Self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks and application thereof

Abstract

The invention belongs to the technical field of polymers, and discloses a self-healing textile dry and wet crockfastness improver containing multiple dynamic cross-linked networks, the self-healing textile dry and wet crockfastness improver comprises an acrylic polymer; the acrylic polymer is obtained by carrying out free radical polymerization on acrylic acid and 2-vinylpyridine and carrying out crosslinking treatment by taking organic zinc as a crosslinking agent after polymerization; the molar ratio of the acrylic acid to the 2-vinylpyridine is (8-9): (1-2); the molar ratio of the organic zinc to the acrylic acid is 1: (4-6). The dry and wet crockfastness improver breaks through the limitation of single performance of a traditional product, and realizes high crockfastness (dry grade 4-5 and wet grade 3-4), high self-healing efficiency (greater than or equal to 80%) and high washing resistance (wet fastness is greater than or equal to grade 3 after 20 times of washing) at the same time. Meanwhile, the invention further provides application of the dry and wet rubbing fastness improver.

Description

Technical Field

[0001] This invention relates to the field of polymer technology, specifically to a self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks and its application. Background Technology

[0002] Dry and wet rubbing fastness agents are core auxiliaries for finishing reactive dye-dyed fabrics. Acrylic and polyurethane products account for about 70% of the market share due to their stable film-forming properties, but they face three irreconcilable technical bottlenecks in high-abrasion scenarios:

[0003] Weak energy dissipation: Traditional products rely on single covalent crosslinking (such as epoxy resin crosslinking) or physical film formation (such as polyvinyl alcohol film formation), without "sacrificial bond" design. According to GB / T 3920-2008 test, after 10 washes, the wet rubbing fastness drops from the initial level 3 to level 1-2; in the Martindale abrasion resistance test (GB / T 21196.2-2007, pressure 12kPa), after 5000 rubs, the coating peeling rate exceeds 40%, and the main chain breakage rate reaches more than 20%.

[0004] No self-healing properties: micro-cracks in the coating (width ≥ 2μm) cannot be repaired, the service life of work clothes and uniforms is only 6 months, and the dye on sofa fabrics is lost due to coating damage, resulting in a color difference ΔE exceeding 3.0 (national standard requires ≤ 2.0).

[0005] The conflict between environmental protection and wearability: Products that add 10-15% nano-silica to improve abrasion resistance reduce fabric breathability (GB / T 5453-1997) by 30-40% (from 80L / m²·s to below 50L / m²·s), and hand stiffness (AATCCEP5-2011) from level 4 to level 2-3; solvent-based products emit VOCs exceeding 80g / L, far exceeding GB 38508-2020 "Limits of Volatile Organic Compounds in Cleaning Agents" (≤50g / L), and wastewater treatment costs reach 80-100 yuan / ton (this invention costs only 20-30 yuan / ton).

[0006] In summary, the industry urgently needs to overcome the technical contradiction that "wear-resistant materials cannot be self-healing, and self-healing materials cannot be wear-resistant," and develop new dry and wet friction fasteners that combine gradient energy dissipation, self-healing, and environmental compliance. Summary of the Invention

[0007] One of the objectives of this invention is to provide a self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks. This dry and wet rubbing fastness improver breaks through the limitation of traditional products with "single performance" and simultaneously achieves high rubbing fastness (dry grade 4-5, wet grade 3-4), high self-healing efficiency (≥80%), and high water washability (wet fastness ≥3 after 20 washes).

[0008] In addition, the present invention also provides the application of the above-mentioned dry and wet friction fastness improving agent.

[0009] To achieve the above objectives, the present invention provides a self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, wherein the self-healing textile dry and wet rubbing fastness improver comprises acrylic polymers;

[0010] The acrylic polymer is obtained by free radical polymerization of acrylic acid and 2-vinylpyridine, followed by crosslinking treatment with organozinc as a crosslinking agent after polymerization.

[0011] The molar ratio of acrylic acid to 2-vinylpyridine is 8~9:1~2;

[0012] The molar ratio of the organic zinc to the acrylic acid is 1:4~6.

