A kind of high resilience active dyeable polyurethane urea elastic fiber

Abstract

The present invention is a high-resilience active dyeable polyurethane urea elastic fiber, which contains a polyhydroxy structure in its molecular chain, and the polyhydroxy structure is introduced into the polyurethane urea elastic fiber molecular chain in the form of a capping agent. The preparation method is as follows: in the presence of a solvent, a polyurethane prepolymer, a chain extender and a capping agent are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, a high-resilience active dyeable polyurethane urea elastic fiber is prepared by dry spinning. On the one hand, it does not affect the soft and hard segment structure of polyurethane urea, has little effect on the performance of the original polyurethane urea molecular chain, and can significantly provide the applicability of the fiber; on the other hand, polyhydroxy alcohol amine forms a covalent bond with a reactive dye in the subsequent dyeing process, and the reactive dye is fixed on the polyurethane urea fiber, thereby improving the coloring rate of the fiber to the reactive dye, and further introducing a polyamide-amine dendritic polymer polyamide-amine resin can greatly improve the color fastness.

Description

Technical Field

[0001] The invention belongs to polyurethane urea elastic fibers, and relates to high-rebound active dyeable polyurethane urea elastic fibers. Background Art

[0002] Polyurethane urea elastic fiber has excellent properties such as high elongation and high resilience, and is widely used in fabric fields such as clothing, so it is known as the "fabric MSG". In recent years, with the continuous expansion of polyurethane urea elastic fiber production capacity, the downstream market has also put forward new requirements for the performance of spandex. When spandex is used in combination with cotton, protein fiber, etc., it often causes white leakage due to insufficient coloring of reactive dyes. This is mainly because the macromolecular structure of fiber-forming polyurethane lacks active groups that can combine with dyes like cellulose or protein, and it is difficult for dye molecules to enter the fiber, making dyeing difficult. Therefore, there are still some problems in the dyeing of polyurethane urea elastic fiber: low color fastness, dyeability, and weak rebound after dyeing and finishing. Therefore, the development of highly efficient reactive dyeable spandex is crucial to promote the rapid and sustainable development of dyeable polyurethane fibers.

[0003] Regarding the preparation method of polyurethane urea elastic fiber easily dyed with reactive dyes, the development is mainly based on the following two methods: one is by adding functional dyeable auxiliaries, such as Hyosung's patent CN108138388A discloses adding 0.1wt%-20wt% of materials containing alkaline earth metal elements with an electronegativity (Pauling scale) of 1.2 or more, materials containing metalloid elements with an electronegativity (Pauling scale) of 1.8 or more, or materials containing post-transition metal elements with an electronegativity (Pauling scale) of 1.5 or more to polyurethane or polyurethane urea elastic fibers. The added auxiliaries react chemically with reactive dyes to form covalent bonds, thereby improving the colorability of polyurethane or polyurethane urea elastic fibers in reactive dyes. However, the alkaline metal substances added by this method will accelerate the breakage and aging of spandex macromolecules during subsequent dyeing and finishing applications, greatly reducing the performance of spandex. Another method is to chemically modify the elastic fiber so that the fiber molecular chain contains functional groups that can react with active dye molecules, thereby improving the colorability. Patent CN113337916A discloses the introduction of a dihydroxy polymer containing a tertiary amine group into the spandex soft segment, combined with the addition of an organic compound of lithium into the spandex spinning aid. The modified spandex molecular chain contains a dihydroxy polymer with a tertiary amine group and an organic compound of lithium dispersed therein, which can form a covalent bond with the active group of the active dye, making the connection between the active dye molecule and the spandex molecular chain more firmly, and effectively improving the dyeing rate of the active dye on the spandex. However, the performance of the spandex prepared by this method changes greatly, and the added lithium-based compound will accelerate the degradation of the spandex performance; Patent CN114438619A discloses that by using terminal hydroxyl polybutadiene as part of the diol raw material of the cortex, nucleophilic hydroxyl and amino groups are introduced into the main chain of the polyurethane polymer. In the subsequent dyeing process, the group has a strong electron-withdrawing property and can form a covalent bond with the active dye with a polyhydroxy group, fixing the active dye on the polyurethane fiber, thereby improving the dyeing rate and fixation rate of the spandex on the active dye. The spandex is made into a skin-core structure, and the polyurethane of the core layer can be used to ensure the fiber performance of the spandex. Although this method solves the problem of spandex performance degradation during the modification process, it has high requirements for equipment, thereby greatly increasing the production cost.

