Preparation method of structure-controllable fluorine-free waterproof agent
Triblock copolymers were prepared by segmental polymerization of RAFT reagent and blocked acryloyloxyethyl isocyanate, which solved the problems of poor durability and waterproof performance of fluorine-free waterproofing agents, and realized the preparation of efficient and energy-saving waterproofing agents, which are suitable for textiles and other fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HEFEI UNIV OF TECH
- Filing Date
- 2026-06-16
- Publication Date
- 2026-07-24
AI Technical Summary
The existing preparation process of fluorine-free waterproofing agents is difficult to control, resulting in a wide distribution of polymer molecular weight and random molecular structure. It is impossible to achieve precise control of polymer chain sequence and block length, which leads to poor product performance stability, large batch-to-batch differences, and poor durability and waterproofing performance.
A triblock copolymer composed of octadecyl acrylate, blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane was prepared by segmental polymerization using RAFT reagent and blocked acryloyloxyethyl isocyanate (APU). Adhesion and durability were improved by reversible dynamic oxime-carbamate bonds, and the polymer structure was precisely controlled by low-temperature curing technology.
It significantly improves the durability and waterproof performance of fluorine-free waterproofing agents. Fabrics retain good hydrophobicity and water-repellent properties even after twenty washes, reducing production energy consumption and making it suitable for large-scale continuous production.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of fine polymer materials technology, specifically relating to a fluorine-free waterproofing agent with controllable structure and its preparation method. Background Technology
[0002] Waterproofing agents, as important functional additives, are widely used in textiles, non-woven fabrics, paper, leather, building materials, and other fields. The core function of waterproofing agents is to form a hydrophobic protective layer on the substrate surface, preventing liquid water penetration while preserving the substrate's inherent properties such as breathability and feel, thus extending the substrate's lifespan and expanding its application scenarios. Acrylic ester-based fluorine-free waterproofing agents are currently the mainstream because their preparation process avoids the large-scale use of organic solvents, making the process relatively simple and environmentally friendly. One method involves introducing long-chain alkyl acrylates (such as octadecyl acrylate) to provide hydrophobic side chains and preparing waterproofing agents using emulsion polymerization. These products have good film-forming properties, but their waterproofing effect often depends on the directional arrangement of the hydrophobic segments. Once the coating is subjected to friction or washing, the surface structure is easily damaged, leading to a significant decrease in waterproofing performance and insufficient durability. Another method involves preparing a fluorine-free waterproofing agent through a composite of polyacrylate microspheres and silica (SiO2) nanoparticles. This waterproofing agent exhibits good waterproofing effects, but the nanoparticles are prone to aggregation, affecting the coating's function and resulting in insufficient durability. Another method utilizes bio-based polyurethane monomers and functional crosslinking monomers with bio-based acrylates via free radical polymerization to obtain fluorine-free water repellents. By introducing hydrophobic groups onto the side groups of the long chains of bio-based acrylates, the emulsion maintains a high bio-based content while also achieving excellent spray waterproofing and wash resistance. However, current acrylic waterproofing agents still suffer from drawbacks such as insufficient waterproofing performance, poor durability, and unpleasant hand feel of waterproof fabrics.
[0003] The preparation of existing fluorine-free waterproofing agents mostly adopts the traditional free radical polymerization process. The reaction conditions of this process are difficult to control, and the resulting polymers have a wide molecular weight distribution, random molecular structure, and severe branching and cross-linking. It is impossible to achieve precise control of the polymer molecular chain sequence and block length, resulting in poor product performance stability and large batch-to-batch differences.
[0004] Therefore, developing a fluorine-free waterproofing agent with controllable structure, excellent performance, wide compatibility, and environmental safety, as well as its preparation method, to overcome many shortcomings of existing technologies, has become a technical challenge that needs to be addressed by those skilled in the art. Summary of the Invention
[0005] To address the insufficient durability of existing fluorine-free acrylic waterproofing agents, this invention provides a method for preparing a fluorine-free waterproofing agent with controllable structure.
[0006] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0007] (1) Acryloyloxyethyl isocyanate (AOI) and butanone oxime (MEKO) were taken in a molar ratio of 1:1 and heated to 70°C under nitrogen protection and mechanically stirred for 6 hours to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0008] (2) Mix and dissolve cationic surfactant, nonionic surfactant and deionized water in a mass ratio of 1:1:145~170 to prepare an emulsifier solution;
[0009] The cationic surfactant is octadecyltrimethylammonium chloride (1831).