[0013] The core mechanism of this invention lies in:

[0014] Carboxyl groups (-COOH) and pyridine groups (-C5H4N) are introduced into the side chains of acrylic copolymers via free radical copolymerization, using zinc acetate (Zn) 2+ Using hydrogen bonds as dynamic crosslinking centers, a three-level dynamic crosslinking network of "hydrogen bonds-ionic bonds-coordination bonds" is constructed:

[0015] Hydrogen bond construction: Reversible hydrogen bonds (-COOH…O=C-) are formed between the carboxyl groups of the copolymer side chains. These bonds act as primary energy dissipation units and break preferentially under frictional stress, thus avoiding direct stress on the main chain.

[0016] Ionic bond construction: Zn 2+ It forms an ion cluster (-COO) with the carboxyl group. - …Zn 2+ … - OOC-), as a secondary energy dissipation unit, breaks when the external force increases, thus protecting the fiber-dye bond;

[0017] Coordinate bond construction: Zn 2+ It forms a stable coordination bond with the pyridine group (-C5H4N→Zn) 2+ Coordination constant K=10 5 -10 6 As a third-level energy dissipation unit, it fractures at the peak of external force, while relying on the reversibility of coordination bonds to endow it with self-healing ability.

[0018] In this invention, if the proportion of coordination bonds is too high (excess zinc acetate), the coating becomes brittle and lacks self-healing properties; if the proportion of hydrogen bonds is too high (insufficient 2-vinylpyridine), the wear resistance is reduced.

[0019] This invention is the first to resolve the industry contradiction of "poor wear resistance of self-healing materials and lack of self-healing in wear-resistant materials", achieving a synergistic effect of "high friction fastness + self-healing + water resistance".

[0020] By adjusting the molar ratio of acrylic acid to 2-vinylpyridine (8-9:1-2) and the molar ratio of zinc acetate to carboxyl group (1:4.5~5.5), the proportion of the three dynamic bonds is balanced, thus breaking through the limitation of "single performance" of traditional products. At the same time, it achieves high rubbing fastness (dry grade 4-5, wet grade 3-4), high self-healing efficiency (≥80%), and high water washability (wet fastness ≥3 after 20 washes).

[0021] The polymerization method of this invention is solution polymerization, and the finishing process is conventional pad-dip baking (140-150℃). No modification to existing production lines is required, and small and medium-sized textile enterprises can start production directly. The core raw materials are commercially available industrial grade (acrylic acid, 2-vinylpyridine), which are not scarce, and the cost per ton is about 12,000 yuan, which is lower than that of imported similar products (25,000 yuan / ton).

[0022] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks, the preparation method of the acrylic polymer includes the following steps:

[0023] Step 1: Free radical solution polymerization was carried out using acrylic acid and 2-vinylpyridine as monomers to obtain intermediate products;

[0024] Step 2: Add organozinc to the intermediate product to cause cross-linking of the intermediate product;

[0025] Step 3: Adjust the pH of the product from Step 2 to 5.5-6.5.

[0026] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks, the reaction temperature of step 1 is 70~75℃, and the reaction temperature of step 2 is 45~50℃.

[0027] In the aforementioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks, step 1 specifically comprises:

[0028] Under inert atmosphere conditions, the polymerizable monomer and initiator are added dropwise to the substrate over 2-2.5 hours and reacted at a temperature of 70-75°C. After the addition is completed, the reaction is maintained at 70-75°C for 4-5 hours. The substrate is deionized water. The weight of the substrate is equivalent to 1.5-2 times the weight of the polymerizable monomer.

[0029] In the aforementioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, step 2 specifically involves: adding the cross-linking agent to the system of step 1 by dropwise or batchwise addition under stirring at 300-400 r / min; and monitoring Zn during the reaction process. 2+ Aggregate particle size <50nm;

[0030] Step 3 specifically involves: adding alkali to adjust the pH of the system to 5.5-6.5; and maintaining the reaction until the reaction endpoint.

[0031] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, after step 3, there is a step 4: after the reaction is completed, the temperature is lowered to room temperature and filtered.

[0032] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, the initiator in step 1 is a redox initiator or a peroxide initiator; the amount of the initiator is equivalent to 0.5~1.0% of the weight of the polymer monomer; the initiator is one or a combination of potassium persulfate, sodium persulfate, and ammonium persulfate.

[0033] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, the organic zinc is one or more combinations of zinc acetate, zinc oxalate, zinc citrate, and zinc lactate.

[0034] In the above-mentioned self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks, the solid content of the self-healing textile dry and wet rubbing fastness improver is 30±2wt%; the appearance is a light blue transparent viscous liquid.

