A long-acting moisture-resistant antigen fibrillation aid and a method for preparing the same

Abstract

This invention belongs to the field of fabric finishing technology, specifically relating to a long-lasting, wet-friction-resistant anti-fibrotic agent and its preparation method. By employing a specific functionalized modifier for in-situ passivation pretreatment of nano-inorganic particles, the silane groups of the functionalized modifier are pre-hydrolyzed and condensed to form an organic coating layer on the surface of the nanoparticles, effectively reducing the direct contact and uncontrollable reaction between the surface hydroxyl groups and isocyanate groups. This invention simultaneously introduces a hydrophilic chain extender containing tertiary amines and a hydrophobic associative chain extender containing long-chain alkyl groups during the chain extension stage, constructing a buffer layer with hydrophobic protective function around the nanoparticles. This hydrophobic associative structure provides additional steric hindrance and hydrophobic stabilization in the emulsion, effectively preventing the slow aggregation and sedimentation of nanoparticles during long-term storage.

Description

Technical Field

[0001] This invention belongs to the field of fabric finishing technology, specifically relating to a long-lasting, wet-friction-resistant antigenic fiberizing agent and its preparation method. Background Technology

[0002] Fibrillation manifests as the gradual splitting of a single fiber into fine fibers along its length on the surface. It is easily generated when fibers are in a state of swelling and under mechanical action, leading to the formation of "white spots," "frost patterns," and tangling into fuzzy balls in fabrics. Fibrillation is a common characteristic of all cellulosic fibers, but it is more pronounced in lyocell fibers. The fibrillation properties of lyocell fibers depend on the highly oriented and crystalline fiber structure formed during the spinning stage. These structures endow the fibers with excellent strength, luster, drape, and moisture absorption.

[0003] Currently, the fibrillation problem of lyocell is mainly addressed through methods such as controlling the spinning process, crosslinking treatment during spinning, cellulase washing, post-fibrillation crosslinking treatment, or resin finishing. CN118441367A discloses obtaining low-crystallinity lyocell fibers with antigen fibrillation by adjusting the discharge speed of the spinning mixture from the nozzle and the fiber traction speed. WO95 / 28516A discloses a crosslinking agent with multiple acrylamide groups, preferably 1,3,5-triacryloyl-hexahydrotriazine, which effectively reduces the fibrillation tendency of solution-spun cellulose fibers. By utilizing acidic cellulase to decompose the microfibrils on the fabric surface, fibrillation recurs after the fabric is washed again, and the cellulase reduces fiber weight. CN114457591A discloses preparing cellulose fibers with antigen fibrillation by adding an aldehyde-free glycidyl ether type epoxy resin as a crosslinking agent to cellulose fibers during spinning or post-treatment. CN103306136A discloses a method using a composition of oligomeric polyacids and C2-C6 polyacids as a crosslinking agent to improve the antigen-fibrillating properties of fibers through high-temperature heating. While the aforementioned patent can achieve antigen-fibrillating effects, it also has some drawbacks, such as complex processes, expensive and poorly water-soluble crosslinking agents, and yellowing, decreased mechanical properties, and poor hand feel of the treated fibers or fabrics.

[0004] Currently, crosslinking agents with excellent anti-fibrillation effects are all used in the filament formation stage, while fibrillation that occurs in fabrics during dyeing and finishing is an industry problem that urgently needs to be solved. Therefore, there is a need to develop a versatile, green, and efficient anti-fibrillation finishing agent. Summary of the Invention

[0005] Industrially used antigen-fibrillating agents are mainly cationic waterborne polyurethanes. These pure organic polyurethane films are prone to swelling, softening, and decreased mechanical strength in wet conditions, resulting in insufficient wet rubbing fastness and failing to meet the long-lasting antigen-fibrillating requirements of repeated washing and demanding applications. The purpose of this invention is to provide a long-lasting wet rubbing-resistant antigen-fibrillating agent and its preparation method.

[0006] The first aspect of this invention discloses a method for preparing a wet-friction-resistant antigenic fibrinolytic agent, comprising the following steps:

[0007] S1: Nanoscale inorganic particles and functional modifiers are pretreated in an aqueous medium to obtain a surface-passivated nanoparticle slurry; the functional modifier is a compound whose molecular structure contains both end-capped groups and hydrolyzable silane groups.

[0008] S2: The surface passivated nanoparticle slurry is mixed with a polyol, dehydrated, and then diisocyanate and a catalyst are added to it to react and obtain a polyurethane prepolymer containing nanoparticles.

