Modified polyether polyurethane for ski suit fabric as well as preparation method and application of modified polyether polyurethane

Abstract

The invention belongs to the technical field of high polymer materials, and relates to modified polyether polyurethane for a ski suit fabric as well as a preparation method and application of the modified polyether polyurethane. The preparation method comprises the following steps: reacting diphenylmethane-4, 4-diisocyanate and polytetrahydrofuran at 80-90 DEG C to generate a prepolymer, firstly controlling part of the prepolymer in a reaction system to react with tris (2-ethoxyl) isocyanurate at 70-80 DEG C, then controlling the residual prepolymer in the reaction system to react with syringic acid at 100-120 DEG C, and finally, adding a proper amount of a catalyst to react, so as to obtain the polyurethane prepolymer. The modified polyether polyurethane for the ski suit fabric is obtained. The base material of the polyurethane microporous moisture-permeable film is the modified polyether polyurethane for the ski suit fabric. The ski suit fabric is formed by sequentially compounding the polyurethane microporous moisture-permeable film, the chemical fiber fabric and the screen cloth through polyurethane glue, and the polyurethane microporous moisture-permeable film is the polyurethane microporous moisture-permeable film. The ski suit fabric has excellent hydrostatic pressure, moisture permeability and air permeability.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a modified polyether polyurethane for skiwear fabric, its preparation method, and its application. Background Technology

[0002] With social development and the continuous improvement of people's living standards, the demand for functional clothing is increasing, especially in sportswear fabrics such as windproof jackets, mountaineering clothing, and ski suits, which require excellent waterproof and breathable properties. This not only needs to prevent rain and snow from penetrating the fabric but also allows sweat to be transferred to the outside as moisture through the fabric to ensure wearing comfort. In recent years, waterproof and breathable fabrics have developed rapidly, and their applications are no longer limited to military supplies and medical protective equipment but are also rapidly expanding into outdoor leisure sportswear and equipment. As a material for waterproof and breathable fabrics, the research on the preparation methods of waterproof and breathable polyurethane is of great significance.

[0003] Patent application CN108976766A discloses a waterproof and breathable polyurethane microporous film and its preparation method, comprising the following components by weight: 0.01-20 parts of aqueous ultrafine powder and 80-99 parts of polyurethane. By controlling different proportions and properties of the aqueous ultrafine powder, waterproof and breathable microporous polyurethane films with different properties can be prepared. The micropores generated by the aqueous ultrafine powder enable the polyurethane film to achieve its waterproof and breathable function. By controlling the size and distribution of the micropores, the prepared waterproof and breathable microporous polyurethane films can have different waterproof and breathable effects. However, the micropores in this method are generated by the incompatibility between the ultrafine powder and the polyurethane matrix, which inevitably affects the mechanical properties and hydrostatic pressure of the polyurethane film. The larger the micropores, the greater the impact on the mechanical properties and hydrostatic pressure of the polyurethane film.

[0004] Patent application CN106867017A discloses a microporous membrane with controllable pore size and its preparation method. This microporous membrane is a polyurethane resin membrane with a pore size of 0.5-20 μm and an acid-soluble microparticle content of less than 5%. The method involves using acid-soluble microparticles in a coating resin, followed by acid treatment to dissolve them and form micropores, thus obtaining a microporous membrane with controllable pore size. However, this method may result in insufficient dissolution of the acid-soluble microparticles, affecting the porosity and preventing the membrane's moisture permeability from reaching the expected level.

[0005] Patent applications with publication numbers US5208313A and US5461122A both disclose an improved method for manufacturing waterproof and breathable polyurethane. This method not only reacts isocyanate monomers containing bifunctional groups with polyethylene glycol, but also adds hydrophobic intermediates containing dihydroxyl groups, such as organosilicon, polytetramethylene ether glycol (PTMEG), or polyester, to react. Although this type of polyurethane monolayer can improve hydrostatic pressure, its moisture permeability is not high, and it cannot meet the requirements of both high hydrostatic pressure and high moisture permeability.

[0006] In summary, existing polyurethane single-layer membranes still cannot meet the requirements of high hydrostatic pressure and high moisture permeability. Therefore, it is necessary to develop a polyurethane material that can achieve both high hydrostatic pressure and high moisture permeability. Summary of the Invention

[0007] The purpose of this invention is to solve the problems existing in the prior art and to provide a modified polyether polyurethane for skiwear fabric, its preparation method and application.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing modified polyether polyurethane for skiwear fabrics involves reacting diphenylmethane-4,4-diisocyanate (MDI, OCN-C6H4-CH2-C6H4-NCO) and polytetrahydrofuran (PTHF, HO-(C4H8O)nH) at 80-90℃ to generate a prepolymer. Then, a portion of the prepolymer and tris(2-hydroxyethyl) isocyanurate (THEIC) in the reaction system are controlled to react at 70-80℃. Finally, the remaining prepolymer and eugenol in the reaction system are controlled to react at 100-120℃ to obtain the modified polyether polyurethane for skiwear fabrics.

[0010] The amounts of each reactant added, by weight, are as follows: 87.5-100 parts of diphenylmethane-4,4-diisocyanate, 340-380 parts of polytetrahydrofuran (a low molecular weight polymer with an average molecular weight of 2000 g / mol), 10-14 parts of tris(2-hydroxyethyl)isocyanurate, and 8-12 parts of eugenol.

[0011] The principle of the preparation process of the modified polyether polyurethane for ski suit fabric of the present invention is as follows:

[0012] The isocyanate group (NCO) in diphenylmethane-4,4-diisocyanate reacts with the hydroxyl group (OH) in polytetrahydrofuran at 80-90℃ to form a urethane bond, yielding a prepolymer. The reaction equation is as follows:

[0013] OCN-C6H4-CH2-C6H4-NCO+HO-(C4H8O)nH→OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO;

[0014] After the reaction system is cooled to 70-80℃, tris(2-hydroxyethyl) isocyanurate (C9H) 15 The three hydroxyethyl groups in the N3O6 molecule react with one NCO group from a portion of the prepolymer (while another portion of the prepolymer does not participate in the reaction; this unreacted prepolymer is called the residual prepolymer), forming a rigid three-dimensional network structure. The reaction equations are as follows:

[0015] 3OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO+C9H 15 N3O6→[OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3;

[0016] After the reaction system is heated to 100-120℃, syringic acid (C9H) 10 The phenolic hydroxyl group of O5 reacts with one NCO of the remaining prepolymer, and the reaction equation is as follows:

[0017] C9H 10 O5+OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO→

[0018] C9H9O4-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO;

[0019] The phenolic hydroxyl group of eugenol preferentially reacts with one of the OCNs in the remaining prepolymer, rather than with the terminal OCN in [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3. This is because the prepolymer has a more linear structure and less steric hindrance, and the terminal NCO of the prepolymer is exposed on the molecular surface, allowing the eugenol molecule to easily approach one of the N-terminal OCNs in the remaining prepolymer. CO, and reacts with it; while [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3 is a rigid three-dimensional network structure with a complex spatial configuration. The terminal NCOs are enclosed inside the network, surrounded by many molecular chains and groups, resulting in large steric hindrance. Syringic acid molecules have difficulty accessing these enclosed and spatially confined NCOs. Therefore, syringic acid reacts with [OCN-C6H4-

[0020] The terminal OCN of CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3 does not react;

[0021] In addition, the carboxyl and phenolic hydroxyl groups of eugenol can form crosslinks, such as hydrogen bonds, with groups such as urethane groups in the reaction system. These crosslinks are weak and low in density, and are dynamically reversible, without affecting the reaction of eugenol with the remaining prepolymer.

[0022] As a preferred technical solution:

[0023] In the preparation method of modified polyether polyurethane for skiwear fabric as described above, before the reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran, diphenylmethane-4,4-diisocyanate is first vacuum dehydrated at 100-130℃ for 1-4 hours.

[0024] As described above, a method for preparing modified polyether polyurethane for skiwear fabric involves reacting diphenylmethane-4,4-diisocyanate and polytetrahydrofuran under nitrogen or inert gas protection for 2-3 hours. In the reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran, no additional solvent is typically required. This is because diphenylmethane-4,4-diisocyanate has a melting point of 39-42°C, while polytetrahydrofuran is a waxy semi-solid at room temperature, and its fluidity significantly improves when heated above 50°C. Heating to 80°C allows the two to melt and dissolve together, directly forming a homogeneous system. Furthermore, the solvent-free system avoids subsequent solvent removal steps, reducing energy consumption and the risk of impurity residue, and improving the uniformity of the prepolymer's molecular weight.

[0025] The above-described method for preparing modified polyether polyurethane for skiwear fabric involves reacting a portion of the prepolymer and tris(2-hydroxyethyl) isocyanurate in the reaction system under the action of a first catalyst, which is a (3-trimethoxysilylpropylthiolsyl)dibutyltin acetate complex. The amount of the first catalyst added is 0.5-2 parts by weight, and the reaction time is 1-3 hours.

