CN119409921A - A kind of high recovery spandex fiber and preparation method thereof - Google Patents

A kind of high recovery spandex fiber and preparation method thereof Download PDF

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Publication number
CN119409921A
CN119409921A CN202510000900.4A CN202510000900A CN119409921A CN 119409921 A CN119409921 A CN 119409921A CN 202510000900 A CN202510000900 A CN 202510000900A CN 119409921 A CN119409921 A CN 119409921A
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chain extender
spandex fiber
spandex
mixed solution
furan
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CN119409921B (en
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蔡华峻
蔡函烨
苏宁杰
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Zhuji Huahai New Material Co ltd
ZHUJI HUAHAI SPANDEX CO Ltd
Hangzhou Lizhu Cultural And Creative Technology Co ltd
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Zhuji Huahai New Material Co ltd
ZHUJI HUAHAI SPANDEX CO Ltd
Hangzhou Lizhu Cultural And Creative Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3228—Polyamines acyclic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Artificial Filaments (AREA)

Abstract

本发明公开了一种高回复氨纶纤维及其制备方法，属于弹性纤维技术领域，本发明的氨纶纤维采用聚四氢呋喃和MDI制备预聚物溶液，并将预聚物溶液与扩链剂混合溶液反应形成聚氨酯脲溶液，采用聚氨酯脲溶液干法纺丝获得高回弹氨纶；其中，扩链剂混合溶液含有二乙醇胺、对苯二胺、二乙烯三胺，还含有2,6‑二氨基吡啶和/或2,5‑二(氨基甲基)呋喃。本发明能够提高所得氨纶纤维的性能，提高纤维的断裂伸长率以及弹性回复率，并能提高所得氨纶纤维的吸湿性能，从而提高利用该氨纶纤维所得织物的舒适度。

The invention discloses a high-recovery spandex fiber and a preparation method thereof, and belongs to the technical field of elastic fibers. The spandex fiber of the present invention uses polytetrahydrofuran and MDI to prepare a prepolymer solution, and the prepolymer solution is reacted with a chain extender mixed solution to form a polyurethane urea solution, and high-resilience spandex is obtained by dry spinning of the polyurethane urea solution; wherein the chain extender mixed solution contains diethanolamine, p-phenylenediamine, diethylenetriamine, and also contains 2,6-diaminopyridine and/or 2,5-bis(aminomethyl)furans. The present invention can improve the performance of the obtained spandex fiber, improve the elongation at break and the elastic recovery rate of the fiber, and can improve the hygroscopic properties of the obtained spandex fiber, so as to improve the comfort of the fabric obtained by using the spandex fiber.

Description

High-recovery spandex fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of elastic fibers, and particularly relates to a high-recovery spandex fiber and a preparation method thereof.
Background
Spandex, which is a high-elasticity textile fiber, has the advantages of high strength, light specific gravity, high elastic recovery rate and the like at normal temperature, is generally used for weaving elastic fabrics, is widely applied to the traditional clothing industry, is gradually applied to the fields of medical treatment, fire protection, communication and the like at present, and has wide application prospect.
The spandex is mainly applied to the braid, high-temperature shaping treatment is needed after the braiding process of the braid, the ordinary spandex can lose the high-resilience effect after shaping, and the elastic recovery rate is obviously reduced. In order to solve the problem, the traditional method mainly enhances the rebound performance of the spandex yarn by adjusting the number of holes of the heavy denier yarn and the spinning channel process. On one hand, the number of spandex yarns is increased under the same fineness condition, and on the other hand, the temperature of a spinning upper channel is increased, so that the breaking strength index of spandex yarns is improved, but the lifting space is limited, and the lifting amplitude is less obvious after heat setting.
Disclosure of Invention
The invention aims to provide a high-recovery spandex fiber and a preparation method thereof, which can improve the performance of the obtained spandex fiber, the elongation at break and the elastic recovery rate of the fiber, and the moisture absorption performance of the obtained spandex fiber, so that the comfort level of a fabric obtained by using the spandex fiber is improved.
