A bio-based fluorine-free water repellent and a method for preparing the same

Abstract

The application belongs to the technical field of new materials, and particularly relates to a bio-based fluorine-free waterproof agent and a preparation method thereof. The bio-based fluorine-free waterproof agent provided by the application comprises the following raw materials and mass fractions: water-repellent polymer 150-200 parts, emulsifier 25-35 parts, and water 400-500 parts; the water-repellent polymer is obtained by reacting bio-based cardanol dimer and bio-based aliphatic isocyanate under the action of a catalyst. The bio-based fluorine-free waterproof agent provided by the application takes natural, non-food chain, annually renewable bio-based materials as main raw materials, can effectively reduce carbon emissions, and makes a positive contribution to the global greenhouse gas emission reduction plan, and the bio-based fluorine-free waterproof agent provided by the application is a novel environment-friendly fluorine-free waterproof agent product with the advantages of high washability and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of new materials, and in particular relates to a bio-based fluorine-free waterproofing agent and a preparation method thereof. Background Art

[0002] The use of fossil fuels (coal, oil, and natural gas) releases carbon trapped on Earth for eons back into the atmosphere, accumulating to create a greenhouse effect. Climate change and the resulting need to reduce greenhouse gas emissions necessitate a shift in human thinking. A more ideal solution is to replace fossil fuels with bio-based products. Plants absorb carbon dioxide from the air through photosynthesis. Using this carbon from plant or microbial biomass in manufacturing removes CO2 from the environment while ensuring that the natural biocarbon cycle is not disrupted. While oil won't be completely replaced, even partial replacement can significantly reduce our carbon footprint. In recent years, bio-based chemicals have experienced rapid development, with breakthroughs in key technologies, a rapidly expanding product range, and enhanced economics. Bio-based chemicals are becoming a hotspot for industrial investment, demonstrating strong momentum. my country has also formulated a corresponding national standard, GB / T39514-2020, "Definitions, Terminology, and Labeling of Bio-based Materials." This standard, which will standardize the definitions, terminology, and labeling of bio-based materials, is a crucial component of the bio-based materials standards system and will significantly promote their development. As individuals and industries seek ways to reduce their environmental footprint, demand for bio-based chemicals is expected to grow strongly in the coming years. In the new materials industry, the share of bio-based products and processing aids continues to grow. Compared with materials synthesized from fossil raw materials, bio-based products can effectively help reduce carbon dioxide emissions.

[0003] Waterproofing agents are functional finishing agents that impart water-repellency to fabrics treated with them. They are widely used in outdoor sportswear, umbrellas, tents, and other applications. Traditional waterproofing agents are generally perfluoroalkyl acrylate polymer emulsions. For example, Chinese patent application CN105777977A discloses a fluorine-containing fabric waterproofing agent composed of the following raw materials by weight: 6% to 14% perfluoroalkyl ethyl acrylate, 9% to 17% acrylic resin, 9% to 13% octamethyltetrasiloxane, 1% to 5% carboxymethyl cellulose, 5% to 13% polyvinyl alcohol, 1% to 9% crosslinking monomer, 0.2% to 0.5% surfactant, 0.5% to 0.9% initiator, and 60% to 70% deionized water. Chinese patent application CN111321595A discloses a method for preparing a waterproofing agent resistant to harsh environments, comprising the following steps: S1) adding 10%-30% of a special waterproofing agent B to 86.2%-63.1% of a conventional waterproofing agent A; S2) adding 3%-5% of isopropyl alcohol; S3) adding 0.5%-1.2% of a fatty alcohol polyoxyethylene ether while stirring; S4) adding 0.3%-0.7% of a stabilizer C while stirring, and stirring until uniformly mixed to produce the novel waterproofing agent. A is a perfluoroalkyl acrylate copolymer, B is a perfluoroalkyl acrylate copolymer, and C is an alkyl phosphate and fatty alcohol ethoxylate compound. While this type of waterproofing agent offers excellent water and oil resistance, excellent washability, and low cost, its use is restricted due to the presence of fluorine-containing waterproofing agents, such as PFOS and PFOA, which are known to cause serious environmental pollution.