[0035] Meanwhile, the present invention also discloses the use of a self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks as described above to treat fabrics and achieve color fixation finishing of the fabrics.

[0036] Compared with the prior art, the present invention has at least the following advantages:

[0037] The core advantages of this invention, which differs from existing technologies, are as follows: It employs a design based on "multiple dynamic bond coordination + gradient energy dissipation":

[0038] Synergistic mechanism innovation: It is not a simple superposition of hydrogen bonds, ionic bonds, and coordination bonds, but through a gradient design of "weak bonds breaking first and strong bonds breaking later" (hydrogen bond → ionic bond → coordination bond), it achieves the first synergy of "self-healing and wear resistance" - hydrogen bonds contribute 40% of primary energy consumption, ionic bonds contribute 35% of intermediate energy consumption, and coordination bonds contribute 25% of advanced energy consumption, forming a wide range of energy absorption spectrum (DMA test tanδ peak width of 60℃, while traditional single-bond products are only 30℃).

[0039] Significant performance breakthroughs: Under room temperature (25℃) and RH 50-60% conditions, the repair rate of ≤5μm microcracks is ≥80% within 24 hours, the Martindale abrasion resistance reaches 15,000 cycles (compared to 5,000 cycles for traditional products), and the wet rubbing fastness is still ≥3 after 20 washes (compared to 2 for traditional products).

[0040] Excellent environmental and economic benefits: The entire process is an aqueous solution system with VOC emissions of 5-8g / L. The raw material cost is 50% of that of special polyurethane systems, reducing industrial production costs by 20-30%. The monomer residue in the wastewater is <10mg / L (HPLC detection), and the COD removal rate of conventional biochemical treatment is ≥90%. Detailed Implementation

[0041] The present invention will be further described below with reference to embodiments, but this does not constitute any limitation on the present invention. Any limited modifications made within the scope of the claims of the present invention are still within the scope of the claims of the present invention.

[0042] Raw material description:

[0043] The raw material information used in this invention is shown in Table 1;

[0044] Raw material categories Specific types and specifications Selection criteria Supplier Examples monomer Acrylic acid (AA): Purity ≥ 99.5%, water content ≤ 0.1%, polymerization inhibitor (MEHQ) ≤ 200 ppm It provides carboxyl groups, exhibits high copolymerization activity (copolymerization conversion rate with 2-VP ≥90%), and has low cost (8000 yuan / ton). Shandong Wanhua Chemical and Jiangsu Sirbang Petrochemical 2-Vinylpyridine (2-VP): Purity ≥ 98%, Water content ≤ 0.5%, 2-substitution rate ≥ 99%. <![CDATA[Provide a pyridine group, which coordinates with Zn 2+ The coordination constant K = 10 5 -10 6 , and its stability is better than that of amino groups]]> Shanghai Maclean Biochemistry, Aladdin Reagent Initiator Ammonium persulfate (APS): Purity ≥ 98%, Water solubility ≥ 99%, Decomposition temperature ≥ 120℃ The half-life is 1-2 hours at 70-75℃, the initiation efficiency is ≥85%, and the decomposition product is ammonium sulfate (no residue). Sinopharm Chemical Reagents, Shanghai Lingfeng Chemical Crosslinking agent <![CDATA[Zinc acetate: The content of Zn(CH3COO)2·2H2O ≥ 99%, heavy metals ≤ 10 ppm, solubility 43 g / 100 mL (20 °C)]]> <![CDATA[Zn 2+ Ionic radius 0.074 nm, compatible with carboxyl / pyridine groups, non-corrosive (superior to zinc chloride) Zhejiang Huayou Cobalt Industry and Hunan Hengguang Technology pH adjuster Triethanolamine: Purity ≥99%, hydroxyl value 800-820 mgKOH / g, water content ≤0.5% <![CDATA[Adjust the pH to 5.5 - 6.5, does not react with Zn 2+ and is mild and non - irritating]]> Jiangsu Yangnong Chemical and Shanghai SECCO Petrochemical solvent Deionized water: conductivity ≤10μS / cm, pH 6.5-7.5, TOC ≤5mg / L <![CDATA[Avoid interference of Ca 2+ and Mg 2+ in the coordination reaction and ensure a uniform crosslinking network]]> Homemade (reverse osmosis + EDI)

[0045] Example 1

[0046] (1) Preparation of dehydration and polymerization of multi-component monomers

[0047] Equipment: 500mL four-necked flask (with mechanical stirrer, reflux condenser, constant pressure dropping funnel, and nitrogen delivery tube), precision temperature-controlled oil bath (temperature control accuracy ±1℃).

