阅读说明：本技术 一种高回弹高均一耐高温氨纶纤维的制备方法 (Preparation method of high-resilience, high-uniformity and high-temperature-resistant spandex fiber ) 是由 张经瀚 陈厚翔 蒋曙 杨晓印 史兴 于 2020-11-27 设计创作，主要内容包括：本发明是一种高回弹高均一耐高温氨纶纤维的制备方法,预聚合反应：将二异氰酸酯和聚醚二醇以摩尔比(1.56～2.00):1反应得到NCO封端的预聚物；反应时间1.5～4小时,反应温度70～90℃；将预聚物与溶剂溶解形成质量浓度为30～38％的预聚物溶液；所述的溶剂为二甲基乙酰胺DMAC；扩链反应：将上述预聚物溶液与混合胺溶液进行混合反应,并得到质量浓度为30～38％的聚氨酯脲原液,其中混合胺溶液中端基胺与预聚物溶液中NCO的摩尔比为(1.01～1.04):1；反应温度≤100℃；熟化纺丝：将聚氨酯脲原液熟化形成纺丝原液进行干法纺丝,熟化温度为,40～60℃,时间为24～45小时,得到高回弹高均一耐高温氨纶纤维。其弹性恢复、动态退绕应力值数据的变异系数、耐高温等性能均十分优异。(The invention relates to a preparation method of high-resilience, high-uniformity and high-temperature-resistant spandex fiber, which comprises the following steps of: reacting diisocyanate and polyether diol in a molar ratio (1.56-2.00) to 1 to obtain an NCO-terminated prepolymer; the reaction time is 1.5-4 hours, and the reaction temperature is 70-90 ℃; dissolving a prepolymer and a solvent to form a prepolymer solution with the mass concentration of 30-38%; the solvent is Dimethylacetamide (DMAC); chain extension reaction: mixing the prepolymer solution and a mixed amine solution for reaction to obtain a polyurethane urea stock solution with the mass concentration of 30-38%, wherein the molar ratio of terminal amine in the mixed amine solution to NCO in the prepolymer solution is (1.01-1.04): 1; the reaction temperature is less than or equal to 100 ℃; curing and spinning: curing the polyurethane urea stock solution to form a spinning stock solution, and performing dry spinning at the curing temperature of 40-60 ℃ for 24-45 hours to obtain the high-resilience high-uniformity high-temperature-resistant spandex fiber. The elastic recovery performance, the coefficient of variation of dynamic unwinding stress value data, the high temperature resistance performance and the like are all excellent.)

1. A preparation method of high-resilience, high-uniformity and high-temperature-resistant spandex fibers is characterized by comprising the following steps:

step 1 prepolymerization

Reacting diisocyanate and polyether diol in a molar ratio (1.56-2.00) to 1 to obtain an NCO-terminated prepolymer;

dissolving a prepolymer and a solvent to form a prepolymer solution with the mass concentration of 30-38%; the solvent is Dimethylacetamide (DMAC);

step 2. chain extension reaction

Mixing the prepolymer solution and a mixed amine solution for reaction to obtain a polyurethane urea stock solution with the mass concentration of 30-38%, wherein the molar ratio of terminal amine in the mixed amine solution to NCO in the prepolymer solution is (1.01-1.04): 1;

step 3, ripening and spinning

Curing the polyurethane urea stock solution to form spinning stock solution, and performing dry spinning to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

2. The method for preparing the high resilience, high uniformity and high temperature resistance spandex fiber according to claim 1, characterized in that in the prepolymerization step, the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexanedimethylene diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate.

3. The preparation method of the high-resilience, high-uniformity and high-temperature-resistant spandex fiber according to claim 1, wherein the polyether glycol comprises one or more of polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol and poly-2-methyltetrahydrofuran, and the molecular weight of the polyether glycol is 1500-4000.

4. The preparation method of the high-resilience, high-uniformity and high-temperature-resistant spandex fiber according to claim 1, wherein in the chain extension reaction step, the mixed amine solution comprises a chain extender, a cross-linking agent, a terminator and DMAC; the mass concentration range of the mixed amine solution is 5-12%.

5. The preparation method of the high-resilience, high-uniformity and high-temperature-resistant spandex fiber according to claim 4, wherein the chain extender is a mixture of ethylenediamine and 4, 4-diaminodicyclohexylmethane; the molar ratio of the ethylenediamine to the 4, 4-diaminodicyclohexylmethane is (8.5-19): 1.