[0004] Fluorine-free water repellents offer excellent waterproofing properties and minimal environmental pollution, making them a research hotspot in related fields. However, existing technologies generally use petrochemical raw materials to produce fluorine-free water repellents, which can lead to carbon emissions. Furthermore, current fluorine-free water repellents lack washability. Highly washable fluorine-free water repellents are essential functional finishing agents for various functional textiles. Therefore, the development of a fluorine-free water repellent with low environmental impact and high washability is urgently needed. Summary of the Invention

[0005] In response to the shortcomings of the existing technology, the present invention aims to provide a bio-based fluorine-free waterproofing agent and its preparation method. This bio-based fluorine-free waterproofing agent, primarily made from natural, non-food chain, annually renewable bio-based materials, can effectively reduce carbon emissions and contribute positively to global greenhouse gas reduction initiatives. The bio-based fluorine-free waterproofing agent provided by the present invention is a novel, environmentally friendly fluorine-free waterproofing agent product with advantages such as high washability.

[0006] The technical solution of the present invention is:

[0007] A bio-based fluorine-free waterproofing agent comprises the following raw materials and their weight fractions: 150-200 parts of a water-repellent polymer, 25-35 parts of an emulsifier, and 400-500 parts of water; the water-repellent polymer is obtained by reacting a bio-based cardanol dimer and a bio-based aliphatic isocyanate under the action of a catalyst.

[0008] The present invention uses a diphenol raw material (bio-based cardanol dimer) synthesized from bio-based cardanol to form a polyurethane structure polymer through block copolymerization with a bio-based aliphatic isocyanate as the main component of a bio-based fluorine-free water repellent, solving the carbon emission problem caused by the common use of petrochemical raw materials in the existing technology to produce fluorine-free water repellents. The structure of cardanol is shown in Formula 1 below. The benzene ring of cardanol has a long carbon chain of 15 carbon atoms and an unsaturated double bond on the carbon chain. Two cardanol molecules react through the unsaturated double bond away from the benzene ring to form a diphenol. In this way, the diphenols are connected by a long carbon chain of 30 carbon atoms. This 30-carbon long carbon chain has excellent water repellency and can significantly improve the waterproofing performance of the water repellent.

[0009] .

[0010] Formula 1

[0011] Furthermore, the bio-based cardanol dimer obtained in the present invention has good softness. Its application in a bio-based fluorine-free waterproofing agent can impart excellent softness to the waterproofing agent. Furthermore, the present invention polymerizes the dimerized phenol monomer with a bio-based isocyanate to form a water-repellent polymer with a polyurethane structure as a component of the waterproofing agent of the present invention. The polyurethane structure has active isocyanate functional groups. When applied to a waterproofing finish for fabrics, the isocyanate functional groups undergo a cross-linking reaction with hydroxyl groups, amino groups, and other groups on the fabric surface, forming covalent bonds, resulting in excellent wash resistance.

[0012] Furthermore, the bio-based fluorine-free waterproofing agent includes the following raw materials and their weight proportions: 170.2 parts of water-repellent polymer, 30 parts of emulsifier, and 450 parts of water.

[0013] Furthermore, the bio-based cardanol dimer is obtained by addition polymerization of two cardanols.

[0014] Furthermore, the preparation method of the bio-based cardanol dimer is as follows: adding acidic white clay and lithium carbonate to bio-based cardanol, heating to 220-240°C, keeping warm for 3-5 hours, cooling to room temperature, and filtering to obtain a bio-based cardanol dimer semi-finished product; vacuuming the obtained bio-based cardanol dimer semi-finished product, heating it, and performing reduced pressure distillation, and the remaining liquid in the kettle is the purified bio-based cardanol dimer.