[0010] The nonionic surfactant is sorbitan monooleate (Span80).
[0011] (3) Add octadecyl acrylate (SA), cosolvent and RAFT reagent to the emulsifier solution at a mass ratio of 500:20:3, stir to obtain a crude emulsion, and then homogenize to form a fine emulsion;
[0012] The cosolvent is diethylene glycol (DEG).
[0013] The RAFT reagent is 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valeric acid;
[0014] (4) Weigh the initiator, blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane in a mass ratio of 3:50-100:50-150;
[0015] An initiator was added to the fine emulsion and reacted at 70 °C for 4 hours; the initiator was azobisisobutyramidine hydrochloride (AIBA).
[0016] Add blocked acryloyloxyethyl isocyanate (APU) dropwise and keep the reaction at the temperature for 2 hours;
[0017] Then add monoacrylate-terminated polysiloxane, keep warm for 2 hours to obtain a fluorine-free waterproofing agent with a solid content of 30 wt%.
[0018] The fluorine-free waterproofing agent is a triblock copolymer composed of octadecyl acrylate blocks, blocked acryloyloxyethyl isocyanate blocks, and monoacrylate-terminated polysiloxane blocks, with the following structural formula:
[0019]
[0020] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:1-2:1-3. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.2-6.9 and a viscosity of 50-54 mPa·s.
[0021] Fabrics treated with the fluorine-free waterproofing agent prepared according to the present invention were cured under the following high-temperature conditions: 150 °C for 1 minute.
[0022] The properties that fabrics treated with the fluorine-free waterproofing agent prepared according to this invention can achieve are as follows:
[0023] Water contact angle is 157°~161°, water resistance rating is 5; after 20 washes: water contact angle is 155°~157°, water resistance rating is 5.
[0024] Further technical solutions are as follows:
[0025] In step (1), the mechanical stirring reaction is an oil bath mechanical stirring reaction.
[0026] In step (3), the stirring conditions are: a rotation speed of 1500 rpm.
[0027] In step (3), the homogenization conditions are: in a cell disruptor, ultrasonic power 2400 W, time 10 min.
[0028] Compared with existing technologies, the beneficial technical effects of the present invention are reflected in the following aspects:
[0029] 1. This invention is the first to use blocked acryloyloxyethyl isocyanate in a fluorine-free waterproofing agent. In step (1), blocked acryloyloxyethyl isocyanate (AOI) is prepared by reacting acryloyloxyethyl isocyanate (AOI) with butanone oxime (MEKO). The double bond at one end of the blocked acryloyloxyethyl isocyanate can participate in free radical polymerization. The introduced reversible dynamic oxime-carbamate bond dissociates during high-temperature treatment, and the resulting free isocyanate groups can undergo irreversible reactions with the hydroxyl groups on the fabric surface. At the same time, there is a hydrogen bonding effect between the carbamate and the hydroxyl group, which improves the adhesion and durability of the fluorine-free treatment agent on the fabric. As can be seen from the results in Example 2, after 20 washes, the water contact angle of the fabric reaches 159±0.7°, and the water repellency rating is still level 5, indicating that it has excellent durability.
[0030] 2. In steps (3) and (4), this invention employs the RAFT reagent 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valerate and a segmented monomer reaction. Relying on the active polymerization mechanism of the RAFT reagent 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valerate, octadecyl acrylate containing active dormant species is first polymerized. Then, blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds and organosilicon macromonomers are added dropwise in stages, allowing crosslinking groups and hydrophobic segments of the organosilicon to be precisely and quantitatively attached to the polymer chain ends, resulting in a triblock copolymer composed of octadecyl acrylate blocks, blocked acryloyloxyethyl isocyanate blocks, and monoacrylate-terminated polysiloxane. This method produces a polymer with a triblock sequence structure, avoiding the random copolymerization of traditional free radical polymerization. It designs waterproofing and interfacial behavior at the molecular level, giving it better durability. The results of Comparative Example 4 show that the water contact angle of the fabric treated with emulsion obtained by random copolymerization decreased significantly after 20 washes, from the initial 148±1.8° to 125±1.7°, and the water repellency rating also dropped from level 4 to level 2, indicating poor durability. In contrast, the waterproofing agent polymerized by RAFT in Example 2 has excellent durability.
