CN117845366A - Spandex for breathable fabric and preparation method thereof - Google Patents
Spandex for breathable fabric and preparation method thereof Download PDFInfo
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- CN117845366A CN117845366A CN202410096557.3A CN202410096557A CN117845366A CN 117845366 A CN117845366 A CN 117845366A CN 202410096557 A CN202410096557 A CN 202410096557A CN 117845366 A CN117845366 A CN 117845366A
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- spandex
- polyurethane
- breathable fabric
- polyurethane prepolymer
- polyol
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 53
- 239000004759 spandex Substances 0.000 title claims abstract description 53
- 239000004744 fabric Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 39
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 29
- 239000011550 stock solution Substances 0.000 claims abstract description 26
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000000578 dry spinning Methods 0.000 claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 8
- 239000004814 polyurethane Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- 125000004427 diamine group Chemical group 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- -1 small-molecule polyol Chemical class 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 208000012886 Vertigo Diseases 0.000 description 24
- 239000000835 fiber Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Abstract
The invention provides polyurethane for breathable fabric and a preparation method thereof, wherein the polyurethane is a polyurethane-urea reaction product obtained by polyurethane prepolymer and mixed amine, and the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol; the preparation method comprises the following steps: prepolymerization reaction: carrying out a prepolymerization reaction on polyisocyanate and polyol to obtain polyurethane prepolymer, and dissolving the polyurethane prepolymer and a solvent to obtain a polyurethane prepolymer-containing solution; chain extension reaction: reacting the polyurethane prepolymer solution with a mixed amine solution to prepare a stock solution containing polyurethane-urea; curing and spinning: curing the stock solution containing polyurethane-urea, adding a glidant into the stock solution, and obtaining the spandex for the breathable fabric by taking the cured polyurethane-urea stock solution as a raw material and performing dry spinning. The spandex has low denier, good rebound resilience, simple preparation method, and good spinning stability, and can be prepared by adopting spandex conventional polymerization equipment.
Description
Technical Field
The invention relates to the field of spandex, in particular to spandex for breathable fabric and a preparation method thereof.
Background
Because of the excellent elasticity, the spandex fiber is compatible with cotton, terylene, nylon, silk and other yarns to weave the fabric, so that the fabric has soft hand feeling, good rebound resilience and comfortable wearing. Through years of development, the manufacturing cost of the spandex fiber is gradually reduced, and the spandex fiber is widely applied to fabric, but the prepared fabric is low in comfort, poor in air permeability, low in draping feeling and low in wrinkle resistance due to high denier per filament and high rebound resilience, and is not as good as viscose fiber, cellulose acetate fiber and the like in the high-end field.
Patent CN104651974a discloses a superfine denier spandex fiber and a preparation method thereof, which has good drapability and water absorbability, so that the usability and comfort of the cloth can be improved, but the spandex is of a sheath-core structure, has higher production cost and lower yield, and is not suitable for mass production. Patent CN110331467a discloses a superfine denier spandex interwoven with polyester and a preparation method thereof, and the superfine denier spandex spinnability is improved by composite spinning of polyether polyurethane and polyester polyurethane, the composite spandex is easy to hydrolyze under alkaline condition, so that the fabric is fluffier, the comfort of the fiber is also improved, but the polyester spandex is eliminated by alkali liquor, the spandex in the fabric is uneven in thickness, the stress is different, internal breakage is easy to occur, the waste of the polyester spandex is caused, and the cost is increased. The superfine denier spandex of the patent CN115710752A, CN102051705A, CN102021666A and the like is prepared by direct spinning and melt spinning, and has the advantages of small yield, high energy consumption and high cost, and occupies smaller area in the current industrial production.
Disclosure of Invention
Technical problems: aiming at the defects of the prior art, the invention aims to provide the spandex for the breathable fabric and the preparation method thereof, wherein the spandex has low denier, good rebound resilience, simple preparation method, and good spinning stability, can adopt spandex conventional polymerization equipment, is not easy to break yarn in the blending process with other yarns, and the prepared fabric has soft hand feeling, comfort and good air permeability.