According to one aspect of the present invention, there is provided a chain extender mixed solution for preparing spandex fiber, in which Diethanolamine (DEA), p-Phenylenediamine (PDA), ethylenediamine (EDA) and Diethylenetriamine (DETA) are dissolved in DMAc as a solvent.
Preferably, in the chain extender mixed solution, the mass ratio of DEA, PDA, EDA, DETA is 1:3-8:5-15:5-15, and the mass ratio of EDA to DMAc is 1g:15-30mL.
By adopting the technical scheme, on the basis of the conventional polyurethane production amine formula (DEA+PDA+EDA), the DETA is added, and the trace addition of the amine can increase the crosslinking among the macromolecules of the polyurethane stock solution polymer, so that the promotion of the molecular weight of a soft chain segment part in the obtained polyurethane fiber is facilitated, the number of hydrogen bonds is increased, and the rebound performance of the polyurethane fiber is facilitated to be improved.
Further, the mixed solution of the chain extender also contains 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan.
Preferably, in the chain extender mixed solution, the mass ratio of EDA to 2, 6-diaminopyridine to 2, 5-di (aminomethyl) furan is 1:0.5-3:0.5-3.
The addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan introduces pyridine and/or furan groups into the mixed solution of the chain extender, and the existence of the heterocyclic groups helps to improve the molecular crosslinking degree in the process of reacting with the prepolymer solution used for preparing spandex, thereby improving the tensile property and elastic recovery rate of the obtained spandex fiber, improving the softness of the obtained fabric and ensuring the comfort level.
And the existence of pyridine and/or furan groups is also beneficial to improving the surface structure of the obtained spandex fiber, so that the surface roughness of the spandex fiber is improved, and the existence of pyridine and/or furan groups is also beneficial to the formation of hydrogen bonds, so that the combination property of the spandex fiber and water molecules can be improved, the moisture absorption property of the obtained fabric is improved, and the comfort is ensured.
According to one aspect of the invention, a high recovery spandex fiber is provided, wherein a prepolymer solution is prepared by adopting polytetrahydrofuran and MDI, the prepolymer solution is reacted with a mixed solution of a chain extender to form a polyurethane urea solution, and the polyurethane urea solution is adopted for dry spinning to obtain the high recovery spandex fiber, wherein the mixed solution of the chain extender takes DMAc as a solvent, and Diethanolamine (DEA), p-Phenylenediamine (PDA), ethylenediamine (EDA) and Diethylenetriamine (DETA) are dissolved in the mixed solution of the chain extender.
Further, the mixed solution of the chain extender also contains 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan.
According to one aspect of the present invention, there is provided a method for preparing a high recovery spandex fiber, comprising the steps of:
s1, reacting polytetrahydrofuran and MDI at 70-90 ℃ for 90-180min to obtain capped polytetrahydrofuran, and then mixing and dissolving the capped polytetrahydrofuran with a solvent to form a prepolymer solution;
S2, adding MDI into the prepolymer solution obtained in the step S1, uniformly stirring, and cooling to 5-15 ℃ to form a polymer solution;
S3, rapidly adding a chain extender mixed solution into the polymer solution obtained in the step S2 while stirring to react to form a polyurethane urea solution;
S4, extruding the polyurethane urea solution obtained in the step S3 through a spinneret plate, and carrying out dry spinning in a channel to form the high-resilience spandex.
By adopting the technical scheme, the addition proportion of the main raw materials PTMEG and MDI is adjusted, so that the NCO group content in the polyurethane fiber obtained by the reaction can be improved.
The preparation method of the chain extender mixed solution in the step S3 comprises the steps of dissolving diethanolamine, p-phenylenediamine and diethylenetriamine in DMAc to form the chain extender mixed solution.
