A self-healing wrinkle-resistant shirt fabric and its preparation process

Abstract

This invention discloses a self-healing wrinkle-resistant shirt fabric and its preparation process, belonging to the field of fabric technology. First, ε-caprolactone and bis(2-hydroxyethyl) disulfide are reacted under a catalyst. After the reaction, the solvent is removed by distillation, the precipitate is collected, and dried to obtain polycaprolactone diol containing disulfide bonds. This precipitate is then dispersed in a solvent, and diphenylmethane diisocyanate and a catalyst are added and mixed to obtain an isocyanate-terminated prepolymer. Next, the isocyanate-terminated prepolymer is mixed with 1,4-butanediol, and a titanium carbide nanosheet dispersion is added to react. A terminating agent is then added for terminating, and after degassing, a shape memory polyurethane spinning solution is obtained. The spinning solution is spun into shape memory polyurethane fibers. Finally, the shape memory polyurethane fibers are composited onto cotton fibers, and the fabric is woven to obtain the final product. The fabric provided by this invention employs a synergistic mechanism of photothermal triggering, shape memory recovery, and disulfide bond self-repair, exhibiting excellent wrinkle resistance and self-repairing properties.

Description

Technical Field

[0001] This invention relates to the field of fabric technology, specifically to a self-healing wrinkle-resistant shirt fabric and its preparation process. Background Technology

[0002] As an indispensable part of everyday attire, the smoothness of a shirt directly impacts the wearer's professional image and social experience. However, cotton shirts are prone to wrinkling during wear, washing, and storage. Traditional solutions mainly rely on chemical cross-linking anti-wrinkle finishing, which utilizes formaldehyde resins to cross-link with cellulose molecules, forming a rigid network on the surface of cotton fibers to restrict molecular chain slippage. While this technology improves the fabric's wrinkle resistance to some extent, its inherent drawbacks are becoming increasingly apparent: formaldehyde release poses a potential threat to the wearer's health, and long-term exposure may induce skin allergies and respiratory diseases; chemical cross-linking leads to fiber brittleness, significantly reducing fabric strength, making it stiff like paper, and losing the original soft and skin-friendly properties of cotton fabrics. Furthermore, once wrinkles form, they can only be maintained by repeated ironing, but high-temperature ironing is not only time-consuming and laborious but may also cause heat damage and luster degradation to the fabric, failing to meet the demands of modern fast-paced life for efficient, convenient, and healthy care methods.

[0003] To address the aforementioned issues, the introduction of shape memory polymer (SMP) technology offers a new approach to wrinkle-resistant treatment of shirt fabrics. Shape memory polyurethane (SMPU), as a typical example, can recover from a temporary shape to a preset shape under specific temperature stimuli, theoretically enabling the active elimination of wrinkles. Existing technologies include research on blending SMPU fibers with cotton fibers to prepare wrinkle-free shirt fabrics. This involves triggering the shape memory effect through body temperature or ironing, allowing the fabric to return to its smooth state after heating. However, such solutions still have significant limitations. The introduction of SMPU fibers is mostly through physical blending or simple coating, resulting in weak bonding between the functional components and the matrix interface. The shape memory effect weakens significantly after repeated washing, leading to insufficient durability. Furthermore, existing SMPU fibers also suffer from microscopic damage repair issues; internal cracks generated during repeated deformation gradually accumulate, eventually causing functional failure, and the fabric still cannot escape the predicament of becoming more wrinkled with each wash.

[0004] Given the aforementioned shortcomings, it is essential to propose a new self-healing, wrinkle-resistant shirt fabric. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a self-healing wrinkle-resistant shirt fabric and its preparation process.

[0006] The first aspect of this invention is to provide a process for preparing a self-healing, wrinkle-resistant shirt fabric, comprising the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide and catalyst I are added to solvent I to react. After the reaction, the solvent is removed by distillation, the precipitate is transferred to a precipitant to collect the precipitate, and then dried to obtain polycaprolactone diol containing disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in solvent II, and diphenylmethane diisocyanate and catalyst II are added and reacted to obtain isocyanate-terminated prepolymer; S3: The modified titanium carbide nanosheets are dispersed in solvent III to obtain a titanium carbide nanosheet dispersion. S4: Mix isocyanate-terminated prepolymer and 1,4-butanediol, add titanium carbide nanosheet dispersion for reaction, then add end-capping agent for end-capping, and after degassing, obtain shape memory polyurethane spinning solution; S5: The shape memory polyurethane spinning solution is spun into shape to obtain shape memory polyurethane fiber; S6: Shape memory polyurethane fibers are composited onto cotton fibers to obtain the fabric weft yarn, which, after weaving, results in a self-healing and wrinkle-resistant shirt fabric.