6. the method for preparing the high-resilience, high-uniformity and high-temperature resistant spandex fiber according to claim 4, wherein the cross-linking agent is diethyl triamine DETA; the terminator is diethylamine.

7. The preparation method of the high-resilience high-uniformity high-temperature-resistant spandex fiber according to claim 4, wherein the molar ratio of the chain extender to the terminator is (12-16): 1, the addition amount of the cross-linking agent accounts for 0.006-0.02% of the total mass of the fiber.

8. The method for preparing the high-resilience, high-uniformity and high-temperature-resistant spandex fiber according to claim 1, wherein the polyurethaneurea stock solution is selectively added with functional additives, including one or more of an antioxidant, an ultraviolet absorber, a lubricant, a dyeing assistant and a stabilizer.

9. The method for preparing the high-resilience, high-uniformity and high-temperature resistant spandex fiber according to claim 8, wherein the addition amount of the functional additive is calculated according to the mass of the spandex fiber obtained, and the antioxidant is: 0.1-15%, ultraviolet absorbent: 0.1-0.5%, lubricant: 0.1-1.0%, dyeing assistant: 0.1-1.0%, stabilizer: 0.01 to 0.1 percent.

10. The method for preparing the high-resilience, high-uniformity and high-temperature-resistant spandex fiber according to claim 8, wherein the stabilizer is alkane diamine with side methyl groups, and the number of main chain carbons is not more than 8.

Technical Field

The invention belongs to a preparation method of spandex fibers, and particularly relates to a high-resilience, high-uniformity and high-temperature-resistant spandex fiber and a preparation method thereof.

Background

In the early stage, the price of spandex in the textile industry is higher, the yield is lower, the spandex is called as 'fabric monosodium glutamate', and the spandex is added into the textile in a small amount to endow the textile with excellent elasticity and soft hand feeling, so that the comfort level of the textile is obviously improved. Along with the improvement of the living standard of people, the quality requirement on textiles is higher and higher, so that the market application of spandex is wider and wider, and high-quality differentiated spandex appears. With the continuous improvement of market demand, the collection of multiple performances gradually becomes a trend to meet the daily life demands of people.

It can be seen from the molecular structure of spandex that it has high elasticity because its polymer chain is composed of a matrix of low-melting, amorphous "soft" segments and embedded therein high-melting, crystalline "hard" segments. The soft segment molecular chains form a certain network structure through certain crosslinking, and the interaction force among the molecular chains is small, so that the soft segment can freely stretch and contract, and better elongation performance is caused. The binding force of the hard chain segment molecular chain is larger, the molecular chain can not extend without limit, and the fiber has high resilience. Therefore, to further improve the resilience of spandex, the molecular chain length of spandex needs to be increased, the length of a hard segment in the molecular chain segment needs to be increased, and the degree of microphase separation needs to be increased. The resilience of spandex is improved by changing methods such as a formula and a process in patents CN108642573A, CN107338501A, CN101469463A and CN 108264626A. However, the spandex filaments obtained by the methods have low uniformity, the coefficient of variation CV of dynamic unwinding stress value data is large, and the patent CN105624822B adopts single amine ethylenediamine as a chain extender and diethylenetriamine as a molecular weight control agent to prepare the high-uniformity spandex fibers. The patents CN106757486A and CN109825895A prepare the high temperature resistant spandex fiber through formula design and selection of an antioxidant, and the resilience of the high uniform high temperature resistant spandex fiber is poor.

Disclosure of Invention

The technical problem is as follows: the invention aims to provide a preparation method of high-resilience high-uniformity high-temperature-resistant spandex fiber, which has excellent elastic recovery, coefficient of variation of dynamic unwinding stress value data, high temperature resistance and other properties.

The technical scheme is as follows: the preparation method of the high-resilience high-uniformity high-temperature-resistant spandex fiber comprises the following steps of:

step 1 prepolymerization

Reacting diisocyanate and polyether diol in a molar ratio (1.56-2.00) to 1 to obtain an NCO-terminated prepolymer;

dissolving a prepolymer and a solvent to form a prepolymer solution with the mass concentration of 30-38%; the solvent is Dimethylacetamide (DMAC);

step 2. chain extension reaction

Mixing the prepolymer solution and a mixed amine solution for reaction to obtain a polyurethane urea stock solution with the mass concentration of 30-38%, wherein the molar ratio of terminal amine in the mixed amine solution to NCO in the prepolymer solution is (1.01-1.04): 1; the reaction temperature is less than or equal to 100 ℃;

step 3, ripening and spinning

Curing the polyurethane urea stock solution to form spinning stock solution, and performing dry spinning to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Wherein:

in the prepolymerization step, the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate.