In addition, according to the technical scheme, DETA is added on the basis of a conventional polyurethane production amine formula (DEA+PDA+EDA), and the trace addition of the amine can increase the crosslinking among macromolecules of the polyurethane stock solution polymer, increase the number of hydrogen bonds and contribute to improving the rebound performance of the polyurethane fiber.
Further, 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan are added to the chain extender mixed solution.
Further, in step S1, the solvent is DMAc.
Further, in step S1, the mass ratio of PTMEG (polytetrahydrofuran) to MDI is 5-10:1. The mass volume ratio of MDI to DMAc is 1g:5-15mL.
The MDI consumption in step S2 is 2-10% of the MDI consumption in step S1.
The DMAc amount in the chain extender mixture is 10-25% of the DMAc amount in step S1.
In the chain extender mixed solution, the mass ratio of DEA, PDA, EDA is 1:3-8:7-15, the mass volume ratio of EDA to DMAc is 1g:15-30mL, and the mass ratio of EDA to DETA is 1:0.5-3.
In step S4, tiO 2, tinuvin622, tinuvin328, TSA-011 and TSA-245 are added into the polyurethane urea solution obtained in step S3 and mixed uniformly before dry spinning.
Preferably, the mass ratio of TiO 2, tinuvin622, tinuvin328, TSA-011, TSA-245 is 1:2-3:0.5-2:0.5-2:0.5-2, and the mass ratio of the total amount of TiO 2, tinuvin622, tinuvin328, TSA-011, TSA-245 to PTMEG in step S1 is 1:50-80.
Further, a mixed solution of a chain extender is provided, in which DEA, PDA, EDA, DETA, 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan, and 3,3' -diaminobenzidine are dissolved in DMAc as a solvent.
Preferably, in the mixed solution of the chain extender, the mass ratio of EDA to 3,3' -diaminobenzidine is 1:0.5-3.
The addition of 3,3 '-diamino benzidine has a polyamino structure, so that a plurality of components in the mixed solution of the chain extender can generate a branched chain structure in the reaction process, and the addition of the 3,3' -diamino benzidine is beneficial to improving the molecular crosslinking degree of the obtained spandex fiber in the process of being matched with a plurality of short-chain amines, so that the tensile property of the obtained spandex fiber is further ensured.
Compared with the prior art, the invention has the following beneficial effects:
1. The chain extender mixed solution for preparing the spandex fiber is provided, and on the basis of a conventional spandex production amine formula, DETA is added, and the trace addition of the amine can increase the crosslinking among macromolecules of the spandex stock solution polymer, so that the improvement of the molecular weight of a soft chain segment part in the obtained spandex fiber is facilitated, the number of hydrogen bonds is increased, and the rebound performance of the spandex fiber is facilitated to be improved.
2. The addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan to the chain extender mixed solution can further improve the tensile property and rebound resilience of the obtained spandex fiber, and the addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan can also help to improve the moisture regain of the obtained spandex fiber. This is probably because pyridine and/or furan groups are introduced into the chain extender mixed solution, so that the surface roughness of the spandex fiber is improved, more grooves and holes are formed, the combination of the spandex fiber and water molecules is more solution, and the existence of the pyridine and/or furan groups is also helpful for the formation of hydrogen bonds, so that the water absorption and water locking performance of the fabric obtained by using the spandex fiber are further improved.
3. 3,3' -Diaminobenzidine is further added into the chain extender mixed solution and is matched with a plurality of short-chain amines for use, so that the molecular crosslinking degree of the obtained spandex fiber is improved, and the tensile property of the obtained spandex fiber is further ensured to improve the mechanical property of the obtained spandex fiber.