[0007] It should be noted that this invention first uses bis(2-hydroxyethyl) disulfide as an initiator to initiate the ring-opening polymerization of ε-caprolactone under catalysis, forming a polycaprolactone diol soft segment with hydroxyl groups at both ends and a disulfide bond in the middle. Then, this soft segment reacts with excess diphenylmethane diisocyanate under catalysis, and the isocyanate group adds to the hydroxyl group to form a urethane bond, resulting in a prepolymer with isocyanate groups at both ends. Then, 1,4-butanediol, as a chain extender, continues to react with the isocyanate groups at the end of the prepolymer to extend the molecular chain. At the same time, the amino groups on the surface of the amino-modified titanium carbide nanosheets react with the isocyanate groups at the end of the prepolymer to form urea bonds, covalently anchoring the titanium carbide nanosheets in the polyurethane network, obtaining shape memory polyurethane fibers anchored with photothermal fillers. These fibers are then combined with cotton fibers in a core-spun yarn structure to obtain the self-healing and wrinkle-resistant shirt fabric of this invention.

[0008] In some embodiments, the mass ratio of ε-caprolactone, bis(2-hydroxyethyl) disulfide, and catalyst I is 48-52:1.3-2.5:0.3-0.7; the mass of solvent I is 1.8-2.2 times the mass of ε-caprolactone.

[0009] The CAS number for ε-caprolactone is 502-44-3; the CAS number for bis(2-hydroxyethyl) disulfide is 1892-29-1.

[0010] In some embodiments, catalyst I is selected from at least one of stannous octoate, stannous chloride, and tetrabutyl titanate; solvent I is toluene or xylene; and precipitant is diethyl ether or n-hexane.

[0011] In some embodiments, the mass ratio of disulfide-bonded polycaprolactone diol, diphenylmethane diisocyanate, and catalyst II is 18-22:4-6:0.04-0.07; catalyst II is selected from at least one of dibutyltin dilaurate, stannous octoate, and triethylenediamine; solvent II is dimethylformamide or dimethyl sulfoxide; and the mass of solvent II is 2-3 times the mass of disulfide-bonded polycaprolactone diol.

[0012] In some embodiments, solvent III is selected from at least one of dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone; the mass amount of solvent III is 50-60 times that of the modified titanium carbide nanosheets.

[0013] In some embodiments, the mass ratio of the isocyanate-terminated prepolymer, 1,4-butanediol, and titanium carbide nanosheet dispersion is 24-26:1:20-22; the mass amount of the end-capping agent is 1.4-1.8 times the mass amount of the amino-modified titanium carbide nanosheets; and the end-capping agent is selected from at least one of methanol, ethanol, and n-butanol.

[0014] In some embodiments, the modified titanium carbide nanosheets are made by grafting amino groups onto the surface of titanium aluminum carbide.

[0015] In some embodiments, in S1, the reaction is carried out at 110-130°C for 5-7 hours; in S2, the reaction is carried out at 65-75°C for 1.5-2.5 hours; in S4, the reaction is carried out at 40-60°C for 1.5-2.5 hours, and the end-capping is carried out at 45-55°C for 25-35 minutes.

[0016] A second aspect of the present invention is to provide a self-healing, wrinkle-resistant shirt fabric.

[0017] In some implementations, the mass ratio of cotton fibers to shape memory polyurethane fibers is 94-95:5-6.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention innovatively utilizes the reaction of amino groups on the surface of modified titanium carbide nanosheets with the terminal isocyanate groups of polyurethane prepolymer to form urea bonds. This allows the photothermal filler to be firmly embedded in the polymer network rather than simply physically doped. This ensures that the titanium carbide nanosheets remain uniformly dispersed without agglomeration or shedding during spinning, stretching, and repeated washing, reducing photothermal efficiency decay and extending the functional lifespan of the fabric. The titanium carbide nanosheets in the fabric can rapidly convert near-infrared light into heat energy, quickly raising the temperature to the required shape memory recovery temperature. This differs from the slow and inefficient traditional heat conduction heating mode, avoiding the problem of localized overheating and heat damage to cotton fibers caused by contact heating.

[0019] 2. The fabric provided by this invention employs a synergistic mechanism of photothermal triggering, shape memory recovery, and disulfide bond self-repair. Unlike existing technologies that only possess single anti-wrinkle or single repair functions, this invention achieves a one-time completion of wrinkle elimination and fabric damage repair, significantly extending the fabric's functional durability. Amino-modified titanium carbide nanosheets absorb near-infrared light and undergo surface plasmon resonance, converting light energy into heat energy and rapidly conducting it to the surrounding polyurethane matrix. This raises the local temperature above the melting temperature of polycaprolactone. At this point, the soft segment molecular chains obtain sufficient thermal energy, and the conformation recovers from folding to extension, achieving macroscopic wrinkle elimination. Simultaneously, the heat energy activates the dynamic exchange reaction of disulfide bonds, causing broken disulfide bonds to re-pair with adjacent thiol groups to form new chemical bonds. This allows microcracks caused by repeated deformation within the fiber to heal at the molecular level, completing microscopic reconstruction. Detailed Implementation

[0020] The present invention will now be described in further detail with reference to specific embodiments.