The polyether glycol comprises one or more of polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol or poly 2-methyltetrahydrofuran, and the molecular weight is 1500-4000.

In the step of chain extension reaction, the mixed amine solution comprises a chain extender, a cross-linking agent, a terminator and DMAC; the mass concentration range of the mixed amine solution is 5-12%.

The chain extender is a mixture of ethylenediamine and 4, 4-diaminodicyclohexylmethane; the molar ratio of the ethylenediamine to the 4, 4-diaminodicyclohexylmethane is (8.5-19): 1.

the cross-linking agent is diethyl triamine (DETA); the terminator is diethylamine.

The molar ratio (12-16) of the chain extender to the terminator is as follows: 1, the addition amount of the cross-linking agent accounts for 0.006-0.02% of the total mass of the fiber.

The polyurethane urea stock solution is selectively added with functional additives, including one or more of an antioxidant, an ultraviolet absorbent, a lubricant, a dyeing assistant and a stabilizer.

The addition amount of the functional additive is calculated according to the mass of the obtained spandex fiber, and the antioxidant: 0.1-15%, ultraviolet absorbent: 0.1-0.5%, lubricant: 0.1-1.0%, dyeing assistant: 0.1-1.0%, stabilizer: 0.01 to 0.1 percent.

The stabilizer is alkane diamine with lateral methyl, and the number of main chain carbons is not more than 8.

The functional additive slurry is DMAC mixed liquor with the solid content of 35%, and the pH value of the functional additive slurry is 7-9.

Has the advantages that: in the production process of spandex, amine solution formed by mixing a plurality of chain extenders, terminators and cross-linking agents is introduced for chain extension reaction, so that spandex fibers have high resilience; the spandex fiber has high uniformity by controlling solvent indexes, stabilizing polymerization process conditions and introducing a gel removal agent; the spandex fiber has high temperature resistance by controlling the proportion of the mixed amine and compounding various antioxidants in the additive. The high-resilience high-uniformity high-temperature-resistant spandex fiber is obtained by the method.

Detailed Description

The invention regulates and controls the strict control of various formula monomer types, chain extender types, cross-linking agent types, additive types and technological process, so that the spandex fiber can meet the level requirements of high resilience, high uniformity and high temperature resistance.

The method comprises the following steps:

(1) prepolymerization reaction

Reacting diisocyanate and polyether diol in a molar ratio (1.56-2.00) to 1 to obtain an NCO-terminated prepolymer;

and dissolving the prepolymer and a solvent to form a prepolymer solution with the concentration of 30-38%.

(2) Chain extension reaction

And (3) carrying out mixing reaction on the prepolymer solution and the mixed amine solution to obtain a polyurethane urea stock solution with the concentration of 30-38%, wherein the molar ratio of the terminal amine in the mixed amine solution to the NCO in the prepolymer solution is (1.01-1.04): 1.

(3) Curing the spun yarn

Curing the polyurethane urea stock solution to form spinning stock solution, and performing dry spinning to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

In the step of prepolymerization, the reaction time is 1.5-4 hours, and the reaction temperature is 70-90 ℃;

in the step of prepolymerization, the solvent is Dimethylacetamide (DMAC);

in the prepolymerization step, the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate;

the polyether glycol has a selective molecular weight of 1500-4000 and comprises one or more of polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol and poly 2-methyltetrahydrofuran.

In the step of chain extension reaction, the reaction temperature is less than or equal to 100 ℃;

in the step of chain extension reaction, the mixed amine solution comprises a chain extender, a cross-linking agent, a terminator and DMAC;

the chain extender comprises a mixture of ethylenediamine and 4, 4-diaminodicyclohexylmethane;

the molar ratio of the ethylenediamine to the 4, 4-diaminodicyclohexylmethane is (8.5-19): 1;

the cross-linking agent is diethyl triamine DETA;

the terminator is diethylamine;

the molar ratio (12-16) of the chain extender to the terminator is as follows: 1, the addition amount of the cross-linking agent accounts for 0.006-0.02% of the total mass of the fiber;

the mass concentration range of the mixed amine solution is 5-12%.