Drawings
Fig. 1 is an SEM image of the high recovery spandex fiber obtained according to example 2 of the invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the detailed description and the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Preparation method of high-recovery spandex fiber
S1, reacting PTMEG and MDI at 85 ℃ for 120: 120 min to obtain end-capped PTMEG, which is prepolymer, mixing and dissolving the prepolymer and a solvent DMAc to form a prepolymer solution;
s2, adding MDI into the prepolymer solution obtained in the step S1, uniformly stirring, and cooling to 10 ℃ to form a polymer solution;
S3, preparing a chain extender mixed solution, and dissolving DEA, PDA, EDA and DETA in DMAc to form the chain extender mixed solution;
s4, rapidly adding the chain extender mixed solution obtained in the step S3 into the polymer solution obtained in the step S2 while stirring to react to form a polyurethane urea solution;
and S5, adding TiO 2, tinuvin622, tinuvin328, TSA-011 and TSA-245 into the polyurethane urea solution obtained in the step S4, uniformly mixing, and extruding by a spinneret plate to form the high-resilience spandex through dry spinning in a channel.
In step S1, the mass ratio of PTMEG to MDI is 8:1. The mass to volume ratio of MDI to DMAc was 1g:10mL.
The MDI content in step S2 was 3% of the MDI content in step S1.
The amount of DMAc in step S3 was 15% of the amount of DMAc in step S1.
In step S3, the mass ratio of DEA, PDA, EDA, DETA to 5 to 10, and the mass-to-volume ratio of EDA to DMAc is 1g to 20mL.
In the step S5, the mass ratio of TiO 2 to Tinuvin622 to Tinuvin328 to TSA-011 to TSA-245 is 1:2:1:1, and in the step S5, the mass ratio of the total amount of TiO 2 to Tinuvin622 to Tinuvin328 to TSA-011 to TSA-245 to PTMEG in the step S1 is 1:60.
Example 2
This embodiment differs from embodiment 1 in that:
In step S3, 2, 6-diaminopyridine and 2, 5-bis (aminomethyl) furan are added to a DMAc solution of DEA, PDA, EDA, DETA when preparing a chain extender mixture. Wherein the mass ratio of EDA to 2, 6-diaminopyridine to 2, 5-di (aminomethyl) furan is 1:1:1. Other steps and conditions were the same.
SEM images of the spandex fibers obtained in this example are shown in fig. 1. As can be seen from the figure, the surface of the spandex fiber obtained by the method is rough, a plurality of hole structures are irregularly distributed, and a plurality of discontinuous grooves are formed along the axial direction of the fiber, and the grooves are different in depth, so that the surface of the spandex fiber is uneven and smooth.
Example 3
This embodiment differs from embodiment 1 in that:
In step S3, 2, 6-diaminopyridine and 2, 5-bis (aminomethyl) furan are added to a DMAc solution of DEA, PDA, EDA, DETA when preparing a chain extender mixture. Wherein the mass ratio of EDA to 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan is 1:1.5:1.5. Other steps and conditions were the same.
Example 4
This embodiment differs from embodiment 1 in that:
in step S3, 2, 6-diaminopyridine and 2, 5-bis (aminomethyl) furan are added to a DMAc solution of DEA, PDA, EDA, DETA when preparing a chain extender mixture. Wherein the mass ratio of EDA to 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan is 1:2:2. Other steps and conditions were the same.
Example 5
This embodiment differs from embodiment 1 in that:
In step S3, when preparing the chain extender mixture, 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan are added to the DMAc solution of DEA, PDA, EDA, DETA, and 3,3' -diaminobenzidine is also added. Wherein the mass ratio of EDA to 2, 6-diaminopyridine to 2, 5-di (aminomethyl) furan 3,3' -diaminobenzidine is 1:1:1:1. Other steps and conditions were the same.
Example 6
This embodiment differs from embodiment 1 in that:
In step S3, when preparing the chain extender mixture, 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan are added to the DMAc solution of DEA, PDA, EDA, DETA, and 3,3' -diaminobenzidine is also added. Wherein the mass ratio of EDA to 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan 3,3' -diaminobenzidine is 1:1:1:1.5. Other steps and conditions were the same.