[0048] Procedure: Add 180 parts by weight of deionized water (conductivity ≤10μS / cm, pH 6.5-7.5) to a four-necked flask, heat to 70-75℃, purge with nitrogen (purity ≥99.99%, flow rate 20-30mL / min) for 30min, and detect the oxygen concentration in the system by gas chromatography to ≤0.5% to avoid oxygen inhibition.

[0049] (2) Synthesis of acrylic acid copolymer

[0050] Monomer preparation: Mix 85 parts by weight of acrylic acid (1.18 mol) and 15 parts by weight of 2-vinylpyridine (0.14 mol), stir magnetically for 10 min, and measure the refractive index using an Abbe refractometer to ensure uniformity.

[0051] Initiator solution preparation: Dissolve 1.0 part by weight of ammonium persulfate (purity ≥98%) in 20 parts by weight of deionized water, sonicate for 5 min, and the transmittance of the solution is ≥98% (visible spectrophotometer, 600 nm).

[0052] Droplet addition and polymerization: The monomer solution and initiator solution were added dropwise simultaneously. After the addition was completed in 2 hours, the reaction was maintained at 70°C for 4.5 hours. The reaction was stopped when the viscosity of the solution reached 250-300 mPa·s (25°C) as measured by an Ubbelohde viscometer. The solution was then cooled to room temperature to obtain a copolymer matrix solution with a solid content of 32% (GPC number average molecular weight 7 × 10⁻⁶). 4 (PDI=12.0).

[0053] (3) Multiple dynamic cross-linking reaction (core step)

[0054] Crosslinking agent addition: Add 52 parts of zinc acetate dihydrate (0.237 mol) in three portions, 10 min apart, while stirring at 400 rpm. Measure Zn using a laser particle size analyzer. 2+ Aggregate particle size <50nm (to avoid uneven coating), reaction temperature is room temperature.

[0055] pH adjustment: Add 2 parts of triethanolamine (purity ≥99%, hydroxyl value ≥800mgKOH / g) to adjust the pH of the system to 6.0 (precision pH meter, accuracy ±0.01). This range avoids the influence of Zn. 2+ Zinc hydroxide precipitate is formed (Zn(OH)2 solubility product Ksp = 3 × 10⁻⁶) -17 ).

[0056] Reaction endpoint determination: After heating to 50℃ and stirring for 1 hour, the reaction is determined to be complete using two directly verifiable indicators:

[0057] Viscosity matching: The reaction solution was tested with an Ubbelohde viscometer (25℃), and the viscosity of the system reached 350~400 mPa·s (an increase of 30%~40% compared with 250~300 mPa·s before crosslinking);

[0058] Uniformity confirmation: When stirring at 400 r / min, the reaction solution is uniformly light blue and transparent, with no flocculent precipitate / local turbidity; when 5 mL of the reaction solution is left to stand for 10 min, there is no stratification on the surface and no particle sedimentation at the bottom.

[0059] When both indicators are met, the reaction is considered complete.

[0060] (4) Product finalization

[0061] Operation: Cool to 30℃, filter through a 100-mesh nylon filter (filtration pressure 0.1MPa) to remove a small amount of unreacted particles, and further dilute with deionized water until the solid content of the product is 30±2%. The product is a light blue transparent viscous liquid (transmittance ≥95%, 25℃).

[0062] Example 2

[0063] The composition is largely the same as in Example 1, except that the molar ratio of acrylic acid to 2-vinylpyridine is 8:2, and the amount of acrylic acid is 73.2 parts by weight (1.01 mol). In this case, the solid content of the copolymer matrix solution is 26.7% (GPC number average molecular weight 6 × 10⁻⁶). 4 (PDI=2.0).

[0064] Finally, deionized water was used to further dilute the product to a solid content of 30±2%, and the product was a light blue transparent viscous liquid (transmittance ≥95%, 25℃).