[0021] Example 1 A self-healing, wrinkle-resistant shirt fabric is prepared by the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide, and stannous octoate in a mass ratio of 50:1.8:0.5 were added to toluene and reacted at 120°C for 6 h. After the reaction, the solvent was removed by distillation, and the precipitate was collected in diethyl ether and dried at 50°C for 24 h to obtain polycaprolactone diol containing disulfide bonds; wherein the mass of toluene was twice the mass of ε-caprolactone. A small amount of the product (polycaprolactone diol containing disulfide bonds) was dissolved in dimethyl sulfoxide and then reduced with dithiothreitol. DTNB reagent was then added. The solution showed a distinct yellow absorption peak at 412 nm, indicating that the product produced free thiol groups after reduction and that the molecular chain contained disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in dimethylformamide, and diphenylmethane diisocyanate and dibutyltin dilaurate are added and mixed. The mixture is reacted at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer. The mass ratio of polycaprolactone diol containing disulfide bonds, diphenylmethane diisocyanate and dibutyltin dilaurate is 20:5:0.05. The mass of dimethylformamide is 2.5 times the mass of polycaprolactone diol containing disulfide bonds. S3: Modified titanium carbide nanosheets were dispersed in dimethylformamide and sonicated for 30 min to obtain a titanium carbide nanosheet dispersion; wherein, the mass of dimethylformamide was 55 times that of the modified titanium carbide nanosheets. The modified titanium carbide nanosheets were prepared by the following steps: 2 parts by mass of titanium aluminum carbide powder were slowly added to 40 parts by mass of hydrofluoric acid (40%, an etchant for selectively etching the aluminum layer), and the mixture was magnetically stirred at 35°C for 24 hours. After the reaction, the mixture was centrifuged and washed until the pH was approximately 6. The precipitate was dispersed in 100 parts by mass of anhydrous ethanol and sonicated at 200 W (to aid in exfoliation and promote interlayer exfoliation) for 2 hours. The supernatant was then centrifuged and the suspension was collected. The suspension was vacuum dried at 60°C for 12 hours to obtain few-layer titanium carbide nanosheets. 0.5 parts by mass of the few-layer titanium carbide nanosheets were dispersed in 100 parts by mass of anhydrous ethanol and sonicated for 30 minutes. 2 parts by mass of aminopropyltriethoxysilane were added, and glacial acetic acid was added dropwise to adjust the pH to 4-5. The mixture was refluxed at 60°C for 4 hours under nitrogen protection (to prevent oxidation). Finally, the unreacted silane was removed by centrifugation and washing, and the mixture was vacuum dried at 60°C for 12 hours to obtain the modified titanium carbide nanosheets.

[0022] S4: The isocyanate-terminated prepolymer and 1,4-butanediol were mixed and stirred at 50°C for 1 hour. Titanium carbide nanosheet dispersion was added, and the mixture was reacted at 50°C for 2 hours. Then methanol was added, and the mixture was reacted at 50°C for 30 minutes. After vacuum degassing for 30 minutes, shape memory polyurethane spinning solution was obtained. The mass ratio of isocyanate-terminated prepolymer, 1,4-butanediol and titanium carbide nanosheet dispersion was 25:1:21, and the mass of methanol was 1.6 times the mass of amino-modified titanium carbide nanosheets. S5: The shape memory polyurethane spinning solution is preheated to 45°C, extruded through a 0.10mm spinneret, and placed in a coagulation bath in a mixture of dimethylformamide, water, and ethanol with a volume ratio of 3:6:1. The temperature of the first section (0~0.5m) of the coagulation bath is 25°C, and the temperature of the second section (0.5~1.5m) is 40°C. The coagulation time is 3~5min, the winding speed is 15m / min, and the draw ratio is 3. The coagulated fiber is then passed through three water washing tanks (40°C, 50°C, and 60°C) in sequence, and left in each tank for 3min. The fiber is then placed in an oven in a relaxed state and heat-set at 60°C for 30min, followed by heat-setting at 120°C for 10min. After natural cooling to room temperature, it is spun into shape memory polyurethane fiber. S6: The shape memory polyurethane fiber is used as the sheath layer material and the combed cotton sliver is used as the core layer material. The two are compounded on a ring spinning machine and wound into a bobbin yarn to obtain the fabric weft yarn. After weaving, the self-healing and wrinkle-resistant shirt fabric is obtained. The mass ratio of cotton fiber to shape memory polyurethane fiber is 94:6.