[0026] The (3-trimethoxysilylpropylthio)dibutyltin acetate complex is a highly selective organotin alkoxylation catalyst synthesized via 3-mercaptopropyltrimethoxysilane and dibutyltin diacetate. The CAS number for 3-mercaptopropyltrimethoxysilane is 4420-74-0, and the CAS number for dibutyltin diacetate is 1067-33-0. In the molecular structure of the (3-trimethoxysilylpropylthio)dibutyltin acetate complex, the sulfur atom is coordinated to the tin center. The prepolymer is associated with [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)]. n Compared to [OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3, the prepolymer has less steric hindrance, and its -OCN group readily approaches the active center (tin atom) of the acetic acid (3-trimethoxysilylpropylthio)dibutyltin complex. Therefore, the acetic acid (3-trimethoxysilylpropylthio)dibutyltin complex can efficiently catalyze the addition reaction between the prepolymer's -OCN and the hydroxyl group of tris(2-hydroxyethyl)isocyanurate to form a carbamate bond, thereby generating [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)]. n -OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3, but [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)] n The steric hindrance of [OCN-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3 inhibits the activity of its terminal OCN, making it difficult for this terminal OCN to approach the active site of the (3-trimethoxysilylpropylthio)dibutyltin acetate complex. Therefore, tris(2-hydroxyethyl)isocyanurate will only react with the -OCN of the prepolymer and not with [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)]. n The -OCN of -OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3 further reacts.

[0027] The preparation method of modified polyether polyurethane for skiwear fabric as described above involves the reaction of the remaining prepolymer and eugenol in the reaction system under the action of a second catalyst, p-toluenesulfonic acid, in parts by weight of 0.5-2 parts. The viscosity of the reaction system is adjusted to 6000-9000 mPa·s by adding butanone, and the reaction time is 3-5 h. This process utilizes the compounds C9H9O4-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO and [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO and [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-O ... n The steric hindrance of [OCN-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3 is relatively large, while the steric hindrance of the remaining prepolymer is relatively small. This ensures that the product formed when eugenol reacts with the remaining prepolymer is C9H9O4-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO. Furthermore, eugenol is added to the reaction system slowly, for example, at a dropping rate of 0.3-1.8 parts by weight / min. This allows eugenol to preferentially contact the -OCN component of the remaining prepolymer, which has less steric hindrance, and react with it. This also helps to prevent the reaction between eugenol and [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)]3-C3N3O3. n The -OCN in -OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2CH2]3-C3N3O3 and C9H9O4-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO reacts upon contact.

[0028] The preparation method of modified polyether polyurethane for ski suit fabric as described above involves reacting the remaining prepolymer and eugenol in the reaction system, followed by filtration and vacuum drying, with the vacuum drying time being 15-30 hours.

[0029] The present invention also provides a modified polyether polyurethane for skiwear fabric, which is prepared by the method described in any of the preceding claims.

[0030] The present invention also provides a polyurethane microporous breathable membrane, wherein the substrate is a modified polyether polyurethane for skiwear fabric as described above.

[0031] As a preferred technical solution:

[0032] The preparation process of the polyurethane microporous breathable membrane described above is as follows: By weight, 40-50 parts of skiwear fabric are mixed evenly with modified polyether polyurethane, 40-50 parts of DMF, 3-10 parts of acetophenone, 1-3 parts of leveling agent (TEGO Glide432), and 1-3 parts of foaming agent (PU1231) to form a coating slurry. The coating slurry is then coated onto the base fabric. The DMF is removed by using a coagulation bath (i.e., soaking in a DMF aqueous solution with a DMF content of 15-30% at a temperature of 25-45℃ for 20-40 minutes). After drying (at a temperature of 80-120℃ for 30-60 minutes), the base fabric is removed to obtain the polyurethane microporous breathable membrane.

[0033] In the phase separation process of preparing polyurethane microporous breathable membranes from modified polyether polyurethane for skiwear fabrics, the high polarity of tris(2-hydroxyethyl) isocyanurate enhances the interaction between the modified polyether polyurethane for skiwear fabrics and the solvent, slowing down the solvent evaporation rate. The carboxyl groups of eugenol can form a transient hydrogen bond network with non-solvents (such as water), guiding the polyurethane segments to form a finer primary pore structure during phase separation. Moreover, the crosslinking points of eugenol are pH / temperature responsive, partially decrosslinking during the micropore formation stage (high temperature, acidic conditions), allowing the segments to rearrange and optimize the pore structure. Crosslinking is restored in the finished product stage to maintain structural stability. The combination of the delayed volatilization of tris(2-hydroxyethyl) isocyanurate and the transient template effect of eugenol enables the micropore formation to undergo a slow nucleation-rapid growth process, ultimately forming a three-dimensional pore network with narrow pore size distribution and good permeability.

[0034] The polyurethane microporous breathable membrane has a thickness of 30-33 μm and a pore size of 300-500 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12000-13000 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16000-17000 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 11000-12000 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 10500-11000 g / (m³). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.4-0.5mm / s.

[0035] The present invention also provides a ski suit fabric, which is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric sequentially bonded together with a polyurethane adhesive. The polyurethane microporous breathable membrane is a polyurethane microporous breathable membrane as described above.

[0036] As a preferred technical solution:

[0037] As described above, the ski suit fabric has the following characteristics: the synthetic fiber fabric has a thickness of 200-300 μm, a pore size of 4-5 μm (to ensure water vapor molecules can pass through while preventing liquid water penetration), a porosity ≥35% (to enhance gas diffusion efficiency), and a water contact angle >130° (to reduce surface adhesion energy, which can be achieved through treatment with a C6 waterproofing agent); the mesh fabric has a thickness of 150-200 μm, a mesh density of 20-30 mesh, a pore size >100 μm (to optimize air convection channels), and the area ratio of irregularly shaped fibers (such as cross-shaped or Y-shaped) in the fiber cross-section is >60% (to increase specific surface area and capillary effect), with a surface resistivity <10 Ω·cm. 9 Ω (the purpose is to avoid electrostatic adsorption of water vapor, and the corresponding surface resistance can be obtained through antistatic treatment), and the warp and weft tensile rates are both >30% (the purpose is to ensure the deformation synergy between the mesh and the chemical fiber fabric, and to avoid structural failure due to large differences in deformation capacity).

[0038] Ski suit fabrics possess excellent hydrostatic pressure, breathability, and moisture permeability. The hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 10600-12000 mmH2O; the hydrostatic pressure, measured according to JIS L1092-2009 standard, is 15000-16000 mmH2O; and the moisture permeability, measured according to GBT12704.1-2009 standard, is 7000-8000 g / (m²). 2 •24h), the water permeability measured according to JIS L1099-2006 standard is 6000-7000 g / (m²). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.4-0.5mm / s.

[0039] Beneficial effects:

[0040] (1) In the modified polyether polyurethane for ski suit fabric of the present invention, the product formed by tris(2-hydroxyethyl) isocyanurate constitutes the main network skeleton, and the product formed by syringic acid is introduced into the secondary network skeleton. The main network skeleton mainly bears mechanical stress, and the secondary network skeleton mainly dissipates energy through bonding-debonding cycle. This dual mechanism maintains the stability of the microporous structure of the modified polyether polyurethane for ski suit fabric, prevents the micropores from collapsing during use, and ensures moisture permeability and breathability.

[0041] (2) In the modified polyether polyurethane for ski suit fabric of the present invention, the highly polar triazine ring of tris(2-hydroxyethyl) isocyanurate and the highly polar carboxyl group of syringic acid improve the surface hydrophilicity of the modified polyether polyurethane, while the aromatic benzene ring structure of syringic acid forms hydrophobic microregions. This "hydrophilic-hydrophobic mosaic" surface structure can promote water vapor adsorption / desorption, allowing gaseous water molecules to quickly penetrate through hydrogen bonds, while avoiding liquid water penetration, thus achieving moisture permeability and water resistance.

[0042] (3) In the modified polyether polyurethane for ski suit fabric of the present invention, the rigidity of the triazine ring of tri(2-hydroxyethyl) isocyanurate inhibits the crystallization of hard segments of polyurethane, and eugenol promotes the orderly arrangement of soft segments. The synergy of the two enables the polyurethane material to form an alternating structure of amorphous and semi-crystalline regions, which ensures both moisture permeability and mechanical properties. Attached Figure Description

[0043] Figure 1 This is the infrared spectrum of the prepolymer of Example 1;

[0044] Figure 2 The infrared spectrum of the intermediate product obtained in step (4) of Example 1;

[0045] Figure 3 The infrared spectrum is the reaction product of the prepolymer of Example 1 and tris(2-hydroxyethyl) isocyanurate;

[0046] Figure 4 The image shows the infrared spectrum of the reaction product of the prepolymer and syringic acid in Example 1. Detailed Implementation

[0047] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0048] The following are the test methods for the relevant performance indicators in each embodiment and comparative example:

[0049] (1) Static water pressure: Tested in accordance with GB / T 4744-2013 or JIS L1092-2009 standards.

[0050] (2) Moisture permeability: Tested in accordance with GBT12704.1-2009 or JIS L1099-2006 standards.

[0051] (3) Air permeability: Tested in accordance with GB / T 5453-2025 standard.

[0052] (4) Infrared spectrum: The test was performed using a Thermo Scientific Nicoleti S5 Fourier transform infrared spectrometer (FT-IR) (KBr pellet method).