[0009] S3: A chain extender is added to the prepolymer of S2 to carry out a chain extension reaction. After the chain extension reaction is completed, a salt-forming agent is added to the product to carry out a neutralization reaction. After the neutralization reaction is completed, water is added for emulsification and dispersion to obtain the antigen fibrinolytic agent.

[0010] The chain extender described therein comprises hydrophilic chain extenders containing tertiary amines and hydrophobic associative chain extenders containing long-chain alkyl groups.

[0011] The nano-sized inorganic particles mentioned in S1 are at least one of nano-silica sol, nano-silica, and nano-alumina, and the amount used is 1%-5% of the total mass of the antigen fibrinating agent raw materials.

[0012] The functionalized modifier described in S1 is a product obtained by reacting a compound containing a capping group with a silane coupling agent containing an isocyanate group. One end of the molecule is a capping group, and the other end is a hydrolyzable silane group. Preferably, the compound containing the capping group is selected from at least one of butanone oxime, sodium bisulfite, acetanilide, and phenol; the silane coupling agent containing the isocyanate group is selected from at least one of propyltriethoxysilane isocyanate and propyltrimethoxysilane isocyanate.

[0013] The pretreatment temperature in S1 is 25-40℃, and the treatment time is 30-60 minutes; the amount of the functional modifier is 5%-20% of the mass of the nano-sized inorganic particles.

[0014] The molar ratio of the hydrophilic chain extender containing a tertiary amine to the hydrophobic associating chain extender containing a long-chain alkyl group in S3 is 7-9:1-3. Preferably, the hydrophilic chain extender containing a tertiary amine is selected from at least one of N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and triethanolamine; the hydrophobic associating chain extender containing a long-chain alkyl group is at least one of alkyl diethanolamines with a carbon chain length of C12-C18.

[0015] The second aspect of this invention discloses a wet-rub resistant antigen-fibrillating agent, which is prepared by the above-described preparation method.

[0016] The third aspect of this invention discloses the application of the above-mentioned antigenic fibrillating agent in the treatment of Lyocell fibers.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] Compared with the prior art, the antigen fibrinolytic agent and its preparation method provided by the present invention have the following beneficial effects:

[0019] This invention employs a specific functionalized modifier to perform in-situ passivation pretreatment on nano-inorganic particles, thereby pre-hydrolyzing and condensing the silane groups of the functionalized modifier to form an organic coating layer on the surface of the nanoparticles. This effectively reduces the direct contact and uncontrollable reaction between the surface hydroxyl groups and isocyanate groups.

[0020] This invention constructs a buffer layer with hydrophobic protection around nanoparticles by simultaneously introducing a hydrophilic chain extender containing a tertiary amine and a hydrophobic associative chain extender containing a long-chain alkyl group during the chain extension stage. This hydrophobic associative structure provides additional steric hindrance and hydrophobic stabilization in the emulsion, effectively preventing the slow aggregation and sedimentation of nanoparticles during long-term storage. Detailed Implementation

[0021] The technical solutions of the present invention will be described in detail below with reference to embodiments, but this does not limit the present invention to the scope of the embodiments described. Experimental methods and techniques in the following embodiments that do not specify specific conditions are generally performed according to conventional conditions in the relevant art or according to the conditions recommended by the manufacturer.

[0022] Raw material sources and pretreatment:

[0023] Polyethylene glycol (PEG1000, PEG2000, industrial grade);

[0024] Isoflurone diisocyanate (IPDI, industrial grade);

[0025] N-Methyldiethanolamine (MDEA, industrial grade);

[0026] N-Octadectoalkyldiethanolamine (C18-MDEA, purity >95%)

[0027] Nano silica sol (solid content 30%, particle size 10-20nm);

[0028] Preparation of functionalized modifier A: 1 mol of butanone oxime was dissolved in acetone and added dropwise to a reaction flask containing 1 mol of propyltriethoxysilane isocyanate (IPTS). The reaction was carried out at 40-50°C for 2 hours. Acetone was removed under reduced pressure to obtain compound A, which has a butanone oxime-terminated group at one end and a triethoxysilyl group at the other end. The butanone oxime-terminated group was unconjugated at >110°C and the compound was stable under the reaction conditions of this invention. The structure was verified by IR spectroscopy, and the NCO peak disappeared.

[0029] All other reagents are industrial grade.

[0030] Test method:

[0031] Emulsion stability: After standing at room temperature for 3 months, observe for sedimentation and stratification, and determine particle size changes using the transmittance method.