[0015] The bio-based cardanol dimer obtained in the present invention can be well polymerized with diisocyanate to form a polyurethane polymer substance, which is the waterproofing agent component of the present invention, to improve the waterproof and washing resistance.

[0016] Furthermore, the mass ratio of the bio-based cardanol, acidic clay and lithium carbonate is 80-120:10-15:0.3-0.7.

[0017] Furthermore, the mass ratio of the bio-based cardanol, acidic clay and lithium carbonate is 100:12:0.5.

[0018] Furthermore, the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0019] Furthermore, the preparation method of the water-repellent polymer is as follows: adding a solvent and a catalyst to the bio-based cardanol dimer, introducing nitrogen, raising the temperature to 65-90° C., adding a bio-based aliphatic isocyanate dropwise, and after the addition is complete, keeping the temperature to react and cooling to room temperature to obtain the water-repellent polymer.

[0020] Furthermore, the catalyst is an organic bismuth catalyst, and the solvent is acetone.

[0021] Furthermore, the catalyst is an organic bismuth catalyst Coscat® 83.

[0022] Furthermore, the mass ratio of the bio-based cardanol dimer, bio-based aliphatic isocyanate and catalyst is 80-120:45-55:0.001-0.003.

[0023] Furthermore, the mass ratio of the bio-based cardanol dimer, bio-based aliphatic isocyanate and catalyst is 100:52.2:0.0025.

[0024] Furthermore, the emulsifier includes cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride.

[0025] Furthermore, the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a mass ratio of 15-25:7-10.

[0026] Furthermore, the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a mass ratio of 21:9.

[0027] The emulsifier, formulated from cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride, enhances emulsion stability, making the bio-based fluorine-free waterproofing agent less susceptible to demulsification during application, thereby maintaining excellent performance. The addition of bio-based cardanol polyoxyethylene ether to the emulsification system achieves efficient emulsification while reducing carbon emissions associated with traditional petrochemical-based emulsifiers.

[0028] The present invention also provides a method for preparing the bio-based fluorine-free waterproofing agent, comprising the following steps:

[0029] S1: adding an emulsifier to a water-repellent polymer, stirring and mixing the mixture to obtain a mixture;

[0030] S2: adding the mixture obtained in step S1 into water for dispersion and emulsification to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent;

[0031] In step S3, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S2 is homogenized in a high-pressure homogenizer, filtered, discharged and packaged to obtain the bio-based fluorine-free waterproofing agent.

[0032] Furthermore, the dispersion and emulsification speed in step S2 is 2500-3500 rpm.

[0033] The present invention first uses a high-speed dispersing disk to add deionized water in the presence of an emulsifier, and obtains a bio-based fluorine-free waterproofing agent pre-emulsion through a phase inversion emulsification method, and then homogenizes it multiple times with a high-pressure homogenizer to obtain an emulsion with uniform particle size and good stability.

[0034] In the preparation method of the bio-based fluorine-free waterproofing agent of the present invention, an emulsifier is added to a water-repellent polymer, stirred and mixed uniformly to obtain a mixture, water is added under high-speed stirring, and as water is continuously added, the mixture undergoes emulsification and phase transition, and the viscosity gradually increases when water is initially added and sharply decreases after the phase transition occurs. Stirring and emulsification are continued to obtain a semi-finished product of the bio-based fluorine-free waterproofing agent, and the semi-finished product of the bio-based fluorine-free waterproofing agent is cyclically homogenized four times in a high-pressure homogenizer, filtered, discharged and packaged to obtain the target product of the present invention, the bio-based fluorine-free waterproofing agent.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] The main raw materials of the bio-based fluorine-free waterproofing agent of the present invention are all natural, non-food chain, annually renewable bio-based materials. Compared with traditional fluorine-free waterproofing agents based on petrochemical raw materials, it can effectively reduce carbon emissions and make positive contributions to the global greenhouse gas emission reduction plan.