The technical scheme is as follows: the invention provides polyurethane for breathable fabric, which is a polyurethane-urea reaction product obtained by mixing polyurethane prepolymer and mixed amine, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol.
The polyalcohol comprises macromolecular polyether glycol and micromolecular polyalcohol; the molar ratio of the macromolecular polyether glycol to the micromolecular polyol is 99.5:0.5-95:5.
The macromolecular polyether glycol comprises polytetramethylene ether glycol, and the number average molecular weight is 1500-2500 g/mol.
The hydroxyl functionality of the micromolecular polyol is 3-5, and the carbon number is 3-5.
The small molecular polyalcohol comprises more than one of glycerol, tetrol, pentaerythritol and xylitol.
The polyisocyanate comprises diphenylmethane diisocyanate.
The NCO mass content of the polyurethane prepolymer is 2.2-3.5 wt%.
The mixed amine comprises a diamine chain extender and a monoamine end-capping agent, wherein the diamine chain extender comprises one or more of ethylenediamine, propylenediamine and 2-methyl-1, 5-pentanediamine; the monoamine blocking agent comprises one or more of diethylamine, dipropylamine and n-hexylamine; the molar ratio of the diamine chain extender to the monoamine end capping agent is 12:1-22:1.
The performance spandex for the breathable fabric also contains less than 5% of glidant; the glidant comprises more than one of polyethylene glycol dimethacrylate, polypropylene glycol acrylate and polybutylene glycol acrylate, and the number average molecular weight is 400-800 g/mol.
The preparation method of the spandex for the breathable fabric adopts polyurethane-urea reaction products as spinning raw materials and is obtained through dry spinning, and specifically comprises the following steps:
step 1, prepolymerization reaction: carrying out a prepolymerization reaction on polyisocyanate and polyol to obtain polyurethane prepolymer, and dissolving the polyurethane prepolymer and a solvent to obtain a polyurethane prepolymer-containing solution;
step 2, chain extension reaction: reacting the polyurethane prepolymer solution with a mixed amine solution to prepare a stock solution containing polyurethane-urea;
step 3, curing and spinning: curing the stock solution containing polyurethane-urea, adding a glidant into the stock solution, and obtaining the spandex for the breathable fabric by taking the cured polyurethane-urea stock solution as a raw material and performing dry spinning.
The polyalcohol comprises macromolecular polyether glycol and micromolecular polyalcohol; the molar ratio of the macromolecular polyether glycol to the micromolecular polyol is 99.5:0.5-95:5;
the mass concentration of the stock solution containing polyurethane-urea is 35-37 wt%, and the viscosity of the stock solution is 3500-4500 poise (40 ℃); the mixed amine comprises a diamine chain extender and a monoamine end-capping agent, and the molar ratio of the diamine chain extender to the monoamine end-capping agent is 12:1-22:1;
the glidant is added into the stock solution in the curing spinning step.
The beneficial effects are that: the spandex fiber prepared by the specific polymerization formula and the spinning process has the advantages of low denier, good rebound resilience, simple preparation method, capability of adopting spandex conventional polymerization equipment, good spinning stability, difficulty in yarn breakage in the blending process with other yarns, and soft hand feeling, comfort and good air permeability. Because of the ultra-low linear density, the fabric is applied to the light and thin fabric, has excellent air permeability and ice feel, and simultaneously gives the fabric higher rebound performance.
Detailed Description
The polyurethane for the breathable fabric comprises polyurethane-urea reaction products obtained by polyurethane prepolymer and mixed amine, wherein the polyurethane prepolymer comprises polyisocyanate and polyol which are reacted;
wherein the polyol comprises a combination of macromolecular polyether glycol and micromolecular polyol, and the molar ratio of the macromolecular polyether glycol to the micromolecular polyol is 99.5:0.5-95:5;
the polyisocyanate comprises diphenylmethane diisocyanate;
the macromolecular polyether glycol comprises polytetramethylene ether glycol, and the number average molecular weight is 1500-2500 g/mol, preferably 1500-2200 g/mol;
the hydroxyl functionality of the micromolecular polyol is 3-5;
the carbon number of the micromolecular polyol is 3-5;
further, the small molecular polyalcohol comprises more than one of glycerol, tetrol, pentaerythritol and xylitol;
the NCO mass content of the polyurethane prepolymer is 2.2-3.5 wt%.
