CN112127006A - Easy-to-dye spandex fiber and preparation method thereof - Google Patents
Easy-to-dye spandex fiber and preparation method thereof Download PDFInfo
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- CN112127006A CN112127006A CN202010864827.2A CN202010864827A CN112127006A CN 112127006 A CN112127006 A CN 112127006A CN 202010864827 A CN202010864827 A CN 202010864827A CN 112127006 A CN112127006 A CN 112127006A
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- diphenylmethane diisocyanate
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 60
- 239000004759 spandex Substances 0.000 title claims abstract description 60
- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 67
- 238000004043 dyeing Methods 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000006224 matting agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 79
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—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
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
An easy-to-dye spandex fiber and a preparation method thereof, 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol are subjected to prepolymerization reaction to obtain a prepolymer with isocyanate end capping, and the prepolymer is dissolved in a solvent to form a prepolymerization solution; carrying out chain extension reaction on the pre-polymerization solution and the mixed amine to obtain a polyurethane polymer solution with the required viscosity; adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber. Compared with the common spandex fiber, the easy-dyeing spandex product prepared by the invention has more excellent dye uptake and better color fastness.
Description
Technical Field
The invention relates to a fiber preparation method, in particular to an easily-dyed spandex fiber and a preparation method thereof.
Background
Because the molecular structure of the spandex is free of coloring groups, the spandex is often dyed insufficiently under normal dyeing conditions when being blended with other fibers and is dyed under excessively intense dyeing conditions, and the elasticity and the use of the fabric are affected due to the fact that spandex filaments are melted. With the increasing requirements of people on the quality of elastic fabrics, overcoming the dyeing defect of spandex becomes urgent.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a novel easy-to-dye spandex fiber and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an easy-to-dye spandex fiber comprises the following steps:
(1) carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution;
(2) carrying out chain extension reaction on the pre-polymerization solution and the mixed amine to obtain a polyurethane polymer solution with the required viscosity;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber.
The further improvement of the invention is that in the step (1), the using amount of the 2, 4-diphenylmethane diisocyanate is 5-20% of the mass of the 4, 4-diphenylmethane diisocyanate.
The invention further improves the method that in the step (1), the molar ratio of the total substance amount of the 2, 4-diphenylmethane diisocyanate and the 4, 4-diphenylmethane diisocyanate to the polytetramethylene ether glycol is (1.65-2.15): 1.
the invention further improves the method in that in the step (1), the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is 30-35% of that of the prepolymer solution.
The invention is further improved in that the temperature of the polymerization reaction is 65-75 ℃ and the time is 45-90 min.
The further improvement of the invention is that in the step (2), the molar ratio of the isocyanate at the end of the prepolymer to the amine group in the mixed amine is 1: (1.02-1.05).
The further improvement of the invention is that in the step (2), the mixed amine is a mixture of ethylenediamine and diethylamine, wherein the molar ratio of ethylenediamine to diethylamine is (6-9): 1; the temperature of the chain extension reaction is 85-95 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s.
The invention is further improved in that in the step (3), the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent.
The further improvement of the invention is that in the step (3), the mass of the antioxidant is 0.5-2.0% of the solid content of the spinning solution, the mass of the lubricant is 0.1-0.5% of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 0.5-2.5% of the solid content of the spinning solution, the mass of the dyeing assistant is 0.5-2.5% of the solid content of the spinning solution, and the matting agent accounts for 0.5-1.5% of the solid content of the spinning solution.
An easy-dyeing spandex fiber, the dye-uptake of which is 94.3-99.5% and the color fastness is 82.3-89.3%.