[0037] (2) The bio-based fluorine-free waterproofing agent provided by the present invention is a new type of environmentally friendly fluorine-free waterproofing agent product with the advantages of high wash resistance and soft feel. In terms of waterproof performance, it reaches or approaches the level of traditional C8 waterproofing agent, has a soft feel, and its wash resistance reaches or exceeds the level of fluorine-containing waterproofing agent. DETAILED DESCRIPTION

[0038] The present invention is further illustrated below by describing specific implementation methods, but this is not intended to limit the present invention. Those skilled in the art can make various modifications or improvements based on the basic ideas of the present invention, but as long as they do not deviate from the basic ideas of the present invention, they are all within the scope of the present invention.

[0039] Unless otherwise specified, the raw materials used in this invention are commercially available. For example, bio-based cardanol can be purchased from Cardolite Chemicals (Zhuhai) Co., Ltd., model number NX-2024; the organobismuth catalyst is a product of Vertellus (USA), trade name Coscat® 83; and bio-based 1,5-pentamethylene diisocyanate is a product of Mitsui Chemicals Inc. (Japan), trade name STABiO PDI.

[0040] Example 1: A bio-based fluorine-free waterproofing agent

[0041] The bio-based fluorine-free waterproofing agent comprises the following raw materials and their weight fractions: 150 parts of a water-repellent polymer, 25 parts of an emulsifier, and 400 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 15:10;

[0042] The water-repellent polymer includes the following raw materials and their weight fractions: 80 parts of bio-based cardanol dimer, 15 parts of solvent, 0.001 parts of catalyst, and 45 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is the organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0043] The preparation method of the water-repellent polymer comprises the following steps: adding bio-based cardanol dimer into a reaction kettle, adding a solvent, adding a catalyst, starting stirring, introducing nitrogen to replace oxygen for 10 minutes, controlling the heating rate at 2°C / min to heat to 65°C, and adding bio-based aliphatic isocyanate dropwise at a rate of 0.5 kg / min. After the addition is complete, the mixture is kept warm for 4 hours and then cooled to room temperature to obtain the water-repellent polymer.

[0044] The bio-based cardanol dimer includes the following raw materials and their weight proportions: 80 parts of bio-based cardanol, 10 parts of acid clay, and 0.3 parts of lithium carbonate.

[0045] The method for synthesizing the bio-based cardanol dimer comprises the following steps:

[0046] (1) Add bio-based cardanol into a clean enamel reactor, start stirring, add acidic white clay and lithium carbonate, introduce nitrogen, replace oxygen for 10 minutes, control the heating rate to 2°C / min, heat to 220°C, keep warm for 3 hours, cool to room temperature, and filter the reaction liquid into a filter press to obtain a bio-based cardanol dimer semi-finished product;

[0047] (2) The semi-finished product of the bio-based cardanol dimer obtained in step (1) is added to a reactor, vacuumed to 60 Pa, and the temperature is raised to 300 ° C at a controlled heating rate of 2 ° C / min. Unreacted raw materials are removed by vacuum distillation until no distillate flows out. The remaining liquid in the reactor is the purified bio-based cardanol dimer.

[0048] The preparation method of the bio-based fluorine-free waterproofing agent comprises the following steps:

[0049] S1: mixing cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride to obtain an emulsifier;

[0050] S2: adding the emulsifier obtained in step S1 to the water-repellent polymer, stirring and mixing uniformly to obtain a mixture;

[0051] S3: adding the mixture obtained in step S2 to an emulsifying kettle equipped with a high-speed dispersing disk, turning on the high-speed dispersing disk, and adding deionized water at a speed of 30 L / min for high-speed dispersing and emulsification. The dispersing and emulsifying speed during high-speed dispersing and emulsification is 2500 rpm. After all the water is added, the dispersing and emulsifying time is continued for 0.5 hour to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent;

[0052] In step S4, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S3 is fed into a high-pressure homogenizer for homogenization through a delivery pump. The homogenization pressure is set to 45 MPa, the rated flow rate of the homogenizer is 3000 L / hour, and the product is circulated and homogenized for 4 times. The product is filtered, discharged, and packaged to obtain the bio-based fluorine-free waterproofing agent.