[0053] Example 1A

[0054] A method for preparing modified polyether polyurethane for skiwear fabric, the specific steps of which are as follows:

[0055] (1) Raw material preparation;

[0056] Diphenylmethane-4,4-diisocyanate: 87.5 parts by weight, molecular weight 250 g / mol;

[0057] Polytetrahydrofuran: 340 parts by weight, with an average molecular weight of 2000 g / mol;

[0058] Protective gas: Nitrogen;

[0059] Tris(2-hydroxyethyl)isocyanurate: 10 parts by weight, with a molecular weight of 261, its structure is shown in Formula I;

[0060]

[0061] First catalyst: 0.5 parts by weight of dibutyltin acetate (3-trimethoxysilylpropylthio)dibutyltin complex; the preparation method of dibutyltin acetate (3-trimethoxysilylpropylthio)dibutyltin complex is as follows: Equimolar amounts of dibutyltin diacetate (CAS No. 1067-33-0) and 3-mercaptopropyltrimethoxysilane (CAS No. 4420-74-0) are mixed uniformly, heated to 90℃ and reacted for 6 hours. After the reaction is completed, the mixture is subjected to vacuum distillation at 110℃ and a vacuum of 0.001 MPa for 2 hours. The residue is collected to obtain the dibutyltin acetate (3-trimethoxysilylpropylthio)dibutyltin complex. FT-IR: 1720 cm⁻¹ -1 (Ester group C=O), 2580cm -1 (SH disappeared), 1080cm -1 (Si-OC);

[0062] Syringic acid: 10 parts by weight, molecular weight 198 g / mol, structure as shown in Formula II;

[0063]

[0064] Second catalyst: p-Toluenesulfonic acid, 0.5 parts by weight;

[0065] Anhydrous cyclohexane: 50 parts by weight;

[0066] Butanone;

[0067] (2) Dehydration treatment of diphenylmethane-4,4-diisocyanate;

[0068] Diphenylmethane-4,4-diisocyanate was dehydrated at 100°C and 0.001 MPa for 1 h.

[0069] (3) The reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran;

[0070] After the dehydrated diphenylmethane-4,4-diisocyanate and polytetrahydrofuran were mixed evenly, they were reacted at 80°C for 2 hours under a protective gas atmosphere to generate a prepolymer. The reaction equation was OCN-C6H4-CH2-C6H4-NCO+HO-(C4H8O)nH→OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO. After the reaction was completed, the temperature was lowered to 40°C, and then 30 parts by weight of butanone were added to dilute the reaction mixture. The reaction system is designed to facilitate subsequent filtration and simultaneous termination of the reaction. Unreacted diphenylmethane-4,4-diisocyanate monomers are removed from the reaction system using a thin-film evaporation method. The thin-film evaporation method is performed at a temperature of 95℃, a vacuum degree of 0.4kPa, and a rotation speed of 280rpm to obtain an evaporation concentrate. The evaporation concentrate is then transferred to a reaction vessel, where anhydrous cyclohexane is added for azeotropic dehydration to facilitate solvent displacement and dehydration, preventing water from reacting with -NCO to generate CO2. The product in the reaction vessel is then spray-dried (inlet 180℃, outlet 80℃) to obtain a white powder, which is the prepolymer.

[0071] Infrared spectra of the prepolymer as follows Figure 1 As shown, 2270cm -1 (-NCO), 1700-1730cm -1 (carbamate bond C=O), 1110cm -1 (ether bond COC); the structure of the prepolymer is shown in Formula III;

[0072]

[0073] (4) Reaction of tris(2-hydroxyethyl) isocyanurate;

[0074] After uniformly mixing the first catalyst, tris(2-hydroxyethyl) isocyanurate, 50 parts by weight of butanone, and the prepolymer obtained in step (3), the mixture was reacted at 80°C for 1 hour. Part of the -NCO group of the prepolymer reacted with the hydroxyl groups of tris(2-hydroxyethyl) isocyanurate. The reaction equation was 3OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO+C9H 15 N3O6→[OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3;

[0075] After the reaction, primary filtration was performed using a Whatman GF / A glass fiber membrane (1.6 μm pore size), and the primary filtrate was collected. The purpose of primary filtration was to trap and remove the first catalyst and agglomerated particles. The primary filtrate was then subjected to final filtration using a Millipore PTFE needle filter (0.45 μm pore size), and the final filtrate was collected. The purpose of final filtration was to remove submicron-sized impurities. The vacuum level for both primary and final filtration was 0.03 MPa to prevent membrane rupture and maintain a stable flow rate.

[0076] The final filtrate was sampled, and the sample was vacuum dried at a vacuum level of 0.01 MPa, a temperature of 65°C, and a time of 5 hours to obtain an intermediate product. This intermediate product was then subjected to infrared spectroscopy analysis, and the results are as follows: Figure 2 As shown, 3300cm -1 (carbamate-NH-), 1560cm -1 (THEIC's triazine ring), -2270cm -1 (-NCO);

[0077] and Figure 1 Compared to the infrared spectrum of the prepolymer shown, Figure 2 The newly added 3300cm -1 It is the coupled vibration of urethane-NH- under the influence of the triazine ring group through intermolecular hydrogen bonds, and Figure 2 1700-1730cm disappeared -1 (carbamate bond C=O) and 1110cm -1 (Ether bond COC) This may be because the conjugated carbonyl group in the triazine ring of THEIC has extremely high absorption intensity, which overlaps with the C=O peak of the urethane bond, thus masking the latter; the rigid nodes of the triazine ring restrict the rotational freedom of the polyether chain segment, which weakens the stretching vibration amplitude of the ether bond (COC) and significantly reduces the absorption intensity; the high polarity of the triazine ring reduces the electron cloud density of the ether bond (COC), causing the absorption peak to shift to higher wavenumbers, and after overlapping with other peaks, it appears to disappear;

[0078] and Figure 1 compared to, Figure 2 -2270cm shown -1 The intensity of the -NCO peak at the point decreased significantly, indicating that the -NCO of the prepolymer was partially consumed and that some of the -NCO of the prepolymer reacted with tris(2-hydroxyethyl) isocyanurate. Figure 2 -2270cm shown -The -NCO peak at position 1 is the -NCO of the remaining prepolymer, not the -NCO of [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3. This is likely because in the [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3 molecule, the triazine ring transfers electron deficiency through chemical bonds, significantly weakening the terminal -NCO vibration intensity of the molecule; the urethane -NH- forms hydrogen bonds with ether and ester bonds, greatly restricting the degree of freedom of the terminal -NCO vibration of the molecule; the long-chain polyether (-(C4H8O) n The rigid structure of the triazine ring and the terminal -NCO of the molecule significantly reduces its infrared response; therefore, in the reaction system after the reaction in step (4), there are still residual prepolymers, which do not react with tris(2-hydroxyethyl)isocyanurate.

[0079] (5) The reaction of eugenol;

[0080] To the final filtrate obtained in step (4), first add the second catalyst, then slowly add syringic acid dropwise while stirring the reaction system. The stirring speed is 450 rpm, and the dropping rate of syringic acid is 0.3 parts by weight / min. Then, react at 100°C for 3 h. During the reaction, the viscosity of the reaction system is adjusted to 6000 mPa·s by adding methyl ethyl ketone. The reaction equation is C9H 10 O5+OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO→C9H9O4-OOC-NH-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO;

[0081] (6) Post-processing;

[0082] After the reaction was completed, the reaction system was cooled to room temperature (25°C) and nanofiltration was performed using a nanofiltration membrane with a molecular weight cutoff of 300-500 Da to remove the second catalyst and any possible residual syringic acid. The mother liquor after nanofiltration was collected and then vacuum dried at a vacuum degree of 0.01 MPa, a temperature of 90°C, and a time of 15 h to obtain the modified polyether polyurethane for skiwear fabric.

[0083] (7) Component analysis;

[0084] 0.5g of ski suit fabric was dissolved in 20mL of modified polyether polyurethane in a mobile phase consisting of dichloromethane and methanol at a volume ratio of 85:15. The solution was then loaded onto a chromatographic column with a length of 30cm, an inner diameter of 2.5cm, a height-to-diameter ratio of 12:1, a theoretical plate number greater than 2000, and Merck Silica Gel 60 packing material with a particle size of 400 mesh and a specific surface area of ​​500m². 2 / g, the packing material has a pore size of 6nm; the column packing pressure is 0.8MPa, and the column is packed with homogenized slurry under constant pressure; a 5cm long guard column is placed in front of the column to intercept and degrade impurities, and the packing material of the guard column is the same as that of the column; elution is performed by the mobile phase, and the eluent is collected in separate tubes to obtain two eluents. The two eluents are concentrated under a vacuum of 0.01MPa and a temperature of 50℃ to obtain component A and component B, and finally infrared spectroscopy analysis is performed;

[0085] The infrared spectrum of component A is as follows Figure 3 As shown, 3300cm -1 (The urethane-NH- group, under the influence of the triazine ring group in THEIC, undergoes coupled vibrations through intermolecular hydrogen bonding), 1560 cm⁻¹ -1 (THEIC triazine ring), the structural formula of component A is: [OCN-C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NH-COO-CH2-CH2]3-C3N3O3, the structure is shown in formula IV;

[0086]

[0087] The infrared spectrum of component B is as follows Figure 4 As shown, 3300cm -1 (The coupled vibration of urethane-NH- under the influence of the eugenol group through intermolecular hydrogen bonding), 1735 cm⁻¹ -1 (C=O stretching vibration of eugenol ester bond), 1260 cm⁻¹ -1 (C stretching vibration of eugenol ester bond), the structural formula of component B is: C9H9O4-OOC-NH--C6H4-CH2-C6H4-NH-COO-(C4H8O)n-OOC-NH-C6H4-CH2-C6H4-NCO, the structure is shown in formula V;

[0088]

[0089] As can be seen from the above, the modified polyether polyurethane for ski suit fabric is mainly composed of component A and component B. Component A is a THEIC-modified polyether polyurethane, and component B is a syringic acid-modified polyether polyurethane.