In the step of curing spinning, the curing temperature is 40-60 ℃ and the time is 24-45 hours.

Functional additives commonly used in the field can be selectively added into the polyurethane urea stock solution, and comprise one or more than one of an antioxidant, an ultraviolet absorbent, a lubricant, a dyeing auxiliary agent and a stabilizer.

Preferably, the functional additives include:

antioxidant: 0.1 to 15 percent

Ultraviolet absorber: 0.1 to 0.5 percent

Lubricant: 0.1 to 1.0%

Dyeing auxiliary agent: 0.1 to 1.0%

A stabilizer: 0.01 to 0.1 percent

Wherein the stabilizer is alkane diamine with side methyl, the number of main chain carbons is not more than 8,

the addition amount of the functional additive is calculated according to the mass of the obtained spandex fiber.

The functional additive slurry is DMAC mixed liquor with the solid content of 35%, and the pH value of the functional additive slurry is 7-9.

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

In the embodiment of the invention, the dimethylacetamide is a solvent purified by a rectifying tower and exchange resin, the water content of DMAC is less than or equal to 50ppm, the conductance is less than or equal to 0.05 mu S, and the pH value is as follows: 6.3-7.3, and the purity is more than or equal to 99.95%.

Preferably, the functional additives include:

antioxidant 1790: 0.1 to 1.0%

Antioxidant 626: 0.1 to 0.5 percent

Ultraviolet absorber UV-320: 0.1 to 0.5 percent

Lubricant magnesium stearate: 0.1 to 1.0%

Dyeing assistant 4, 4' -dicyclohexylmethane diisocyanate polymer with N-tert-butyldiethanolamine: 0.1 to 1.0%

A stabilizer: 0.01 to 0.1 percent

Wherein the stabilizer is alkane diamine with side methyl, and the number of main chain carbons is not more than 8.

The functional additive slurry is DMAC mixed liquor with the solid content of 35%, and the pH value of the functional additive slurry is 7-9. The addition amount of the functional additive is calculated according to the mass of the obtained spandex fiber.

Comparative example 1

4, 4' -diphenylmethane diisocyanate with the flow rate of 110g/min and polytetramethylene ether glycol with the flow rate of 579g/min and the molecular weight of 1800 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35.5 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 1, 2-propanediamine and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 9:1:0.77, and the addition amount of the diethyltriamine accounts for the mass of the silk thread: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein an antioxidant 1790 accounts for the mass of the silk threads: 1.0 percent, and the ultraviolet absorbent UV-320 accounts for the mass of the silk thread: 0.2 percent, and lubricant magnesium stearate accounting for the mass of the silk thread: 0.22 percent of dyeing auxiliary agent 4, 4' -dicyclohexylmethane diisocyanate and N-tertiary butyl diethanol amine, wherein the polymer accounts for the mass of the silk threads: and (3) curing the mixture by using a storage tank to obtain spinning stock solution with the pH value of 7.4 and 1.0%, and carrying out dry spinning on the stock solution to obtain the conventional spandex fiber.

Comparative example 2

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 1, 4-diaminocyclohexane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution through curing in a storage tank, and spinning the stock solution by a dry method to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Comparative example 3

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 1, 2-propanediamine and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 1

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution through curing in a storage tank, and spinning the stock solution by a dry method to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Example 2

4, 4' -diphenylmethane diisocyanate with the flow rate of 91g/min and polytetramethylene ether glycol with the flow rate of 373g/min and the molecular weight of 1800 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35.5 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 9:1:0.67, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.1%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.2% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.1% and the pH of the slurry was 8.4. And (3) obtaining spinning stock solution through curing in a storage tank, and spinning the stock solution by a dry method to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Example 3

4, 4' -diphenylmethane diisocyanate with the flow rate of 108g/min and polytetramethylene ether glycol with the flow rate of 457g/min and the molecular weight of 1800 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35.5 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 9:1:0.75, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 0.8%, antioxidant 626: 0.15%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.2% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.03%, and the pH of the slurry was 7.8. And (3) obtaining spinning stock solution through curing in a storage tank, and spinning the stock solution by a dry method to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Example 4

4, 4' -diphenylmethane diisocyanate with the flow rate of 113g/min and polytetramethylene ether glycol with the flow rate of 474g/min and the molecular weight of 2600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with an end NCO end capping, and the prepolymer is prepared into a prepolymer solution with the concentration of 35.5 percent through a dissolving machine. And (3) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.4, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.2%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.22% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05% and the pH of the slurry was 8.2. And (3) obtaining spinning stock solution through curing in a storage tank, and spinning the stock solution by a dry method to obtain the high-resilience, high-uniformity and high-temperature-resistant spandex fiber.