[0065] Example 3

[0066] The composition is largely the same as in Example 1, except that the molar ratio of acrylic acid to 2-vinylpyridine is 9:1, and the amount of acrylic acid is 86.1 parts by weight (1.19 mol). In this case, the solid content of the copolymer matrix solution is 30%, and the number-average molecular weight (GPC test) is 7.2 × 10⁻⁶. 4 (PDI=1.9).

[0067] Finally, deionized water was used to further dilute the product to a solid content of 30±2%, and the product was a light blue transparent viscous liquid (transmittance ≥95%, 25℃).

[0068] Example 4

[0069] The method is largely the same as in Example 1, except that the molar ratio of zinc acetate dihydrate to acrylic acid is 1:4.5, and the amount of zinc acetate dihydrate is 58 parts by weight (0.262 mol).

[0070] Finally, deionized water was used to further dilute the product to a solid content of 30±2%, and the product was a light blue transparent viscous liquid (transmittance ≥94%, 25℃).

[0071] Example 5

[0072] The method is generally the same as in Example 1, except that the molar ratio of zinc acetate dihydrate to acrylic acid is 1:5.5, and the amount of zinc acetate dihydrate is 47 parts by weight (0.2145 mol).

[0073] Finally, deionized water was used to further dilute the product to a solid content of 30±2%, and the product was a light blue transparent viscous liquid (transmittance ≥96%, 25℃).

[0074] Comparative Example 1

[0075] The method is largely the same as in Example 1, except that the molar ratio of acrylic acid to 2-vinylpyridine is 8:4 (pyridine groups are in excess).

[0076] Monomer ratio: 57.8 parts by weight (0.80 mol) of acrylic acid, 42.2 parts by weight (0.40 mol) of 2-vinylpyridine.

[0077] Dosage of zinc acetate dihydrate: Calculated based on a molar ratio of 1:5 with acrylic acid, add 36 parts (0.164 mol).

[0078] Product specifications: copolymer matrix solution solids content 33% (GPC test number average molecular weight 4×10⁻⁶) 4 (PDI=2.3), and finally further diluted with deionized water to a solid content of 30±2%. The product is a light blue transparent viscous liquid with a light transmittance ≥92% (25℃).

[0079] Comparative Example 2

[0080] The method is largely the same as in Example 1, except that the molar ratio of acrylic acid to 2-vinylpyridine is 10:1.

[0081] Monomer ratio: 87.3 parts by weight (1.21 mol) of acrylic acid, 12.7 parts by weight (0.12 mol) of 2-vinylpyridine.

[0082] Dosage of zinc acetate dihydrate: Calculated based on a molar ratio of 1:5 with acrylic acid, add 54 parts (0.246 mol).

[0083] Product specifications: copolymer matrix solution solids content 33% (GPC test number average molecular weight 8×10⁻⁶) 4 PDI=2.1), the final product has a solid content of 32.6% and a light transmittance of ≥95% (25℃).

[0084] Comparative Example 3

[0085] The method is largely the same as in Example 1, except that the molar ratio of zinc acetate dihydrate to acrylic acid is 1:3 (zinc acetate dihydrate is in excess).

[0086] Dosage of zinc acetate dihydrate: calculated proportionally to 86 parts (0.392 mol);

[0087] Process parameters: Zn at a stirring rate of 400 r / min 2+ The aggregated particle size still reaches 80 nm in some areas;

[0088] Product specifications: The final product was further diluted with deionized water to a solid content of 30±2%. The product was a light blue transparent viscous liquid with a light transmittance of 88% (25℃) (agglomeration caused a decrease in transparency).

[0089] Comparative Example 4

[0090] The method is largely the same as in Example 1, except that the molar ratio of zinc acetate dihydrate to acrylic acid is 1:8.

[0091] Dosage of zinc acetate dihydrate: calculated proportionally to 32 parts (0.146 mol);

[0092] Product specifications: The final product is further diluted with deionized water to a solid content of 30±2%. The product is a light blue transparent viscous liquid with a light transmittance of ≥95% (25℃).

[0093] Comparative Example 5

[0094] The method is largely the same as in Example 1, except that the conventional crosslinking agent N,N'-methylenebisacrylamide (MBA) is used instead of organic zinc.