[0090] and Figure 1 compared to, Figure 3 1700-1730cm disappeared -1 (carbamate bond C=O) and 1110cm -1 (Ether bond COC) This may be because the conjugated carbonyl group in the triazine ring of THEIC has extremely high absorption intensity, which overlaps with the C=O peak of the urethane bond, thus masking the latter; the rigid nodes of the triazine ring restrict the rotational freedom of the polyether chain segment, which weakens the stretching vibration amplitude of the ether bond (COC) and significantly reduces the absorption intensity; the high polarity of the triazine ring reduces the electron cloud density of the ether bond (COC), causing the absorption peak to shift to higher wavenumbers, and after overlapping with other peaks, it appears to disappear;

[0091] and Figure 1 compared to, Figure 4 1700-1730cm disappeared -1 (carbamate bond C=O) and 1110cm -1 (Ether bond COC) This may be because the phenolic hydroxyl oxygen of eugenol undergoes p-π conjugation with the urethane bond C=O, reducing the electron density of the urethane bond C=O; when the phenolic hydroxyl oxygen is substituted at the para and meta positions, the dipole moment and absorption intensity of the urethane bond C=O decrease significantly; the large volume of the phenolic ring compresses adjacent groups, resulting in limited vibration amplitude of the C=O bond; the rigidity of the phenolic ring and its direct connection with the polyether chain lead to the loss of torsional freedom of the ether bond COC.

[0092] and Figure 1 compared to, Figure 2 , Figure 3 and Figure 4 3300cm appeared -1 (The coupling vibration of urethane -NH- through intermolecular hydrogen bonds) may be due to the following reasons: the prepolymer only has weak hydrogen bond acceptors such as ether bonds and aromatic rings, and has low electronegativity, so it cannot form strong hydrogen bonds with -NH-. The flexible polyether segments of the prepolymer cause the spatial distribution of -NH- to be diffuse, and it cannot form directional coupling. The carbonyl group (C=O) of the prepolymer adjacent to the urethane cannot approach -NH- due to steric hindrance, and the hydrogen bond acceptor effect is weakened. The rigid triazine ring of THEIC further compresses the molecular chain spacing, so that -NH- and hydrogen bond acceptor groups enter the hydrogen bond interaction threshold. The eugenol benzene ring fixes the adjacent chain segments through π-π stacking, reduces conformational fluctuations, and the antisymmetric stretching of the urethane bond C=O resonates with the -NH- vibration, which significantly improves the strength.

[0093] Example 1B

[0094] A polyurethane microporous moisture-permeable membrane, the specific steps of which are as follows:

[0095] (1) Prepare the raw materials;

[0096] Modified polyether polyurethane for ski suit fabric: 40 parts by weight, provided by Example 1A above;

[0097] DMF: 40 parts by weight;

[0098] Acetophenone: 3 parts by weight;

[0099] Leveling agent: 1 part by weight, manufactured by Evonik GmbH, Germany, brand name TEGO Glide432;

[0100] Foaming agent: 1 part by weight, manufactured by Xiamen Kaiping Chemical Co., Ltd., brand name PU1231;

[0101] DMF aqueous solution: DMF content is 15 wt%;

[0102] Base fabric: made of PET fiber, 0.4mm thick, manufactured by Dongguan Chuanminyu Textile Co., Ltd., brand name XH1040GSXVFX;

[0103] (2) Preparation process;

[0104] After uniformly mixing modified polyether polyurethane, DMF, acetophenone, leveling agent and foam stabilizer to prepare a coating slurry, the coating slurry is coated onto the base fabric. Then, it is immersed in a DMF aqueous solution at 24°C for 20 minutes to displace the DMF. After drying at 80°C for 30 minutes, the base fabric is removed to obtain a polyurethane microporous breathable membrane.

[0105] The final polyurethane microporous breathable membrane has a thickness of 30 μm and a pore size of 300 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12000 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16000 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 11000 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 10500g / (m²). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.4mm / s.

[0106] Example 1C

[0107] A ski suit fabric is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric sequentially bonded together with polyurethane adhesive. The polyurethane microporous breathable membrane is provided by the above-described Example 1B.

[0108] The chemical fiber fabric has a thickness of 200μm, a pore size of 4μm, a porosity of 35%, and a water contact angle of 133°.

[0109] The mesh fabric has a thickness of 150 μm, a mesh density of 20 meshes, a pore size of 106 μm, and the area ratio of irregularly shaped fibers in the fiber cross-section is 63%, with a surface resistivity of 0.06 × 10⁻⁶. 9 Ω, with a tensile strength of 34% in both the warp and weft directions.

[0110] The final ski suit fabric has a hydrostatic pressure of 10600 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 15000 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 7000 g / (m²) as measured according to GBT12704.1-2009 standard. 2 • 24h), the moisture permeability measured according to JIS L1099-2006 standard is 6000g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.4mm / s.

[0111] Comparative Example 1A

[0112] A method for preparing modified polyether polyurethane for skiwear fabric differs from Example 1A only in that tris(2-hydroxyethyl) isocyanurate is replaced with trimethylolpropane ethoxylate (CAS No. 50586-59-9, molecular formula C). 12 H 26 O6, the structure is shown in equation VI.

[0113]

[0114] A polyurethane microporous breathable membrane, differing from Example 1B only in that the modified polyether polyurethane for ski suit fabric is provided by Comparative Example 1A.

[0115] The final polyurethane microporous breathable membrane has a thickness of 30 μm and a pore size of 300 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12000 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16000 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 10100 g / (m³). 2 • 24h), the permeability measured according to JIS L1099-2006 standard is 9300 g / (m²). 2(24h), the air permeability was measured to be 0.3mm / s according to GB / T 5453-2025 standard.

[0116] Compared with Example 1B, the thickness, pore size, and hydrostatic pressure of the polyurethane microporous breathable membrane prepared in Comparative Example 1B did not change significantly. However, the permeability measured according to GBT12704.1-2009 decreased by 8.2%, the permeability measured according to JIS L1099-2006 decreased by 11.4%, and the air permeability measured according to GB / T 5453-2025 decreased by 25%. This is because the tri(2-hydroxyethyl) isocyanurate core contains a symmetrical six-membered heterocyclic structure (triazine ring), which forms a highly rigid crosslinking point after being introduced into the polyurethane. This inhibits the close packing of polymer chain segments, increases the free volume between molecules, and is conducive to water vapor diffusion. Meanwhile, the flexible chain dominated by the alkane skeleton (-CH2-CH2-) of trimethylolpropane ethoxylate increases the chain segment mobility. After the reaction, the soft segments are more likely to relax and closely pack, reducing the free volume and hindering the permeation of gas / water molecules, thus reducing the air permeability of the polyurethane microporous breathable membrane. The three primary hydroxyl groups in tris(2-hydroxyethyl) isocyanurate are highly reactive and can form a dense cross-linked network with the prepolymer. However, the rigid triazine ring simultaneously promotes the formation of discrete island structures in the hard segment microregions, while retaining the continuous soft segment phase as a diffusion channel. Meanwhile, the flexible chain of trimethylolpropane ethoxylate reduces the degree of microphase separation, enhances the compatibility of hard and soft segments, forms a more homogeneous and dense membrane structure, blocks the diffusion path, and reduces the moisture permeability of the polyurethane microporous permeable membrane.

[0117] Comparative Example 1C

[0118] A ski suit fabric, differing from Example 1C only in that: the polyurethane microporous breathable membrane is provided by Comparative Example 1B.

[0119] The final skiwear fabric has a hydrostatic pressure of 10600 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 15000 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 6200 g / (m²) as measured according to GBT12704.1-2009 standard. 2 • 24h), the moisture permeability measured according to JIS L1099-2006 standard is 5300g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.3mm / s.

[0120] Compared with the skiwear fabric of Example 1C, the hydrostatic pressure index of the skiwear fabric of Comparative Example 1C did not change significantly. However, the moisture permeability measured according to GBT12704.1-2009 decreased by 11.4%, the moisture permeability measured according to JIS L1099-2006 decreased by 11.7%, and the air permeability measured according to GB / T 5453-2025 decreased by 25%. This is because the tri(2-hydroxyethyl) isocyanurate core contains a symmetrical six-membered heterocyclic structure (triazine ring), which forms a high-rigidity crosslinking point after being introduced into polyurethane. This inhibits the close packing of polymer chain segments, increases the free volume between molecules, and is conducive to water vapor diffusion. Meanwhile, the flexible chain dominated by the alkane skeleton (-CH2-CH2-) of trimethylolpropane ethoxylate increases the chain segment mobility. After the reaction, the soft segments are more likely to relax and closely arrange, reducing the free volume and hindering the permeability of gas / water molecules, thus reducing the air permeability of the skiwear fabric. The three primary hydroxyl groups in tris(2-hydroxyethyl) isocyanurate are highly reactive and can form a dense cross-linked network with the prepolymer. However, the rigid triazine ring simultaneously promotes the formation of discrete island structures in the hard segment microregions, while retaining the continuous soft segment phase as a diffusion channel. Meanwhile, the flexible chain of trimethylolpropane ethoxylate reduces the degree of microphase separation, enhances the compatibility of hard and soft segments, forms a more homogeneous and dense membrane structure, blocks the diffusion path, and reduces the moisture permeability of skiwear fabric.