Compared with the prior art, the invention has the beneficial effects that:
compared with the dyeing performance of common spandex products, the easy-to-dye spandex fiber prepared by the method has more excellent dyeing property and color fastness. This is mainly because the spandex molecular chain mainly includes two parts, namely a hard segment region and a soft segment region, wherein the hard segment region serves as a main dyeing-suitable part of the dye. The main raw material diisocyanate for providing the hard chain segment function by the conventional spandex is only 4, 4-diphenylmethane diisocyanate (4,4-MDI), the regularity of the hard chain segment of the finally formed spandex molecular chain is high, the molecular chain segments in a crystal region are tightly stacked, dye molecules cannot diffuse into the crystal region, and the dye uptake is very low. According to the invention, one kind of 4, 4-diphenylmethane diisocyanate (4,4-MDI) is changed into two kinds of 4, 4-diphenylmethane diisocyanate (4,4-MDI) and 2, 4-diphenylmethane diisocyanate (2,4-MDI) by changing the proportion of main raw material diisocyanate, the regularity of a hard chain segment crystalline region in a spandex molecular chain is damaged, dye molecules can be diffused into the crystalline region in the later dyeing process and are not easy to separate, and the dye uptake and the color fastness of spandex fibers are greatly improved.
Detailed Description
The present invention will be described in detail below with reference to specific examples.
The invention relates to a preparation method of an easy-to-dye spandex fiber, which comprises the following steps:
(1) carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol (PTMG) at 65-75 ℃ for 45-90min to prepare a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution;
(2) carrying out chain extension reaction on the pre-polymerization solution and the mixed amine through a dynamic mixer in proportion, and controlling the temperature of the dynamic mixer to be 85-95 ℃ to prepare a polyurethane polymer solution with required viscosity;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing the mixture by a static mixer to obtain a spinning stock solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber.
Preferably, in the step (1), the amount of the 2, 4-diphenylmethane diisocyanate is 5-20% of the mass of the 4, 4-diphenylmethane diisocyanate.
Preferably, in the step (1), the molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate (4,4-MDI) to the polytetramethylene ether glycol is (1.65-2.15): 1;
preferably, in the step (1), the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass addition ratio of the prepolymer to the solvent is 1: (30-35).
Preferably, in the step (2), in the chain extension reaction, the molar ratio of the isocyanate at the end of the prepolymer to the amine group in the mixed amine is 1: (1.02-1.05);
preferably, in the step (2), the mixed amine is a mixed amine of ethylenediamine and diethylamine, wherein the molar ratio of ethylenediamine to diethylamine is (6-9): 1;
preferably, in the step (2), the viscosity of the polyurethane polymer prepared after the chain extension is completed is 200-500 PA.s;
preferably, in the step (3), the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent.
Preferably, the antioxidant accounts for 0.5-2.0% of the mass of the solid content of the final spinning dope, the lubricant accounts for 0.1-0.5% of the mass of the solid content of the final spinning dope, the chlorine-resistant agent accounts for 0.5-2.5% of the mass of the solid content of the final spinning dope, the dyeing assistant accounts for 0.5-2.5% of the mass of the solid content of the final spinning dope, and the matting agent accounts for 0.5-1.5% of the mass of the solid content of the final spinning dope.
The dye-uptake rate of the easy-to-dye spandex fiber prepared by the method is 94.3-99.5%, and the color fastness is 82.3-89.3%.
The following are specific examples.
Example 1
Carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate (2,4-MDI), 4-diphenylmethane diisocyanate (4,4-MDI) and polytetramethylene ether glycol (PTMG) at 70 ℃ for 60min to obtain a prepolymer with isocyanate groups at two ends, wherein the molar ratio of the total mass of the 2, 4-diphenylmethane diisocyanate and the 4, 4-diphenylmethane diisocyanate to the polytetramethylene ether glycol is 2.03: 1; the amount of 2, 4-diphenylmethane diisocyanate used was 5% by mass of 4, 4-diphenylmethane diisocyanate. Then, adding the prepolymer with isocyanate groups at two ends into N, N-dimethylacetamide, and dissolving to obtain 35 wt% of prepolymer solution;
adding ethylenediamine and diethylamine into the prepolymerization solution, carrying out chain extension reaction at 90 ℃ to obtain a polyurethane solution with the viscosity of 200-500PA.s, adding an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent into the polyurethane polymer solution, uniformly mixing to obtain a spandex spinning stock solution with the solid content of 35%, curing the spinning stock solution, and spinning. Wherein, the mass of the antioxidant is 1.0 percent of the solid content of the spinning solution, the mass of the lubricant is 0.2 percent of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 1.5 percent of the solid content of the spinning solution, and the mass of the dyeing assistant is the spinning solution; the molar ratio of ethylenediamine to diethylamine was 6.8: the mass of 1, 2, 4-diphenylmethane diisocyanate (2,4-MDI) was 5% of the mass of 4, 4-diphenylmethane diisocyanate (4, 4-MDI).
