Fluorine-free non-hazardous chemical substance waterproof agent and preparation method thereof

Abstract

The invention relates to a fluoride-free non-hazardous chemical substance waterproof agent and a preparation method thereof. The waterproof agent is prepared from the following raw materials in parts by weight: 10-110 parts of organic silicon resin, 10-100 parts of silicone oil and an isoparaffin solvent with the flash point of more than 62 DEG F, wherein the organic silicon resin comprises at least one of methyl MQ resin and vinyl MQ resin. The preparation method comprises the following steps: stirring a part of the solvent and the organic silicon resin at 40-50 DEG C for 1-3 hours to form a transparent solution; adding silicone oil and stirring for 30-60 minutes to obtain a mixed solution A; supplementing the residual solvent, and continuously stirring at 40-50 DEG C for 30-60 minutes to obtain a mixed solution B; and cooling to room temperature and filtering to obtain a finished product. According to the invention, perfluoro / polyfluoroalkyl compounds are completely not contained, so that the persistent pollution to the environment is avoided; a high-flash-point isoparaffin solvent (greater than 62 DEG F) is adopted, flammable and explosive risks are remarkably reduced, strict safety standards of transportation, storage and production are met, and the waterproof coating has efficient waterproof performance and ecological sustainability and meets the requirements of international environmental protection regulations.

Description

Technical Field

[0001] The present application relates to the technical field of waterproofing agents, and more specifically, to a fluorine-free and non-hazardous chemical waterproofing agent and a preparation method thereof. Background Art

[0002] Waterproofing agents are widely used in textiles, leather, paper, building materials, and industrial protection. By imparting hydrophobicity to materials, they enhance their stain resistance, weather resistance, and longevity. With the rapid development of outdoor sportswear, medical protective equipment, and environmentally friendly packaging materials, market demand for efficient, long-lasting, and environmentally friendly waterproofing technologies has surged.

[0003] At present, mainstream waterproofing agents rely on perfluoro / polyfluoroalkyl compounds, such as C8 / C6 fluorocarbon resins, which dominate the market due to their excellent hydrophobicity / oleophobicity and chemical stability. However, they have serious defects. Perfluoro / polyfluoroalkyl compounds are difficult to degrade and pose a great threat to the environment. In addition, some short-chain perfluoro / polyfluoroalkyl compounds are reproductive toxic and pose a serious threat to human health.

[0004] The industry has tried to develop fluorine-free solutions, and some non-fluorine waterproofing agents on the market use toxic cross-linking agents (such as formaldehyde resin) or organic solvents (toluene, xylene), which make the products flammable and explosive. Safety risks, classified as hazardous chemicals, restrict the product's export to high-end markets.

[0005] Therefore, the development of a fluorine-free, non-hazardous chemical waterproofing agent that is highly effective in waterproofing, environmentally sustainable, and safe to use has become an urgent need in the industry. Summary of the Invention

[0006] In order to solve the problems of the prior art, the present application provides a fluorine-free, non-hazardous chemical waterproofing agent and a preparation method thereof, which has high efficiency waterproofing, environmental sustainability and safety in use.

[0007] In the first aspect, the present application provides a fluorine-free and non-hazardous chemical waterproofing agent, which adopts the following technical solution:

[0008] A fluorine-free and non-hazardous chemical waterproofing agent, comprising the following raw materials in parts by weight:

[0009] 10-110 parts of silicone resin;

[0010] 10-100 parts of silicone oil;

[0011] Appropriate amount of solvent

[0012] The organic silicone resin includes at least one of methyl MQ resin and vinyl MQ resin, and the solvent is an isomer alkane with a flash point greater than 62F.

[0013] Preferably, the following raw materials are included in parts by weight:

[0014] 70-90 parts of silicone resin;

[0015] 10-30 parts of silicone oil;

[0016] Appropriate amount of solvent;

[0017] This raw material composition is used for fabrics.

[0018] Preferably, the following raw materials are included in parts by weight:

[0019] 10-30 parts of silicone resin;

[0020] 70-90 parts of silicone oil;

[0021] Appropriate amount of solvent;

[0022] This raw material composition is used for leather.

[0023] Preferably, the silicone oil is methyl silicone oil.

[0024] Preferably, the solvent is at least one of isotridecane, isotetradecane and isohexadecane.

