CN112281247B - Method for preparing high-uniformity spandex through continuous polymerization - Google Patents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- 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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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—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
- C08G18/6685—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 C08G18/3225 or polyamines of C08G18/38
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The method for preparing the high-uniformity spandex by continuous polymerization comprises the following steps: prepolymerization: continuously adding polytetramethylene ether glycol, diphenylmethane diisocyanate and a polymerization inhibitor into a tubular static mixer for mixing, reacting and cooling to obtain a prepolymer with NCO of 1.0-4.0% by mass; polymerization: continuously adding the prepolymer and a dimethylacetamide solvent into a dynamic mixer A for uniform mixing and dispersion to obtain a prepolymer solution with the mass concentration of 30-70%; continuously adding the prepolymer solution and the mixed amine solution into a dynamic mixer B for chain extension reaction; curing and spinning: adding a gel removing agent into the polyurethane urea solution, and fully stirring and mixing; and (3) after curing, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
Description
Technical Field
The invention relates to a method for preparing high-uniformity spandex by continuous polymerization, belonging to the technical field of polyurethane elastic fiber material manufacture.
Background
Spandex is a special textile fiber and is widely applied to the fields of various covered yarns, circular knitting machines and warp knitting fabrics. The fields with higher requirement on the uniformity of spandex are high-grade circular knitting machines and warp knitting fabrics, and the uniformity of the conventional spandex basically cannot meet the use requirement. Aiming at the uniformity improvement of spandex products, a great deal of research work is done by spandex manufacturers and researchers at home and abroad on key preparation technology in the spandex production process, and the following approaches are mainly concluded:
1. the preparation of spandex with high uniformity by improving the uniformity of prepolymers and stock solutions in the spandex production process is currently the most common technical means. The patent CN105624822A controls the molecular weight and molecular distribution of the polymer by reducing solvent impurities and small molecular impurities in the raw materials, and the uniformity of the spandex yarn coil is obviously improved. Patent CN101096782B carries out solution polymerization in low temperature solvent through changing current bulk polymerization mode, has improved the degree of consistency of prepolymerization midbody and polymerization stoste, prepares homogeneous, pure prepolymer, and the high-quality polyurethane elastic fiber who prepares has advantages such as shaping is good, the evenness of yarn is excellent, has simplified production control. The polyurethaneurea component prepared in patent CN1250783C has both alkyl urethane and monoalkylurea end groups, the ratio of monoalkylurea end groups to alkyl urethane end groups being at least about 1:1 and at most about 5.4: 1.
2. By adopting more excellent or efficient key equipment such as polymerization, spinning and the like, the method is also one of the current technical means for improving the uniformity of spandex. The dynamic mixer disclosed by patent CN207898787U directly changes the addition of additives in the polymer stock solution into dynamic mixing, greatly improves the efficiency of the whole production line, and stably improves the uniformity of products. The false twisting unit disclosed in patent CN107956009A has no contact and abrasion of moving parts, and excellent uniformity, and overcomes the defects of high running cost, poor uniformity, high noise, high labor intensity and the like of the conventional false twister. The literature, "research and application on spinning channels of spandex fibers" also reports that theoretical research and experiments on the spinning channels show that: the aperture ratio of the pore plate of the spinning channel is optimized, the blowing uniformity is improved, and the uniformity of the quality of spandex fibers can be improved.
Because the spandex production process is complex and the control difficulty is high, the spandex uniformity influence factors are numerous. Most of the researches only analyze a single factor, and the overall research on the production process of spandex is lacked, so that the effect of the spandex is still insufficient in industrial application. The invention designs and bases on the continuous polymerization production conditions and production process of the prior dry spinning spandex, systematically studies the uniformity of the spandex and provides corresponding solving measures.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a method for preparing high-uniformity spandex by continuous polymerization so as to solve the technical problem.