[0032] Film appearance: The emulsion is cast onto a glass plate and dried at 80°C to form a film. Visually inspect for cracking and transparency.

[0033] Color fastness to rubbing: Prepare a finishing solution of 100 g / L using the auxiliary agent, and apply it to the Lyocell woven fabric with two dips and two nips (80% pick-up rate), then bake at 140℃ for 3 minutes. Test the dry and wet rubbing fastness according to GB / T 3920-2008, and evaluate the staining grade (grade 1 is the worst, grade 5 is the best).

[0034] Example 1

[0035] (1) Pretreatment (in-situ passivation): In a reactor equipped with a stirrer, add 3.0 parts by weight of nano-silica sol (SiO2), 0.3 parts by weight of functional modifier A, and 0.8 parts by weight of deionized water. Stir and hydrolyze at 30°C for 50 minutes to obtain surface passivated nano-silica slurry.

[0036] (2) Dehydration: Add 22 parts by weight of PEG1000 to the previous step slurry, mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0037] (3) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and a polyurethane prepolymer containing nano-silicon is obtained.

[0038] (4) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add a mixed chain extender consisting of 1.2 parts by weight of MDEA and 0.8 parts by weight of C18-MDEA (molar ratio of about 82:18), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0039] (5) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0040] (6) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain a stable emulsion with a solid content of about 35% and a semi-transparent bluish appearance.

[0041] Example 2

[0042] (1) Pretreatment (in-situ passivation): In a reactor equipped with a stirrer, add 3.0 parts by weight of nano-silica sol (SiO2), 0.5 parts by weight of functional modifier A, and 0.8 parts by weight of deionized water. Stir and hydrolyze at 30°C for 50 minutes to obtain surface passivated nano-silica slurry.

[0043] (2) Dehydration: Add 22 parts by weight of PEG1000 to the previous step slurry, mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0044] (3) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and a polyurethane prepolymer containing nano-silicon is obtained.

[0045] (4) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add a mixed chain extender consisting of 1.2 parts by weight of MDEA and 0.8 parts by weight of C18-MDEA (molar ratio of about 82:18), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0046] (5) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0047] (6) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain a stable emulsion with a solid content of about 35% and a semi-transparent bluish appearance.

[0048] Example 3

[0049] (1) Pretreatment (in-situ passivation): In a reactor equipped with a stirrer, add 5.0 parts by weight of nano-silica sol (SiO2), 0.3 parts by weight of functional modifier A, and 0.8 parts by weight of deionized water. Stir and hydrolyze at 30°C for 50 minutes to obtain surface passivated nano-silica slurry.

[0050] (2) Dehydration: Add 22 parts by weight of PEG1000 to the nano-silica slurry obtained in step (1), mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0051] (3) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and a polyurethane prepolymer containing nano-silicon is obtained.

[0052] (4) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add a mixed chain extender consisting of 1.2 parts by weight of MDEA and 0.8 parts by weight of C18-MDEA (molar ratio of about 82:18), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0053] (5) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0054] (6) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain a stable emulsion with a solid content of about 35% and a semi-transparent bluish appearance.

[0055] Example 4

[0056] (1) Pretreatment (in-situ passivation): In a reactor equipped with a stirrer, add 3.0 parts by weight of nano-silica sol (SiO2), 0.3 parts by weight of functional modifier A, and 0.8 parts by weight of deionized water. Stir and hydrolyze at 30°C for 50 minutes to obtain surface passivated nano-silica slurry.

[0057] (2) Dehydration: Add 22 parts by weight of PEG1000 to the nano-silica slurry obtained in step (1), mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0058] (3) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and a polyurethane prepolymer containing nano-silicon is obtained.

[0059] (4) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add a mixed chain extender consisting of 1.2 parts by weight of MDEA and 0.8 parts by weight of N-dodecyl diethanolamine (molar ratio about 82:18), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0060] (5) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0061] (6) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain a stable emulsion with a solid content of about 35% and a semi-transparent bluish appearance.

[0062] Comparative Example 1 (Original scheme without nano-silicon)

[0063] (1) Dehydration: In a reactor equipped with a stirrer, add 22 parts by weight of PEG1000, heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0064] (2) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and polyurethane prepolymer is obtained.

[0065] (3) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add 1.5 parts by weight of chain extender MDEA dropwise, and after the dropwise addition is complete, raise the temperature to 75°C and react at a constant temperature for 1 hour.

[0066] (4) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0067] (5) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain an emulsion with a solid content of about 35% and a transparent appearance.