[0095] Crosslinking agent dosage: MBA 0.5 parts by weight (0.0032 mol, equivalent to 0.32 wt% of the total monomer weight), added in the later stage of polymerization, no need to control the agglomeration particle size;

[0096] Product specifications: The final product was further diluted with deionized water to a solid content of 30±2%. The product was a light blue transparent viscous liquid with a light transmittance of 92% (25℃).

[0097] Comparative Example 6

[0098] It is largely the same as Example 1, except that N-vinylpyrrolidone (NVP) is used instead of 2-vinylpyridine.

[0099] Monomer ratio: 87.6 parts by weight (1.21 mol) of acrylic acid, 12.4 parts by weight (0.11 mol) of NVP.

[0100] Dosage of zinc acetate dihydrate: Calculated based on a molar ratio of 1:5 with acrylic acid, add 54 parts (0.246 mol).

[0101] Product specifications: Copolymer matrix solution solids content 33.3% (GPC test number average molecular weight 6.5×10⁻⁶) 4 (PDI=2.2).

[0102] The final product was further diluted with deionized water to a solid content of 30±2%. The product was a light blue transparent viscous liquid with a light transmittance of ≥93% (25℃).

[0103] Comparative Example 7

[0104] The method is largely the same as in Example 1, except that N-vinylcaprolactam (NVCL) is used instead of 2-vinylpyridine.

[0105] Monomer ratio: 81.3 parts by weight (1.13 mol) of acrylic acid, 18.7 parts by weight (0.13 mol) of NVCL.

[0106] Dosage of zinc acetate dihydrate: Calculated based on a molar ratio of 1:5 with acrylic acid, add 50 parts (0.228 mol).

[0107] Product specifications: Copolymer matrix solution solids content 33.3% (GPC test number average molecular weight 5.8×10⁻⁶) 4 (PDI=2.3)

[0108] The final product was further diluted with deionized water to a solid content of 30±2%. The product was a light blue transparent viscous liquid with a light transmittance of ≥92% (25℃).

[0109] Application testing

[0110] The above-described embodiments and comparative samples of the present invention were treated with cotton and cotton / polyester blends;

[0111] The specific process steps for treating cotton fabric are as follows: adopt a two-dip and two-padding process, with a padding temperature of 28-30℃, a padding liquid pressure of 0.25-0.3MPa, and control the liquid carry-over rate to 80-85%. Then bake at 140-150℃ for 2-3 minutes to complete the color fixing process.

[0112] The specific process steps for treating cotton / polyester blended fabrics are as follows: adopt a two-dip and two-padding process, with a padding temperature of 27-29℃, a padding liquid pressure of 0.23-0.27MPa, and control the liquid carry-over rate of 78-82%. Then bake at 140-150℃ for 2-3 minutes to complete the color fixation finishing.

[0113] The specific process parameters for processing the two materials mentioned above can be found in Table 2.

[0114] Table 2 Specific process parameters Fabric type Rolling temperature (°C) Rolling fluid pressure (MPa) Liquid carryover rate (%) Baking temperature (°C) Baking time (min) in accordance with Cotton (200g / m²) 28-30 0.25-0.3 80-85 140-150 2-3 Cotton is highly absorbent and requires a high liquid retention rate to ensure cross-linking. Cotton / polyester blend (65 / 35, 180g / m²) 27-29 0.23-0.27 78-82 140-150 2-3 Balancing the moisture absorption and heat resistance of the two fibers

[0115] For relevant indicators of cotton and cotton / polyester blends after treatment, please refer to Table 3;

[0116] Table 3 Reference Table of Relevant Indicators

[0117] Serial Number project index Test standards and methods 1 Dry rubbing fastness (cotton fabric) ≥4 levels GB / T 3920-2008: Friction tester (pressure 9N, friction cycles 10 times), gray scale rating 2 Wet rubbing fastness (cotton fabric, before washing) ≥3 levels As above, the moisture content of the friction cloth is 100%. 3 Wet rubbing fastness (after 20 washes) ≥3 levels GB / T 3921-2008 5A program wash 20 times, then test according to GB / T 3920-2008. 4 Self-healing efficiency (24h) ≥80% AFM observation: A 5μm wide crack was artificially prepared and placed at 25℃ and 55% RH for 24 hours. Crack closure rate = (initial width - 24-hour width) / initial width × 100% 5 Martindale abrasion resistance rating (sofa fabric) ≥15000 times GB / T 21196.2-2007: Pressure 12 kPa, grinding disc diameter 120 mm, stop when obvious wear of the coating appears. 6 Breathability (cotton fabric) ≥80L / m²·s GB / T 5453-1997: Pressure difference 100 Pa, test area 20 cm²

[0118] The test results for cotton / polyester blended fabrics are shown in Table 4; the test results for cotton fabrics are shown in Table 5.