[0053] Example 2: A bio-based fluorine-free waterproofing agent

[0054] The bio-based fluorine-free waterproofing agent includes the following raw materials and their weight fractions: 200 parts of water-repellent polymer, 35 parts of emulsifier, and 500 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 25:7;

[0055] The water-repellent polymer includes the following raw materials and their weight fractions: 120 parts of bio-based cardanol dimer, 20 parts of solvent, 0.003 parts of catalyst, and 55 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is the organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0056] The preparation method of the water-repellent polymer comprises the following steps: adding bio-based cardanol dimer into a reaction kettle, adding a solvent, adding a catalyst, starting stirring, introducing nitrogen to replace oxygen for 20 minutes, controlling the heating rate to be 2°C / minute, heating to 90°C, adding bio-based aliphatic isocyanate dropwise at a rate of 1.0 kg / min, and after the addition is complete, keeping the temperature for 8 hours and cooling to room temperature to obtain the water-repellent polymer.

[0057] The bio-based cardanol dimer includes the following raw materials and their weight proportions: 120 parts of bio-based cardanol, 15 parts of acidic clay, and 0.7 parts of lithium carbonate.

[0058] The method for synthesizing the bio-based cardanol dimer comprises the following steps:

[0059] (1) Add bio-based cardanol into a clean enameled reactor, start stirring, add acidic white clay and lithium carbonate, introduce nitrogen, replace oxygen for 20 minutes, control the heating rate to 2°C / min, heat to 240°C, keep warm for 5 hours, cool to room temperature, and filter the reaction liquid into a filter press to obtain a bio-based cardanol dimer semi-finished product;

[0060] (2) The semi-finished product of the bio-based cardanol dimer obtained in step (1) is added to a reactor, vacuumed to 60 Pa, and the temperature is raised to 300 ° C at a controlled heating rate of 2 ° C / min. Unreacted raw materials are removed by vacuum distillation until no distillate flows out. The remaining liquid in the reactor is the purified bio-based cardanol dimer.

[0061] The preparation method of the bio-based fluorine-free waterproofing agent comprises the following steps:

[0062] S1: mixing cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride to obtain an emulsifier;

[0063] S2: adding the emulsifier obtained in step S1 to the water-repellent polymer, stirring and mixing uniformly to obtain a mixture;

[0064] S3: adding the mixture obtained in step S2 to an emulsifying kettle equipped with a high-speed dispersing disk, turning on the high-speed dispersing disk, and adding deionized water at a speed of 30 L / min for high-speed dispersing and emulsification. The dispersing and emulsifying speed during high-speed dispersing and emulsification is 3500 rpm. After all the water is added, the dispersing and emulsifying time is continued for 1.5 hours to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent;

[0065] In step S4, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S3 is fed into a high-pressure homogenizer for homogenization through a delivery pump. The homogenization pressure is set to 45 MPa, the rated flow rate of the homogenizer is 3000 L / hour, and the product is circulated and homogenized for 4 times. The product is filtered, discharged, and packaged to obtain the bio-based fluorine-free waterproofing agent.

[0066] Example 3: A bio-based fluorine-free waterproofing agent

[0067] The bio-based fluorine-free waterproofing agent includes the following raw materials and their weight fractions: 170.2 parts of a water-repellent polymer, 30 parts of an emulsifier, and 450 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 21:9;

[0068] The water-repellent polymer includes the following raw materials and their weight fractions: 100 parts of bio-based cardanol dimer, 18 parts of solvent, 0.0025 parts of catalyst, and 52.2 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is an organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0069] The preparation method of the water-repellent polymer comprises the following steps: adding bio-based cardanol dimer into a reaction kettle, adding a solvent, adding a catalyst, starting stirring, introducing nitrogen to replace oxygen for 15 minutes, controlling the heating rate to be 2°C / min, heating to 75°C, adding bio-based aliphatic isocyanate dropwise at a rate of 0.6 kg / min, and after the addition is complete, keeping the temperature for 6 hours and cooling to room temperature to obtain the water-repellent polymer.