Example 5

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 6

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0% and the pH of the slurry was 7.5. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 7

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, dodecyl diamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 8

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 19:1:1.5, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 168: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.4. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 9

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (2) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 7:1:0.60, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

Example 10

4, 4' -diphenylmethane diisocyanate with the flow rate of 90g/min and polytetramethylene ether glycol with the flow rate of 374g/min and the molecular weight of 1600 are uniformly mixed in a static mixer, the mixture is heated to 90 ℃ to react for 4 hours to obtain a prepolymer with the end NCO being blocked, and the prepolymer is prepared into a prepolymer solution with the concentration of 35 percent through a dissolving machine. And (3) placing the prepolymer solution and the mixed amine solution into a second reactor for reaction, wherein the reaction temperature is 90 ℃, the ethylenediamine, the 4, 4-diaminodicyclohexylmethane and the diethylamine in the mixed amine solution are mixed according to the molar ratio of 22:1:1.73, and the addition amount of the diethyltriamine is as follows: 0.008 percent. Adding additive slurry into stock solution obtained after chain extension in a mixing tank, wherein the ratio of antioxidant 1790: 1.0%, antioxidant 626: 0.3%, ultraviolet absorber UV-320: 0.2%, lubricant magnesium stearate: 0.15% of a polymer of dyeing auxiliary 4, 4' -dicyclohexylmethane diisocyanate and N-tert-butyldiethanolamine: 1.0%, stabilizer 2-methylpentamethylenediamine: 0.05%, and the pH of the slurry was 8.0. And (3) obtaining spinning stock solution by curing in a storage tank, and spinning the stock solution by a dry method to obtain the spandex fiber.

The test method comprises the following steps: the test methods involved in the present invention are as follows

And (3) viscosity testing: the dope was placed in a viscometer, and the apparent viscosity of the dope was measured at 40 ℃.

And (3) elastic recovery test: and vertically clamping the silk thread on a clamping opening of a universal drawing machine, drawing the silk thread for 5 times in length, staying for 60 seconds in the 5 th time, and drawing to break the silk in the 6 th time. Elastic recovery rate (3 times length of filament-6 th time to no tension out length)/2 times length of filament x 100%

Variation CV test of dynamic unwind stress value data: and detecting the variation coefficient of the tension of the spandex yarn under a fixed drafting multiplying power under the condition of a fixed input and output speed by adopting an electronic constant tension transmission unwinder.

And (3) high temperature resistance test: setting the temperature of the oven at 185 ℃, and stripping the outer layer wires of the spinning cakes. Winding the wire on a square iron frame for 15-20 circles, and then drawing the finished wire by using a rectangular iron frame. After being placed in an oven for 1 minute, the mixture was cooled at room temperature. Preparing a dye solution in an iron cup: 0.4g of dispersing orange, 0.33g of dispersing agent, 0.17g of leveling agent and 120g of water, and the pH value of the dye solution is adjusted to 6 by using acetic acid with the pH value of 6.5. The drawn silk is immersed in the dyeing liquor and the iron cup is placed at the temperature of 40 ℃ in the high-temperature high-pressure sample dyeing machine. The temperature is raised to 130 ℃ and kept for 40 minutes, and samples are prepared for secondary high temperature resistance experiments. The sample is taken out and tested by a universal drawing machine, and the ratio of the breaking strength to the breaking strength without high-temperature treatment represents the high-temperature resistance level.

Table 1: comparison result of performance of the example of the invention and the conventional spandex comparative example

As can be seen from Table 1, the spandex filament prepared by the invention has greatly improved resilience (elasticity recovery test), certain improved uniformity (unwinding stress variation coefficient) and greatly improved high temperature resistance level.

The invention has been described in terms of detailed embodiments and specific examples. It will be apparent to persons skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.