[0023] Example 2 A self-healing, wrinkle-resistant shirt fabric is prepared by the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide, and stannous chloride in a mass ratio of 52:2.5:0.7 were added to xylene and reacted at 130°C for 5 h. After the reaction, the solvent was removed by distillation, and the precipitate was collected in n-hexane and dried at 50°C for 24 h to obtain polycaprolactone diol containing disulfide bonds. The mass of xylene was 2.2 times the mass of ε-caprolactone. A small amount of the product (polycaprolactone diol containing disulfide bonds) was dissolved in dimethyl sulfoxide and then reduced with dithiothreitol. DTNB reagent was then added. The solution showed a distinct yellow absorption peak at 412 nm, indicating that the product produced free thiol groups after reduction and that the molecular chain contained disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in dimethyl sulfoxide, and then mixed with diphenylmethane diisocyanate and stannous octoate. The mixture is reacted at 75°C for 1.5 h to obtain an isocyanate-terminated prepolymer. The mass ratio of polycaprolactone diol containing disulfide bonds, diphenylmethane diisocyanate, and stannous octoate is 22:6:0.07. The mass of dimethyl sulfoxide is three times the mass of polycaprolactone diol containing disulfide bonds. S3: Modified titanium carbide nanosheets were dispersed in dimethyl sulfoxide and sonicated for 30 min to obtain a titanium carbide nanosheet dispersion; wherein, the mass of dimethyl sulfoxide was 60 times that of the modified titanium carbide nanosheets. The modified titanium carbide nanosheets were prepared by the following steps: 2 parts by mass of titanium aluminum carbide powder were slowly added to 40 parts by mass of hydrofluoric acid (40%, an etchant for selectively etching the aluminum layer), and the mixture was magnetically stirred at 35°C for 24 hours. After the reaction, the mixture was centrifuged and washed until the pH was approximately 6. The precipitate was dispersed in 100 parts by mass of anhydrous ethanol and sonicated at 200 W (to aid in exfoliation and promote interlayer exfoliation) for 2 hours. The supernatant was then centrifuged and the suspension was collected. The suspension was vacuum dried at 60°C for 12 hours to obtain few-layer titanium carbide nanosheets. 0.5 parts by mass of the few-layer titanium carbide nanosheets were dispersed in 100 parts by mass of anhydrous ethanol and sonicated for 30 minutes. 2 parts by mass of aminopropyltriethoxysilane were added, and glacial acetic acid was added dropwise to adjust the pH to 4-5. The mixture was refluxed at 60°C for 4 hours under nitrogen protection (to prevent oxidation). Finally, the unreacted silane was removed by centrifugation and washing, and the mixture was vacuum dried at 60°C for 12 hours to obtain the modified titanium carbide nanosheets.

[0024] S4: The isocyanate-terminated prepolymer and 1,4-butanediol were mixed and stirred at 50°C for 1 h. Titanium carbide nanosheet dispersion was added, and the mixture was reacted at 60°C for 1.5 h. Then, ethanol was added, and the mixture was reacted at 55°C for 25 min. After vacuum degassing for 30 min, shape memory polyurethane spinning solution was obtained. The mass ratio of isocyanate-terminated prepolymer, 1,4-butanediol and titanium carbide nanosheet dispersion was 26:1:22, and the mass of ethanol was 1.8 times the mass of amino-modified titanium carbide nanosheets. S5: The shape memory polyurethane spinning solution is preheated to 50°C, extruded through a 0.10mm spinneret, and placed in a coagulation bath in a mixture of dimethylformamide, water, and ethanol with a volume ratio of 3:6:1. The temperature of the first section (0~0.5m) of the coagulation bath is 25°C, and the temperature of the second section (0.5~1.5m) is 40°C. The coagulation time is 5min, the winding speed is 20m / min, and the draw ratio is -4. The coagulated fiber is then passed through three water washing tanks (40°C, 50°C, and 60°C) in sequence, and left in each tank for 3min. The fiber is then placed in an oven in a relaxed state and heat-set at 60°C for 30min, followed by heat-setting at 120°C for 10min. After natural cooling to room temperature, it is spun into shape memory polyurethane fiber. S6: The shape memory polyurethane fiber is used as the sheath layer material and the combed cotton sliver is used as the core layer material. The two are compounded on a ring spinning machine and wound into a bobbin yarn to obtain the fabric weft yarn. After weaving, the self-healing and wrinkle-resistant shirt fabric is obtained. The mass ratio of cotton fiber to shape memory polyurethane fiber is 95:6.

[0025] Example 3 A self-healing, wrinkle-resistant shirt fabric is prepared by the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide, and tetrabutyl titanate in a mass ratio of 48:1.3:0.3 were added to toluene and reacted at 110°C for 7 h. After the reaction, the solvent was removed by distillation, and the precipitate was collected in diethyl ether and dried at 50°C for 24 h to obtain polycaprolactone diol containing disulfide bonds. The mass of toluene was 1.8 times the mass of ε-caprolactone. A small amount of the product (polycaprolactone diol containing disulfide bonds) was dissolved in dimethyl sulfoxide and then reduced with dithiothreitol. DTNB reagent was then added. The solution showed a distinct yellow absorption peak at 412 nm, indicating that the product produced free thiol groups after reduction and that the molecular chain contained disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in dimethylformamide, and then diphenylmethane diisocyanate and triethylenediamine are added and mixed. The mixture is reacted at 65°C for 2.5 h to obtain an isocyanate-terminated prepolymer. The mass ratio of polycaprolactone diol containing disulfide bonds, diphenylmethane diisocyanate and triethylenediamine is 18:4:0.04. The mass of dimethylformamide is twice the mass of polycaprolactone diol containing disulfide bonds. S3: The modified titanium carbide nanosheets were dispersed in N-methylpyrrolidone and sonicated for 30 min to obtain a titanium carbide nanosheet dispersion; wherein, the mass of N-methylpyrrolidone was 50 times that of the modified titanium carbide nanosheets. The modified titanium carbide nanosheets were prepared by the following steps: 2 parts by mass of titanium aluminum carbide powder were slowly added to 40 parts by mass of hydrofluoric acid (40%, an etchant for selectively etching the aluminum layer), and the mixture was magnetically stirred at 35°C for 24 hours. After the reaction, the mixture was centrifuged and washed until the pH was approximately 6. The precipitate was dispersed in 100 parts by mass of anhydrous ethanol and sonicated at 200 W (to aid in exfoliation and promote interlayer exfoliation) for 2 hours. The supernatant was then centrifuged and the suspension was collected. The suspension was vacuum dried at 60°C for 12 hours to obtain few-layer titanium carbide nanosheets. 0.5 parts by mass of the few-layer titanium carbide nanosheets were dispersed in 100 parts by mass of anhydrous ethanol and sonicated for 30 minutes. 2 parts by mass of aminopropyltriethoxysilane were added, and glacial acetic acid was added dropwise to adjust the pH to 4-5. The mixture was refluxed at 60°C for 4 hours under nitrogen protection (to prevent oxidation). Finally, the unreacted silane was removed by centrifugation and washing, and the mixture was vacuum dried at 60°C for 12 hours to obtain the modified titanium carbide nanosheets.