Example 2
According to the proportion in the proportion table, the dyeable spandex fiber is prepared by the same method as that described in example 1, wherein the content of 2, 4-diphenylmethane diisocyanate (2,4-MDI) in 4, 4-diphenylmethane diisocyanate (4,4-MDI) is 10%.
Example 3
According to the proportion in the proportion table, the dyeable spandex fiber is prepared by the same method as that in example 1, wherein the content of 2, 4-diphenylmethane diisocyanate (2,4-MDI) in 4, 4-diphenylmethane diisocyanate (4,4-MDI) is 15%.
Example 4
According to the proportion in the proportion table, the dyeable spandex fiber is prepared by the same method as that described in example 1, wherein the content of 2, 4-diphenylmethane diisocyanate (2,4-MDI) in 4, 4-diphenylmethane diisocyanate (4,4-MDI) is 20%.
Comparative example
The difference from example 1 is that: the main raw material adopts conventional 4, 4-diphenylmethane diisocyanate (4,4-MDI), wherein the content of 2, 4-diphenylmethane diisocyanate (2,4-MDI) is less than or equal to 1 percent.
Table 1 table of the proportions of the dyeable spandex spinning dope:
| example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| 4,4-MDI/2,4-MDI | 1900/100 | 1800/200 | 1700/300 | 1600/400 | 1990/10 |
| PTMG (molecular weight 2000) | 7800 | 7800 | 7800 | 7800 | 7800 |
| Dimethylacetamide | 18200 | 18200 | 18200 | 18200 | 18200 |
| Mixed amine (amine concentration 7%) | 2850 | 2850 | 2850 | 2850 | 2850 |
| Mixed auxiliary materials (concentration 35%) | 970 | 970 | 970 | 970 | 970 |
The novel easy-to-dye spandex fiber with 560D fineness prepared in the embodiment is subjected to traditional mechanical property, acid dye-uptake performance and fixation rate tests, and the data pair is shown in a table 2:
TABLE 2 data of mechanical properties and dyeing properties of 560D denier spandex fiber prepared by the method of the present invention and conventional spandex fiber
As can be seen from Table 2, the novel easy-dyeing spandex with the titer of 560D prepared by the invention is compared with the common spandex product in terms of mechanical property and dyeing property, the mechanical property is basically kept unchanged, and the novel easy-dyeing spandex has more excellent dyeing property and color fastness. In addition, the higher the content of 2, 4-diphenylmethane diisocyanate (2,4-MDI) in the 4, 4-diphenylmethane diisocyanate (4,4-MDI) serving as the main raw material is, the lower the strength of the product is, and the better the elongation and dyeing properties are.
Example 5
(1) Carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution; wherein the using amount of the 2, 4-diphenylmethane diisocyanate is 5 percent of the mass of the 4, 4-diphenylmethane diisocyanate. The molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.65: 1; the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is 32% of that of the prepolymer solution.
