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CN-122013368-A - Hydrophobic spandex, preparation method thereof and fabric thereof

CN122013368ACN 122013368 ACN122013368 ACN 122013368ACN-122013368-A

Abstract

The invention provides a hydrophobic polyurethane and a preparation method thereof and a fabric thereof, wherein the hydrophobic polyurethane is provided with a sheath and an inner core, the sheath component comprises hydrophobic modified polyurethane urea and polymers except polyurethane urea, the hydrophobic modified polyurethane urea is a continuous phase of the sheath component, the polymers are disperse phases of the sheath component, the inner core component comprises polyurethane urea, and the sheath mass accounts for 10% -25% of the total mass of the hydrophobic polyurethane fiber. The hydrophobic spandex fabric is waterproof fabric, the hydrophobic spandex and other hydrophobic fibers are mixed to be woven into fabric, and small molecular siloxane is introduced into polyurethane urea of the spandex skin material in a chemical grafting mode, so that the hydrophobic performance of the spandex can be remarkably improved, and the hydrophobic effect is durable.

Inventors

  • CHEN LING
  • JIN ZHONGCHENG
  • YANG XIAOYIN
  • LING YUN
  • Zhong Jianglai
  • QIAN JIN
  • ZHOU ZHIWEI

Assignees

  • 华峰化学股份有限公司

Dates

Publication Date
20260512
Application Date
20260309

Claims (10)