[0121] Comparative Example 2A

[0122] A method for preparing modified polyether polyurethane for skiwear fabric, differing from Example 1A only in that syringic acid is replaced with tannic acid.

[0123] Comparative Example 2B

[0124] A polyurethane microporous breathable membrane, differing from Example 1B only in that the modified polyether polyurethane for ski suit fabric is provided by Comparative Example 2A.

[0125] The final polyurethane microporous breathable membrane has a thickness of 30 μm and a pore size of 300 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 10100 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 13600 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 9300 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 8900 g / (m³). 2 (24h), the air permeability was measured to be 0.3mm / s according to GB / T 5453-2025 standard.

[0126] Compared with the polyurethane microporous breathable membrane of Example 1B, the thickness and pore size of the polyurethane microporous breathable membrane of Comparative Example 2B did not change significantly. However, the hydrostatic pressure measured according to GB / T 4744-2013 decreased by 15.8%, the hydrostatic pressure measured according to JIS L1092-2009 decreased by 15%, the humidity permeability measured according to GBT12704.1-2009 decreased by 15.5%, the humidity permeability measured according to JIS L1099-2006 decreased by 15.2%, and the air permeability measured according to GB / T 5453-2025 decreased by 25%. This is because the molecular weight of tannic acid is much larger than that of syringic acid. Its large rigid structure will hinder the regular arrangement of chain segments during polymerization, reduce the crystallization zone, and the reduced crystallinity will increase the internal free volume of the polyurethane membrane, resulting in a decrease in the hydrostatic pressure of the polyurethane microporous breathable membrane. The number of phenolic hydroxyl groups in tannic acid molecules is more than five times that of eugenol. When reacting with isocyanate groups (-NCO), it forms a network structure with an ultra-high cross-linking density. This excessive cross-linking reduces the free volume of polymer chain segments and decreases the mobility of molecular chains, leading to obstructed gas diffusion channels and a decrease in the air permeability of polyurethane microporous breathable membranes. Tannic acid contains a large number of benzene rings and ester groups, making it significantly more hydrophobic than eugenol, which contains carboxyl groups and ether bonds. The introduction of tannic acid makes the hydrophobicity of the hard segment regions of polyurethane too strong, inhibiting the formation of hydrophilic microdomains of polytetrahydrofuran soft segments. Water molecules must permeate through the pathway formed by the hydrophilic chain segments. The increased hydrophobicity caused by the introduction of tannic acid directly reduces the moisture permeability of polyurethane microporous breathable membranes.

[0127] Comparative Example 2C

[0128] A ski suit fabric, differing from Example 1C only in that: the polyurethane microporous breathable membrane is provided by Comparative Example 2B.

[0129] The final skiwear fabric has a hydrostatic pressure of 9000 mmH2O as measured by GB / T 4744-2013 standard, a hydrostatic pressure of 13000 mmH2O as measured by JIS L1092-2009 standard, and a moisture permeability of 6000 g / (m²) as measured by GBT12704.1-2009 standard. 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 5200g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.3mm / s.

[0130] Compared with the skiwear fabric of Example 1C, the skiwear fabric of Comparative Example 2C showed a significant decrease in hydrostatic pressure, moisture permeability, and air permeability. The hydrostatic pressure measured according to GB / T 4744-2013 standard decreased by 15.1%, the hydrostatic pressure measured according to JIS L1092-2009 standard decreased by 13.3%, the moisture permeability measured according to GBT12704.1-2009 standard decreased by 14.3%, the moisture permeability measured according to JIS L1099-2006 standard decreased by 13.3%, and the air permeability measured according to GB / T 5453-2025 standard decreased by 25%. This is because the molecular weight of tannic acid is much larger than that of syringic acid. Its large rigid structure hinders the regular arrangement of chain segments during polymerization, reduces the crystalline region, and the reduced crystallinity increases the internal free volume of the polyurethane film, resulting in a decrease in the hydrostatic pressure of the skiwear fabric. The number of phenolic hydroxyl groups in tannic acid molecules is more than five times that of eugenol. When reacting with isocyanate groups (-NCO), it forms a network structure with an ultra-high cross-linking density. This excessive cross-linking reduces the free volume of polymer chain segments and decreases the mobility of molecular chains, leading to obstructed gas diffusion channels and reduced breathability of skiwear fabrics. Tannic acid contains a large number of benzene rings and ester groups, making it significantly more hydrophobic than eugenol, which contains carboxyl groups and ether bonds. The introduction of tannic acid makes the hydrophobicity of the hard segment regions of polyurethane too strong, inhibiting the formation of hydrophilic microregions of polytetrahydrofuran soft segments. Water molecules must penetrate through the pathway formed by the hydrophilic chain segments. The increased hydrophobicity caused by the introduction of tannic acid directly reduces the moisture permeability of skiwear fabrics.

[0131] Comparative Example 3A

[0132] A method for preparing modified polyether polyurethane for skiwear fabric, differing from Example 1A only in that: eugenol is 2 parts by weight.

[0133] Comparative Example 3B

[0134] A polyurethane microporous breathable membrane, differing from Example 1B only in that the modified polyether polyurethane for ski suit fabric is provided by Comparative Example 3A.

[0135] The final polyurethane microporous breathable membrane has a thickness of 30 μm and a pore size of 300 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 10700 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 14500 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 9800 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 9500g / (m²). 2 (24h), the air permeability was measured to be 0.3mm / s according to GB / T 5453-2025 standard.

[0136] Compared with the polyurethane microporous breathable membrane of Example 1B, the polyurethane microporous breathable membrane of Comparative Example 3B showed no significant changes in thickness and pore size, but its hydrostatic pressure, humidity permeability, and air permeability were all significantly reduced. The hydrostatic pressure measured according to GB / T 4744-2013 standard decreased by 10.8%, the hydrostatic pressure measured according to JIS L1092-2009 standard decreased by 9.4%, the humidity permeability measured according to GB / T 12704.1-2009 standard decreased by 10.9%, the humidity permeability measured according to JIS L1099-2006 standard decreased by 9.5%, and the air permeability measured according to GB / T The air permeability measured by the 5453-2025 standard decreased by 25%. This is because eugenol contains phenolic hydroxyl and carboxyl groups, which can form strong hydrogen bonds with the urethane groups in the polyurethane chain. When the amount of eugenol added decreases, the density of the hydrogen bonds decreases, which leads to a weakening of the intermolecular forces, a looser chain arrangement, and an increase in free volume. Water molecules can more easily penetrate this loose structure, resulting in a decrease in the hydrostatic pressure of the polyurethane microporous breathable membrane. Eugenol, as a multifunctional monomer, contains multiple active groups and can crosslink with tris(2-hydroxyethyl) isocyanurate structural parts and prepolymers. Reducing its dosage leads to a decrease in crosslinking point density, a looser network structure, increased molecular chain mobility, a decrease in the degree of microphase separation between hard segments (MDI / THEIC / eugenol) and soft segments (polytetrahydrofuran), and disruption of the continuity of hard segment regions. Microphase separation is key to gas diffusion channels, and discontinuity in hard segment regions will obstruct the diffusion path of gas molecules, reducing the permeability of polyurethane microporous breathable membranes. At the same time, water vapor permeation depends on hydrophilic channels such as the polar groups between hard segments. When the crosslinking density decreases, the distribution of hydrophilic groups becomes disordered, reducing the interaction between polyurethane microporous breathable membranes and water molecules, thereby reducing the moisture permeability of polyurethane microporous breathable membranes.

[0137] Comparative Example 3C

[0138] A ski suit fabric, differing from Example 1C only in that: the polyurethane microporous breathable membrane is provided by Comparative Example 3B.

[0139] The final skiwear fabric has a hydrostatic pressure of 9500 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 13300 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 6100 g / (m²) as measured according to GBT12704.1-2009 standard. 2 • 24h), the moisture permeability measured according to JIS L1099-2006 standard is 5300g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.3mm / s.

[0140] Compared with the skiwear fabric of Example 1C, the skiwear fabric of Comparative Example 3C showed a significant decrease in hydrostatic pressure, moisture permeability, and air permeability. The hydrostatic pressure measured according to GB / T 4744-2013 standard decreased by 10.4%, the hydrostatic pressure measured according to JIS L1092-2009 standard decreased by 11.3%, the moisture permeability measured according to GBT12704.1-2009 standard decreased by 12.9%, the moisture permeability measured according to JIS L1099-2006 standard decreased by 11.7%, and the air permeability measured according to GB / T 5453-2025 standard decreased by 25%. This is because eugenol contains phenolic hydroxyl and carboxyl groups, which can form strong hydrogen bonds with the urethane groups in the polyurethane chain. When the amount of eugenol added decreases, the density of hydrogen bonds formed decreases, which leads to a weakening of the intermolecular chain forces, a looser chain segment arrangement, and an increase in free volume. Water molecules can more easily penetrate this loose structure, thus causing a decrease in the hydrostatic pressure of the skiwear fabric. Syringic acid, as a multifunctional monomer, contains multiple active groups and can crosslink with tris(2-hydroxyethyl) isocyanurate structural parts and prepolymers. Reducing its usage leads to a decrease in crosslinking point density, a looser network structure, increased molecular chain mobility, a decrease in the degree of microphase separation between hard segments (MDI / THEIC / syringic acid) and soft segments (polytetrahydrofuran), and disruption of the continuity of hard segment regions. Microphase separation is key to gas diffusion channels, and discontinuity in hard segment regions will obstruct the diffusion path of gas molecules, reducing the breathability of skiwear fabrics. At the same time, water vapor permeates through hydrophilic channels such as the polar groups between hard segments. When the crosslinking density decreases, the distribution of hydrophilic groups becomes disordered, reducing the interaction between skiwear fabrics and water molecules, thereby reducing the moisture permeability of skiwear fabrics.