The mixed amine comprises a diamine chain extender and a monoamine end-capping agent, wherein the diamine chain extender comprises one or more of ethylenediamine, propylenediamine and 2-methyl-1, 5-pentanediamine; the monoamine end capping agent is one or more of diethylamine, dipropylamine and n-hexylamine;
the diamine chain extender and the monoamine end capping agent are 12:1-22:1.
The performance spandex for the breathable fabric contains less than 5% of glidant;
preferably, the composition contains 0.05-5% of a glidant, calculated on the basis of the mass of spandex;
the glidant comprises more than one of polyethylene glycol dimethacrylate, polypropylene glycol acrylate and polybutylene glycol acrylate, and the number average molecular weight is 400-800 g/mol.
The denier of the spandex fiber is 3-10 denier.
The invention provides a preparation method of spandex for breathable fabric, which is obtained by taking a polyurethane-urea reaction product as a spinning raw material through dry spinning;
specifically, the preparation method comprises the following steps:
prepolymerization reaction: carrying out a prepolymerization reaction on polyisocyanate and polyol to obtain polyurethane prepolymer and dissolving the polyurethane prepolymer in a solvent to obtain a polyurethane prepolymer-containing solution;
chain extension reaction: reacting the polyurethane prepolymer solution with a mixed amine solution to obtain a stock solution containing polyurethane-urea;
curing and spinning: curing the stock solution, and obtaining spandex for breathable fabric by dry spinning with the cured polyurethane-urea stock solution as a raw material; preferably, the mass concentration of the stock solution is 35-37%, and the viscosity of the stock solution is 3500-4500 poise (40 ℃);
preferably, the glidant is added into the stock solution in the curing spinning step;
preferably, the solvent comprises N, N-dimethylacetamide DMAc, N-methyl-2-pyrrolidone NMP and dimethylformamide DMF; as an example, the solvent is DMAc;
in some examples of the invention, the mass concentration of the polyurethane prepolymer solution of step 1) is 30-40%, preferably 30-36%;
the concentration of the mixed amine solution in the chain extension reaction step is 3% -10%;
the molar ratio of the total amine groups of the mixed amine in the chain extension reaction step to the isocyanate groups (NCO) of the polyurethane prepolymer is 1.10:1 to 1.40:1, preferably 1.25:1 to 1.35:1;
optionally, diethylenetriamine can be added in the chain extension reaction step, wherein the addition amount is 80-150 ppm, calculated based on the mass of spandex.
Furthermore, other functional additives can be added into the polyurethane-urea stock solution, so long as the performance of the product is not degraded. Such as one or more of lubricant, antioxidant, anti-ultraviolet agent, delustrant, dyeing auxiliary agent, chlorine-resistant auxiliary agent and lubricant.
In the invention, the dry spinning comprises the steps of spraying, stretching, drying, false twisting and winding into filaments;
further, a spandex finish may be applied to the spandex surface after the false twisting step.
In some examples of the present invention, the preparation method of spandex for breathable fabric specifically includes:
prepolymerization reaction: the polyol and diisocyanate react in a molar ratio of 1 (1.56-1.75) to obtain 2.2-3.5 wt% of NCO-terminated polyurethane prepolymer, wherein the polyol comprises a combination of macromolecular polyether glycol and micromolecular polyol, and the molar ratio of the macromolecular polyether glycol to the micromolecular polyol is 99.5:0.5-95:5; the polyurethane prepolymer is dissolved with a solvent to form polyurethane prepolymer solution with the mass concentration of 32-38%, wherein the solvent is dimethylacetamide (DMAc).