The technical scheme is as follows: the invention relates to a method for preparing high-uniformity spandex by continuous polymerization, which comprises the following steps:
step 1, prepolymerization: continuously adding polytetramethylene ether glycol, diphenylmethane diisocyanate and a polymerization inhibitor into a tubular static mixer for mixing, reacting and cooling to obtain a prepolymer with NCO of 1.0-4.0% by mass;
step 2, polymerization: continuously adding the prepolymer and a dimethylacetamide solvent into a dynamic mixer A for uniform mixing and dispersion to obtain a prepolymer solution with the mass concentration of 30-70%; continuously adding the prepolymer solution and the mixed amine solution into a dynamic mixer B for chain extension reaction, wherein the ratio of amine end groups to NCO end groups is 1.01-1.1: 1, so as to obtain a low-viscosity polyurethane urea solution, and conveniently controlling the viscosity growth rate and the final spinning viscosity of the polyurethane stock solution in the curing process;
step 3, curing spinning: adding a gel removing agent into the polyurethane urea solution, and fully stirring and mixing; and (3) after curing, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
Wherein the content of the first and second substances,
the polymerization inhibitor is any one of acetyl chloride, benzoyl chloride, oxalyl chloride, hydrochloric acid or phosphoric acid.
The polymerization inhibitor accounts for 100-2000 ppm of the mass of the prepolymer;
the mixed amine solution is a mixture of a chain extender and a permanent chain terminator;
the chain extender is any one of ethylenediamine, 1, 3-propanediamine or 1, 4-butanediamine;
the permanent chain terminator is monoamine with 3-20 carbon atoms;
the permanent chain terminator is a linear monoamine with 10-20 carbon atoms and/or a cyclic monoamine with 4-20 carbon atoms.
Further, the number of carbon atoms contained in the linear monoamine is any one of 14, 15, 16, 17, 18, 19 and 20;
further, the number of carbon atoms contained in the cyclic monoamine is any one of 6, 8, 10, 12, 14, 16, 18 and 20;
further, the number of carbon atoms contained in the linear monoamine is any one of 16, 17, 18, 19 and 20;
the molar ratio of the amine end groups of the chain extender to the amine end groups of the permanent chain terminator is 20-30: 1.
The viscosity of the low-viscosity polyurethane urea solution is 500-1000 poise at 40 ℃; the viscosity growth rate of the polyurethane stock solution is 60-100 poise per hour; the final spinning viscosity is 3000-4000 poise at 40 ℃.
The gel removing agent is aliphatic secondary amine.
The aliphatic secondary amine is any one of dibutylamine, dihexylamine, dioctylamine or didecylamine.
The gel removing agent accounts for 50-3000 ppm of the spandex filament.
In the spinning step, functional additives such as an antioxidant and an cohesion auxiliary are selectively added.
Has the advantages that: the invention adopts a continuous polymerization method to prepare the spandex with high uniformity, and has the following advantages: (1) the invention uses a continuous polymerization mode, and all raw and auxiliary materials are stably added, so that the spinning product has no batch difference; (2) the invention has stable process, and effectively improves the uniformity of the prepolymer by optimizing prepolymerization reaction; in the chain extension reaction stage, through the synergistic cooperation of the linear chain diamine and the permanent chain terminator, the mechanical property of the spandex is not reduced, the temperature resistance is obviously improved, and more importantly, the structural regularity and the uniformity of the polymer are obviously improved. (3) The spinning solution of the invention basically does not produce gel in the storage process, the solution does not have interlayer difference, and the uniformity of the spinning product can be ensured after the solution is cured under the conditions of low viscosity and high fluidity; compared with the conventional product, the dynamic unwinding stress variation coefficient CV value of the spandex with high uniformity is greatly reduced, and the stress fluctuation R value is smaller.
Detailed Description
The invention is described in detail below with reference to examples, which are not to be construed as limiting the invention in any way.