[0141] Example 2A

[0142] A method for preparing modified polyether polyurethane for skiwear fabric, the specific steps of which are as follows:

[0143] (1) Raw material preparation;

[0144] Diphenylmethane-4,4-diisocyanate: 100 parts by weight;

[0145] Polytetrahydrofuran: 380 parts by weight;

[0146] Protective gas: Nitrogen;

[0147] Tris(2-hydroxyethyl) isocyanurate: 14 parts by weight;

[0148] First catalyst: 0.1 parts by weight of acetic acid (3-trimethoxysilylpropylthioyl)dibutyltin complex, prepared by the same method as in Example 1A;

[0149] Clove acid: 8 parts by weight;

[0150] Second catalyst: p-Toluenesulfonic acid, 1 part by weight;

[0151] Anhydrous cyclohexane: 50 parts by weight;

[0152] Butanone;

[0153] (2) Dehydration treatment of diphenylmethane-4,4-diisocyanate;

[0154] Diphenylmethane-4,4-diisocyanate was dehydrated at 110°C and 0.001 MPa for 2 hours.

[0155] (3) The reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran;

[0156] After dehydration treatment, diphenylmethane-4,4-diisocyanate and polytetrahydrofuran were mixed evenly and reacted at 83°C for 2.5 h under a protective gas atmosphere. After the reaction was completed, the temperature was lowered to 40°C, and 30 parts by weight of butanone were added to dilute the reaction system, facilitating subsequent filtration and terminating the reaction. Unreacted diphenylmethane-4,4-diisocyanate monomers in the reaction system were removed by thin-film evaporation at a temperature of 95°C, a vacuum of 0.4 kPa, and a rotation speed of 280 rpm to obtain a concentrated evaporator. The concentrated evaporator was transferred to a reactor, and anhydrous cyclohexane was added for azeotropic dehydration to facilitate solvent displacement and dehydration, preventing water from reacting with -NCO to generate CO2. The product in the reactor was spray-dried (inlet 180°C, outlet 80°C) to obtain a white powder, which is the prepolymer.

[0157] (4) Reaction of tris(2-hydroxyethyl) isocyanurate;

[0158] After the first catalyst, tris(2-hydroxyethyl) isocyanurate, 50 parts by weight of butanone and the prepolymer obtained in step (3) were mixed evenly, the reaction was carried out at 70°C for 2 hours. Part of the -NCO of the prepolymer reacted with the hydroxyl groups of tris(2-hydroxyethyl) isocyanurate.

[0159] After the reaction, primary filtration was performed using a Whatman GF / A glass fiber membrane (1.6 μm pore size), and the primary filtrate was collected. The purpose of primary filtration was to trap and remove the first catalyst and agglomerated particles. The primary filtrate was then subjected to final filtration using a Millipore PTFE needle filter (0.45 μm pore size), and the final filtrate was collected. The purpose of final filtration was to remove submicron-sized impurities. The vacuum level for both primary and final filtration was 0.03 MPa to prevent membrane rupture and maintain a stable flow rate.

[0160] (5) The reaction of eugenol;

[0161] Add the second catalyst to the final filtrate obtained in step (4), and then slowly add syringic acid while stirring the reaction system. The stirring speed is 450 rpm and the syringic acid is added at a rate of 0.8 parts by weight / min. Then react at 105°C for 4 hours. During the reaction, the viscosity of the reaction system is adjusted to 7000 mPa·s by adding methyl ethyl ketone.

[0162] (6) Post-processing;

[0163] After the reaction was completed, the reaction system was cooled to room temperature (25°C) and nanofiltration was performed using a nanofiltration membrane with a molecular weight cutoff of 300-500 Da to remove the second catalyst and any possible residual syringic acid. The mother liquor after nanofiltration was collected and then vacuum dried at a vacuum degree of 0.01 MPa, a temperature of 90°C, and a time of 15 h to obtain the modified polyether polyurethane for skiwear fabric.

[0164] (7) Component analysis;

[0165] 0.5g of ski suit fabric was dissolved in 20mL of modified polyether polyurethane in a mobile phase consisting of dichloromethane and methanol at a volume ratio of 85:15. The solution was then loaded onto a chromatographic column with a length of 30cm, an inner diameter of 2.5cm, a height-to-diameter ratio of 12:1, a theoretical plate number greater than 2000, and Merck Silica Gel 60 packing material with a particle size of 400 mesh and a specific surface area of ​​500m². 2 / g, the packing material has a pore size of 6nm; the column packing pressure is 0.8MPa, and the column is packed with homogenized slurry under constant pressure; a 5cm long guard column is placed in front of the column to intercept and degrade impurities, and the packing material of the guard column is the same as that of the column; elution is performed by the mobile phase, and the eluent is collected in separate tubes to obtain two eluents. The two eluents are concentrated under a vacuum of 0.01MPa and a temperature of 50℃ to obtain component A and component B, and finally infrared spectroscopy analysis is performed;

[0166] FT-IR of component A: 3300 cm⁻¹ -1 (Coupled vibrations of urethane-NH- through intermolecular hydrogen bonds under the influence of the triazine ring group), 1560 cm⁻¹ -1 (THEIC's triazine ring);

[0167] FT-IR of component B: 3300 cm⁻¹ -1 (The coupled vibration of urethane-NH- under the influence of the eugenol group through intermolecular hydrogen bonding), 1735 cm⁻¹ -1 (C=O stretching vibration of eugenol ester bond), 1260 cm⁻¹ -1 (C-stretching vibration of eugenol ester bond).

[0168] Example 2B

[0169] A polyurethane microporous moisture-permeable membrane, the specific steps of which are as follows:

[0170] (1) Prepare the raw materials;

[0171] Modified polyether polyurethane for ski suit fabric: 43 parts by weight, provided by Example 2A above;

[0172] DMF: 43 parts by weight;

[0173] Acetophenone: 5 parts by weight;

[0174] Leveling agent: 2 parts by weight, manufactured by Evonik GmbH, Germany, brand name TEGO Glide432;

[0175] Foaming agent: 2 parts by weight, manufactured by Xiamen Kaiping Chemical Co., Ltd., brand name PU1231;

[0176] DMF aqueous solution: DMF content is 20 wt%;

[0177] Base fabric: made of PET fiber, 0.4mm thick, manufactured by Dongguan Chuanminyu Textile Co., Ltd., brand name XH1040GSXVFX;

[0178] (2) Preparation process;

[0179] After uniformly mixing modified polyether polyurethane, DMF, acetophenone, leveling agent and foam stabilizer to prepare a coating slurry, the coating slurry is coated onto the base fabric. Then, it is immersed in a DMF aqueous solution at 30°C for 25 minutes to displace the DMF. After drying at 90°C for 40 minutes, the base fabric is removed to obtain a polyurethane microporous breathable membrane.

[0180] The final polyurethane microporous breathable membrane has a thickness of 32 μm and a pore size of 400 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12300 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16300 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 11400 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 10700g / (m²). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.4mm / s.

[0181] Example 2C

[0182] A ski suit fabric is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric sequentially bonded together with a polyurethane adhesive. The polyurethane microporous breathable membrane is provided by the above-described Example 2B.

[0183] The chemical fiber fabric has a thickness of 240μm, a pore size of 4μm, a porosity of 47%, and a water contact angle of 151°.

[0184] The mesh fabric has a thickness of 170 μm, a mesh density of 23 meshes, a pore size of 125 μm, and an area ratio of shaped fibers in the fiber cross-section of 77%. Its surface resistivity is 0.3 × 10⁻⁶. 9 Ω, with a tensile strength of 47% in both the warp and weft directions.

[0185] The final skiwear fabric has a hydrostatic pressure of 11000 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 15300 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 7400 g / (m²) as measured according to GBT12704.1-2009 standard. 2 • 24h), the moisture permeability measured according to JIS L1099-2006 standard is 6300g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.4mm / s.

[0186] Example 3A

[0187] A method for preparing modified polyether polyurethane for skiwear fabric, the specific steps of which are as follows:

[0188] (1) Raw material preparation;

[0189] Diphenylmethane-4,4-diisocyanate: 95 parts by weight;

[0190] Polytetrahydrofuran: 370 parts by weight;

[0191] Protective gas: Nitrogen;

[0192] Tris(2-hydroxyethyl) isocyanurate: 12 parts by weight;

[0193] First catalyst: 1.5 parts by weight of acetic acid (3-trimethoxysilylpropylthioyl)dibutyltin complex, prepared by the same method as in Example 1A;

[0194] Clove acid: 8 parts by weight;

[0195] Second catalyst: p-Toluenesulfonic acid, 1.5 parts by weight;

[0196] Anhydrous cyclohexane: 50 parts by weight;

[0197] Butanone;

[0198] (2) Dehydration treatment of diphenylmethane-4,4-diisocyanate;

[0199] Diphenylmethane-4,4-diisocyanate was dehydrated at 120°C and 0.001 MPa for 3 hours.