[0031] 3. When the fluorine-free waterproofing agent prepared by this invention is used to treat fabrics, the curing conditions only require curing at 150 ℃ for 1 minute. Compared with the traditional process of curing at 170 ℃ for more than 3 minutes, it greatly improves production efficiency, significantly reduces energy consumption costs, and achieves faster, more energy-efficient, lower temperature and safer curing, making it suitable for large-scale continuous production. Detailed Implementation
[0032] The present invention will be further described in detail below through examples.
[0033] The substances used in the examples were as follows: octadecyl acrylate and cosolvent were purchased from BASF AG; organosilicon monomers were purchased from Guangzhou Sloco New Materials Co., Ltd.; RAFT reagent and azobisisobutyramidine hydrochloride were purchased from Aladdin Reagent Co., Ltd.; methyl ethyl ketone oxime and acryloyloxyethyl isocyanate were purchased from Maclean Biotech Co., Ltd.; surfactants were purchased from Alfaesa (China) Chemical Co., Ltd.; and deionized water was prepared in the laboratory.
[0034] The raw material formulations for the embodiments and comparative examples of the present invention are shown in Table 1.
[0035] Table 1. Raw material formulations (parts by mass) for examples and comparative examples of structure-controllable fluorine-free waterproofing agents.
[0036] Experimental materials Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 APU 10 15 20 15 15 0 15 0 15 Organosilicon monomers 20 20 20 10 30 0 0 20 20 SA 100 100 100 100 100 100 100 100 100
[0037] Table 2. Water contact angles before and after washing in Examples 1-5 and Comparative Examples 1-4 - Unit (°)
[0038] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 initial 158±1.2 161±0.4 160±0.8 159±1.3 157±1.3 135±0.9 132±1.6 137±1.4 148±1.8 Twenty washes 155±0.9 159±0.7 157±1.4 156±1.4 155±1.7 104±1.3 119±1.9 106±2.1 125±1.7
[0039] Table 3. Water repellency ratings of emulsion-coated fabrics from Examples 1-5 and Comparative Examples 1-4
[0040] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 initial 5 5 5 5 5 3 3 2 4 Twenty washes 5 5 5 5 5 0 2 0 2
[0041] Table 4. Flexibility test results of Examples 1-5 and Comparative Examples 1-4
[0042] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Creases Not obvious Not obvious Not obvious Not obvious Not obvious obvious More obvious More obvious More obvious
[0043] Table 5. Results of emulsion stability tests in Examples 1-5 and Comparative Examples 1-4
[0044] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Emulsion stability Stablize Stablize Stablize Stablize Stablize Stablize Stablize Stablize Stablize
[0045] Example 1
[0046] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0047] (1) 7.06 g of acryloyloxyethyl isocyanate (AOI) and 4.36 g of butanone oxime (MEKO) (equimolar) were reacted under nitrogen protection at 70 °C with mechanical stirring for 6 hours to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0048] (2) Mix and dissolve 0.26 g of octadecyltrimethylammonium chloride (1831), 0.26 g of sorbitan monooleate (Span80) and 39 g of deionized water in a mass ratio of 1:1:150 to prepare an emulsifier solution;
[0049] (3) Mix 13 g of octadecyl acrylate (SA), 5.2 g of diethylene glycol (DEG) and 0.078 g of 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valeric acid (RAFT reagent) in a mass ratio of 500:20:3 and add them to the above emulsifier solution. Stir to obtain a crude emulsion, and then homogenize to form a fine emulsion.
[0050] (4) Weigh azobisisobutyramidine hydrochloride (AIBA), blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane in a mass ratio of 3:50:100.
[0051] Specific procedure: Add 0.078 g of azobisisobutyramidine hydrochloride (AIBA) to 57.8 g of fine emulsion and react at 70°C for 4 hours; add 1.3 g of blocked acryloyloxyethyl isocyanate (APU) dropwise, maintain the temperature at 70°C, and react for 2 hours; then add 2.6 g of monoacrylate-terminated polysiloxane dropwise, maintain the temperature at 70°C, and react for 2 hours to obtain a fluorine-free waterproofing agent with a solid content of 30 wt%.
[0052] The fluorine-free waterproofing agent with controllable structure prepared in Example 1 is a triblock copolymer composed of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block, with the following structural formula:
[0053] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:1:2. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.2, a viscosity of 50 mPa·s, and an average particle size of 135 nm.