The first embodiment is as follows:
(1) adding the polytetramethylene ether glycol 476.7g/min, the diphenylmethane diisocyanate 110.9g/min and the phosphoric acid 0.6g/min into a tubular static mixer continuously for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A for uniform mixing and dispersion according to the flow rates of 587.7g/min of the prepolymer and 904.2g/min of a dimethylacetamide solvent to obtain a prepolymer solution; continuously adding the prepolymer solution into a dynamic mixer B for amine reaction according to the flow rates of 1491.2g/min of the prepolymer solution and 247.3g/min of the mixed amine solution, wherein the chain extender in the mixed amine is ethylenediamine, the permanent chain terminator is cyclooctylamine, and the molar ratio of the ethylenediamine to the amine end group of the cyclooctylamine is 22: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 800poise at 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the gel removing agent in the functional auxiliary agent is dibutylamine, and the mass ratio of the dibutylamine is 0.17%; curing for 30hr until the spinning viscosity reaches 3700poise, and spraying and stretching the polyurethane stock solution into filaments by a dry spinning system, wherein the high-uniformity spandex is obtained along with solvent volatilization and drying.
The second embodiment is as follows:
(1) adding the polytetramethylene ether glycol 556.1g/min, the diphenylmethane diisocyanate 129.4g/min and the acetyl chloride 1.4g/min into a tubular static mixer continuously and uninterruptedly for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A for uniform mixing and dispersion according to the flow rates of 685.6g/min of the prepolymer and 1054.9g/min of a dimethylacetamide solvent to obtain a prepolymer solution; continuously adding the prepolymer solution 1740.5g/min and the mixed amine solution 288.6g/min into a dynamic mixer B for amine reaction, wherein the chain extender in the mixed amine is 1, 3-propane diamine, the permanent chain terminator is octadecylamine, and the molar ratio of the amine end groups of the 1, 3-propane diamine to the octadecylamine is 30: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 1000poise at 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the gel removing agent in the functional auxiliary agent is dioctylamine, and the mass ratio of the gel removing agent in the functional auxiliary agent is 0.3%; curing for 30hr, spraying and stretching the polyurethane spinning solution to form filament with the aid of a dry spinning system after the spinning viscosity reaches 4000poise, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
The third embodiment is as follows:
(1) adding the polytetramethylene ether glycol 476.7g/min, the diphenylmethane diisocyanate 110.9g/min and the phosphoric acid 0.6g/min into a tubular static mixer continuously for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A for uniform mixing and dispersion according to the flow rates of 587.7g/min of the prepolymer and 904.2g/min of a dimethylacetamide solvent to obtain a prepolymer solution; continuously adding the prepolymer solution into a dynamic mixer B for amine reaction according to the flow rates of 1491.2g/min of the prepolymer solution and 247.3g/min of the mixed amine solution, wherein the chain extender in the mixed amine is ethylenediamine, the permanent chain terminator is cyclooctylamine, and the molar ratio of the ethylenediamine to the amine end group of the cyclooctylamine is 18: 1; controlling the adding amount of excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 700poise at 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the gel removing agent in the functional auxiliary agent is dibutylamine, and the mass ratio of the dibutylamine is 0.17%; curing for 30hr, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system after the spinning viscosity reaches 3300poise, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
The first comparative example:
(1) continuously adding the polytetramethylene ether glycol 476.7g/min and the diphenylmethane diisocyanate 110.9g/min into a tubular static mixer for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A at the flow rates of 587.7g/min of the prepolymer and 904.2g/min of a dimethylacetamide solvent for uniform mixing and dispersion to obtain a prepolymer solution; continuously adding the prepolymer solution into a dynamic mixer B for amine reaction according to the flow rates of 1491.2g/min of the prepolymer solution and 247.3g/min of the mixed amine solution, wherein the chain extender in the mixed amine is ethylenediamine, the permanent chain terminator is cyclooctylamine, and the molar ratio of the ethylenediamine to the amine end group of the cyclooctylamine is 22: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 800poise at 40 ℃;
(3) adding the functional assistant into the polyurethane urea solution according to the flow of 72.8g/min, and fully stirring and mixing, wherein the gel removing agent in the functional assistant is dibutylamine, and the mass ratio of the dibutylamine to the functional assistant is 0.17%; curing for 30hr, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system after the spinning viscosity reaches 4000poise, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