[0004] Therefore, on the basis of the existing knowledge, the present invention develops a polyurethane urea elastic fiber easily dyed with reactive dyes and a preparation technology thereof. Compared with the previous technical means, the spandex prepared by the present invention not only greatly enhances the dyeing rate and fixation rate of reactive dyes, but also has a simple production technology. The subsequent application performance of the prepared reactive dyeable polyurethane urea elastic fiber is not significantly different from that of conventional elastic fibers. Summary of the invention

[0005] Technical problem: The purpose of the present invention is to provide a method for preparing polyurethane urea elastic fiber with excellent coloring performance with reactive dyes.

[0006] Technical solution: The present invention provides a high-resilience active dyeable polyurethane urea elastic fiber, wherein the molecular chain of the polyurethane urea elastic fiber contains a polyhydroxy structure, and the polyhydroxy structure is introduced into the molecular chain of the polyurethane urea elastic fiber in the form of a capping agent.

[0007] The end-capping agent contains polyhydroxy alcohol amine and small molecule monoamine; the polyhydroxy alcohol amine contains not less than 2 hydroxyl groups and only contains 1 secondary amine group; the small molecule monoamine includes C2-C20 monoamines, including one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, and cyclohexylamine, preferably diethylamine; the molar content of the polyhydroxy alcohol amine in the end-capping agent is 5%-80%; preferably, the molar content of the polyhydroxy alcohol amine in the end-capping agent is 20%-60%.

[0008] The polyhydroxy alcohol amine includes one or more of diethanolamine, dipropanolamine and dibutanolamine, preferably diethanolamine.

[0009] Furthermore, the molecular chain of the polyurethane urea elastic fiber also contains a ring structure, and the ring structure is introduced into the molecular chain of the polyurethane urea elastic fiber in the form of a chain extender;

[0010] The chain extender includes alicyclic diamine and aliphatic diamine;

[0011] The molar content of the alicyclic diamine in the chain extender is 5% to 30%;

[0012] The alicyclic diamines include diamines containing a cyclohexane structure, including one or more of cyclohexyl diamine and methyl cyclohexyl diamine;

[0013] The aliphatic diamine includes one or more of ethylenediamine, propylenediamine, butylenediamine, tetramethylethylenediamine, pentamethylenediamine, and hexamethylenediamine, preferably ethylenediamine.

[0014] The preparation method of the high-resilience active dyeable polyurethane urea elastic fiber of the present invention comprises:

[0015] In the presence of a solvent, a polyurethane prepolymer, a chain extender and a capping agent are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, a high-resilience active dyeable polyurethane urea elastic fiber is prepared by dry spinning.

[0016] The polyurethane prepolymer is obtained by reacting a polyhydroxy polymer and a polyisocyanate;

[0017] The polyurethane prepolymer has an NCO mass content of 2 to 5%, preferably 2% to 3.7%, and more preferably 2.2wt% to 3.65wt%;

[0018] The polyhydroxy polymer includes polyether diol and / or polyester diol; the number average molecular weight of the polyhydroxy polymer is 1000 to 4000;

[0019] The polyisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and / or derivatives and / or modified polymers.

[0020] The polyether diol includes at least one of polyoxyethylene ether diol, polyoxypropylene ether diol and polytetramethylene ether diol;

[0021] The polyester diol includes one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, and polycaprolactone diol; preferably, the polyether diol includes polytetramethylene ether glycol.

[0022] The molar ratio of the total amine groups of the end capping agent and the chain extender to the NCO of the polyurethane prepolymer is 1.0-1.1, preferably 1.01-1.08; preferably, the molar ratio of the chain extender to the end capping agent is 5-30, preferably 10-25.

[0023] The polyurethane urea elastic fiber contains 0.1% to 5% of polyamide amine resin, calculated based on the mass of the polyurethane urea elastic fiber.

[0024] The polyamidoamine resin contains a dendritic structure and has a number average molecular weight of 1000 to 10000;

[0025] Preferably, the polyamide amine resin is added to a polyurethane-urea polymer stock solution.