[0025] In the second aspect, the present application provides a method for preparing a fluorine-free and non-hazardous chemical waterproofing agent, which adopts the following technical solution:

[0026] A method for preparing a fluorine-free and non-hazardous chemical waterproofing agent comprises the following steps: Step S1: In a reaction kettle equipped with a mechanical stirrer and a temperature control device, add a portion of an isoparaffin solvent with a flash point greater than 62°F, start stirring, slowly add the formulated amount of silicone resin, slowly raise the temperature to 40-50°C, and continue stirring for 1-3 hours to obtain a uniform, transparent solution.

[0027] Step S2: Slowly add the formulated amount of silicone oil to the transparent solution of step S1, and keep stirring for 30-60 minutes to obtain a mixed solution A;

[0028] Step S3: slowly adding the remaining isoparaffin solvent to the mixed solution A in step S2, and continuing stirring at 40-50° C. for 30-60 minutes to ensure that all components are extremely evenly mixed to obtain a mixed solution B;

[0029] Step S4: Stop heating, continue stirring the mixed solution B until it cools to room temperature, and filter the cooled liquid through a filter to obtain a waterproofing agent.

[0030] The technical effects of this application are:

[0031] 1. The system utilizes methyl / vinyl MQ resin and silicone oil, completely free of perfluorinated / polyfluorinated alkyl compounds, preventing the accumulation of persistent organic pollutants in the environment and complying with international environmental regulations. Formaldehyde-based crosslinkers and benzene-based solvents are eliminated, eliminating reproductive toxicity and carcinogenic risks, ensuring user health and safety. Solvents are limited to high-flashpoint isoparaffins with a flash point > 62°F, significantly reducing flammability and explosion risks and meeting safety standards for transportation, storage, and production.

[0032] 2. A high resin ratio of 70-90 parts is used to enhance film-forming properties and durability, and is suitable for waterproofing fabrics; a high silicone oil ratio of 70-90 parts is used to improve permeability and softness, and is suitable for waterproofing leather.

[0033] 3. In the preparation method of the present application, the temperature is controlled at 40-50°C throughout the entire process, and a low-temperature process is adopted to avoid high-temperature decomposition or volatility hazards. The step-by-step addition of isoparaffin ensures that the silicone resin is fully dispersed to form a stable and uniform solution, thereby ensuring the integrity of the waterproof film. DETAILED DESCRIPTION

[0034] The present invention is further described in detail below using specific examples. Unless otherwise specified, the raw materials, reagents, and apparatus used in the examples and comparative examples are available from conventional commercial sources or by conventional methods. Unless otherwise specified, all experimental or testing methods are conventional in the art.

[0035] Example 1

[0036] The present application provides a fluorine-free and non-hazardous chemical waterproofing agent, comprising the following raw materials by weight: 800g of methyl MQ resin, 200g of methyl silicone oil, and 1500g of isotridecane.

[0037] Based on the above raw materials, the present application provides a method for preparing a fluorine-free and non-hazardous chemical waterproofing agent, comprising the following steps: Step S1: In a reactor equipped with a mechanical stirrer and a temperature control device, 1000 g of isotridecane was added and stirring was started at 200 r / min. Then, 800 g of methyl MQ resin was slowly added. The temperature was slowly raised to 50°C and stirring was continued for 2 hours to obtain a uniform and transparent solution.

[0038] Step S2: Slowly add 200 g of methyl silicone oil to the transparent solution of step S1, and stir at a stirring speed of 400 r / min for 40 minutes to obtain a mixed solution A;

[0039] Step S3: Slowly add 500 g of isoparaffin solvent to the mixed solution A in step S2, and continue stirring at 400 r / min at 50° C. for 60 minutes to ensure that all components are mixed very evenly to obtain a mixed solution B;

[0040] Step S4: Stop heating, continue stirring the mixed solution B at 200 r / min until it cools to room temperature, and filter the cooled liquid through a 200-mesh filter to obtain a waterproofing agent with a solid content of 40%.

[0041] In the above embodiment, the methyl MQ resin has a high-strength hydrophobic skeleton, its Q unit forms a rigid siloxane skeleton, and the M unit provides a hydrophobic methyl group to form a low surface energy network, which directly gives the coating water repellency, and the Si-OH group in the molecule can form a hydrogen bond or covalent bond with the hydroxyl group on the substrate surface to enhance adhesion; methyl silicone oil has the effect of reducing surface tension to make the solution easy to spread, covering the micropores on the substrate surface, methyl silicone oil fills the gaps in the MQ resin network, alleviates brittleness, and enhances the flexibility of the coating, and the methyl groups of the methyl silicone oil are arranged toward the air, further enhancing water repellency. A composite system with a high proportion of methyl MQ resin and a low proportion of methyl silicone oil is used, so that the waterproofing agent has the characteristics of adapting to dynamic deformation and is suitable for use on fabrics.