[0054] The active ingredient in the fluorine-free waterproofing agent prepared in Example 1 is a triblock copolymer composed of octadecyl acrylate, blocked acryloyloxyethyl isocyanate, and monoacrylate-terminated polysiloxane. This triblock copolymer is insoluble in water and, under the action of an emulsifier, is uniformly dispersed in the aqueous phase as nano-sized spherical or near-spherical particles, forming a stable polymer emulsion. The average particle size refers to the average diameter of these polymer latex particles. Since the fluorine-free waterproofing agent prepared in Example 1 is an aqueous emulsion rather than a powder, the average particle size characterizes the size of the copolymer particles dispersed in the continuous aqueous phase, and the measured value is 135 nm.
[0055] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Example 1 are as follows:
[0056] The fiber fabric was immersed in a fluorine-free waterproofing agent diluted to a concentration of 40 g / L for 60 seconds; then it was put into a padding machine for padding treatment with a padding pressure of 50 N and a padding speed of 10 cm / min; finally, the padded fabric was baked and cooled at 150°C for 1 minute to obtain the fiber fabric treated with fluorine-free waterproofing agent.
[0057] Performance testing:
[0058] Hydrophobicity test
[0059] Test method: The hydrophobicity of the samples was measured at 25 ℃ using a contact angle meter with deionized water as the medium. The water contact angle of each sample was measured at 5 different locations. The highest and lowest values were removed, and the average of the remaining values was taken.
[0060] Performance indicators: When applied to fabrics, the waterproofing agent exhibits good hydrophobic properties when the water contact angle θ > 140°.
[0061] The initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Example 1 was measured to be 158±1.2°.
[0062] Water-repellent performance test
[0063] Test method: The water repellency rating of the fabric was determined using the method in GB / T 4745-2012, and the water repellency performance of the fabric was evaluated accordingly.
[0064] Performance indicators: In fabric applications, waterproofing agents are generally required to achieve a rating of 4 or higher to be considered to have a good waterproofing effect.
[0065] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Example 1 was measured to be 5.
[0066] Washability test
[0067] Test method: The washing standard in GB / T 8629-2017 was adopted. The fabric was cyclically washed using the 4N program of a type A standard washing machine. After each wash, the fabric was dried at 60 ℃. After twenty washes, the hydrophobic and water-repellent properties of the fabric were tested as described above.
[0068] Performance indicators: Only when the fabric achieves a water repellency rating of 4 or higher and a water contact angle of 140° or higher after 20 washes does it possess good washability.
[0069] The fabric treated with the fluorine-free waterproofing agent prepared in Example 1 was measured to have a water contact angle of 155±0.9° and a water repellency rating of 5 after twenty washes.
[0070] Flexibility testing
[0071] Test method: At 25 ℃, a 200 g weight was pressed on the fabric treated in Example 1. After 1 h, the weight was removed and the crease was observed. To eliminate errors, a 200 g weight was pressed again in the direction perpendicular to the first crease. After 1 h, the weight was removed and the crease was observed.
[0072] Performance indicators: Observe the degree of creases on the fabric surface. If there are no obvious creases, the fabric is flexible.
[0073] The fabric treated with the fluorine-free waterproofing agent prepared in Example 1 showed no obvious creases.
[0074] Stability test
[0075] Test method: Place the waterproofing agent in a specific high-temperature oven at 50°C for one week and observe whether there is any layering, demulsification, or thickening to determine the stability of the waterproofing agent.
[0076] Performance indicators: The fluorine-free waterproofing agent is a uniform milky white liquid, without layering or sedimentation, indicating that the fluorine-free waterproofing agent is stable.
[0077] The fluorine-free waterproofing agent prepared in Example 1 was found to be stable.
[0078] Example 2
[0079] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0080] (1) The operation of step (1) in this Example 2 is the same as step (1) in Example 1, to obtain a blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0081] (2) The operation of step (2) in this Example 2 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:157 to prepare an emulsifier solution;
[0082] (3) The operation of step (3) in this embodiment 2 is the same as step (3) in embodiment 1, to obtain a fine emulsion;
[0083] (4) The operation of step (4) in this Example 2 is the same as step (4) in Example 1, except that: the mass ratio of azobisisobutyramidine hydrochloride (AIBA): blocked acryloyloxyethyl isocyanate (APU): monoacrylate-terminated polysiloxane is 3:75:100, and a fluorine-free waterproofing agent with a solid content of 30 wt% is obtained.
[0084] The fluorine-free waterproofing agent with controllable structure prepared in Example 2 is a triblock copolymer composed of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block and monoacrylate-terminated polysiloxane block, with the same structural formula as in Example 1.
[0085] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:1.5:2. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.7 and a viscosity of 52 mPa·s. The average particle size of the polymer latex particles in the fluorine-free waterproofing agent prepared in Example 2 is 128 nm.