[0068] Comparative Example 2 (Direct addition of unpassivated nano-silicon)

[0069] (1) Mixing and dehydration: In a reactor equipped with a stirrer, add 3.0 parts by weight of nano-silica sol (SiO2) and 22 parts by weight of PEG1000, mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0070] (2) Prepolymerization: Cool to 55°C, add 0.02 parts by weight of dibutyltin dilaurate, and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C. Experimental phenomena: After raising the temperature to 70°C, the viscosity of the system increases sharply, and gelation occurs after about 40 minutes. Stirring cannot continue, and the polymerization is explosive, making it impossible to obtain an emulsifiable prepolymer.

[0071] Comparative Example 3 (with passivation but without hydrophobic chain extender)

[0072] (1) Pretreatment (in-situ passivation): In a reactor equipped with a stirrer, add 3.0 parts by weight of nano-silica sol (SiO2), 0.3 parts by weight of functional modifier A, and 0.8 parts by weight of deionized water. Stir and hydrolyze at 30°C for 50 minutes to obtain surface passivated nano-silica slurry.

[0073] (2) Dehydration: Add 22 parts by weight of PEG1000 to the previous step slurry, mix and heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0074] (3) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and a polyurethane prepolymer containing nano-silicon is obtained.

[0075] (4) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, stir evenly; add 1.5 parts by weight of chain extender MDEA (C18-MDEA without hydrophobic association chain extender), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0076] (5) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0077] (6) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain an emulsion with a solid content of about 35%.

[0078] Comparative Example 4 (with hydrophobic chain extender but without nano-silicon)

[0079] (1) Dehydration: In a reactor equipped with a stirrer, add 22 parts by weight of PEG1000, heat to 120℃, and dehydrate under reduced pressure at -0.09MPa for 3h.

[0080] (2) Prepolymerization: Cool down to 55°C, add 0.02 parts by weight of dibutyltin dilaurate and stir evenly; add 9.5 parts by weight of IPDI dropwise, and after the dropwise addition is completed, raise the temperature to 75°C and react at a constant temperature for 2 hours. The NCO content is determined by the di-n-butylamine method to reach the theoretical value (R value 1.9), and polyurethane prepolymer is obtained.

[0081] (3) Chain extension: Cool down to 60°C, add 3 parts by weight of N-methylpyrrolidone to reduce viscosity, and stir evenly; add a mixed chain extender consisting of 1.2 parts by weight of MDEA and 0.8 parts by weight of C18-MDEA (molar ratio of about 82:18) (the same hydrophobic associative chain extender ratio as in Example 1, but without any nano-silicon), and after the addition is complete, heat up to 75°C and react at a constant temperature for 1 hour.

[0082] (4) Salt formation: Cool down to 60°C, add 0.4 parts by weight of glacial acetic acid, and react for 15 minutes.

[0083] (5) Emulsification: Cool down to 50°C, slowly add 65 parts by weight of deionized water while stirring at high speed, and continue stirring for 1 hour after the addition is complete to obtain an emulsion with a solid content of about 35% and a semi-transparent appearance.

[0084] Performance Comparison Table

[0085] sample Aggregation process Emulsion stability (3 months) Film appearance Dry rubbing fastness (grade) Wet rubbing fastness (grade) Example 1 Stable and controllable No sedimentation, particle size variation <5% Uniformly transparent, without cracks 4-5 4 Example 2 Stable and controllable No sedimentation, particle size variation <8% Uniformly transparent, without cracks 4-5 4 Example 3 Stable and controllable Slight blue light, very little sedimentation Transparent, extremely fine cracks 4-5 3-4 Example 4 Stable and controllable No sedimentation, particle size variation <10% Uniformly transparent, without cracks 4-5 3-4 Comparative Example 1 smooth Stable, colorless and transparent Transparent and crack-free 3-4 2-3 Comparative Example 2 Aggregation, gelation - - - - Comparative Example 3 Stable and controllable Two months later, the bottom showed obvious subsidence. Numerous microcracks, foggy appearance 4 2-3 Comparative Example 4 smooth Stable, semi-transparent Transparent, extremely fine cracks 3-4 3

[0086] Conclusion: A comparison of Comparative Example 2 and Example 1 shows that if the nano-silica sol is directly mixed with polyol and added to the subsequent polymerization reaction without any pretreatment, the viscosity of the system increases sharply after the addition of diisocyanate and heating, and irreversible bursting of gelation occurs in about 40 minutes, making it impossible to obtain an emulsifiable and dispersible prepolymer product. In Example 1, by first pretreating the nano-silica sol with functionalized modifier A in an aqueous medium, the silane groups of the functionalized modifier undergo hydrolysis and condensation to achieve in-situ passivation and coating of the nano-silica surface. This pretreatment is then introduced into subsequent dehydration, prepolymerization, and chain extension steps, resulting in a stable and controllable polymerization process and ultimately a stable emulsion product.