[0042] Examples 2-4

[0043] The difference between Examples 2-4 and Example 1 lies in the different amounts, types and processes of raw materials, as shown in Table 1 below.

[0044]

[0045] Example 2 differs from Example 1 in that the organosilicon in Example 2 utilizes a vinyl MQ resin, and a platinum catalyst and hydrogenated silicone oil are added during the preparation process. The platinum catalyst and hydrogenated silicone oil are added together with the silicone oil in step S2. In this example, the vinyl MQ resin incorporates a vinyl group into a conventional MQ resin. This vinyl group can crosslink with the hydrogenated silicone oil through a platinum-catalyzed hydrosilylation reaction, forming a dense three-dimensional network structure with excellent waterproofing properties.

[0046] The difference between Example 3 and Example 1 is that the amounts of methyl MQ resin, methyl silicone oil, and isotridecane are different. By forming a composite system with a low proportion of methyl MQ resin and a high proportion of methyl silicone oil, the waterproofing agent has the characteristic of adapting to dynamic deformation and is suitable for use in leather.

[0047] The difference between Example 4 and Example 1 is that Example 4 uses silicone and vinyl MQ resin, and adds platinum catalyst and hydrogen-containing silicone oil in the preparation method. The platinum catalyst and hydrogen-containing silicone oil are added together with the silicone oil in step S2, and a composite system of a low proportion of methyl MQ resin and a high proportion of methyl silicone oil is formed, so that the waterproofing agent has the characteristics of adapting to dynamic deformation and is suitable for use in leather.

[0048] Comparative Example 1

[0049] Comparative Example 1

[0050] The difference between this comparative example and Example 1 is that this comparative example uses a commercially available fluorine-containing waterproofing agent, specifically purchased from Suzhou Heming Textile Auxiliary Agent Co., Ltd., and the model is Teflon three-proof finishing agent CP-SLA.

[0051] Comparative Example 2

[0052] Comparative Example 1

[0053] The difference between this comparative example and Example 1 is that this comparative example uses a commercially available fluorine-containing waterproofing agent, specifically purchased from Suzhou Heming Textile Auxiliary Agent Co., Ltd., and the model is Teflon three-proof finishing agent CP-SLA.

[0054] Performance Testing

[0055] The products prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were applied to fabrics and subjected to water repellency tests, anti-siphonage tests, and dynamic waterproofing tests. The fabrics were divided into three types: knitted, flywoven, and woven. All three types of fabrics were tested. All three types of fabrics consisted of a lining and an outer fabric. The double-layer fabrics were adhered with a hot-melt adhesive mesh. The lining had a mesh size of less than 0.5 mm and a tightness of less than 3000 mm / s. The outer fabric had a mesh size of less than 0.7 mm and a tightness of less than 3000 mm / s. The tightness of the combined double-layer fabrics was less than 1000 mm. The products prepared in Example 3, Comparative Example 1, and Comparative Example 2 were applied to leather and subjected to water repellency tests, anti-siphonage tests, and dynamic waterproofing tests.

[0056] During sample preparation, both fabric and leather were dried and cleaned. The fabric was then soaked in the waterproofing agents of Examples 1-2 and Comparative Examples 1-2 for 10 minutes. The fabric was removed after soaking, excess liquid was drained, and the fabric was placed in a well-ventilated, cool, and dry place for 48 hours. The leather was soaked in the waterproofing agents of Examples 2-4 and Comparative Examples 1-2 for 5 minutes. The leather was removed after soaking, excess liquid was drained, and the leather was placed in a well-ventilated, cool, and dry place for 48 hours.

[0057] This application's water repellency test references the AATCC 22 standard. Specific steps and judgment criteria are shown in Tables 2 and 3 below.

[0058] Table 2 Water repellency test method

[0059]

[0060] Table 3 Judgment criteria

[0061]

[0062] The anti-siphonage test in this application refers to the experimental method of SATRA TM163. The specific steps and judgment criteria are shown in Table 4 below.