[0026] S4: The isocyanate-terminated prepolymer and 1,4-butanediol were mixed and stirred at 50°C for 1 h. The titanium carbide nanosheet dispersion was added, and the mixture was reacted at 40°C for 2.5 h. Then, n-butanol was added, and the mixture was reacted at 45°C for 35 min. After vacuum degassing for 30 min, the shape memory polyurethane spinning solution was obtained. The mass ratio of the isocyanate-terminated prepolymer, 1,4-butanediol, and titanium carbide nanosheet dispersion was 24:1:20, and the mass of n-butanol was 1.4 times the mass of amino-modified titanium carbide nanosheets. S5: The shape memory polyurethane spinning solution is preheated to 40°C, extruded through a 0.10mm spinneret, and placed in a coagulation bath in a mixture of dimethylformamide, water, and ethanol with a volume ratio of 3:6:1. The temperature of the first section (0~0.5m) of the coagulation bath is 25°C, and the temperature of the second section (0.5~1.5m) is 40°C. The coagulation time is 3min, the winding speed is 10m / min, and the draw ratio is 2. The coagulated fiber is then passed through three water washing tanks (40°C, 50°C, and 60°C) in sequence, and left in each tank for 2min. The fiber is then placed in an oven in a relaxed state and heat-set at 60°C for 30min, followed by heat-setting at 120°C for 10min. After natural cooling to room temperature, it is spun into shape memory polyurethane fiber. S6: The shape memory polyurethane fiber is used as the sheath layer material and the combed cotton sliver is used as the core layer material. The two are compounded on a ring spinning machine and wound into a bobbin yarn to obtain the fabric weft yarn. After weaving, the self-healing and wrinkle-resistant shirt fabric is obtained. The mass ratio of cotton fiber to shape memory polyurethane fiber is 94:6.

[0027] Example 4 A self-healing, wrinkle-resistant shirt fabric is prepared by the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide, and stannous octoate in a mass ratio of 49:1.5:0.4 were added to toluene and reacted at 115°C for 5.5 h. After the reaction, the solvent was removed by distillation, and the precipitate was collected in diethyl ether and dried at 50°C for 24 h to obtain polycaprolactone diol containing disulfide bonds. The mass of toluene was 1.8 times the mass of ε-caprolactone. A small amount of the product (polycaprolactone diol containing disulfide bonds) was dissolved in dimethyl sulfoxide and then reduced with dithiothreitol. DTNB reagent was then added. The solution showed a distinct yellow absorption peak at 412 nm, indicating that the product produced free thiol groups after reduction and that the molecular chain contained disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in dimethyl sulfoxide, and then mixed with diphenylmethane diisocyanate and dibutyltin dilaurate. The mixture is reacted at 65°C for 2 hours to obtain an isocyanate-terminated prepolymer. The mass ratio of polycaprolactone diol containing disulfide bonds, diphenylmethane diisocyanate, and dibutyltin dilaurate is 19:5:0.05. The mass of dimethyl sulfoxide is 2.2 times the mass of polycaprolactone diol containing disulfide bonds. S3: Modified titanium carbide nanosheets were dispersed in dimethyl sulfoxide and sonicated for 30 min to obtain a titanium carbide nanosheet dispersion; wherein, the mass of dimethyl sulfoxide was 53 times that of the modified titanium carbide nanosheets. The modified titanium carbide nanosheets were prepared by the following steps: 2 parts by mass of titanium aluminum carbide powder were slowly added to 40 parts by mass of hydrofluoric acid (40%, an etchant for selectively etching the aluminum layer), and the mixture was magnetically stirred at 35°C for 24 hours. After the reaction, the mixture was centrifuged and washed until the pH was approximately 6. The precipitate was dispersed in 100 parts by mass of anhydrous ethanol and sonicated at 200 W (to aid in exfoliation and promote interlayer exfoliation) for 2 hours. The supernatant was then centrifuged and the suspension was collected. The suspension was vacuum dried at 60°C for 12 hours to obtain few-layer titanium carbide nanosheets. 0.5 parts by mass of the few-layer titanium carbide nanosheets were dispersed in 100 parts by mass of anhydrous ethanol and sonicated for 30 minutes. 2 parts by mass of aminopropyltriethoxysilane were added, and glacial acetic acid was added dropwise to adjust the pH to 4-5. The mixture was refluxed at 60°C for 4 hours under nitrogen protection (to prevent oxidation). Finally, the unreacted silane was removed by centrifugation and washing, and the mixture was vacuum dried at 60°C for 12 hours to obtain the modified titanium carbide nanosheets.