[0086] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Example 2 are as follows:
[0087] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 2 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0088] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Example 2 was measured to be 161±0.4°.
[0089] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Example 2 was measured to be 5.
[0090] The fabric treated with the fluorine-free waterproofing agent prepared in Example 2 was measured to have a water contact angle of 159±0.7° and a water repellency rating of 5 after twenty washes.
[0091] The fabric treated with the fluorine-free waterproofing agent prepared in Example 2 showed no obvious creases.
[0092] The fluorine-free waterproofing agent prepared in Example 2 was found to be stable.
[0093] Example 3
[0094] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0095] (1) The operation of step (1) in this embodiment 3 is the same as step (1) in embodiment 1, to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0096] (2) The operation of step (2) in this Example 3 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:163 to prepare an emulsifier solution;
[0097] (3) The operation of step (3) in this embodiment 3 is the same as step (3) in embodiment 1, to obtain a fine emulsion;
[0098] (4) The operation of step (4) in this embodiment 3 is the same as step (4) in embodiment 1, except that: the mass ratio of azobisisobutyramidine hydrochloride (AIBA): blocked acryloyloxyethyl isocyanate (APU): monoacrylate-terminated polysiloxane is 3:100:100, and a fluorine-free waterproofing agent with a solid content of 30 wt% is obtained.
[0099] The fluorine-free waterproofing agent with controllable structure prepared in Example 3 is a triblock copolymer composed of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block and monoacrylate-terminated polysiloxane block, with the same structural formula as in Example 1.
[0100] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:2:2. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.6 and a viscosity of 51 mPa·s. The average particle size of the polymer latex particles in the fluorine-free waterproofing agent prepared in Example 3 is 123 nm.
[0101] The specific steps for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Example 3 are as follows:
[0102] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 3 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0103] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Example 3 was measured to be 160±0.8°.
[0104] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Example 3 was measured to be 5.
[0105] The fabric treated with the fluorine-free waterproofing agent prepared in Example 3 was measured to have a water contact angle of 157±1.4° and a water repellency rating of 5 after twenty washes.
[0106] The fabric treated with the fluorine-free waterproofing agent prepared in Example 3 was found to have inconspicuous creases.
[0107] The fluorine-free waterproofing agent prepared in Example 3 was found to be stable.
[0108] Example 4
[0109] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0110] (1) The operation of step (1) in this Example 4 is the same as step (1) in Example 1, to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0111] (2) The operation of step (2) in this Example 4 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:145 to prepare an emulsifier solution;
[0112] (3) The operation of step (3) in this embodiment 4 is the same as step (3) in embodiment 1, to obtain a fine emulsion;
[0113] (4) The operation of step (4) in this embodiment 4 is the same as step (4) in embodiment 1, except that: the mass ratio of azobisisobutyramidine hydrochloride (AIBA): blocked acryloyloxyethyl isocyanate (APU): monoacrylate-terminated polysiloxane is 3:75:50, and a fluorine-free waterproofing agent with a solid content of 30 wt% is obtained.
[0114] The fluorine-free waterproofing agent with controllable structure prepared in Example 4 is a triblock copolymer composed of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block and monoacrylate-terminated polysiloxane block, with the same structural formula as in Example 1.
[0115] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:1.5:1. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.5 and a viscosity of 52 mPa·s. The average particle size of the polymer latex particles in the fluorine-free waterproofing agent prepared in Example 4 is 132 nm.
[0116] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Example 4 are as follows:
[0117] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 4 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0118] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Example 4 was measured to be 159±1.3°.
[0119] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Example 4 was measured to be 5.
[0120] The fabric treated with the fluorine-free waterproofing agent prepared in Example 4 was measured to have a water contact angle of 156±1.4° and a water repellency rating of 5 after twenty washes.
[0121] The fabric treated with the fluorine-free waterproofing agent prepared in Example 4 showed no obvious creases.
[0122] The fluorine-free waterproofing agent prepared in Example 4 was found to be stable.
[0123] Example 5
[0124] The preparation steps of a structure-controllable fluorine-free waterproofing agent are as follows:
[0125] (1) The operation of step (1) in this embodiment 5 is the same as step (1) in embodiment 1, to obtain a blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0126] (2) The operation of step (2) in this Example 5 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:170 to prepare an emulsifier solution;
[0127] (3) The operation of step (3) in this embodiment 5 is the same as step (3) in embodiment 1, to obtain a fine emulsion;
[0128] (4) The operation of step (4) in this embodiment 5 is the same as step (4) in embodiment 1, except that: the mass ratio of azobisisobutyramidine hydrochloride (AIBA): blocked acryloyloxyethyl isocyanate (APU): monoacrylate-terminated polysiloxane is 3:75:150, and a fluorine-free waterproofing agent with a solid content of 30 wt% is obtained.