[0026] Furthermore, the preparation method of the high-resilience active dyeable polyurethane urea elastic fiber comprises:

[0027] The polyurethane prepolymer is fully dissolved in a solvent to form a polyurethane prepolymer solution, the chain extender and the end-capping agent are fully dissolved in the solvent to form a mixed amine solution, the polyurethane prepolymer solution and the mixed amine solution are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, it is prepared into a high-resilience active dyeable polyurethane urea elastic fiber by dry spinning.

[0028] Wherein, the mass concentration of the prepolymer is 30wt% to 60wt%, the mass concentration of the mixed amine solution is 3wt% to 8wt%; the mass concentration of the polyurethane-urea polymer stock solution is 30wt% to 38wt%;

[0029] Beneficial effects: Introducing polyhydroxy alcohol amine into polyurethane urea elastic fiber in the form of a capping agent through chemical bonding, on the one hand, does not affect the soft and hard segment structure of polyurethane urea, has little effect on the performance of the original polyurethane urea molecular chain, and can significantly improve the applicability of the fiber; on the other hand, polyhydroxy alcohol amine forms a covalent bond with the reactive dye in the subsequent dyeing process, fixes the reactive dye on the polyurethane urea fiber, thereby improving the coloring rate of the fiber for the reactive dye, and further introducing polyamide amine dendrimer polymer polyamide amine resin can greatly improve the dyeing fastness. DETAILED DESCRIPTION

[0030] The elastic and dyeable polyurethane urea elastic fiber contains a polyhydroxy structure in its molecular chain, and the polyhydroxy structure is introduced into the polyurethane urea elastic fiber molecular chain in the form of a capping agent and is obtained by dry spinning;

[0031] The end-capping agent contains polyhydroxy alcohol amine and small molecular monoamine;

[0032] The polyhydroxy alcohol amine contains not less than 2 hydroxyl groups and only one secondary amine group, including at least one of diethanolamine, dipropanolamine, and dibutanolamine, preferably diethanolamine;

[0033] Small molecule monoamines include C2-C20 monoamines, including one or more of n-propylamine, isopropylamine, n-butylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, and cyclohexylamine, preferably diethylamine;

[0034] The molar content of the polyhydroxy alcohol amine in the end-capping agent is 5% to 80%;

[0035] Preferably, the molar content of the polyhydroxy alcohol amine in the capping agent is 20% to 60%;

[0036] Furthermore, the molecular chain of the polyurethane urea elastic fiber also contains a ring structure, and the ring structure is introduced into the molecular chain of the polyurethane urea elastic fiber in the form of a chain extender;

[0037] Further, the chain extender includes alicyclic diamine and aliphatic diamine;

[0038] The molar content of the alicyclic diamine in the aliphatic diamine is 5% to 30%;

[0039] The alicyclic diamines include diamines containing a cyclohexane structure;

[0040] Preferably, the diamine containing a cyclohexane structure includes one or more of cyclohexyldiamine and methylcyclohexyldiamine;

[0041] As an example, the cyclohexanediamine includes one or more of 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, and 1-methyl-2,4-cyclohexanediamine;

[0042] The aliphatic diamine includes one or more of cycloethylenediamine, propylenediamine, butylenediamine, tetramethylethylenediamine, pentamethylenediamine, and hexamethylenediamine, with ethylenediamine being preferred as an example;

[0043] The polyurethane urea elastic fiber is obtained by dry spinning, which includes the following steps:

[0044] Furthermore, the polyurethane urea elastic fiber is obtained by reacting a polyurethane prepolymer terminated with isocyanate, a chain extender, and a capping agent to obtain a polyurethane-urea polymer, and the polyurethane-urea polymer is used as a spinning solution raw material through dry spinning;

[0045] The polyurethane prepolymer is obtained by reacting a polyhydroxy polymer and a polyisocyanate;

[0046] The NCO mass content of the polyurethane prepolymer is 2-5%, preferably 2%-3.7%, more preferably 2.2wt%-3.65wt%;

[0047] The polyhydroxy polymer includes polyether diol and / or polyester diol;

[0048] Preferably, the number average molecular weight of the polyhydroxy polymer is 1000 to 4000;