[0028] S4: The isocyanate-terminated prepolymer and 1,4-butanediol were mixed and stirred at 50°C for 1 hour. Titanium carbide nanosheet dispersion was added, and the mixture was reacted at 45°C for 2 hours. Then methanol was added, and the mixture was reacted at 45°C for 25 minutes. After vacuum degassing for 30 minutes, shape memory polyurethane spinning solution was obtained. The mass ratio of isocyanate-terminated prepolymer, 1,4-butanediol and titanium carbide nanosheet dispersion was 24:1:21, and the mass of methanol was 1.5 times the mass of amino-modified titanium carbide nanosheets. S5: The shape memory polyurethane spinning solution is preheated to 45°C, extruded through a 0.10mm spinneret, and placed in a coagulation bath in a mixture of dimethylformamide, water, and ethanol with a volume ratio of 3:6:1. The temperature of the first section (0~0.5m) of the coagulation bath is 25°C, and the temperature of the second section (0.5~1.5m) is 40°C. The coagulation time is 4min, the winding speed is 15m / min, and the draw ratio is 3. The coagulated fiber is then passed through three water washing tanks (40°C, 50°C, and 60°C) in sequence, and left in each tank for 3min. The fiber is then placed in an oven in a relaxed state and heat-set at 60°C for 30min, followed by heat-setting at 120°C for 10min. After natural cooling to room temperature, it is spun into shape memory polyurethane fiber. S6: The shape memory polyurethane fiber is used as the sheath layer material and the combed cotton sliver is used as the core layer material. The two are compounded on a ring spinning machine and wound into a bobbin yarn to obtain the fabric weft yarn. After weaving, the self-healing and wrinkle-resistant shirt fabric is obtained. The mass ratio of cotton fiber to shape memory polyurethane fiber is 94.5:5.5.

[0029] Example 5 A self-healing, wrinkle-resistant shirt fabric is prepared by the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide, and stannous chloride in a mass ratio of 51:2:0.6 were added to xylene and reacted at 125°C for 6 h. After the reaction, the solvent was removed by distillation, and the precipitate was collected in diethyl ether and dried at 50°C for 24 h to obtain polycaprolactone diol containing disulfide bonds; wherein the mass of xylene was 2.1 times the mass of ε-caprolactone. A small amount of the product (polycaprolactone diol containing disulfide bonds) was dissolved in dimethyl sulfoxide and then reduced with dithiothreitol. DTNB reagent was then added. The solution showed a distinct yellow absorption peak at 412 nm, indicating that the product produced free thiol groups after reduction and that the molecular chain contained disulfide bonds. S2: Polycaprolactone diol containing disulfide bonds is dispersed in dimethyl sulfoxide, and then mixed with diphenylmethane diisocyanate and stannous octoate. The mixture is reacted at 70°C for 2.3 h to obtain an isocyanate-terminated prepolymer. The mass ratio of polycaprolactone diol containing disulfide bonds, diphenylmethane diisocyanate, and stannous octoate is 21:6:0.06. The mass of dimethyl sulfoxide is 2.8 times the mass of polycaprolactone diol containing disulfide bonds. S3: The modified titanium carbide nanosheets were dispersed in N-methylpyrrolidone and sonicated for 30 min to obtain a titanium carbide nanosheet dispersion; wherein, the mass of N-methylpyrrolidone was 58 times that of the modified titanium carbide nanosheets. The modified titanium carbide nanosheets were prepared by the following steps: 2 parts by mass of titanium aluminum carbide powder were slowly added to 40 parts by mass of hydrofluoric acid (40%, an etchant for selectively etching the aluminum layer), and the mixture was magnetically stirred at 35°C for 24 hours. After the reaction, the mixture was centrifuged and washed until the pH was approximately 6. The precipitate was dispersed in 100 parts by mass of anhydrous ethanol and sonicated at 200 W (to aid in exfoliation and promote interlayer exfoliation) for 2 hours. The supernatant was then centrifuged and the suspension was collected. The suspension was vacuum dried at 60°C for 12 hours to obtain few-layer titanium carbide nanosheets. 0.5 parts by mass of the few-layer titanium carbide nanosheets were dispersed in 100 parts by mass of anhydrous ethanol and sonicated for 30 minutes. 2 parts by mass of aminopropyltriethoxysilane were added, and glacial acetic acid was added dropwise to adjust the pH to 4-5. The mixture was refluxed at 60°C for 4 hours under nitrogen protection (to prevent oxidation). Finally, the unreacted silane was removed by centrifugation and washing, and the mixture was vacuum dried at 60°C for 12 hours to obtain the modified titanium carbide nanosheets.