[0087] Comparative Example 3 employed the same in-situ passivation pretreatment steps as Example 1, but used only a conventional hydrophilic chain extender containing tertiary amines (MDEA) during the chain extension stage, instead of a hydrophobic associative chain extender containing long-chain alkyl groups (C18-MDEA). The results showed that although Comparative Example 3 could also smoothly complete the polymerization reaction and obtain an emulsion product, its storage stability was significantly reduced, with noticeable sedimentation at the bottom after only two months of standing at room temperature. Simultaneously, its film appearance showed numerous microcracks and a hazy appearance, indicating significant phase separation and stress concentration between the inorganic nanoparticles and the organic polymer matrix. The wet rubbing fastness (grade 2-3) of Comparative Example 3 was worse than that of Comparative Example 1 without any nanoparticles. This means that simply introducing nanoparticles without addressing their interfacial compatibility with the matrix and film-forming flexibility can actually impair wet abrasion resistance due to stress concentration defects.

[0088] In Example 1, based on the introduction of passivated silicon nanoparticles, both a hydrophilic chain extender containing tertiary amines and a hydrophobic associative chain extender containing long-chain alkyl groups were used in the chain extension stage. The resulting emulsion was stable during storage (no sedimentation after 3 months), formed a uniform, transparent film without cracks, and achieved a wet rubbing fastness of grade 4. The introduction of the hydrophobic associative chain extender avoided the risk of internal defects caused by the introduction of nanoparticles.

[0089] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a moisture-resistant antigenic fibrinolytic agent, characterized in that, Includes the following steps: S1: Nanoscale inorganic particles and functional modifiers are pretreated in an aqueous medium to obtain a surface-passivated nanoparticle slurry; the functional modifier is a compound whose molecular structure contains both end-capped groups and hydrolyzable silane groups. S2: The surface passivated nanoparticle slurry is mixed with a polyol, dehydrated, and then diisocyanate and a catalyst are added to it to react and obtain a polyurethane prepolymer containing nanoparticles. S3: Add a chain extender to the prepolymer of S2 to carry out a chain extension reaction. After the chain extension reaction is completed, add a salt forming agent to the product to carry out a neutralization reaction. After the neutralization reaction is completed, add water to carry out emulsification and dispersion to obtain the antigen fibrillation aid. The chain extender described therein comprises hydrophilic chain extenders containing tertiary amines and hydrophobic associative chain extenders containing long-chain alkyl groups.

2. The preparation method according to claim 1, characterized in that, The nanoscale inorganic particles mentioned in S1 are at least one of nano-silica sol, nano-silica, and nano-alumina, and the amount used is 1%-5% of the total mass of the final emulsion of the antigen fibrinating aid.

3. The preparation method according to claim 1, characterized in that, The functionalized modifier described in S1 is a product obtained by reacting a compound containing a capped group with a silane coupling agent containing an isocyanate group. One end of its molecule is a capped group, and the other end is a hydrolyzable silane group.

4. The preparation method according to claim 3, characterized in that, The compound containing the end-capping group is selected from at least one of methyl ethyl ketone oxime, sodium bisulfite, acetanilide, and phenol; the silane coupling agent containing the isocyanate group is selected from at least one of propyltriethoxysilane isocyanate and propyltrimethoxysilane isocyanate.

5. The preparation method according to claim 1, characterized in that, The pretreatment temperature in S1 is 25-40℃, and the treatment time is 30-60 minutes; the amount of the functional modifier is 5%-20% of the mass of the nano-sized inorganic particles.

6. The preparation method according to claim 1, characterized in that, The molar ratio of the hydrophilic chain extender containing tertiary amino groups to the hydrophobic associative chain extender containing long-chain alkyl groups in S3 is 7-9:1-3.

7. The preparation method according to claim 6, characterized in that, The hydrophilic chain extender containing tertiary amino groups is selected from at least one of N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and triethanolamine; the hydrophobic associative chain extender containing long-chain alkyl groups is at least one of alkyl diethanolamines with a carbon chain length of C12-C18.

8. A wet-rub resistant antigen-fibrillating agent, characterized in that, It is prepared by any one of claims 1 to 7.

9. The application of the antigen-fibrillating agent as described in claim 8 in the treatment of Lyocell fibers.