[0049] The polyether diol includes one or more of polyoxyethylene ether diol, polyoxypropylene ether diol and polytetramethylene ether diol;

[0050] The polyester diol includes one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol and polycaprolactone diol;

[0051] Preferably, the polyether diol comprises polytetramethylene ether glycol;

[0052] The polyisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and / or derivatives and / or modified polymers;

[0053] In some embodiments of the present invention, the polyisocyanate is diphenylmethane diisocyanate;

[0054] The molar ratio of the total amine groups of the end capping agent and the chain extender to the NCO of the polyurethane prepolymer is 1.0 to 1.1, preferably 1.01 to 1.08;

[0055] Preferably, the molar ratio of the chain extender to the end-capping agent is 5 to 30, preferably 10 to 25;

[0056] Furthermore, the polyurethane urea elastic fiber contains 0.1% to 5% of polyamide amine resin, calculated based on the mass of the polyurethane urea elastic fiber;

[0057] The polyamidoamine resin contains a dendritic structure and has a number average molecular weight of 1000 to 20000;

[0058] More preferably, the polyamide amine resin is added to a polyurethane-urea polymer stock solution;

[0059] In some examples of the present invention, the polyamide amine resin can be directly used as a commercial product, such as CYD-120A / CYD-120H, CDY-130A / CDY-130H, CDY-140A / CYD-140H of Weihai Chenyuan Molecular New Materials Co., Ltd.;

[0060] The method for preparing the high-resilience active dyeable polyurethane urea elastic fiber comprises the following steps:

[0061] In the presence of a solvent, a polyurethane prepolymer, a chain extender and a capping agent are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, a high-resilience active dyeable polyurethane urea elastic fiber is prepared by dry spinning.

[0062] Preferably, the polyurethane prepolymer is fully dissolved in a solvent to form a polyurethane prepolymer solution, the chain extender and the end-capping agent are fully dissolved in the solvent to form a mixed amine solution, the polyurethane prepolymer solution and the mixed amine solution are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, it is prepared into a high-resilience active dyeable polyurethane urea elastic fiber by dry spinning.

[0063] Wherein, the mass concentration of the prepolymer is 30wt% to 60wt%, the mass concentration of the mixed amine solution is 3wt% to 8wt%; the mass concentration of the polyurethane-urea polymer stock solution is 30wt% to 38wt%;

[0064] Wherein, the solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, or a combination of the two;

[0065] As an example, the solvent is N,N-dimethylacetamide (DMAc);

[0066] As an example, the preparation of the polyurethane prepolymer includes: adding a polyhydroxy polymer and a polyisocyanate into a reactor, and fully reacting at 60° C. to 90° C. to obtain a polyurethane prepolymer, and the reaction process is carried out under nitrogen protection.

[0067] Optionally, optional additives can be added to the spinning solution during the aging process. The additives can be obtained by grinding dispersants, antioxidants, lubricants, matting agents, cohesion aids, anti-yellowing agents, antioxidants, and ultraviolet absorbers and mixing them with organic solvents to obtain additive slurry. The concentration of the additive slurry is controlled at 25-40%. There is no special requirement for the amount of additives added as long as it does not affect the performance of the fiber itself.

[0068] In some embodiments of the present invention, the method for preparing the high-resilience active dyeable polyurethane urea elastic fiber comprises the following specific steps:

[0069] Polyurethane prepolymer solution steps:

[0070] Using DMAc as solvent, fully dissolving the polyurethane prepolymer through a high-speed dissolver to obtain a polyurethane prepolymer solution with a mass concentration of 30wt% to 60wt%;

[0071] Steps for mixing amine solution:

[0072] Dissolving the chain extender and the end-capping agent in DMAc solvent to obtain a mixed amine solution with a total mass concentration of 3 wt% to 8 wt%;

[0073] Polymerization steps:

[0074] Adding the polyurethane prepolymer solution and the mixed amine solution into a reactor for reaction to obtain a polyurethane-urea polymer stock solution with a mass concentration of 30 wt% to 38 wt%;

[0075] A viscosity stabilizer, such as diethylenetriamine, may be optionally added during the above polymerization process to control the viscosity of the polymer;

[0076] Ripening spinning steps:

[0077] The polyurethane-urea polymer stock solution is matured to form a spinning solution, and the polyurethane-urea elastic fiber is prepared by dry spinning technology;

[0078] Wherein, the polyamide amine resin can be selectively added to the polyurethane-urea polymer stock solution during the aging process;

[0079] The dry spinning technology of the present invention comprises the steps of spraying and stretching the spinning solution, high-temperature drying, oiling with an oil agent, winding and forming, etc., to obtain high-resilience active dyeable polyurethane urea elastic fibers.