[0070] The bio-based cardanol dimer includes the following raw materials and their weight proportions: 100 parts of bio-based cardanol, 12 parts of acidic clay, and 0.5 parts of lithium carbonate.

[0071] The method for synthesizing the bio-based cardanol dimer comprises the following steps:

[0072] (1) Add bio-based cardanol into a clean enameled reactor, start stirring, add acidic white clay and lithium carbonate, introduce nitrogen, replace oxygen for 15 minutes, control the heating rate to 2°C / min, heat to 230°C, keep warm for 4 hours, cool to room temperature, and filter the reaction liquid into a filter press to obtain a bio-based cardanol dimer semi-finished product;

[0073] (2) The semi-finished product of the bio-based cardanol dimer obtained in step (1) is added to a reactor, vacuumed to 60 Pa, and the temperature is raised to 300 ° C at a controlled heating rate of 2 ° C / min. Unreacted raw materials are removed by vacuum distillation until no distillate flows out. The remaining liquid in the reactor is the purified bio-based cardanol dimer.

[0074] The preparation method of the bio-based fluorine-free waterproofing agent comprises the following steps:

[0075] S1: mixing cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride to obtain an emulsifier;

[0076] S2: adding the emulsifier obtained in step S1 to the water-repellent polymer, stirring and mixing uniformly to obtain a mixture;

[0077] S3: adding the mixture obtained in step S2 to an emulsifying kettle equipped with a high-speed dispersing disk, turning on the high-speed dispersing disk, and adding deionized water at a speed of 30 L / min for high-speed dispersing and emulsification. The dispersing and emulsifying speed during high-speed dispersing and emulsification is 3000 rpm. After all the water is added, the dispersing and emulsifying time is continued for 1 hour to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent;

[0078] In step S4, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S3 is fed into a high-pressure homogenizer for homogenization through a delivery pump. The homogenization pressure is set to 45 MPa, the rated flow rate of the homogenizer is 3000 L / hour, and the product is circulated and homogenized for 4 times. The product is filtered, discharged, and packaged to obtain the bio-based fluorine-free waterproofing agent.

[0079] Comparative Example 1

[0080] The bio-based fluorine-free waterproofing agent includes the following raw materials and their weight fractions: 170.2 parts of a water-repellent polymer, 30 parts of an emulsifier, and 450 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 21:9;

[0081] The water-repellent polymer includes the following raw materials and their weight fractions: 100 parts of bio-based cardanol dimer, 18 parts of solvent, 0.0025 parts of catalyst, and 52.2 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is an organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based L-lysine diisocyanate.

[0082] The preparation methods of the water-repellent polymer, bio-based cardanol dimer, and bio-based fluorine-free waterproofing agent are similar to those in Example 3;

[0083] The difference from Example 3 is that bio-based L-lysine diisocyanate is used instead of bio-based 1,5-pentamethylene diisocyanate.

[0084] Comparative Example 2

[0085] The bio-based fluorine-free waterproofing agent includes the following raw materials and their weight fractions: 170.2 parts of a water-repellent polymer, 30 parts of an emulsifier, and 450 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 21:9;

[0086] The water-repellent polymer includes the following raw materials and their weight fractions: 100 parts of bio-based oleic acid dimer (dimer acid), 18 parts of solvent, 0.0025 parts of catalyst, and 52.2 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is the organic bismuth catalyst Coscat® 83; the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate; the bio-based oleic acid dimer (dimer acid) is produced by Croda Chemicals of the United Kingdom and is traded under the name Pripol 1013;

[0087] The preparation methods of the water-repellent polymer and the bio-based fluorine-free waterproofing agent are similar to those in Example 3;

[0088] The difference from Example 3 is that bio-based oleic acid dimer is used instead of bio-based cardanol dimer.