  1. 1. The hydrophobic polyurethane is characterized by comprising a sheath and an inner core, wherein the sheath component comprises hydrophobic modified polyurethane urea and polymers except polyurethane urea, the hydrophobic modified polyurethane urea is a continuous phase of the sheath component, the polymers are disperse phases of the sheath component, and the inner core component comprises polyurethane urea.
  2. 2. A hydrophobic spandex according to claim 1, wherein the polymer has a melting temperature of 170 ℃ or higher, preferably 200-280 ℃ or lower, and is insoluble in N, N-dimethylacetamide DMAc and/or N, N-dimethylformamide DMF, preferably 100 ℃ or lower.
  3. 3. The hydrophobic polyurethane according to claim 1, wherein the polymer comprises at least one of a polyester, a polycarbonate, a polylactic acid and a polybutylene terephthalate, wherein the polybutylene terephthalate comprises at least one of a polyethylene terephthalate, a polypropylene terephthalate and a polybutylene terephthalate, the mass content of the polymer is 5-30% calculated on the basis of the mass of the skin layer, and the polymer is in the form of solid particles with a particle size of 5-10 μm.
  4. 4. A hydrophobic polyurethane as claimed in claim 3 wherein the preparation materials of the hydrophobically modified polyurethane urea of the sheath component comprise a polymer polyol, a polyisocyanate, a chain extender, a capping agent and a hydroxy siloxane; the preparation raw materials of the polyurethane of the inner core component comprise polymer polyol, polyisocyanate, chain extender and blocking agent; Wherein the polymer polyol preferably comprises any one or a combination of at least two of polytetramethylene ether glycol, polyethylene glycol or polypropylene glycol, more preferably polytetramethylene ether glycol, the polyether polyol has a number average molecular weight of 1000-4000 g/mol, further the polyether polyol of the sheath component has a number average molecular weight of 3000-4000 g/mol, and the polyether polyol of the core component has a number average molecular weight of 1000-3000 g/mol.
  5. 5. The hydrophobic urethane elastic fiber according to claim 4, wherein the end-capping agent comprises monoamine having 2 to 20 carbon atoms, preferably any one or a combination of at least two of diethylamine, isopropylamine, n-butylamine, t-butylamine, hexylamine diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, diisopropylamine, diethylamine, dipropylamine, cyclohexylamine and ethanolamine, and the chain extender comprises diamine having 2 to 30 carbon atoms, and further comprises any one or a combination of at least two of ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, methylpentylenediamine, hexamethylenediamine, xylylenediamine, phenylenediamine, diaminocyclohexane, hexamethylenediamine and 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane.
  6. 6. The hydrophobic urethane elastic fiber of claim 5, wherein the hydroxyl siloxane comprises one or more of hexadecyl-1, 15-dihydroxyoctasiloxane, 1, 3-di (4-hydroxybutyl) -1, 3-tetramethyl disiloxane and 1, 3-di (3-hydroxypropyl) -1, 3-tetramethyl disiloxane.
  7. 7. A hydrophobic urethane elastic fiber according to claim 6, wherein said polyisocyanate comprises any one or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate, and further preferably diphenylmethane diisocyanate.
  8. 8. The hydrophobic spandex of claim 7, wherein the sheath is 10% -25% of the total weight of the hydrophobic spandex fiber.
  9. 9. A process for the preparation of a hydrophobic spandex as claimed in any one of claims 1 to 8, The preparation method of the spinning solution of the sheath comprises the following steps: The preparation method of the hydrophobic modified polyurethane urea comprises the steps of reacting polymer polyol, hydroxyl siloxane and polyisocyanate to obtain an isocyanate end-capped prepolymer, dissolving the prepolymer in a solvent, adding a chain extender and an end-capping agent, and continuing to react to obtain a hydrophobic modified polyurethane urea solution, wherein the isocyanate group mass content of the isocyanate end-capped prepolymer is 1.5-2.2%, the mass ratio of the hydroxyl siloxane is 5-15% based on the mass of the polymer polyol and the hydroxyl siloxane, the mole ratio of the chain extender to the end-capping agent is 6:1-10:1, the mole ratio of amine groups in the chain extender to the end-capping agent to NCO groups of the prepolymer is 1.02:1-1.1, and the solvent comprises N, N-dimethylacetamide DMAc and/or N, N-dimethylformamide DMF; adding the polymer into the hydrophobically modified polyurethane urea solution, and uniformly mixing to obtain a sheath spinning solution; The preparation method of the spinning solution of the inner core comprises the following steps: The preparation method comprises the steps of reacting polymer polyol and polyisocyanate to obtain an isocyanate end-capped prepolymer, dissolving the prepolymer in a solvent, adding a chain extender and an end-capping agent, and continuously reacting to obtain an inner core spinning stock solution containing polyurethane urea, wherein the isocyanate group mass content of the isocyanate end-capped prepolymer is 2.4-3.0%, the molar ratio of the chain extender to the end-capping agent is 6:1-10:1, the molar ratio of an amine group in the chain extender to the end-capping agent to an NCO group in the prepolymer is 1.02:1-1.1:1, and the solvent comprises N, N-dimethylacetamide DMAc and/or N, N-dimethylformamide DMF; the preparation method of the hydrophobic spandex comprises the following steps: And respectively introducing the sheath spinning solution and the inner core spinning solution into spinneret sheath-core assemblies with two flow paths of sheath and core layers for spinning, finally converging and extruding the sheath-core assemblies into filaments, and obtaining the hydrophobic spandex with the sheath-core structure, wherein the spinning is dry spinning, and the spinning temperature is preferably 240-260 ℃ in an upper channel, 210-220 ℃ in a middle channel and 170-190 ℃ in a lower channel.
  10. 10. The waterproof fabric according to any one of claims 1-8, wherein the waterproof fabric comprises a fabric woven with a blend of hydrophobic spandex and other hydrophobic fibers, the other hydrophobic fibers comprising one of modified polyester and/or nylon.