[0080] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0081] In order to more directly illustrate the beneficial effects of the present invention and reduce the performance fluctuation caused by the change of the polyurethane prepolymer preparation method, the examples of the present invention and the comparative examples all adopt the same preparation method to prepare the polyurethane prepolymer and the polyurethane prepolymer solution, and the specific preparation is as follows:

[0082] The measured polytetramethylene ether glycol (molecular weight 1800) and diphenylmethane-4,4'-diisocyanate are simultaneously and continuously fed into a static mixer, and after mixing, they are fed into a reactor at 80° C. to react for 135 minutes, and a polyurethane prepolymer having an NCO mass fraction of 2.20 to 3.63% is obtained by controlling the input amounts of the polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate;

[0083] Preparation of polyurethane prepolymer solution:

[0084] The polyurethane prepolymer is cooled to 40°C and stored for more than 5 hours, then the polyurethane prepolymer and DMAc are continuously put into a high shear dissolver to completely dissolve the prepolymer, and then cooled to obtain a polyurethane prepolymer solution (PPs) with a mass concentration of 30% to 60%.

[0085] The resilience and dyeing properties proposed in the following examples were tested as follows

[0086] (1) Spandex resilience

[0087] The sample is subjected to a stretching recovery cycle between 0% and 300% elongation using a constant rate elongation testing machine under constant temperature and humidity conditions of 20℃±1℃ and 65%±5%. Then, after a delay of a specified time, its 300% elastic recovery rate is calculated based on the change in the corresponding indicators before and after stretching.

[0088] Where:

[0089] Eri——300% elastic recovery rate of a single specimen, %;

[0090] L1——Length at 300% elongation, in millimeters (mm);

[0091] L2——The length of the sixth loading and stretching to the pre-tensioning point, in millimeters (mm);

[0092] L0 – Clamping length at 0% elongation, in millimeters (mm).

[0093] (2) Fiber dyeing

[0094] Weigh the dye solution with a dye concentration of 10g / L, add anhydrous sodium sulfate with a concentration of 20g / L, and the bath ratio is 1:50. Turn on the high-temperature dyeing machine, when the water temperature rises to 30℃, put the dyeing cup into the kettle, and heat it to 85℃ at a rate of 1℃ / min, continue to add anhydrous sodium sulfate (compared to the above dye solution concentration of 20g / L) and anhydrous sodium carbonate to the dye tank (compared to the above dye solution concentration of 10g / L), and keep warm for 40min.

[0095] Reactive red was selected as the carrier dye and dyeing was carried out according to the above method. The maximum absorbance of the dye solution before and after dyeing was measured using an ultraviolet-visible spectrophotometer to calculate the dye uptake.

[0096] Calculation formula: dye uptake = A0-A1 / A0×100%, where A0 and A1 are the absorbance of the dye solution before and after dyeing, respectively.

[0097] The present invention is described in detail below using examples, but these examples should not be construed as limiting the present invention in any sense.

[0098] Example 1

[0099] Design process:

[0100] The -NCO end group content in the prepolymer PP is 2.64%;

[0101] The mass concentration of the prepolymer solution PPs is 38.41%;

[0102] The molar content of diethanolamine in the capping agent is 5%;

[0103] The molar content of 1,4-cyclohexanediamine in the chain extender is 5%;

[0104] The content of diethylenetriamine in the active dyeable polyurethane urea elastic fiber is 120ppm;

[0105] The molar ratio of the amount of chain extender diamine added to the amount of chain terminator monoamine added is 13;

[0106] The concentration of DMAC mixed amine solution is 7wt%;

[0107] The polyamide amine resin accounts for 3% of the reactive dyeable polyurethane urea elastic fiber;