Comparative example 1
This comparative example differs from example 2 in that:
In step S3, 2, 5-bis (aminomethyl) furan is replaced with an equivalent mass of 2, 6-diaminopyridine. Other steps and conditions were the same.
Comparative example 2
This comparative example differs from example 2 in that:
In step S3, 2, 6-diaminopyridine is replaced with an equal mass of 2, 5-bis (aminomethyl) furan. Other steps and conditions were the same.
Test examples
Moisture regain test
The spandex fibers obtained in examples 1-6 and comparative examples 1-2 were tested for moisture regain (moisture regain is the percentage of the difference in wet weight to dry weight of the sample to be tested versus the dry weight) using a vented oven. The testing method comprises the steps of weighing the spandex fiber under the environment of 20 ℃ and 65% of relative humidity to obtain the actual weight of the spandex fiber, placing the spandex fiber in an oven, testing the quality every 20min at 45 ℃, and recording the dry weight of the spandex fiber after the numerical value is stable. The spandex fibers obtained in each of the examples and comparative examples were weighed three times and the average value was calculated, and the moisture regain was calculated, and the results are shown in table 1.
Table 1 moisture regain of spandex fiber obtained in each of examples and comparative examples
Referring to the data in Table 1, the moisture regain of the spandex fiber prepared in examples 2-6 and comparative examples 1-2 was improved relative to example 1, and it was found that the addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan to the chain extender mixed solution during the preparation of the spandex fiber significantly improved the moisture regain of the spandex fiber obtained. This is probably because the spandex fiber prepared by adding 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan has a coarser surface than that of example 1, and the presence of grooves, holes and other structures on the fiber surface helps to improve the binding with water molecules, thus exhibiting better moisture absorption performance.
Specifically, the moisture regain of the spandex fibers prepared in examples 2 to 6 and comparative examples 1 to 2 was improved by 16.6%, 19.6%, 23.5%, 31.4%, 36.3%, 8.8% and 12.7%, respectively, relative to example 1.
The moisture regain of the spandex fiber obtained in examples 2 to 4 tended to increase, and it was found that the increase in the amount of 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan in the chain extender mixed solution for preparing the spandex fiber helped to increase the moisture regain of the obtained spandex fiber.
The moisture regain of the spandex fiber obtained in example 2 was higher than that of comparative example 1 and higher than that of comparative example 2, and it was found that the effect of the co-addition of both 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan on the moisture regain of the spandex fiber in the chain extender mixed solution for the preparation of spandex fiber was superior to that of the 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan added alone.
The moisture regain of the spandex fiber obtained in examples 5-6 was increased by 12.6% and 16.8%, respectively, relative to example 2. It was found that the moisture regain of the obtained spandex fiber could be further improved by continuing to add 3,3' -diaminobenzidine to the chain extender mixed solution to which 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan were added.
Tensile Property test
The spandex fibers obtained in examples 1 to 6 and comparative examples 1 to 2 were subjected to a tensile breaking test at a temperature of 20℃and a relative humidity of 65%, the holding length of the fibers was 100mm, the pre-tension force was 0.4cN, the stretching rate was set to 500 mm/min, the test was performed 10 times for each example, and the elongation at break was shown in Table 2.
TABLE 2 elongation at break of spandex fibers obtained in examples and comparative examples
Referring to the data in Table 2, the elongation at break of the spandex fibers prepared in examples 2-6 and comparative examples 1-2 were all improved relative to example 1, and it was found that the addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan to the chain extender mixed solution during the preparation of the spandex fibers significantly improved the elongation at break of the spandex fibers obtained. This is probably because the molecular crosslinking degree of the spandex fiber prepared by adding 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan is improved as compared with example 1, and the molecular weight of the soft segment part is improved in the molecular structure.
Specifically, the elongation at break of the spandex fibers prepared in examples 2 to 6 and comparative examples 1 to 2 was improved by 45.8%, 48.9%, 53.2%, 68.8%, 74.3%, 36.2% and 38.2%, respectively, relative to example 1.