Chain extension reaction: mixing the polyurethane prepolymer solution with a mixed amine solution to obtain polyurethane-urea stock solution with the mass concentration of 30-36%, wherein the molar ratio of the total amine groups of the mixed amine to the isocyanate groups (NCO) of the polyurethane prepolymer is (1.10-1.40): 1; the mixed amine solution comprises diamine chain extender, monoamine end-capping agent, diethylenetriamine and solvent, wherein the mass concentration of the mixed amine solution is 4% -8%, the molar ratio of the diamine chain extender to the monoamine end-capping agent is 12:1-22:1, and the addition amount of the diethylenetriamine is 80-150 ppm, calculated based on the mass of spandex.
Curing and spinning: curing the polyurethane prepolymer stock solution to form spinning solution, introducing the spinning solution into a spinning assembly for spraying, stretching and drying to form tows, and synthesizing, winding and forming by false twisting to form spandex cakes; wherein the mass concentration of the spinning solution is 30-36%, the viscosity of the spinning solution is 3500-4500 poise,
preferably, if an optional glidant or other functional aid is added, it is added during the curing process.
The following examples are presented to describe the invention in detail, but are not to be construed as limiting the invention in any way.
Viscosity test methods of examples and comparative examples of the present invention: the dope was placed in a viscometer, and the apparent viscosity of the dope was measured at 40 ℃.
Example 1
Prepolymerization reaction: the 90g/min flow diphenylmethane diisocyanate (MDI) and 407g/min flow polyol are mixed uniformly in a static mixer, the polyol comprises the mixture of polytetramethyl ether glycol (PTMG) and tetra-amyl alcohol (PETP) with the molar ratio of 96:4, the mixture is heated to 90 ℃ for reaction for 4 hours, the polyurethane prepolymer with the NCO content of 2.62 weight percent is obtained, and the polyurethane prepolymer solution with the mass concentration of 36 percent is prepared by dissolving the prepolymer.
Chain extension reaction: and (3) placing the polyurethane prepolymer solution and the mixed amine solution into a second reactor for reaction, mixing ethylenediamine, 2-methyl-1, 5-pentanediamine and diethylamine in the mixed amine solution according to a molar ratio of 19:1:1.2, wherein the molar ratio of the total amine groups of the mixed amine to NCO of the polyurethane prepolymer is 1.30:1, the adding amount of diethylenetriamine is 120ppm, and obtaining polyurethane-urea stock solution with the mass concentration of 35% after chain extension in a mixing tank.
Curing and spinning: curing polyurethane-urea stock solution in a storage tank to obtain spinning solution, adding 0.2% of flow aid polyethylene glycol dimethacrylate into the spinning solution, introducing the spinning solution into a spinning assembly for spraying, stretching and drying to form tows, and synthesizing, winding and forming by false twisting to obtain spandex spinning cakes; the mass concentration of the spinning solution is 34%, the viscosity of the spinning solution is 4400 poise, the spinning speed is 550m/min, the forming pre-drawing is 9%, and finally the 5-denier spandex fiber is obtained.
The preparation methods of examples 2 to 9 were identical to example 1, and the types and amounts of raw materials for the respective reaction steps were as shown in Table 1 below:
table 1:
table 1 (continuous):
comparative example 1
The difference from example 1 is that the polyol comprises a mixture of polytetramethyl ether glycol (PTMG) and polytetrapentanol (PETP) in a molar ratio of 90:10, the others being unchanged.
Comparative example 2
The difference from example 4 is that the quaternary tetrapentanol (PETP) in the original polyol is replaced with an equimolar amount (PTMG), the polyol is pure polytetramethylene ether glycol (PTMG), the others being unchanged.
Comparative example 3
The difference from example 4 is that the quaternary tetra-pentanol (PETP) in the polyol was not added in the prepolymerization step, the quaternary tetra-pentanol (PETP) was added in the chain extension step, and the mixture was added to the mixed amine solution to react with the prepolymer comparative example 4
The difference from example 4 is that the quaternary tetra-pentanol (PETP) in the crude polyol is replaced with an equimolar amount of pentanediol, the others being unchanged.