[0108] The concentration of the polyurethane urea spinning solution containing polyhydroxyl groups is 35wt%;

[0109] The specific implementation parameters are as follows:

[0110] 1) 175.483 g / min of polytetramethylene ether glycol (molecular weight 1800) and 41.792 g / min of diphenylmethane-4,4'-diisocyanate were simultaneously and continuously fed into a static mixer using a metering pump, and after mixing, the mixture was fed into a first reactor at 80° C. and reacted for 135 minutes. The reaction was adjusted so that the terminal unreacted diisocyanate content became 2.64±0.02 mol %, thereby synthesizing a polyurethane prepolymer as a primary polymer.

[0111] The prepolymer was cooled to 40°C and stored for more than 5 hours, then the prepolymer was continuously added to a high shear dissolver at a flow rate of 216.874 g / min together with 346.558 g / min of N,N-dimethylacetamide to completely dissolve the prepolymer, and cooled to prepare a prepolymer solution (PPs) having a solid content of 38.49 wt% at 40°C.

[0112] 2) Preparation of mixed amine solution: 10 kg of chain extender ethylenediamine, 1 kg of 1,4-cyclohexanediamine, 1.891 kg of chain terminator diethylamine, 0.143 kg of diethanolamine, 0.118 kg of ethylenetriamine and 174.729 kg of N,N-dimethylacetamide were stirred and mixed to prepare 187.881 kg of mixed amine solution with a solid content of 7 wt%.

[0113] 3) The prepolymer solution is added into a chain extension reactor at a flow rate of 563.432 g / min and the mixed amine solution prepared in the above 2) is added at a flow rate of 70.26 g / min by using a metering pump, and a high shear polymerization reaction is carried out to obtain a polyhydroxy-terminated polyurethane urea polymer solution having a solid content of 35 wt%. The apparent viscosity of the polyurethane urea polymer solution is controlled by adjusting the amine / isocyanate equivalent ratio.

[0114] 4) Preparation of mixed slurry: 29.27 kg of polyamidoamine resin and 123.39 kg of solvent N,N-dimethylacetamide were ground and mixed, and dispersed and crushed with a sand mill to prepare an additive slurry composition.

[0115] 5) The polyhydroxy-terminated polyurethane urea polymer solution prepared in 3) above was continuously and uniformly mixed at a flow rate of 633.692 g / min and the additive slurry composition prepared in 4) above was mixed at a flow rate of 48.348 g / min to prepare a spinning solution having a solid content of 35%.

[0116] 6) Polyurethane urea elastic fibers were produced by dry spinning at a spinning speed of 900 m / min in which a fixed amount of the spinning solution was ejected by a gear pump onto a spinning cylinder formed in an atmosphere of 250° C. to 270° C. and the solvent was evaporated.

[0117] Example 2

[0118] In Example 1, the molar content of diethanolamine in the end-capping agent is changed to 80%; the molar content of 1,4-cyclohexanediamine in the chain extender is changed to 30%; the molar content of diethylenetriamine in the reactive dyeable polyurethane urea elastic fiber is changed to 60ppm; and the molar ratio of the added amount of the chain extender diamine to the added amount of the chain terminator monoamine is changed to 5. Other than this, the same method is used for implementation.

[0119] Example 3

[0120] In Example 1, the molar content of diethanolamine in the end-capping agent is changed to 40%; the molar content of 1,4-cyclohexanediamine in the chain extender is changed to 10%; and the molar ratio of the added amount of the chain extender diamine to the added amount of the chain terminator monoamine is changed to 15. Other than this, the same method is used.

[0121] Example 4

[0122] In Example 3, the content of diethylenetriamine in the active dyeable polyurethane urea elastic fiber was changed to 200 ppm; 1,4-cyclohexanediamine was replaced by 1,2-cyclohexanediamine, and the molar ratio of the added amount of the chain extender diamine to the added amount of the chain terminator monoamine was changed to 25. Other than this, the same method was used.

[0123] Example 5

[0124] In Example 3, the -NCO end group content in the prepolymer PP is 2.2%, the content of diethylenetriamine in the active dyeable polyurethane urea elastic fiber is changed to 60 ppm, and the molar ratio of the added amount of the chain extender diamine to the added amount of the chain terminator monoamine is changed to 30. Other than this, the same method is used.