[0063] Table 4 Anti-siphon test method and judgment standard

[0064]

[0065] The dynamic waterproof test of this application refers to the experimental method of ISO 17707. The specific method and judgment criteria are shown in Table 5 below.

[0066] Table 5 Methods and standards for dynamic waterproof testing

[0067]

[0068] The test results of the fabric of this application are shown in Table 6 below.

[0069] Table 6 Test results of fabrics

[0070]

[0071] The test results of the leather of this application are shown in Table 7 below.

[0072] Table 7 Leather test results

[0073]

[0074] Based on the test results in Tables 6 and 7 above, the waterproofing agent prepared using Example 1 of the present application has good static and dynamic waterproofing effects on fabrics. The waterproofing agent prepared using Example 3 of the present application has good static and dynamic waterproofing effects on leather. The fabric achieved a water repellency rating of 4-5 in the water splash test, an excellent anti-siphon test, and a dynamic waterproofing rating of 15,000-30,000 times; the leather achieved a water repellency rating of 5 in the water splash test, an excellent anti-siphon test, and a dynamic waterproofing rating of 10,000 times. The differences in fabric performance are due to the different processes used to produce different fabric tightness. Woven fabrics, being a more compact process, have better dynamic and static waterproofing effects.

[0075] The waterproofing agent prepared in Example 2 is the secondary solution of this application. The waterproofing agent prepared in Example 2 is applied to the fabric. The reason why it is worse than the waterproofing agent prepared in Example 1 is that the resins used are different. The water repellency of vinyl MQ resin is slightly inferior to that of methyl MQ resin.

[0076] In the comparison between Example 1 and Comparative Example 1, it is obvious that the static and dynamic waterproof properties of the fluorine-containing waterproof agent used in Comparative Example 1 are inferior to those of Example 1 when applied to fabrics and leather.

[0077] In the comparison between Example 1 and Comparative Example 2, it is obvious that the static and dynamic waterproof properties of the fluorine-containing waterproof agent used in Comparative Example 2 are inferior to those of Example 1 when applied to fabrics and leather.

Claims

1. A fluorine-free and non-hazardous chemical waterproofing agent, characterized in that: The invention comprises the following raw materials in parts by weight: 10-110 parts of silicone resin; 10-100 parts of silicone oil; Appropriate amount of solvent The organic silicone resin includes at least one of methyl MQ resin and vinyl MQ resin, and the solvent is an isomer alkane with a flash point greater than 62F.

2. The fluorine-free and non-hazardous chemical waterproofing agent according to claim 1, characterized in that: The invention comprises the following raw materials in parts by weight: 70-90 parts of silicone resin; 10-30 parts of silicone oil; Appropriate amount of solvent.

3. The fluorine-free and non-hazardous chemical waterproofing agent according to claim 1, characterized in that: The invention comprises the following raw materials in parts by weight: 10-30 parts of silicone resin; 70-90 parts of silicone oil; Appropriate amount of solvent.

4. A fluorine-free, non-hazardous chemical waterproofing agent according to any one of claims 2-3, characterized in that: The silicone oil is methyl silicone oil.

5. A fluorine-free, non-hazardous chemical waterproofing agent according to any one of claims 2-3, characterized in that: The solvent is at least one of isotridecane, isotetradecane and isohexadecane.

6. The fluorine-free and non-hazardous chemical waterproofing agent according to claim 2, characterized in that: The raw materials are applied to fabrics.

7. The fluorine-free and non-hazardous chemical waterproofing agent according to claim 3, characterized in that: The raw material is applied to leather.

8. The method for preparing a fluorine-free and non-hazardous chemical waterproofing agent according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step S1: In a reaction kettle equipped with a mechanical stirrer and a temperature control device, add a portion of an isoparaffin solvent with a flash point greater than 62°F, start stirring, slowly add the formulated amount of silicone resin, slowly raise the temperature to 40-50°C, and continue stirring for 1-3 hours to obtain a uniform, transparent solution. Step S2: Slowly add the formulated amount of silicone oil to the transparent solution of step S1, and keep stirring for 30-60 minutes to obtain a mixed solution A; Step S3: slowly adding the remaining isoparaffin solvent to the mixed solution A in step S2, and continuing stirring at 40-50° C. for 30-60 minutes to ensure that all components are extremely evenly mixed to obtain a mixed solution B; Step S4: Stop heating, continue stirring the mixed solution B until it cools to room temperature, and filter the cooled liquid through a filter to obtain a waterproofing agent.

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