[0119] Table 4. Results of tests conducted on cotton / polyester blended fabrics.

[0120] Test Project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Dry friction fastness Level 5 Level 4-5 Level 5 Level 4-5 Level 4-5 Level 4 Level 4 Level 4 Level 3-4 Level 3-4 Level 3-4 Level 3 Wet rubbing fastness (before washing) Level 4 Level 3-4 Level 4 Level 3-4 Level 3-4 Level 3 Level 3 Level 3 Level 2-3 Level 2 Level 2 Level 2 Wet rubbing fastness (after 20 washes) Level 3 Level 3 Level 3 Level 2-3 Level 2-3 Level 2 Level 2 Level 2 Level 1-2 Level 1 Level 1-2 Level 1 Self-healing efficiency (24h) 88% 85% 83% 81% 80% 65% 70% 55% 60% 0% 45% 38% Martindale wear resistance times 18,000 times 18,000 times 17,000 times 16,500 times 15500 times 15,000 times 9000 times 10,000 times 8000 times 9500 times 5000 times 6000 times breathability 85L / m²·s 84L / m²·s 86L / m²·s 78L / m²·s 87L / m²·s 75L / m²·s 82L / m²·s 62L / m²·s 80L / m²·s 55L / m²·s 70L / m²·s 65L / m²·s

[0121] Table 5. Results of tests on cotton fabrics

[0122] Test Project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Dry friction fastness Level 5 Level 4-5 Level 5 Level 4-5 Level 4-5 Level 4 Level 4 Level 4 Level 3-4 Level 3-4 Level 3-4 Level 3 Wet rubbing fastness (before washing) Level 4 Level 3-4 Level 4 Level 3-4 Level 3-4 Level 3 Level 3 Level 3 Level 2-3 Level 2 Level 2 Level 2 Wet rubbing fastness (after 20 washes) Level 3 Level 3 Level 3 Level 2-3 Level 2-3 Level 2 Level 2 Level 2 Level 1-2 Level 1 Level 1-2 Level 1 Self-healing efficiency (24h) 88% 85% 83% 81% 80% 65% 70% 55% 60% 0% 45% 38% Martindale wear resistance times 18,000 times 17,000 times 16,500 times 15500 times 15,000 times 9000 times 10,000 times 8000 times 9500 times 5000 times 6000 times 5500 times breathability 85L / m²·s 84L / m²·s 86L / m²·s 78L / m²·s 87L / m²·s 75L / m²·s 82L / m²·s 62L / m²·s 80L / m²·s 55L / m²·s 70L / m²·s 65L / m²·s

[0123] Test Result Analysis:

[0124] Examples 1-5 all met the preset performance targets, with Example 1 (acrylic acid to 2-vinylpyridine molar ratio 8.4:1, zinc acetate to acrylic acid molar ratio 1:5) exhibiting the best overall performance. Its dry rubbing fastness reached grade 5, wet rubbing fastness (before and after washing) was grade 4 and grade 3 respectively, self-healing efficiency was 88%, Martindale abrasion resistance was 18,000 cycles, and air permeability was 85 L / m²·s. This fully demonstrates the synergistic effect of the triple dynamic network of "hydrogen bonds-ionic bonds-coordination bonds," and all parameters strictly adhere to the scope defined in the claims.

[0125] Comparative Example 1 (excess 2-vinylpyridine) suffered from excessive coordination bond ratio, resulting in embrittlement of the coating, a decrease in self-healing efficiency to 65%, and a drop in air permeability to 75 L / m²·s. Comparative Example 2 (insufficient 2-vinylpyridine) had an insufficient number of coordination bonds, resulting in only 10,000 wear cycles and a wet rubbing fastness grade of 2 after 20 washes, thus verifying the key role of pyridine groups in the construction of dynamic networks.