Comparative example two:
(1) adding the polytetramethylene ether glycol 556.1g/min, the diphenylmethane diisocyanate 129.4g/min and the acetyl chloride 1.4g/min into a tubular static mixer continuously and uninterruptedly for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A for uniform mixing and dispersion according to the flow rates of 685.6g/min of the prepolymer and 1054.9g/min of a dimethylacetamide solvent to obtain a prepolymer solution; continuously adding the prepolymer solution into a dynamic mixer B for amine reaction according to the flow rates of 1740.5g/min of the prepolymer solution and 288.6g/min of the mixed amine solution, wherein the chain extender in the mixed amine is 1, 3-propane diamine, the permanent chain terminator is diethylamine, and the molar ratio of the amine end groups of the 1, 3-propane diamine to the diethylamine is 30: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 1200poise at the temperature of 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the gel removing agent in the functional auxiliary agent is dioctylamine, and the mass ratio of the gel removing agent in the functional auxiliary agent is 0.3%; curing for 30hr until the spinning viscosity reaches 4500poise, spraying and stretching the polyurethane spinning solution to form filament with the aid of a dry spinning system, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
Comparative example three:
(1) adding the polytetramethylene ether glycol 556.1g/min, the diphenylmethane diisocyanate 129.4g/min and the acetyl chloride 1.4g/min into a tubular static mixer continuously and uninterruptedly for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A for uniform mixing and dispersion according to the flow rates of 685.6g/min of the prepolymer and 1054.9g/min of a dimethylacetamide solvent to obtain a prepolymer solution; continuously adding the prepolymer solution 1740.5g/min and the mixed amine solution 288.6g/min into a dynamic mixer B for amine reaction, wherein the chain extender in the mixed amine is 1, 3-propane diamine, the permanent chain terminator is octadecylamine, and the molar ratio of the amine end groups of the 1, 3-propane diamine to the octadecylamine is 30: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 1000poise at 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the functional auxiliary agent does not contain a gel removing agent; curing for 30hr, spraying and stretching the polyurethane spinning solution into filaments by a dry spinning system after the spinning viscosity reaches 4000poise, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
Comparative example four:
(1) continuously adding the polytetramethylene ether glycol 476.7g/min and the diphenylmethane diisocyanate 110.9g/min into a tubular static mixer for mixing, reacting and cooling to obtain a prepolymer;
(2) continuously and uninterruptedly adding the prepolymer into a dynamic mixer A at the flow rates of 587.7g/min of the prepolymer and 904.2g/min of a dimethylacetamide solvent for uniform mixing and dispersion to obtain a prepolymer solution; continuously adding the prepolymer solution 1491.2g/min and the mixed amine solution 247.3g/min into a dynamic mixer B for amine reaction, wherein the chain extender in the mixed amine is a mixture of ethylenediamine and 1, 2-propylene diamine, the molar ratio of the ethylenediamine to the 1, 2-propylene diamine is 95:5, the chain terminator is diethylamine, and the molar ratio of the chain extender to the amine end group of the chain terminator is 15: 1; controlling the adding amount of the excessive amine to obtain a polyurethane urea solution with the apparent viscosity of 1400poise at the temperature of 40 ℃;
(3) adding the functional auxiliary agent into the polyurethane urea solution according to the flow of 72.8g/min, fully stirring and mixing, wherein the functional auxiliary agent does not contain a gel removing agent; curing for 30hr, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system after the spinning viscosity reaches 5200poise, and volatilizing and drying the solvent to obtain the high-uniformity spandex.
The products of the above-mentioned embodiment and comparative example and conventional products were tested and compared (40D is an example):
TABLE 1 Spandex Performance comparison
Wherein SS300 is the stress of the product when the product is stretched by 300 percent, and the high temperature resistance is the tensile breaking strength retention rate of the product after the product is stretched by 2.5 times at 130 ℃ for 40 min.
In combination with the data of table 1, it can be found that: the high-uniformity spandex product prepared by the scheme designed by the invention can ensure the mechanical property and high-temperature resistance required in the subsequent use process, and the CV value and fluctuation R value of the dynamic unwinding stress variation coefficient are greatly reduced compared with those of the conventional product, so that the uniformity of the product is remarkably improved.