Description

Hydrophobic spandex, preparation method thereof and fabric thereof Technical Field The invention relates to the field of preparation of high polymer materials, in particular to hydrophobic spandex, a preparation method thereof and a waterproof fabric containing the hydrophobic spandex. Background Spandex belongs to one of the synthetic fibers, and the main component is polyurethane. The polyurethane has more hydrophobic groups in molecules, such as methylene chains and aryl groups, belongs to hydrophobic fibers, and is suitable for the production of clothes with higher waterproof function requirements, such as outdoor sportswear, swimwear and the like. However, the waterproof performance of the spandex material is limited, and the waterproof performance of the spandex material needs to be improved by methods such as dipping treatment, coating treatment, laminating treatment and the like, so that the spandex material is more suitable for the production of waterproof materials. For example, patent CN103741473a forms a waterproof spandex fabric by coating liquid polypropylene and polytetrafluoroethylene on two layers of the surface of the spandex fabric, and patent CN119932918a improves the waterproof property of the spandex fabric by adding two different waterproofing agents containing polyurethane and paraffin and polyurethane to waterproof the spandex fabric. The prior art mainly achieves the waterproof effect by coating waterproof materials on the surfaces of spandex fibers or spandex fabrics, but the method needs to add a subsequent process and operation steps, and in the using process, the chemical waterproof auxiliary agents are added to fall off or weaken along with the time, particularly rubbing and machine washing in the washing of the acquired days, so that the waterproof performance is weakened or even vanished. Disclosure of Invention The invention aims to provide a hydrophobic spandex, a preparation method thereof and a fabric thereof, wherein the fabric has a good waterproof effect for a long time. The technical scheme is that the hydrophobic polyurethane has an outer skin and an inner core, wherein the outer skin component comprises hydrophobic modified polyurethane urea and polymers except polyurethane urea, the hydrophobic modified polyurethane urea is a continuous phase of the outer skin component, the polymers are disperse phases of the outer skin component, and the inner core component comprises polyurethane urea. The polymer has a melting temperature of 170 ℃ or higher, preferably 200-280 ℃, and is insoluble in N, N-dimethylacetamide DMAc and/or N, N-dimethylformamide DMF at 50 ℃ or lower, preferably 100 ℃ or lower. The polymer comprises polyester, at least one of polycarbonate, polylactic acid and polybutylene terephthalate, wherein the polybutylene terephthalate comprises at least one of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, the mass content of the polymer is 5-30% calculated on the basis of the mass of the skin layer, the polymer is solid particles, and the particle size is 5-10 mu m. The preparation raw materials of the hydrophobic modified polyurethane urea of the sheath component comprise polymer polyol, polyisocyanate, chain extender, end capping agent and hydroxysiloxane, and the preparation raw materials of the polyurethane of the inner core component comprise polymer polyol, polyisocyanate, chain extender and end capping agent; Wherein the polymer polyol preferably comprises any one or a combination of at least two of polytetramethylene ether glycol, polyethylene glycol or polypropylene glycol, more preferably polytetramethylene ether glycol, the polyether polyol has a number average molecular weight of 1000-4000 g/mol, further the polyether polyol of the sheath component has a number average molecular weight of 3000-4000 g/mol, and the polyether polyol of the core component has a number average molecular weight of 1000-3000 g/mol. The end capping agent comprises monoamine with 2-20 carbon atoms, preferably any one or a combination of at least two of diethylamine, isopropylamine, n-butylamine, tert-butylamine, hexylamine diethylamine, dimethylamine, di-n-butylamine, di-tert-butylamine, diisobutylamine, diisopropylamine, diethylamine, dipropylamine, cyclohexylamine or ethanolamine, and the chain extender comprises diamine with 2-30 carbon atoms, and further comprises any one or a combination of at least two of ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, methylpentylenediamine, methylpropylenediamine, hexamethylenediamine, xylylenediamine, phenylenediamine, diaminocyclohexane, hexamethylenediamine or 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane. The hydroxyl siloxane comprises one or more of hexadecyl-1, 15-dihydroxyoctasiloxane, 1, 3-bis (4-hydroxybutyl) -1, 3-tetramethyl disiloxane and 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane. The polyisocyanate includes any one or a combination of at l