(2) Carrying out chain extension reaction on the pre-polymerization solution and the mixed amine at 65 ℃ for 90min to prepare a polyurethane polymer solution with the required viscosity; wherein the molar ratio of the isocyanate at the end part of the prepolymer to the amino in the mixed amine is 1: 1.02; the mixed amine is a mixture of ethylenediamine and diethylamine, and the mole ratio of ethylenediamine to diethylamine is 6: 1; the temperature of the chain extension reaction is 95 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber. Wherein the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent. The mass of the antioxidant is 0.5% of the solid content of the spinning solution, the mass of the lubricant is 0.5% of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 2.5% of the solid content of the spinning solution, the mass of the dyeing assistant is 1% of the solid content of the spinning solution, and the mass of the matting agent is 1% of the solid content of the spinning solution.
Example 6
(1) Carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution; wherein the using amount of the 2, 4-diphenylmethane diisocyanate is 20 percent of the mass of the 4, 4-diphenylmethane diisocyanate. The molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate to polytetramethylene ether glycol was 2.15: 1; the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is 35% of that of the prepolymer solution.
(2) Carrying out chain extension reaction on the pre-polymerization solution and the mixed amine at 75 ℃ for 45min to prepare a polyurethane polymer solution with the required viscosity; wherein the molar ratio of the isocyanate at the end part of the prepolymer to the amino in the mixed amine is 1: 1.05; the mixed amine is a mixture of ethylenediamine and diethylamine, and the mole ratio of ethylenediamine to diethylamine is 7: 1; the temperature of the chain extension reaction is 90 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber. Wherein the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent. The mass of the antioxidant is 2% of the solid content of the spinning solution, the mass of the lubricant is 0.4% of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 1% of the solid content of the spinning solution, the mass of the dyeing assistant is 0.5% of the solid content of the spinning solution, and the mass of the matting agent accounts for 1.5% of the solid content of the spinning solution.
Example 7
(1) Carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution; wherein the using amount of the 2, 4-diphenylmethane diisocyanate is 15 percent of the mass of the 4, 4-diphenylmethane diisocyanate. The molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.8: 1; the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is 32% of that of the prepolymer solution.
(2) Carrying out chain extension reaction on the pre-polymerization solution and the mixed amine at 70 ℃ for 60min to prepare a polyurethane polymer solution with the required viscosity; wherein the molar ratio of the isocyanate at the end part of the prepolymer to the amino in the mixed amine is 1: 1.03; the mixed amine is a mixture of ethylenediamine and diethylamine, and the mole ratio of ethylenediamine to diethylamine is 8: 1; the temperature of the chain extension reaction is 85 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber. Wherein the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent. The mass of the antioxidant is 1% of the solid content of the spinning solution, the mass of the lubricant is 0.3% of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 0.5% of the solid content of the spinning solution, the mass of the dyeing assistant is 2% of the solid content of the spinning solution, and the mass of the matting agent is 0.5% of the solid content of the spinning solution.
Example 8
(1) Carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution; wherein the using amount of the 2, 4-diphenylmethane diisocyanate is 10 percent of the mass of the 4, 4-diphenylmethane diisocyanate. The molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate to polytetramethylene ether glycol was 2: 1; the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is 33% of that of the prepolymer solution.
(2) Carrying out chain extension reaction on the pre-polymerization solution and the mixed amine at 67 ℃ for 70min to prepare a polyurethane polymer solution with the required viscosity; wherein the molar ratio of the isocyanate at the end part of the prepolymer to the amino in the mixed amine is 1: 1.04; the mixed amine is a mixture of ethylenediamine and diethylamine, and the mole ratio of ethylenediamine to diethylamine is 9: 1; the temperature of the chain extension reaction is 88 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber. Wherein the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent. The mass of the antioxidant is 1.5% of the solid content of the spinning solution, the mass of the lubricant is 0.2% of the solid content of the spinning solution, the mass of the chlorine-resistant agent is 1.5% of the solid content of the spinning solution, the mass of the dyeing assistant is 2.5% of the solid content of the spinning solution, and the mass of the matting agent accounts for 1.2% of the solid content of the spinning solution.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the easily-dyed spandex fiber is characterized by comprising the following steps of:
(1) carrying out prepolymerization reaction on 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polytetramethylene ether glycol to obtain a prepolymer with an isocyanate end capping, and dissolving the prepolymer in a solvent to form a prepolymerization solution;
(2) carrying out chain extension reaction on the pre-polymerization solution and the mixed amine to obtain a polyurethane polymer solution with the required viscosity;
(3) adding the mixed auxiliary materials into the polyurethane polymer solution, and uniformly mixing to obtain a spinning solution of spandex fibers; and spinning the spinning solution to obtain the easily dyeable spandex fiber.