Claims (6)
1. A method for preparing high-uniformity spandex by continuous polymerization is characterized by comprising the following steps:
step 1, prepolymerization: continuously adding polytetramethylene ether glycol, diphenylmethane diisocyanate and a polymerization inhibitor into a tubular static mixer for mixing, reacting and cooling to obtain a prepolymer with NCO of 1.0-4.0% by mass;
step 2, polymerization: continuously adding the prepolymer and a dimethylacetamide solvent into a dynamic mixer A for uniform mixing and dispersion to obtain a prepolymer solution with the mass concentration of 30-70%; continuously adding the prepolymer solution and the mixed amine solution into a dynamic mixer B for chain extension reaction, wherein the ratio of amine end groups to NCO end groups is 1.01-1.1: 1, so as to obtain a low-viscosity polyurethane urea solution, and conveniently controlling the viscosity growth rate and the final spinning viscosity of the polyurethane stock solution in the curing process;
step 3, curing spinning: adding a gel removing agent into the polyurethane urea solution, and fully stirring and mixing; after curing, spraying and stretching the polyurethane stock solution into filaments by a dry spinning system, and volatilizing and drying the solvent to obtain high-uniformity spandex;
the mixed amine solution is a mixture of a chain extender and a permanent chain terminator;
the chain extender is any one of ethylenediamine, 1, 3-propanediamine or 1, 4-butanediamine;
the permanent chain terminator is a linear chain monoamine with 10-20 carbon atoms and/or a cyclic monoamine with 4-20 carbon atoms;
the polymerization inhibitor is any one of acetyl chloride, benzoyl chloride, oxalyl chloride, hydrochloric acid or phosphoric acid;
the gel removing agent is aliphatic secondary amine, and the aliphatic secondary amine is any one of dibutylamine, dihexylamine, dioctylamine or didecylamine.
2. The method for preparing highly uniform spandex through continuous polymerization according to claim 1, wherein the polymerization inhibitor accounts for 100 to 2000ppm of the mass of the prepolymer.
3. The continuous polymerization method for preparing high-uniformity spandex according to claim 1, wherein the molar ratio of the amine end groups of the chain extender to the permanent chain terminator is 20-30: 1.
4. The method for preparing highly uniform spandex through continuous polymerization according to claim 1, wherein the low-viscosity polyurethaneurea solution has a viscosity of 500 to 1000poise at 40 ℃; the viscosity growth rate of the polyurethane stock solution is 60-100 poise per hour; the final spinning viscosity is 3000-4000 poise at 40 ℃.
5. The method for preparing spandex with high uniformity by continuous polymerization according to claim 1, wherein the gel removal agent accounts for 50-3000 ppm of spandex filament.
6. The method for preparing spandex with high uniformity by continuous polymerization according to claim 1, wherein functional aids of antioxidants and cohesion aids are selectively added in the spinning step.
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| KR100780434B1 (en) * | 2006-07-11 | 2007-11-29 | 태광산업주식회사 | Polyurethaneurea elastic fiber and method for preparation thereof |
| CN101096782B (en) * | 2007-07-06 | 2010-04-21 | 烟台氨纶股份有限公司 | Method for preparing polyurethane snapback fibre with solution polymerization |
| CN104559734B (en) * | 2015-01-26 | 2017-04-19 | 徐州卧牛山新型防水材料有限公司 | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof |
| CN105483856B (en) * | 2015-12-29 | 2017-10-17 | 浙江华峰氨纶股份有限公司 | A kind of method that in-situ polymerization prepares ageing resistance by ultraviolet light spandex |
| CN105908281A (en) * | 2016-04-28 | 2016-08-31 | 浙江开普特氨纶有限公司 | Dyeable spandex fiber preparation method |
| CN109487361B (en) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | Spandex fiber with good heat resistance and low-temperature setting property and preparation method thereof |
| CN109881291A (en) * | 2019-02-18 | 2019-06-14 | 华峰重庆氨纶有限公司 | A kind of acid dyes is easily painted the preparation method of spandex |
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2020
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