[0125] Example 6

[0126] In Example 3, the -NCO end group content in the prepolymer PP is 3.63%, 1,4-cyclohexanediamine is replaced by 1-methyl-2,4-cyclohexanediamine, the content of diethylenetriamine in the active dyeable polyurethane urea elastic fiber is changed to 200ppm, and the molar ratio of the added amount of the chain extender diamine to the added amount of the chain terminator monoamine is changed to 5. Other than this, the same method is used.

[0127] Example 7

[0128] In Example 3, the content of the polyamide amine resin in the reactive dyeable polyurethane urea elastic fiber was changed to 0.1%. Other than this, the same method was used.

[0129] Example 8

[0130] In Example 3, the content of the polyamide amine resin in the reactive dyeable polyurethane urea elastic fiber was changed to 5%. Other than this, the same method was used for the rest.

[0131] Example 9

[0132] In Example 3, the concentration of the mixed amine solution is 3 wt %. Other than this, the same method is used.

[0133] Example 10

[0134] In Example 3, the content of diethylenetriamine in the reactive dyeable polyurethane urea elastic fiber was changed to 60 ppm, and the concentration of the polyurethane urea spinning solution containing polyhydroxyl groups was 30 wt %. Other than this, the same method was used.

[0135] Embodiment 11

[0136] In Example 3, the content of diethylenetriamine in the reactive dyeable polyurethane urea elastic fiber was changed to 150 ppm, and the concentration of the polyurethane urea spinning solution containing polyhydroxyl groups was 38 wt %. Other than this, the same method was used.

[0137] Example 12

[0138] In Example 1, the chain extender does not contain alicyclic diamine, and an equal amount of ethylenediamine is used to replace 1,4-cyclohexanediamine. Other than this, the same method is used.

[0139] Embodiment 13

[0140] In Example 1, an equal amount of ethanolamine was used to replace diethanolamine. Other than this, the same method was used for the rest.

[0141] Embodiment 14

[0142] In Example 1, the end-capping agent does not contain small molecular monoamine, and an equal amount of diethanolamine is used to replace diethylamine. Other than this, the same method is used for the rest.

[0143] Embodiment 15

[0144] In Example 1, the polyamidoamine resin content is 0. Other than this, the same method is used.

[0145] Example 16

[0146] Compared with Example 3, the molar content of diethanolamine in the end-capping agent is changed to 85%. Other than this, the same method is used for the rest.

[0147] Embodiment 17

[0148] Compared with Example 3, the molar content of diethanolamine in the end-capping agent is changed to 40%, and the molar content of 1,4-cyclohexanediamine in the chain extender is changed to 0%. Other than this, the rest is implemented in the same way.

[0149] Embodiment 18

[0150] Compared with Example 3, the content of polyamidoamine resin is 0. Other than this, the same method is used for implementation.

[0151] Comparative Example 1

[0152] Compared with Example 3, the molar content of diethanolamine in the end-capping agent is changed to 0%. Other than this, the same method is used for the rest.

[0153] Comparative Example 2

[0154] Compared with Example 3, the molar content of diethanolamine in the end-capping agent is reduced to 0%; the molar content of 1,4-cyclohexanediamine in the chain extender is reduced to 0%. Other than this, the same method is used.

[0155] The performance evaluation results of the polyurethane urea elastic fiber are presented in Table 1 below:

[0156]

[0157] Remark:

[0158] ① When the end-capping agent does not contain small molecular monoamine, the spinnability of the polyurethane urea stock solution is poor;

[0159] ② Without adding polyamide-amine resin, there is no obvious effect on the dyeability and resilience of the fiber. However, in the subsequent fiber processing, its dyeing fastness will be worse than that of the fiber added with polyamide-amine resin. Polyamide-amine resin can be added or adjusted according to the subsequent processing requirements;

[0160] ③ When the content of diethanolamine in the end-capping agent is greater than 80%, the spinnability of the polyurethane urea stock solution is poor.

[0161] It can be seen from Table 1 that the polyurethane urea elastic fiber of the present invention can provide spandex with better resilience performance on the basis of excellent reactive dyeing colorability. In addition, a small amount of polyamide amine resin is introduced into the polyurethane urea elastic fiber to assist in improving the color fastness of reactive dyes and improve the color fixation effect of subsequent dyeing.

