofing agent, and the preparation method thereof is as follows:

(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 are sequentially added into a high-position mixing tank 1, and stirred at high speed to obtain an opaque stable emulsion mixture A;

(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%;

(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;

(4) After the solution in the reactor 1 becomes a clear solution, i.e. 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 min, and then the mixture is kept at 80° C. for 150 min;

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

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

Example 2

This embodiment provides a fluorine-free waterproofing agent, and the preparation method thereof is as follows:

(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 are sequentially added into a high-position mixing tank 1, and stirred at high speed to obtain an opaque stable emulsion mixture A;

(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%;

(3) Add 335.6 g of deionized water, 14 g of NSS 1305, and 4 g of octadecyl tris(III) into the reaction vessel 1. Methylammonium bromide and 12g natural sulfonated rapeseed oil, stir and heat to 40°C, add 0.4g azobisisobutylamidine hydrochloride and 25g mixture A, quickly heat to 75-82°C, and keep the temperature for 20-30min;

(4) After the solution in the reactor 1 becomes a clear solution, i.e. 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 min, and then the mixture is kept at 80° C. for 150 min;

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

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

Example 3

This embodiment provides a fluorine-free waterproofing agent, and the preparation method thereof is as follows:

(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 are sequentially added into a high-position mixing tank 1, and stirred at a high speed to obtain an opaque stable emulsion mixture A;

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

(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;

(4) After the solution in the reactor 1 becomes a clear solution, i.e. 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 min, and then the mixture is kept at 80° C. for 150 min;

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

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

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 is also required on product stability, the effect on fabric color and anti-yellowing performance.

The present application is further described below in conjunction with comparative examples. The embodiments and comparative examples are only used to help understand the present application and should not be regarded as specific limitations on the present application.

Comparative Example 1

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

1. Physical properties test

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

Table 1

As can be seen from Table 1, the bio-based fluorine-free waterproofing agent product prepared by the present 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.

2. Fluorine-free waterproofing agent application performance test

The bio-based fluorine-free waterproofing agents prepared in the above Examples 1-3 and the commercially commonly used waterproofing agent Comparative Example 1 were subjected to comparative tests.

2.1 Finishing agent application process:

Fabric: 100% cotton woven fabric

Process: Padding and baking

Application of bio-based fluorine-free waterproofing agent embodiments 1-3, padding and baking process:

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

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

S3. Moisture resurgence to evaluate waterproof performance.

2.2 The yellowing and waterproof properties of the embodiments and comparative examples were tested respectively:

(1) Softness evaluation method

Hand feel evaluation: The two fabric samples were evaluated by hand touch method, 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.

(2) Whiteness and color evaluation methods

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 whiteness change, the greater the yellowing. The test results are shown in Table 2.

(3) Waterproof test

Use a round iron ring to tighten the cloth, forming a 45 ^° angle with the water outlet, and the water outlet is 15 cm away from the center of the cloth surface. 100 mL of water is sprinkled vertically at a uniform speed. After the water is sprinkled, knock off the floating water on the cloth surface, observe the number and size of water marks and spots on the tested cloth surface, and score. 100 points means no water marks and spots, and the lower the score, the worse the waterproof effect.

Table 2

It can be seen from Table 2 that the products of Examples 1, 2, and 3 are superior to or close to conventional products on the market, are not easy to change color, and have good anti-yellowing effect. At the same time, the treated fabrics also have excellent hand feel and waterproof performance.

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 ends adhere to the yarn, and the strong adhesion 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 has less yellowing, good waterproof performance, and a soft and non-rough feel. The raw materials of the fluorine-free waterproofing agent made in the present application are derived from bio-based products, which can be completely biodegraded in the natural environment. It is environmentally friendly and safe, and improves the recyclability of the product. Life and environmental friendly values,

The applicant declares that the present application uses the above-mentioned embodiments to illustrate the bio-based fluorine-free waterproofing agent and its preparation method and application, but the present application is not limited to the above-mentioned detailed method, that is, it does not mean that the present application must rely on the above-mentioned detailed method to be implemented. The technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the present application product, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.

Claims (8)

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%; Matrix 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%; Defoamer 0.01%-0.5%; and The balance was deionized water. 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. 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 into 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. 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. 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. 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. 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. 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, a blended fabric of cotton and polyamide fibers, a blended fabric of cotton and polyester fibers, or Tencel.