The elongation at break of the spandex fibers obtained in examples 2 to 4 tended to increase, and it was found that the increase in the amount of 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan in the chain extender mixed solution for preparing the spandex fibers contributed to the improvement of the elongation at break of the obtained spandex fibers.
The elongation at break of the spandex fiber obtained in example 2 is higher than that of comparative example 1 and higher than that of comparative example 2, and it can be seen that the effect of the co-addition of both 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan on the elongation at break of the spandex fiber in the chain extender mixed solution for the preparation of spandex fiber is superior to that of the 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan added alone.
The moisture regain of the spandex fiber obtained in examples 5-6 was increased by 12.6% and 16.8%, respectively, relative to example 2. It was found that the elongation at break of the obtained spandex fiber could be further improved by continuing to add 3,3' -diaminobenzidine to the chain extender mixed solution to which 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan were added. Therefore, the addition of 3,3' -diaminobenzidine can improve the tensile property of the obtained spandex fiber and is beneficial to improving the abrasion resistance of the obtained spandex fabric.
Preparation of core spun yarn
Adopting a twisting machine, setting a pre-drafting multiple of 3.80, coating twist of 600 t/m and a crimping rate of 20 m/min, taking the spandex fibers obtained in examples 1-6 and comparative examples 1-2 as core yarns, taking UHMWPE (ultra high molecular weight polyethylene) continuous filaments as sheath yarns, and coating the 100D UHMWPE continuous filaments with 105D spandex filaments to twist and wrap the core yarns to obtain different core-spun yarns.
Elastic performance test of core spun yarn
The elastic recovery rate of the core spun yarn is tested by adopting a fixed load repeated stretching method with reference to FZ/T01034-2008 'method for testing stretching elasticity of textile woven fabrics'. The clamping length was set at 100 mm, the initial position at 50 mm, and the pretension (0.3.+ -. 0.003) cN. Stretching to 0.2N load at 500 mm/min, keeping 5 s, returning to the initial position at 50 mm at equal speed, keeping 5 s, and circulating for 3 times. The elastic recovery of the core yarns obtained in examples 1-6 and comparative examples 1-2 is shown in Table 3.
TABLE 3 elastic recovery of core spun yarns obtained in examples and comparative examples
Referring to the data in table 3, the elastic recovery of the core spun yarn prepared by examples 2 to 6 and comparative examples 1 to 2 was improved relative to example 1, and it was found that the addition of 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan to the chain extender mixed solution during the preparation of spandex fiber significantly improved the elastic recovery of the core spun yarn prepared by using the obtained spandex fiber. This is probably because the spandex fiber prepared by adding 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan has better tensile properties than example 1.
Specifically, the elastic recovery of the spandex fibers prepared in examples 2-6 and comparative examples 1-2 was improved by 6.8%, 7.2%, 7.9%, 8.7%, 9.0%, 3.9% and 4.9%, respectively, relative to example 1.
The elastic recovery of the spandex fibers obtained in examples 2-4 tended to increase, and it was seen that an increase in the amount of 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan in the chain extender mixed solution for the preparation of spandex fibers helped to increase the elastic recovery of the core-spun yarn prepared from the obtained spandex fibers.
The spandex fiber obtained in example 2 has higher elastic recovery than that in comparative example 1 and that in comparative example 2, and it can be seen that the effect of the combined addition of both 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan in the chain extender mixed solution for preparing spandex fiber on the elastic recovery of the core-spun yarn prepared from spandex fiber is better than that of the addition of 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan alone.
The moisture regain of the spandex fiber obtained in examples 5-6 was increased by 12.6% and 16.8%, respectively, relative to example 2. It was found that the elastic recovery of the core-spun yarn prepared from the obtained spandex fiber could be further improved by further adding 3,3' -diaminobenzidine to the chain extender mixed solution to which 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan were added.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art, and are not described herein.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and that variations or alternatives will be apparent to those skilled in the art within the scope of the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1. A chain extender mixed solution for preparing spandex fiber contains diethanolamine, p-phenylenediamine, diethylenetriamine, and also contains 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan.