Comparative example 5
The difference from example 4 is that the quaternary tetrapentanol (PETP) in the crude polyol is replaced with an equimolar amount of D-mannitol, the others being unchanged.
The following performance tests were performed on the above examples and comparative examples, and the performance results are shown in table 2 below:
strength at 300% elongation: stress at 300% length of spandex filament stretch.
Spinnability: and (3) summarizing production line faults, wherein the average fault number of each unit per day is calculated, the number of the faults is less than 0.4, the spinnability is excellent, the number of the faults is less than 0.8, the spinnability is general, the number of the faults is less than 0.8, the number of the faults is less than 2.0, and the spinnability is poor, and the number of the faults is very poor, and the number of the faults is greater than 2.0.
3.0 times drafting weaving AA ratio: the percentage of intact yarn without break was unwound at an unwinding speed of 10m/min and a 3.0 fold draft.
Cloth cover grammage: taking a finished cloth sample with the same area, and calculating the gram number of unit square meter.
Cloth cover air permeability: according to national standard GB/T5453 determination of textile fabric air permeability, under a specified pressure difference condition, air flow vertically passing through a given area of a sample within a certain time is determined, and air permeability is calculated.
Table 2:
Claims (10)
1. the polyurethane for the breathable fabric is characterized in that the polyurethane is a polyurethane-urea reaction product obtained by mixing polyurethane prepolymer and mixed amine, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol.
2. The spandex for breathable fabric of claim 1, wherein the polyol comprises a macromolecular polyether glycol and a small molecular polyol; the molar ratio of the macromolecular polyether glycol to the micromolecular polyol is 99.5:0.5-95:5.
3. The spandex for breathable fabric according to claim 2, wherein the macromolecular polyether glycol comprises polytetramethylene ether glycol and has a number average molecular weight of 1500-2500 g/mol.
4. The spandex for breathable fabric according to claim 2, wherein the small-molecule polyol has a hydroxyl functionality of 3-5 and a carbon number of 3-5.
5. The spandex for breathable fabric of claim 4, wherein the small-molecule polyol comprises at least one of glycerol, tetrol, pentaerythritol, and xylitol.
6. The breathable fabric spandex of claim 1 wherein said polyisocyanate comprises diphenylmethane diisocyanate.
7. The spandex for breathable fabric according to claim 1, wherein the polyurethane prepolymer has an NCO mass content of 2.2-3.5 wt%.
8. The spandex for breathable fabric according to claim 1, wherein the mixed amine comprises a diamine chain extender and a monoamine capping agent, and the diamine chain extender comprises one or more of ethylenediamine, propylenediamine, 2-methyl-1, 5-pentylene diamine; the monoamine blocking agent comprises one or more of diethylamine, dipropylamine and n-hexylamine; the molar ratio of the diamine chain extender to the monoamine end capping agent is 12:1-22:1.
9. The spandex for breathable fabric according to claim 1, wherein the spandex for breathable fabric further comprises less than 5% of a glidant; the glidant comprises more than one of polyethylene glycol dimethacrylate, polypropylene glycol acrylate and polybutylene glycol acrylate, and the number average molecular weight is 400-800 g/mol.
10. The method for preparing spandex for breathable fabric according to claim 1, characterized in that the spandex is obtained by dry spinning by using polyurethane-urea reaction products as spinning raw materials, and comprises the following steps:
step 1, prepolymerization reaction: carrying out a prepolymerization reaction on polyisocyanate and polyol to obtain polyurethane prepolymer, and dissolving the polyurethane prepolymer and a solvent to obtain a polyurethane prepolymer-containing solution;
step 2, chain extension reaction: reacting the polyurethane prepolymer solution with a mixed amine solution to prepare a stock solution containing polyurethane-urea;
step 3, curing and spinning: curing the stock solution containing polyurethane-urea, adding a glidant into the stock solution, and obtaining the spandex for the breathable fabric by taking the cured polyurethane-urea stock solution as a raw material and performing dry spinning.
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