[0162] The present invention has been described in detail through the technical solution and specific implementation examples. For those skilled in the art, any changes in form or detail made on the basis of the technical solution of the present invention should fall within the scope of protection determined by the claims of the present invention.

Claims

1. A high resilience active dyeable polyurethane urea elastic fiber, characterized in that: The molecular chain of the polyurethane urea elastic fiber contains a polyhydroxy structure, and the polyhydroxy structure is introduced into the molecular chain of the polyurethane urea elastic fiber in the form of a capping agent; The molecular chain of the polyurethane urea elastic fiber also contains a ring structure, and the ring structure is introduced into the molecular chain of the polyurethane urea elastic fiber in the form of a chain extender; The polyurethane urea elastic fiber contains 0.1% to 5% of polyamide amine resin based on the mass of the polyurethane urea elastic fiber; the polyamide amine resin contains a dendritic structure and has a number average molecular weight of 1000 to 10000; The chain extender includes alicyclic diamine and aliphatic diamine, and the alicyclic diamine includes a diamine containing a cyclohexane structure; The end-capping agent contains a polyhydroxy alcohol amine and a small molecular monoamine; the polyhydroxy alcohol amine contains no less than 2 hydroxyl groups and only 1 secondary amine group; The molar content of the polyhydroxy alcohol amine in the end-capping agent is 5% to 80%.

2. The high resilience reactive dyeable polyurethane urea elastic fiber according to claim 1, characterized in that: The molar content of the alicyclic diamine in the chain extender is 5% to 30%; The diamine of cyclohexane structure includes one or more of cyclohexanediamine and methylcyclohexanediamine; The aliphatic diamine includes one or more of ethylenediamine, propylenediamine, butylenediamine, tetramethylethylenediamine, pentamethylenediamine and hexamethylenediamine.

3. The high resilience reactive dyeable polyurethane urea elastic fiber according to claim 1, characterized in that: The molar content of the polyhydroxy alcohol amine in the end-capping agent is 20% to 60%.

4. The high resilience reactive dyeable polyurethane urea elastic fiber according to claim 3, characterized in that: The polyhydroxy alcohol amines include one or more of diethanolamine, dipropanolamine, and dibutanolamine; the small molecule monoamines include C2-C20 monoamines, including one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, and cyclohexylamine.

5. A method for preparing the high-resilience active dyeable polyurethane urea elastic fiber as claimed in claim 4, characterized in that: The method for preparing the high-resilience active dyeable polyurethane urea elastic fiber comprises: In the presence of a solvent, a polyurethane prepolymer, a chain extender and a capping agent are reacted to obtain a polyurethane-urea polymer stock solution; after the polyurethane-urea polymer stock solution is matured, a high-resilience active dyeable polyurethane urea elastic fiber is prepared by dry spinning.

6. The method for preparing the high-resilience active dyeable polyurethane urea elastic fiber according to claim 5, characterized in that: The polyurethane prepolymer is obtained by reacting a polyhydroxy polymer and a polyisocyanate; The polyurethane prepolymer has an NCO mass content of 2-5%; The polyhydroxy polymer is selected from polyether diols and / or polyester diols; the number average molecular weight of the polyhydroxy polymer is 1000-4000; The polyisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.

7. The method for preparing high-resilience active dyeable polyurethane urea elastic fiber according to claim 6, characterized in that: The polyurethane prepolymer has an NCO mass content of 2.2wt% to 3.65wt%.

8. The method for preparing high-resilience active dyeable polyurethane urea elastic fiber according to claim 6, characterized in that: The polyether diol includes at least one of polyoxyethylene ether diol, polyoxypropylene ether diol and polytetramethylene ether diol; The polyester diol includes one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol and polycaprolactone diol.

9. The method for preparing high-resilience active dyeable polyurethane urea elastic fiber according to claim 5, characterized in that: The molar ratio of the total amine groups of the end-capping agent and the chain extender to the NCO of the polyurethane prepolymer is 1.0-1.1, and the molar ratio of the chain extender to the end-capping agent is 5-30.

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