2. The chain extender mixture as claimed in claim 1, wherein,
The chain extender mixed solution takes DMAc as a solvent;
The mass ratio of diethanolamine, p-phenylenediamine, ethylenediamine and diethylenetriamine is 1:3-8:5-15:5-15, the mass volume ratio of ethylenediamine to DMAc is 1g:15-30mL, and the mass ratio of ethylenediamine to 2, 6-diaminopyridine and 2, 5-di (aminomethyl) furan is 1:0.5-3:0.5-3.
3. A high-recovery spandex fiber is characterized in that,
Preparing a prepolymer solution by adopting polytetrahydrofuran and MDI, reacting the prepolymer solution with a chain extender mixed solution to form a polyurethane urea solution, and adopting a polyurethane urea solution dry spinning method to obtain the high-resilience spandex, wherein the chain extender mixed solution contains diethanolamine, p-phenylenediamine, diethylenetriamine, and also contains 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan.
4. The high recovery spandex fiber of claim 3, wherein,
In the chain extender mixed solution, the mass ratio of diethanolamine to p-phenylenediamine to ethylenediamine to diethylenetriamine is 1:3-8:5-15:5-15, and the mass ratio of ethylenediamine to 2, 6-diaminopyridine to 2, 5-di (aminomethyl) furan is 1:0.5-3:0.5-3.
5. The preparation method of the high-recovery spandex fiber is characterized by comprising the following steps of:
s1, reacting polytetrahydrofuran and MDI at 70-90 ℃ for 90-180min to obtain capped polytetrahydrofuran, and then mixing and dissolving the capped polytetrahydrofuran with a solvent to form a prepolymer solution;
S2, adding MDI into the prepolymer solution obtained in the step S1, uniformly stirring, and cooling to 5-15 ℃ to form a polymer solution;
S3, rapidly adding a chain extender mixed solution into the polymer solution obtained in the step S2 while stirring to react to form a polyurethane urea solution;
S4, extruding the polyurethane urea solution obtained in the step S3 through a spinneret plate to form high-resilience spandex through dry spinning in a channel;
In the step S3, the mixed solution of the chain extender contains diethanolamine, p-phenylenediamine, diethylenetriamine, 2, 6-diaminopyridine and/or 2, 5-di (aminomethyl) furan.
6. The method for preparing high recovery spandex fiber according to claim 5, wherein,
In the chain extender mixed solution, the mass ratio of diethanolamine to p-phenylenediamine to ethylenediamine to diethylenetriamine is 1:3-8:5-15:5-15, the mass volume ratio of ethylenediamine to DMAc is 1g:15-30mL, and the mass ratio of ethylenediamine to 2, 6-diaminopyridine to 2, 5-di (aminomethyl) furan is 1:0.5-3:0.5-3.
7. The method for preparing high recovery spandex fiber according to claim 5, wherein,
In the step S1, the solvent is DMAc, and the solvent in the chain extender mixed solution is DMAc.
8. The method for preparing high recovery spandex fiber according to claim 5, wherein,
In the step S1, the mass ratio of polytetrahydrofuran to MDI is 5-10:1, and the mass ratio of MDI to DMAc is 1:6-12;
the MDI consumption in the step S2 is 2-10% of the MDI consumption in the step S1;
The DMAc amount in the chain extender mixture is 10-25% of the DMAc amount in step S1.
9. The method for preparing high recovery spandex fiber according to claim 5, wherein,
In the step S4, before dry spinning, tiO 2, tinuvin622, tinuvin328, TSA-011 and TSA-245 are added into the polyurethane urea solution obtained in the step S3 and mixed uniformly.
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