[0089] Comparative Example 3

[0090] The bio-based fluorine-free waterproofing agent comprises the following raw materials and their weight fractions: 170.2 parts of component A, 30 parts of emulsifier, and 450 parts of deionized water; the emulsifier is composed of cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 21:9;

[0091] Component A includes the following raw materials and their weight fractions: 100 parts of bio-based cardanol, 18 parts of solvent, 0.0025 parts of catalyst, and 52.2 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is an organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0092] The preparation method of component A is as follows: bio-based cardanol is added into a reactor, a solvent is added, a catalyst is added, stirring is started, nitrogen is introduced to replace oxygen for 15 minutes, the temperature is raised to 75°C at a rate of 2°C / min, and bio-based aliphatic isocyanate is added dropwise at a rate of 0.6 kg / min. After the addition is completed, the temperature is kept for 6 hours and then cooled to room temperature to obtain the product.

[0093] The preparation method of the bio-based fluorine-free waterproofing agent comprises the following steps:

[0094] S1: mixing cardanol polyoxyethylene ether and octadecyltrimethylammonium chloride to obtain an emulsifier;

[0095] S2: adding the emulsifier obtained in step S1 to component A, stirring and mixing uniformly to obtain a mixture;

[0096] S3: adding the mixture obtained in step S2 to an emulsifying kettle equipped with a high-speed dispersing disk, turning on the high-speed dispersing disk, and adding deionized water at a speed of 30 L / min for high-speed dispersing and emulsification. The dispersing and emulsifying speed during high-speed dispersing and emulsification is 3000 rpm. After all the water is added, the dispersing and emulsifying time is continued for 1 hour to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent;

[0097] In step S4, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S3 is fed into a high-pressure homogenizer for homogenization through a delivery pump. The homogenization pressure is set to 45 MPa, the rated flow rate of the homogenizer is 3000 L / hour, and the product is circulated and homogenized for 4 times. The product is filtered, discharged, and packaged to obtain the bio-based fluorine-free waterproofing agent.

[0098] Comparative Example 4

[0099] The bio-based fluorine-free waterproofing agent includes the following raw materials and their weight fractions: 170.2 parts of a water-repellent polymer, 30 parts of an emulsifier, and 450 parts of deionized water; the emulsifier is composed of fatty alcohol polyoxyethylene ether and octadecyltrimethylammonium chloride in a weight ratio of 21:9;

[0100] The water-repellent polymer includes the following raw materials and their weight fractions: 100 parts of bio-based cardanol dimer, 18 parts of solvent, 0.0025 parts of catalyst, and 52.2 parts of bio-based aliphatic isocyanate; the solvent is acetone; the catalyst is an organic bismuth catalyst Coscat® 83; and the bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

[0101] The preparation methods of the water-repellent polymer, bio-based cardanol dimer, and bio-based fluorine-free waterproofing agent are similar to those in Example 3;

[0102] The difference from Example 3 is that fatty alcohol polyoxyethylene ether is used instead of cardanol polyoxyethylene ether.

[0103] Test Example 1: Waterproof and washability test

[0104] 1. Test fabrics: 50D polyester filament gray; 20D nylon taffeta brown.

[0105] 2. Test materials: sample (Example / Comparative Example / Waterproofing Agent R3 (Archroma, Switzerland)) + crosslinking agent HF 40.

[0106] 3. Process conditions: one dip and one roll → bake at 170°C for 50 seconds.

[0107] 4. Test method:

[0108] (1) Waterproof performance test: Refer to GB / T4745-2012 "Test and evaluation of waterproof performance of textiles: Water method" to test the waterproof performance of the fabric, with a full score of 100 points.

[0109] (2) Washing resistance test: Wash the fabric in accordance with GB / T8629-2001 “Household washing and drying procedure for textile testing” and then refer to GB / T4745-2012 “Testing and evaluation of the waterproof performance of textiles: Water-impregnation method” for implementation.