[0030] S4: The isocyanate-terminated prepolymer and 1,4-butanediol were mixed and stirred at 50°C for 1 h. Titanium carbide nanosheet dispersion was added and reacted at 55°C for 2.3 h. Then n-butanol was added and reacted at 50°C for 32 min. Vacuum degassing was performed for 30 min to obtain the shape memory polyurethane spinning solution. The mass ratio of isocyanate-terminated prepolymer, 1,4-butanediol and titanium carbide nanosheet dispersion was 25:1:21, and the mass of n-butanol was 1.6 times the mass of amino-modified titanium carbide nanosheets. S5: The shape memory polyurethane spinning solution is preheated to 45°C, extruded through a 0.10mm spinneret, and placed in a coagulation bath in a mixture of dimethylformamide, water, and ethanol with a volume ratio of 3:6:1. The temperature of the first section (0~0.5m) of the coagulation bath is 25°C, and the temperature of the second section (0.5~1.5m) is 40°C. The coagulation time is 5min, the winding speed is 20m / min, and the draw ratio is 4. The coagulated fiber is then passed through three water washing tanks (40°C, 50°C, and 60°C) in sequence, and left in each tank for 3min. The fiber is then placed in an oven in a relaxed state and heat-set at 60°C for 30min, followed by heat-setting at 120°C for 10min. After natural cooling to room temperature, it is spun into shape memory polyurethane fiber. S6: The shape memory polyurethane fiber is used as the sheath layer material and the combed cotton sliver is used as the core layer material. The two materials are compounded on a ring spinning machine and wound into a bobbin yarn to obtain the fabric weft yarn. After weaving, the self-healing and wrinkle-resistant shirt fabric is obtained. The mass ratio of cotton fiber to shape memory polyurethane fiber is 95:5.

[0031] Comparative Example 1 The results are basically the same as in Example 1, except that the modified titanium carbide nanosheets are replaced with the same amount of unmodified titanium carbide nanosheets, and step S3 is omitted.

[0032] Comparative Example 2 It is basically the same as Example 1, except that the disulfide-bonded polycaprolactone diol is replaced with the same amount of polycaprolactone diol, and step S1 is omitted.

[0033] Comparative Example 3 It is basically the same as Example 1, except that diphenylmethane diisocyanate is replaced with the same amount of toluene diisocyanate.

[0034] Comparative Example 4 It is basically the same as Example 1, except that no modified titanium carbide nanosheets are added.

[0035] The fabrics prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to performance tests, and the test results are shown in Table 1.

[0036] Photothermal performance testing: The fabric was cut into 5 cm × 5 cm samples, and an 808 nm near-infrared laser (power density 1.0 W / cm²) was used. 2 Under vertical illumination, an infrared thermal imager records the surface temperature changes in real time, recording the temperature at 30 s and 60 s. Shape memory performance test: Referring to the cyclic folding method, the fabric is folded 180°, 500 g pressure is applied and held for 5 min, and after release, the shape recovery rate (Rr) is measured after 30 s of 808 nm near-infrared irradiation. Self-healing performance test: The fabric was repeatedly folded and recovered in cycles (100 times). After each fold, it was irradiated with 808 nm near-infrared light for 30 seconds to remove wrinkles. The wrinkle recovery angle was recorded after 100 cycles. Wrinkle resistance durability test: Under household washing conditions, 40℃, standard detergent, wash-dry cycle, 808 nm near-infrared irradiation for 30 s after each wash to remove wrinkles, and the wrinkle recovery angle was measured after 50 washes; Titanium carbide dispersion stability test: After washing the fabric 20 times (40℃, standard detergent) and drying it, the temperature was measured by irradiating it with 808 nm near-infrared light for 10s and the retention rate was calculated by comparing it with the initial value.

[0037] Table 1

[0038] As shown in Table 1, the self-healing and wrinkle-resistant shirt fabrics provided in Examples 1-5 of this invention can heat up to 72-78°C within 30 seconds of 808 nm near-infrared irradiation, exceeding the crystallization melting temperature of polycaprolactone. The shape memory recovery rate reaches 85-90%, the wrinkle recovery angle remains at 274-275° after 100 washes, and the wrinkle recovery angle remains at 278-282° after 50 washes. After 20 washes, the titanium carbide retention rate is about 96%, indicating that the synergistic effect of covalent anchoring and dynamic disulfide bond exchange of amino-modified titanium carbide nanosheets endows the fabric with comprehensive properties of rapid response, efficient recovery and long-term durability.