[0200] (3) The reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran;

[0201] After dehydration treatment, diphenylmethane-4,4-diisocyanate and polytetrahydrofuran were mixed evenly and reacted at 86°C for 3 hours under a protective gas atmosphere. After the reaction was completed, the temperature was lowered to 40°C, and 30 parts by weight of butanone were added to dilute the reaction system to facilitate subsequent filtration and terminate the reaction. Unreacted diphenylmethane-4,4-diisocyanate monomers in the reaction system were removed by thin-film evaporation at a temperature of 95°C, a vacuum of 0.4 kPa, and a rotation speed of 280 rpm to obtain a concentrated evaporator. The concentrated evaporator was transferred to a reactor, and anhydrous cyclohexane was added for azeotropic dehydration to facilitate solvent displacement and dehydration, preventing water from reacting with -NCO to generate CO2. The product in the reactor was spray-dried (inlet 180°C, outlet 80°C) to obtain a white powder, which is the prepolymer.

[0202] (4) Reaction of tris(2-hydroxyethyl) isocyanurate;

[0203] After the first catalyst, tris(2-hydroxyethyl) isocyanurate, 50 parts by weight of butanone and the prepolymer obtained in step (3) were mixed evenly, the reaction was carried out at 75°C for 2 hours. Part of the -NCO of the prepolymer reacted with the hydroxyl groups of tris(2-hydroxyethyl) isocyanurate.

[0204] After the reaction, primary filtration was performed using a Whatman GF / A glass fiber membrane (1.6 μm pore size), and the primary filtrate was collected. The purpose of primary filtration was to trap and remove the first catalyst and agglomerated particles. The primary filtrate was then subjected to final filtration using a Millipore PTFE needle filter (0.45 μm pore size), and the final filtrate was collected. The purpose of final filtration was to remove submicron-sized impurities. The vacuum level for both primary and final filtration was 0.03 MPa to prevent membrane rupture and maintain a stable flow rate.

[0205] (5) The reaction of eugenol;

[0206] Add the second catalyst to the final filtrate obtained in step (4), and then slowly add syringic acid while stirring the reaction system. The stirring speed is 450 rpm and the dropping rate of syringic acid is 1.8 parts by weight / min. Then react at 110°C for 4 h. During the reaction, the viscosity of the reaction system is adjusted to 8000 mPa·s by adding methyl ethyl ketone.

[0207] (6) Post-processing;

[0208] After the reaction was completed, the reaction system was cooled to room temperature (25°C) and nanofiltration was performed using a nanofiltration membrane with a molecular weight cutoff of 300-500 Da to remove the second catalyst and any possible residual syringic acid. The mother liquor after nanofiltration was collected and then vacuum dried at a vacuum degree of 0.01 MPa, a temperature of 90°C, and a time of 15 h to obtain the modified polyether polyurethane for skiwear fabric.

[0209] (7) Component analysis;

[0210] 0.5g of ski suit fabric was dissolved in 20mL of modified polyether polyurethane in a mobile phase consisting of dichloromethane and methanol at a volume ratio of 85:15. The solution was then loaded onto a chromatographic column with a length of 30cm, an inner diameter of 2.5cm, a height-to-diameter ratio of 12:1, a theoretical plate number greater than 2000, and Merck Silica Gel 60 packing material with a particle size of 400 mesh and a specific surface area of ​​500m². 2 / g, the packing material has a pore size of 6nm; the column packing pressure is 0.8MPa, and the column is packed with homogenized slurry under constant pressure; a 5cm long guard column is placed in front of the column to intercept and degrade impurities, and the packing material of the guard column is the same as that of the column; elution is performed by the mobile phase, and the eluent is collected in separate tubes to obtain two eluents. The two eluents are concentrated under a vacuum of 0.01MPa and a temperature of 50℃ to obtain component A and component B, and finally infrared spectroscopy analysis is performed;

[0211] FT-IR of component A: 3300 cm⁻¹ -1 (Coupled vibrations of urethane-NH- through intermolecular hydrogen bonds under the influence of the triazine ring group), 1560 cm⁻¹ -1 (THEIC's triazine ring);

[0212] FT-IR of component B: 3300 cm⁻¹ -1 (The coupled vibration of urethane-NH- under the influence of the eugenol group through intermolecular hydrogen bonding), 1735 cm⁻¹ -1 (C=O stretching vibration of eugenol ester bond), 1260 cm⁻¹ -1 (C-stretching vibration of eugenol ester bond).

[0213] Example 3B

[0214] A polyurethane microporous moisture-permeable membrane, the specific steps of which are as follows:

[0215] (1) Prepare the raw materials;

[0216] Modified polyether polyurethane for ski suit fabric: 46 parts by weight, provided by Example 3A above;

[0217] DMF: 46 parts by weight;

[0218] Acetophenone: 7 parts by weight;

[0219] Leveling agent: 2 parts by weight, manufactured by Evonik GmbH, Germany, brand name TEGO Glide432;

[0220] Foaming agent: 2 parts by weight, manufactured by Xiamen Kaiping Chemical Co., Ltd., brand name PU1231;

[0221] DMF aqueous solution: DMF content is 25 wt%;

[0222] Base fabric: made of PET fiber, 0.4mm thick, manufactured by Dongguan Chuanminyu Textile Co., Ltd., brand name XH1040GSXVFX;

[0223] (2) Preparation process;

[0224] After uniformly mixing modified polyether polyurethane, DMF, acetophenone, leveling agent and foam stabilizer to prepare a coating slurry, the coating slurry is coated onto the base fabric. Then, it is immersed in a DMF aqueous solution at 35°C for 30 minutes to displace the DMF. After drying at 110°C for 50 minutes, the base fabric is removed to obtain a polyurethane microporous breathable membrane.

[0225] The final polyurethane microporous breathable membrane has a thickness of 32 μm and a pore size of 450 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12600 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16600 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 11700 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 10800g / (m²). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.5mm / s.

[0226] Example 3C

[0227] A ski suit fabric is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric sequentially bonded together with a polyurethane adhesive. The polyurethane microporous breathable membrane is provided by the above-described Example 3B.

[0228] The chemical fiber fabric has a thickness of 270μm, a pore size of 5μm, a porosity of 39%, and a water contact angle of 138°.

[0229] The mesh fabric has a thickness of 180 μm, a mesh density of 36 meshes, a pore size of 112 μm, and an area ratio of shaped fibers in the fiber cross-section of 72%. Its surface resistivity is 0.12 × 10⁻⁶. 9 Ω, with a tensile strength of 41% in both the warp and weft directions.

[0230] The final skiwear fabric has a hydrostatic pressure of 11500 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 15700 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 7600 g / (m²) as measured according to GBT12704.1-2009 standard. 2 • 24h), the moisture permeability measured according to JIS L1099-2006 standard is 6600 g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.5mm / s.

[0231] Example 4A

[0232] A method for preparing modified polyether polyurethane for skiwear fabric, the specific steps of which are as follows:

[0233] (1) Raw material preparation;

[0234] Diphenylmethane-4,4-diisocyanate: 92.5 parts by weight;

[0235] Polytetrahydrofuran: 360 parts by weight;

[0236] Protective gas: Nitrogen;

[0237] Tris(2-hydroxyethyl) isocyanurate: 10 parts by weight;

[0238] First catalyst: (3-trimethoxysilylpropylthio)dibutyltin acetate complex, 2 parts by weight, prepared by the same method as in Example 1A;

[0239] Syringic acid: 12 parts by weight;

[0240] Second catalyst: p-Toluenesulfonic acid, 2 parts by weight;

[0241] Anhydrous cyclohexane: 50 parts by weight;

[0242] Butanone;

[0243] (2) Dehydration treatment of diphenylmethane-4,4-diisocyanate;

[0244] Diphenylmethane-4,4-diisocyanate was dehydrated at 130°C and 0.001 MPa for 4 hours.

[0245] (3) The reaction of diphenylmethane-4,4-diisocyanate and polytetrahydrofuran;

[0246] After the dehydrated diphenylmethane-4,4-diisocyanate and polytetrahydrofuran were mixed evenly, the mixture was reacted at 90°C for 3 hours under a protective gas atmosphere. After the reaction was completed, the temperature was lowered to 40°C, and 30 parts by weight of butanone were added to dilute the reaction system to facilitate subsequent filtration and terminate the reaction. Unreacted diphenylmethane-4,4-diisocyanate monomers in the reaction system were removed by thin-film evaporation at a temperature of 95°C, a vacuum of 0.4 kPa, and a rotation speed of 280 rpm to obtain a concentrated evaporator. The concentrated evaporator was transferred to a reactor, and anhydrous cyclohexane was added for azeotropic dehydration to facilitate solvent displacement and dehydration, preventing water from reacting with -NCO to generate CO2. The product in the reactor was spray-dried (inlet 180°C, outlet 80°C) to obtain a white powder, which is the prepolymer.

[0247] (4) Reaction of tris(2-hydroxyethyl) isocyanurate;

[0248] After the first catalyst, tris(2-hydroxyethyl) isocyanurate, 50 parts by weight of butanone and the prepolymer obtained in step (3) were mixed evenly, the reaction was carried out at 77°C for 3 hours. Part of the -NCO of the prepolymer reacted with the hydroxyl groups of tris(2-hydroxyethyl) isocyanurate.

[0249] After the reaction, primary filtration was performed using a Whatman GF / A glass fiber membrane (1.6 μm pore size), and the primary filtrate was collected. The purpose of primary filtration was to trap and remove the first catalyst and agglomerated particles. The primary filtrate was then subjected to final filtration using a Millipore PTFE needle filter (0.45 μm pore size), and the final filtrate was collected. The purpose of final filtration was to remove submicron-sized impurities. The vacuum level for both primary and final filtration was 0.03 MPa to prevent membrane rupture and maintain a stable flow rate.