[0110] 5. Test results: The test results are shown in Table 1, Table 2 and Table 3.

[0111] Table 1: Initial waterproof performance test results of 50D polyester filament gray and 20D nylon spun brown fabrics

[0112]

[0113] Table 2: Washability test results of 50D polyester filament gray fabric

[0114]

[0115] Table 3: Washing resistance test results of 20D nylon spun brown fabric

[0116]

[0117] As can be seen from Tables 1 to 3, the bio-based fluorine-free waterproofing agent provided in Examples 1 to 3 of the present invention can make the fabric have good initial waterproof performance when the concentration reaches 60 g / L during use, and 50D polyester filament gray and 20D nylon spun coffee color still have high waterproofness after multiple washing with the bio-based fluorine-free waterproofing agent of the present invention, that is, the washability is also relatively good, and the washability is significantly better than that of Comparative Examples 1-4 and waterproofing agent R3. This shows that the bio-based fluorine-free waterproofing agent provided by the present invention has the advantage of high washability.

Claims

1. A bio-based fluorine-free waterproofing agent, characterized in that: The invention comprises the following raw materials and their weight proportions: 150-200 parts of a water-repellent polymer, 25-35 parts of an emulsifier, and 400-500 parts of water; the water-repellent polymer is obtained by reacting a bio-based cardanol dimer and a bio-based aliphatic isocyanate under the action of a catalyst; The bio-based cardanol dimer is obtained by an addition reaction of two cardanols; The preparation method of the bio-based cardanol dimer comprises: adding acidic white clay and lithium carbonate to the bio-based cardanol, heating the mixture to 220-240° C., keeping the temperature for 3-5 hours, cooling the mixture to room temperature, and performing pressure filtration to obtain a semi-finished bio-based cardanol dimer; evacuating the semi-finished bio-based cardanol dimer, heating the mixture, and performing reduced pressure distillation to obtain the purified bio-based cardanol dimer. The mass ratio of the bio-based cardanol dimer, the bio-based aliphatic isocyanate and the catalyst is 80-120:45-55:0.001-0.

003.

2. The bio-based fluorine-free waterproofing agent according to claim 1, characterized in that The bio-based aliphatic isocyanate is bio-based 1,5-pentamethylene diisocyanate.

3. The bio-based fluorine-free waterproofing agent according to claim 1, characterized in that The preparation method of the water-repellent polymer comprises the following steps: adding a solvent and a catalyst to a bio-based cardanol dimer, introducing nitrogen, heating to 65-90° C., dropwise adding a bio-based aliphatic isocyanate, and after the dropwise addition is complete, keeping the temperature for reaction and cooling to room temperature to obtain the water-repellent polymer.

4. The bio-based fluorine-free waterproofing agent according to claim 3, characterized in that The catalyst is an organic bismuth catalyst, and the solvent is acetone.

5. The bio-based fluorine-free waterproofing agent according to claim 1, characterized in that The emulsifier includes cardanol polyoxyethylene ether and octadecyl trimethyl ammonium chloride, and the mass ratio of cardanol polyoxyethylene ether to octadecyl trimethyl ammonium chloride in the emulsifier is 15-25:7-10.

6. The method for preparing a bio-based fluorine-free waterproofing agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1: adding an emulsifier to a water-repellent polymer, stirring and mixing the mixture to obtain a mixture; S2: adding the mixture obtained in step S1 into water for dispersion and emulsification to obtain a semi-finished product of a bio-based fluorine-free waterproofing agent; In step S3, the semi-finished product of the bio-based fluorine-free waterproofing agent obtained in step S2 is homogenized in a high-pressure homogenizer, filtered, discharged and packaged to obtain the bio-based fluorine-free waterproofing agent.

7. The method for preparing a bio-based fluorine-free waterproofing agent according to claim 6, wherein: The dispersion and emulsification speed in step S2 is 2500-3500 rpm.

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