[0129] The fluorine-free waterproofing agent with controllable structure prepared in Example 5 is a triblock copolymer composed of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block and monoacrylate-terminated polysiloxane block, with the same structural formula as in Example 1.
[0130] The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block, and monoacrylate-terminated polysiloxane block is 10:1.5:3. The fluorine-free waterproofing agent is a milky white liquid with a pH of 6.9 and a viscosity of 54 mPa·s. The average particle size of the polymer latex particles in the fluorine-free waterproofing agent prepared in Example 5 is 131 nm.
[0131] The specific steps for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Example 5 are as follows:
[0132] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 5 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0133] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Example 5 was measured to be 157±1.3°.
[0134] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Example 5 was measured to be 5.
[0135] The fabric treated with the fluorine-free waterproofing agent prepared in Example 5 was measured to have a water contact angle of 155±1.7° and a water repellency rating of 5 after twenty washes.
[0136] The fabric treated with the fluorine-free waterproofing agent prepared in Example 5 was found to have inconspicuous creases.
[0137] The fluorine-free waterproofing agent prepared in Example 5 was found to be stable.
[0138] Comparative Example 1
[0139] Preparation of fluorine-free waterproofing agent
[0140] (1) Mix and dissolve 0.26 g of octadecyltrimethylammonium chloride (1831), 0.26 g of sorbitan monooleate (Span80) and 30.42 g of deionized water in a mass ratio of 1:1:117 to prepare an emulsifier solution;
[0141] (2) 13 g of octadecyl acrylate (SA), 5.2 g of diethylene glycol (DEG) and 0.078 g of 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valeric acid (RAFT reagent) were mixed and added to the above emulsifier solution at a mass ratio of 500:20:3. The mixture was stirred to obtain a crude emulsion, and then homogenized to form a fine emulsion.
[0142] (3) 0.078 g of azobisisobutyramidine hydrochloride (AIBA) was added to 49.2 g of fine emulsion and reacted at 70°C for 6 hours to obtain a fluorine-free waterproofing agent with a solid content of 30 wt%.
[0143] The fluorine-free waterproofing agent prepared in Comparative Example 1 is a homopolymer of octadecyl acrylate, which is a milky white liquid with a pH of 6.3, a viscosity of 53 mPa·s, and an average particle size of 167 nm.
[0144] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Comparative Example 1 are as follows:
[0145] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Comparative Example 1 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0146] Comparative Example 1 is a sample without the addition of blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane, serving as a blank control.
[0147] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 1 was measured to be 135±0.9°.
[0148] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 1 was measured to be 3.
[0149] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 1 was measured to have a water contact angle of 104±1.3° and a water repellency rating of 0 after twenty washes.
[0150] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 1 showed obvious creases.
[0151] The fluorine-free waterproofing agent prepared in Comparative Example 1 was found to be stable.
[0152] Comparative Example 2
[0153] Preparation of fluorine-free waterproofing agent
[0154] (1) The operation of step (1) in Comparative Example 2 is the same as step (1) in Example 1 to obtain a blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0155] (2) The operation of step (2) in Comparative Example 2 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:135 to prepare an emulsifier solution;
[0156] (3) The operation of step (3) in Comparative Example 2 is the same as step (3) in Example 1, to obtain a fine emulsion;
[0157] (4) Weigh azobisisobutyramidine hydrochloride (AIBA) and blocked acryloyloxyethyl isocyanate (APU) at a mass ratio of 1:25. Add 0.078 g to 53.9 g of fine emulsion and react at 70 °C for 4 hours; then add 1.95 g of blocked acryloyloxyethyl isocyanate (APU) dropwise to the reaction and keep the reaction at the temperature for 3 hours to obtain a fluorine-free waterproofing agent with a solid content of 30 wt%.
[0158] The structure-controllable fluorine-free waterproofing agent prepared in Comparative Example 2 is a diblock copolymer composed of octadecyl acrylate block and blocked acryloyloxyethyl isocyanate block, wherein the mass ratio of octadecyl acrylate block to blocked acryloyloxyethyl isocyanate block is 20:3, the appearance is a milky white liquid, the pH value is 6.8, the viscosity is 54 mPa·s, and the average particle size is 157 nm.