[0250] (5) The reaction of eugenol;

[0251] Add the second catalyst to the final filtrate obtained in step (4), and then slowly add syringic acid while stirring the reaction system. The stirring speed is 450 rpm and the syringic acid is added at a rate of 1.2 parts by weight / min. Then react at 120°C for 5 hours. During the reaction, the viscosity of the reaction system is adjusted to 9000 mPa·s by adding methyl ethyl ketone.

[0252] (6) Post-processing;

[0253] After the reaction was completed, the reaction system was cooled to room temperature (25°C) and nanofiltration was performed using a nanofiltration membrane with a molecular weight cutoff of 300-500 Da to remove the second catalyst and any possible residual syringic acid. The mother liquor after nanofiltration was collected and then vacuum dried at a vacuum degree of 0.01 MPa, a temperature of 90°C, and a time of 15 h to obtain the modified polyether polyurethane for skiwear fabric.

[0254] (7) Component analysis;

[0255] 0.5g of ski suit fabric was dissolved in 20mL of modified polyether polyurethane in a mobile phase consisting of dichloromethane and methanol at a volume ratio of 85:15. The solution was then loaded onto a chromatographic column with a length of 30cm, an inner diameter of 2.5cm, a height-to-diameter ratio of 12:1, a theoretical plate number greater than 2000, and Merck Silica Gel 60 packing material with a particle size of 400 mesh and a specific surface area of ​​500m². 2 / g, the packing material has a pore size of 6nm; the column packing pressure is 0.8MPa, and the column is packed with homogenized slurry under constant pressure; a 5cm long guard column is placed in front of the column to intercept and degrade impurities, and the packing material of the guard column is the same as that of the column; elution is performed by the mobile phase, and the eluent is collected in separate tubes to obtain two eluents. The two eluents are concentrated under a vacuum of 0.01MPa and a temperature of 50℃ to obtain component A and component B, and finally infrared spectroscopy analysis is performed;

[0256] FT-IR of component A: 3300 cm⁻¹ -1 (Coupled vibrations of urethane-NH- through intermolecular hydrogen bonds under the influence of the triazine ring group), 1560 cm⁻¹ -1 (THEIC's triazine ring);

[0257] FT-IR of component B: 3300 cm⁻¹ -1 (The coupled vibration of urethane-NH- under the influence of the eugenol group through intermolecular hydrogen bonding), 1735 cm⁻¹ -1 (C=O stretching vibration of eugenol ester bond), 1260 cm⁻¹ -1 (C-stretching vibration of eugenol ester bond).

[0258] Example 4B

[0259] A polyurethane microporous moisture-permeable membrane, the specific steps of which are as follows:

[0260] (1) Prepare the raw materials;

[0261] Modified polyether polyurethane for ski suit fabric: 50 parts by weight, provided by Example 4A above;

[0262] DMF: 50 parts by weight;

[0263] Acetophenone: 10 parts by weight;

[0264] Leveling agent, 3 parts by weight, manufactured by Evonik GmbH, Germany, brand name TEGO Glide432;

[0265] Foaming agent: 3 parts by weight, manufactured by Xiamen Kaiping Chemical Co., Ltd., brand name PU1231;

[0266] DMF aqueous solution: DMF content is 30 wt%;

[0267] Base fabric: made of PET fiber, 0.4mm thick, manufactured by Dongguan Chuanminyu Textile Co., Ltd., brand name XH1040GSXVFX;

[0268] (2) Preparation process;

[0269] After uniformly mixing modified polyether polyurethane, DMF, acetophenone, leveling agent and foam stabilizer to prepare a coating slurry, the coating slurry is coated onto the base fabric. Then, it is immersed in a DMF aqueous solution at 45°C for 40 minutes to displace the DMF. After drying at 120°C for 60 minutes, the base fabric is removed to obtain a polyurethane microporous breathable membrane.

[0270] The final polyurethane microporous breathable membrane has a thickness of 33 μm and a pore size of 500 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 13000 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 17000 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 12000 g / (m³). 2 •24h), the water permeability measured according to JIS L1099-2006 standard is 11000g / (m²). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.5mm / s.

[0271] Example 4C

[0272] A ski suit fabric is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric sequentially bonded together with a polyurethane adhesive. The polyurethane microporous breathable membrane is provided by the above-mentioned Example 4B.

[0273] The chemical fiber fabric has a thickness of 300μm, a pore size of 5μm, a porosity of 42%, and a water contact angle of 145°.

[0274] The mesh fabric has a thickness of 200 μm, a mesh density of 30 meshes, a pore size of 118 μm, and the area ratio of irregularly shaped fibers in the fiber cross-section is 69%, with a surface resistivity of 0.2 × 10⁻⁶. 9 Ω, with a tensile strength of 37% in both the warp and weft directions.

[0275] The final skiwear fabric has a hydrostatic pressure of 12000 mmH2O as measured according to GB / T 4744-2013 standard, a hydrostatic pressure of 16000 mmH2O as measured according to JIS L1092-2009 standard, and a moisture permeability of 8000 g / (m²) as measured according to GBT12704.1-2009 standard. 2 •24h), the moisture permeability measured according to JIS L1099-2006 standard is 7000g / (m²). 2 The air permeability (measured at 24h) according to GB / T5453-2025 standard is 0.5mm / s.

Claims

1. A method for preparing modified polyether polyurethane for skiwear fabric, characterized in that, After reacting diphenylmethane-4,4-diisocyanate and polytetrahydrofuran at 80-90℃ to generate a prepolymer, a portion of the prepolymer and tris(2-hydroxyethyl)isocyanurate in the reaction system are first reacted at 70-80℃, and then the remaining prepolymer and eugenol in the reaction system are reacted at 100-120℃ to obtain modified polyether polyurethane for skiwear fabrics. The amounts of each reactant added, by weight, are as follows: 87.5-100 parts of diphenylmethane-4,4-diisocyanate, 340-380 parts of polytetrahydrofuran, 10-14 parts of tris(2-hydroxyethyl)isocyanurate, and 8-12 parts of eugenol.

2. The method for preparing a modified polyether polyurethane for skiwear fabric according to claim 1, characterized in that, Before reacting diphenylmethane-4,4-diisocyanate with polytetrahydrofuran, diphenylmethane-4,4-diisocyanate is first dehydrated under vacuum at 100-130℃ for 1-4 hours.

3. The method for preparing modified polyether polyurethane for skiwear fabric according to claim 1, characterized in that, Diphenylmethane-4,4-diisocyanate and polytetrahydrofuran react under nitrogen or inert gas protection for 2-3 hours.

4. The method for preparing a modified polyether polyurethane for skiwear fabric according to claim 1, characterized in that, In the reaction system, a portion of the prepolymer and tris(2-hydroxyethyl) isocyanurate react under the action of a first catalyst. The amount of the first catalyst added is 0.5-2 parts by weight, and the reaction time is 1-3 hours.

5. The method for preparing a modified polyether polyurethane for skiwear fabric according to claim 1, characterized in that, The remaining prepolymer and eugenol in the reaction system react under the action of the second catalyst. The amount of the second catalyst added is 0.5-2 parts by weight. The viscosity of the reaction system is adjusted to 6000-9000 mPa·s by adding methyl ethyl ketone during the reaction. The reaction time is 3-5 h.

6. The method for preparing a modified polyether polyurethane for skiwear fabric according to claim 5, characterized in that, After the remaining prepolymer in the reaction system reacts with eugenol, it is then filtered and vacuum dried sequentially.

7. A modified polyether polyurethane for skiwear fabric, characterized in that, It is prepared by the method for preparing a modified polyether polyurethane for skiwear fabric as described in any one of claims 1-6.

8. A polyurethane microporous moisture-permeable membrane, characterized in that, The substrate is a modified polyether polyurethane for skiwear fabric as described in claim 7.

9. A polyurethane microporous moisture-permeable membrane according to claim 8, characterized in that, The preparation process is as follows: By weight, 40-50 parts of skiwear fabric are mixed evenly with modified polyether polyurethane, 40-50 parts of DMF, 3-10 parts of acetophenone, 1-3 parts of leveling agent and 1-3 parts of foaming agent to make a coating slurry. The coating slurry is then coated onto the base fabric. The DMF is replaced by a coagulation bath. After drying, the base fabric is removed to obtain a polyurethane microporous breathable membrane. The polyurethane microporous breathable membrane has a thickness of 30-33 μm and a pore size of 300-500 nm. Its hydrostatic pressure, measured according to GB / T 4744-2013 standard, is 12000-13000 mmH2O; its hydrostatic pressure, measured according to JIS L1092-2009 standard, is 16000-17000 mmH2O; and its moisture permeability, measured according to GBT12704.1-2009 standard, is 11000-12000 g / (m³). 2 • 24h), the water permeability measured according to JIS L1099-2006 standard is 10500-11000 g / (m³). 2 The air permeability (measured at 24h) according to GB / T 5453-2025 standard is 0.4-0.5mm / s.

10. A skiwear fabric, characterized in that, It is composed of a polyurethane microporous breathable membrane, a chemical fiber fabric and a mesh fabric, which are sequentially compounded by polyurethane adhesive. The polyurethane microporous breathable membrane is a polyurethane microporous breathable membrane as described in claim 8 or 9.

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