2. The method for preparing the spandex fiber easy to dye according to claim 1, wherein in the step (1), the amount of 2, 4-diphenylmethane diisocyanate is 5 to 20 percent of the mass of 4, 4-diphenylmethane diisocyanate.
3. The method for preparing the spandex fiber easy to dye according to claim 1, wherein in the step (1), the molar ratio of the total amount of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate to the polytetramethylene ether glycol is (1.65-2.15): 1.
4. the method for preparing the spandex fiber easy to dye according to claim 1, wherein in the step (1), the solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the mass of the prepolymer is (30-35)% of the mass of the prepolymer solution.
5. The preparation method of the spandex fiber easy to dye according to claim 1, wherein the polymerization temperature is 65-75 ℃ and the polymerization time is 45-90 min.
6. The method for preparing the spandex fiber easy to dye according to claim 1, wherein in the step (2), the molar ratio of the isocyanate at the end of the prepolymer to the amine group in the mixed amine is 1: (1.02-1.05).
7. The preparation method of the spandex fiber easy to dye according to claim 1, wherein in the step (2), the mixed amine is a mixture of ethylenediamine and diethylamine, wherein the molar ratio of ethylenediamine to diethylamine is (6-9): 1; the temperature of the chain extension reaction is 85-95 ℃, and the viscosity of the polyurethane polymer solution is 200-500 PA.s.
8. The method for preparing the spandex fiber easy to dye according to claim 1, wherein in the step (3), the mixed auxiliary materials comprise an antioxidant, a lubricant, a chlorine-resistant agent, a dyeing assistant and a delustering agent.
9. The preparation method of the spandex fiber easy to dye according to claim 8, wherein in the step (3), the mass of the antioxidant is 0.5-2.0% of the solid content of the spinning dope, the mass of the lubricant is 0.1-0.5% of the solid content of the spinning dope, the mass of the chlorine-resistant agent is 0.5-2.5% of the solid content of the spinning dope, the mass of the dyeing assistant agent is 0.5-2.5% of the solid content of the spinning dope, and the mass of the matting agent is 0.5-1.5% of the solid content of the spinning dope.
10. The easy-dyeing spandex fiber prepared by the method according to any one of claims 1 to 9, wherein the dye-uptake of the easy-dyeing spandex fiber is 94.3 to 99.5%, and the color fastness is 82.3 to 89.3%.
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| CN113279077A (en) * | 2021-05-20 | 2021-08-20 | 晋大纳米科技（厦门）有限公司 | Efficient zirconium phosphate deodorant and deodorization spandex |
| CN114164519A (en) * | 2021-12-21 | 2022-03-11 | 烟台泰和新材料股份有限公司 | Hollow spandex and preparation method thereof |
| CN114181373A (en) * | 2022-01-29 | 2022-03-15 | 万华化学集团股份有限公司 | Preparation process of comfortable spandex and prepared spandex |
| CN115197391A (en) * | 2022-08-15 | 2022-10-18 | 河北邦泰氨纶科技有限公司 | Fiber-grade polyurethane slice and preparation method and application thereof |
| CN115537962A (en) * | 2022-11-03 | 2022-12-30 | 华峰化学股份有限公司 | Spandex for nylon-spandex fabric with uniform evenness and preparation method |
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