[0159] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Comparative Example 2 are as follows:
[0160] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Comparative Example 2 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0161] Comparative Example 2 does not contain monoacrylate-terminated polysiloxane, but the amount of blocked acryloyloxyethyl isocyanate (APU) added is the same as in Examples 2, 4, and 5, as a comparison.
[0162] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 2 was measured to be 132±1.6°.
[0163] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 2 was measured to be 3.
[0164] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 2 was measured to have a water contact angle of 119±1.9° and a water repellency rating of 2 after twenty washes.
[0165] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 2 showed more obvious creases.
[0166] The fluorine-free waterproofing agent prepared in Comparative Example 2 was found to be stable.
[0167] Comparative Example 3
[0168] Preparation of fluorine-free waterproofing agent
[0169] (1) The operation of step (1) in Comparative Example 3 is the same as that of step (1) in Comparative Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:140 to prepare an emulsifier solution;
[0170] (2) The operation of step (2) in Comparative Example 3 is the same as step (2) in Comparative Example 1, and a fine emulsion is obtained;
[0171] (3) Weigh azobisisobutyramidine hydrochloride (AIBA) and monoacrylate-terminated polysiloxane at a mass ratio of 3:100. Add 0.078 g of azobisisobutyramidine hydrochloride (AIBA) to 55.2 g of fine emulsion and react at 70°C for 4 hours; then add 2.6 g of monoacrylate-terminated polysiloxane dropwise to the reaction and keep the reaction at the temperature for 3 hours to obtain a fluorine-free waterproofing agent with a solid content of about 30 wt%.
[0172] The fluorine-free waterproofing agent with controllable structure prepared in Comparative Example 3 is a diblock copolymer composed of octadecyl acrylate block and monoacrylate-terminated polysiloxane block, wherein the mass ratio of octadecyl acrylate block to monoacrylate-terminated polysiloxane block is 5:1, the appearance is a milky white liquid, the pH value is 6.7, the viscosity is 53 mPa·s, and the average particle size is 155 nm.
[0173] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Comparative Example 3 are as follows:
[0174] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Comparative Example 3 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0175] Comparative Example 3 does not contain blocked acryloyloxyethyl isocyanate (APU), but the content of monoacrylate-terminated polysiloxane added is the same as in Examples 1, 2 and 3, as a comparison.
[0176] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 3 was measured to be 137±1.4°.
[0177] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 3 was measured to be 2.
[0178] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 3 was measured to have a water contact angle of 106±2.1° and a water repellency rating of 0 after twenty washes.
[0179] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 3 showed more obvious creases.
[0180] The fluorine-free waterproofing agent prepared in Comparative Example 3 was found to be stable.
[0181] Comparative Example 4
[0182] Preparation of fluorine-free waterproofing agent
[0183] (1) The operation of step (1) in Comparative Example 4 is the same as step (1) in Example 1, to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds.
[0184] (2) The operation of step (2) in Comparative Example 4 is the same as step (2) in Example 1, except that: the mass ratio of octadecyltrimethylammonium chloride (1831): sorbitan monooleate (Span80): deionized water is 1:1:157 to prepare an emulsifier solution;
[0185] (3) Mix 13 g of octadecyl acrylate (SA), 1.95 g of blocked acryloxyethyl isocyanate (APU), 2.6 g of monoacrylate-terminated polysiloxane and 5.2 g of diethylene glycol (DEG) in a mass ratio of 20:3:4:8 and add them to the above emulsifier solution. Stir to obtain a crude emulsion and then homogenize to form a fine emulsion.
[0186] (4) 0.078 g of azobisisobutyramidine hydrochloride (AIBA) was added to 64.1 g of fine emulsion and reacted at 70 °C for 6 hours to obtain a fluorine-free waterproofing agent with a solid content of about 30 wt%.
[0187] The fluorine-free waterproofing agent prepared in Comparative Example 4 is a random copolymer of octadecyl acrylate, blocked acryloyloxyethyl isocyanate, and monoacrylate-terminated polysiloxane, wherein the mass ratio of octadecyl acrylate, blocked acryloyloxyethyl isocyanate, and monoacrylate-terminated polysiloxane is 10:1.5:2. It is a milky white liquid with a pH of 6.4, a viscosity of 54 mPa·s, and an average particle size of 152 nm.