[0126] Comparative Example 3 (Zinc acetate excess) resulted in Zn 2+ The aggregated particle size exceeded the standard (some reaching 80nm), the air permeability was only 62L / m²·s, and the self-healing efficiency was 55%. In Comparative Example 4 (insufficient zinc acetate), the dynamic cross-linking network was incomplete, and the wet rubbing fastness and abrasion resistance were significantly reduced, proving that the molar ratio of zinc acetate to acrylic acid (1:4~6) is the core parameter for performance assurance.

[0127] Comparative Example 5 (conventional crosslinking agent) lacks a dynamic bond structure and completely lacks self-healing properties. Its wear resistance is only 5000 cycles, and its air permeability is significantly reduced, highlighting the innovation of the dynamic crosslinking design of this invention. Comparative Examples 6-7 (with pyridine groups replaced) suffer from insufficient coordination constants (K<10). 4 The overall performance deteriorated, which verified that the pyridine group provided by 2-vinylpyridine is the core of constructing stable coordination bonds.

[0128] The embodiments presented herein are merely selected implementations based on combinations of all possible embodiments. The appended claims should not be limited to the embodiments described herein. Some numerical ranges used in the claims include sub-ranges within them, and variations within these ranges should also be covered by the appended claims.

Claims

1. A self-healing textile dry and wet rubbing fastness improver containing a multi-layer dynamic cross-linked network, characterized in that, The self-healing textile dry and wet rubbing fastness improver includes acrylic polymers; The acrylic polymer is obtained by free radical polymerization of acrylic acid and 2-vinylpyridine, followed by crosslinking treatment with organozinc as a crosslinking agent after polymerization. The molar ratio of acrylic acid to 2-vinylpyridine is 8~9:1~2; The molar ratio of the organic zinc to the acrylic acid is 1:4.5~5.

5.

2. The self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks according to claim 1, characterized in that, The preparation method of the acrylic polymer includes the following steps: Step 1: Free radical solution polymerization was carried out using acrylic acid and 2-vinylpyridine as monomers to obtain intermediate products; Step 2: Add organozinc to the intermediate product to cause cross-linking of the intermediate product; Step 3: Adjust the pH of the product from Step 2 to 5.5-6.

5.

3. The self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks according to claim 2, characterized in that, The reaction temperature in step 1 is 70~75℃, and the reaction temperature in step 2 is 45~50℃.

4. The self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks according to claim 2, characterized in that, Step 1 specifically involves: Under inert atmosphere conditions, the polymerizable monomer and initiator are added dropwise to the substrate over 2-2.5 hours and reacted at a temperature of 70-75°C. After the addition is completed, the reaction is maintained at 70-75°C for 4-5 hours. The substrate is deionized water. The weight of the substrate is equivalent to 1.5-2 times the weight of the polymerizable monomer.

5. The self-healing textile dry and wet rubbing fastness improver containing a multiple dynamic cross-linked network according to claim 2, characterized in that, Step 2 specifically involves adding the crosslinking agent to the system from step 1 by dropping or adding it in batches while stirring at 300-400 r / min. During the reaction, the Zn content is monitored. 2+ Aggregate particle size <50nm; Step 3 specifically involves: adding alkali to adjust the pH of the system to 5.5-6.5; and maintaining the reaction until the reaction endpoint.

6. The self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linked networks according to claim 2, characterized in that, After step 3 is completed, there is a step 4: after the reaction is complete, cool down to room temperature and filter.

7. The self-healing textile dry and wet rubbing fastness improver containing a multiple dynamic cross-linked network according to claim 2, characterized in that, The initiator in step 1 is a redox initiator or a peroxide initiator; the amount of the initiator is equivalent to 0.5 to 1.0% of the weight of the polymer monomer; the initiator is one or more combinations of potassium persulfate, sodium persulfate, and ammonium persulfate.

8. The self-healing textile dry and wet rubbing fastness improver containing a multiple dynamic cross-linked network according to claim 2, characterized in that, The organic zinc is one or more of zinc acetate, zinc oxalate, zinc citrate, and zinc lactate.

9. The self-healing textile dry and wet rubbing fastness improver containing a multiple dynamic cross-linked network according to claim 1, characterized in that, The solid content of the self-healing textile dry and wet rubbing fastness improver is 30±2wt%; its appearance is a light blue transparent viscous liquid.

10. The fabric is treated with a self-healing textile dry and wet rubbing fastness improver containing multiple dynamic cross-linking networks as described in any one of claims 1 to 9 to achieve the purpose of color fixation finishing of the fabric.