[0039] As can be seen from Comparative Examples 1-4, Comparative Example 1, using unmodified titanium carbide nanosheets in a physical blend, initially exhibited acceptable photothermal performance. However, after 20 washes, the titanium carbide retention rate plummeted to 60%, and after 50 washes, the recovery angle was only 210°. This is because the physical blend lacks chemical bonding, causing the titanium carbide to gradually detach and be lost during washing, leading to a decline in photothermal function, uneven heat conduction, and ultimately a significant decrease in wrinkle resistance and durability. Comparative Example 2, using conventional polycaprolactone diol instead of disulfide-bonded polycaprolactone diol, showed a recovery angle of only 220° after 100 folds. This is because the molecular chain lacks a dynamic exchange mechanism for disulfide bonds, making it impossible to repair microcracks generated by repeated deformation. The accumulated stress concentration leads to rapid functional degradation. Comparative Example 3, which replaced diphenylmethane diisocyanate with toluene diisocyanate, showed a shape memory recovery angle of only 252° after 50 washes. This is because TDI has poorer symmetry than MDI, resulting in insufficient regularity of the hard segment micro-regions, weak shape memory recovery driving force, and poor hydrolysis resistance of the TDI matrix, leading to partial degradation of the hard segments after long-term washing. Comparative Example 4, without modified titanium carbide nanosheets, showed a shape memory recovery angle of only 148° after 30 seconds at a temperature of only 36°C and 50 washes. This is because it lacked near-infrared photothermal conversion filler, and body temperature alone could not activate shape memory, while wrinkles continued to accumulate during repeated washing.

[0040] The above descriptions are merely some embodiments of the present invention. Those skilled in the art can make various modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A preparation process for a self-healing, wrinkle-resistant shirt fabric, characterized in that, Includes the following steps: S1: ε-caprolactone, bis(2-hydroxyethyl) disulfide and catalyst I are added to solvent I to react. After the reaction, the solvent is removed by distillation, the precipitate is transferred to a precipitant to collect the precipitate, and then dried to obtain polycaprolactone diol containing disulfide bonds. S2: The disulfide-bonded polycaprolactone diol is dispersed in solvent II, and diphenylmethane diisocyanate and catalyst II are added and mixed to react to obtain an isocyanate-terminated prepolymer; S3: The modified titanium carbide nanosheets are dispersed in solvent III to obtain a titanium carbide nanosheet dispersion. S4: The isocyanate-terminated prepolymer and 1,4-butanediol are mixed, and the titanium carbide nanosheet dispersion is added to react. Then, a terminating agent is added to terminate the prepolymer. After degassing, shape memory polyurethane spinning solution is obtained. S5: The shape memory polyurethane spinning solution is spun into shape to obtain shape memory polyurethane fiber; S6: The shape memory polyurethane fiber is composited onto cotton fiber to obtain the fabric weft yarn, and after weaving, the self-healing and wrinkle-resistant shirt fabric is obtained.

2. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, The mass ratio of ε-caprolactone, bis(2-hydroxyethyl) disulfide, and catalyst I is 48-52:1.3-2.5:0.3-0.7; the mass amount of solvent I is 1.8-2.2 times the mass amount of ε-caprolactone.

3. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 2, characterized in that, The catalyst I is selected from at least one of stannous octoate, stannous chloride, and tetrabutyl titanate; the solvent I is toluene or xylene; and the precipitant is diethyl ether or n-hexane.

4. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, The mass ratio of the disulfide-bonded polycaprolactone diol, diphenylmethane diisocyanate, and catalyst II is 18-22:4-6:0.04-0.07; the catalyst II is selected from at least one of dibutyltin dilaurate, stannous octoate, and triethylenediamine; the solvent II is dimethylformamide or dimethyl sulfoxide; and the mass of the solvent II is 2-3 times the mass of the disulfide-bonded polycaprolactone diol.

5. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, Solvent III is selected from at least one of dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone; the mass amount of solvent III is 50-60 times that of the modified titanium carbide nanosheets.

6. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, The mass ratio of the isocyanate-terminated prepolymer, 1,4-butanediol, and titanium carbide nanosheet dispersion is 24-26:1:20-22; the mass amount of the end-capping agent is 1.4-1.8 times the mass amount of the amino-modified titanium carbide nanosheets; the end-capping agent is selected from at least one of methanol, ethanol, and n-butanol.

7. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, The modified titanium carbide nanosheets are made by grafting amino groups onto the surface of titanium carbide aluminum.

8. The preparation process of the self-healing wrinkle-resistant shirt fabric according to claim 1, characterized in that, In step S1, the reaction is carried out at 110-130℃ for 5-7 hours; in step S2, the reaction is carried out at 65-75℃ for 1.5-2.5 hours; in step S4, the reaction is carried out at 40-60℃ for 1.5-2.5 hours, and the end-capping is carried out at 45-55℃ for 25-35 minutes.

9. A self-healing wrinkle-resistant shirt fabric prepared by the preparation process of the self-healing wrinkle-resistant shirt fabric according to any one of claims 1-8.

10. The self-healing wrinkle-resistant shirt fabric according to claim 9, characterized in that, The mass ratio of the cotton fiber to the shape memory polyurethane fiber is 94-95:5-6.

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