[0188] The specific procedures for treating fabrics with the structure-controllable fluorine-free waterproofing agent prepared in Comparative Example 4 are as follows:
[0189] The operation of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Comparative Example 4 is the same as that of the structure-controllable fluorine-free waterproofing agent treated fabric prepared in Example 1, resulting in a fluorine-free waterproofing agent treated fiber fabric.
[0190] Comparative Example 4 does not use RAFT polymerization, but the content of blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane is the same as in Example 2, as a comparison.
[0191] According to the test method of Example 1, the initial water contact angle of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 4 was measured to be 148±1.8°.
[0192] The water repellency rating of the fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 4 was measured to be 4.
[0193] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 4 was measured to have a water contact angle of 125±1.7° and a water repellency rating of 2 after twenty washes.
[0194] The fabric treated with the fluorine-free waterproofing agent prepared in Comparative Example 4 showed more obvious creases.
[0195] The fluorine-free waterproofing agent prepared in Comparative Example 4 was found to be stable.
[0196] As can be seen from Tables 2, 3 and 4, the water contact angle, water repellency, washability and flexibility of the fabrics treated with the fluorine-free waterproofing agent prepared in Examples 1 to 5 are all higher than those of the fabrics treated with the fluorine-free waterproofing agent prepared in Comparative Examples 1 to 4. Among them, the fluorine-free waterproofing agent prepared with the mass ratio content of Example 2 has the best performance.
Claims
1. A method for preparing a fluorine-free waterproofing agent with controllable structure, characterized in that, The preparation steps are as follows: (1) Acryloyloxyethyl isocyanate (AOI) and butanone oxime (MEKO) were taken in a molar ratio of 1:1 and heated to 70°C under nitrogen protection and mechanically stirred for 6 hours to obtain blocked acryloyloxyethyl isocyanate (APU) containing carbon-carbon double bonds. (2) Mix and dissolve cationic surfactant, nonionic surfactant and deionized water in a mass ratio of 1:1:145~170 to prepare an emulsifier solution; The cationic surfactant is octadecyltrimethylammonium chloride (1831). The nonionic surfactant is sorbitan monooleate (Span80). (3) Add octadecyl acrylate (SA), cosolvent and RAFT reagent to the emulsifier solution at a mass ratio of 500:20:3, stir to obtain a crude emulsion, and then homogenize to form a fine emulsion; The cosolvent is diethylene glycol (DEG). The RAFT reagent is 4-cyano-4-[[(dodecylthio)thiocarbonyl]thio]valeric acid; (4) Weigh the initiator, blocked acryloyloxyethyl isocyanate (APU) and monoacrylate-terminated polysiloxane in a mass ratio of 3:50-100:50-150; An initiator was added to the fine emulsion and reacted at 70 °C for 4 hours; the initiator was azobisisobutyramidine hydrochloride (AIBA). Add blocked acryloyloxyethyl isocyanate (APU) dropwise and keep the reaction at the temperature for 2 hours; Then add monoacrylate-terminated polysiloxane, keep warm and react for 2 hours to obtain a fluorine-free waterproofing agent with a solid content of 30 wt%. The fluorine-free waterproofing agent is a triblock copolymer composed of octadecyl acrylate blocks, blocked acryloyloxyethyl isocyanate blocks, and monoacrylate-terminated polysiloxane blocks, with the following structural formula: The mass ratio of octadecyl acrylate block, blocked acryloyloxyethyl isocyanate block and monoacrylate-terminated polysiloxane block is 10:1~2:1~3; the fluorine-free waterproofing agent is a milky white liquid with a pH value of 6.2~6.9 and a viscosity of 50~54 mPa·s. Fabrics treated with the fluorine-free waterproofing agent prepared according to the present invention were cured under the following high-temperature conditions: 150 °C for 1 minute. The properties that fabrics treated with the fluorine-free waterproofing agent prepared according to this invention can achieve are as follows: Water contact angle is 157°~161°, water resistance rating is 5; after 20 washes: water contact angle is 155°~157°, water resistance rating is 5.
2. The method for preparing a structure-controllable fluorine-free waterproofing agent according to claim 1, characterized in that: In step (1), the mechanical stirring reaction is an oil bath mechanical stirring reaction.
3. The method for preparing a structure-controllable fluorine-free waterproofing agent according to claim 1, characterized in that: In step (3), the stirring conditions are: a rotation speed of 1500 rpm.
4. The method for preparing a structure-controllable fluorine-free waterproofing agent according to claim 1, characterized in that: In step (3), the homogenization conditions are: in a cell disruptor, ultrasonic power 2400 W, time 10 min.