CN113622050B - Preparation method of high-resilience chlorine-resistant spandex fiber and application of high-resilience chlorine-resistant spandex fiber in diaper - Google Patents
Preparation method of high-resilience chlorine-resistant spandex fiber and application of high-resilience chlorine-resistant spandex fiber in diaper Download PDFInfo
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- CN113622050B CN113622050B CN202110925027.1A CN202110925027A CN113622050B CN 113622050 B CN113622050 B CN 113622050B CN 202110925027 A CN202110925027 A CN 202110925027A CN 113622050 B CN113622050 B CN 113622050B
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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
-
- 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
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
Abstract
The invention discloses a preparation method of high-resilience chlorine-resistant spandex fibers and application of the high-resilience chlorine-resistant spandex fibers in diapers, and relates to the technical field of chemical fiber materials. The preparation method of the high-resilience chlorine-resistant spandex fiber comprises the following steps: taking polyester polyol and isocyanate to react to obtain prepolymer; taking the prepolymer to react with a chain extender and an additive, discharging and curing to obtain polyurethane slices; and melting the polyurethane slices, uniformly mixing the melted polyurethane slices with a chlorine-resistant cross-linking agent, and carrying out melt extrusion, spinning forming and curing to obtain the high-resilience chlorine-resistant spandex fiber. The high-resilience chlorine-resistant spandex fiber prepared by the invention has higher resilience and chlorine resistance, and the stress relaxation rate is low, so that the use safety is effectively improved; meanwhile, the mechanical property is excellent, the creep resistance is stronger, the bonding property with the non-woven fabric is better, and the application field is wide.
Description
Technical Field
The invention belongs to the technical field of chemical fiber materials, and particularly relates to a preparation method of high-resilience chlorine-resistant spandex fibers and application of the high-resilience chlorine-resistant spandex fibers in diapers.
Background
The polyurethane elastic fiber is a high molecular material containing more than 85 wt% of polyurethane chain segment. Because of excellent elasticity and resilience, spandex has wide application in important fields of national economy such as textile clothing, biomedicine and the like. There are many patents related to the production technology of elastic fiber, such as european patents EP0343985, EP1311578, US patents 5340902, US5691441, chinese patents CN1480570A, CN101469463A, etc., however, some of these reports are lack of application in production, and are not industrialized, and some of the invented spandex has not very ideal resilience, which affects the application of elastic fiber in some special fields.
In recent years, along with the popularization of spandex use and application range, people have higher and higher requirements on spandex differentiation performances such as chlorine resistance, high temperature resistance, antistatic property, resilience and the like. The differentiation of the spandex industry in China starts late, the differentiated varieties are few, the added value is low, effective development is not carried out aiming at the subdivided market, the profit rate of products is less than 40% compared with that of high-performance differentiated spandex, and the produced textiles are mainly applied to the middle-end and low-end markets, have low international competitiveness and are seriously inconsistent with the identity and status of the large spinning countries in China. Therefore, the development of a spandex product with differentiated performance has extraordinary significance, and the market has urgent needs.
One of the important indexes of elastic spandex products, the elasticity of the conventional spandex cannot meet the requirements of high-grade textile products, particularly in the field of diapers, the chlorine resistance directly influences the elasticity loss rate of the spandex, and the technical development of the chlorine-resistant high-resilience spandex is particularly important.
Disclosure of Invention
The invention aims to provide a preparation method of high-resilience chlorine-resistant spandex fiber and application of the high-resilience chlorine-resistant spandex fiber in diaper, the spandex fiber has higher resilience and chlorine resistance, the stress relaxation rate is low, and the use safety is effectively improved; meanwhile, the mechanical property is excellent, the creep resistance is stronger, and the bonding property with the non-woven fabric is better.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of high-resilience chlorine-resistant spandex fibers comprises the following steps:
taking polyester polyol and isocyanate to react to obtain prepolymer;
taking the prepolymer to react with a chain extender and an additive, discharging and curing to obtain polyurethane slices;
and melting the polyurethane slices, uniformly mixing the melted polyurethane slices with a chlorine-resistant cross-linking agent, and carrying out melt extrusion, spinning forming and curing to obtain the high-resilience chlorine-resistant spandex fiber.
Furthermore, the preparation method of the high-resilience chlorine-resistant spandex fiber specifically comprises the following steps:
heating and melting polyester polyol and isocyanate, defoaming at 80-90 ℃ and under the vacuum degree of-0.12-0.08 MPa respectively, mixing, adding into a double-screw extruder under the protection of nitrogen, controlling the temperature to be 110-130 ℃, and reacting for 20-50 min to obtain a prepolymer;
adding a chain extender and an additive, controlling the temperature to be 180-200 ℃, reacting for 0.5-2 min, then cutting into particles, drying, and curing at 80-100 ℃ to obtain polyurethane slices;
and melting the dried polyurethane slices, uniformly mixing the melted polyurethane slices with a chlorine-resistant cross-linking agent, performing melt extrusion and spinning molding, and curing at the temperature of 80-100 ℃ for 48-56 hours to obtain the high-resilience chlorine-resistant spandex fiber.
According to a particular embodiment of the invention, the polyester polyol is polytetramethylene ether glycol.
According to a particular embodiment of the invention, the isocyanate is 4, 4' -diphenylmethane diisocyanate.
According to a particular embodiment of the invention, the chain extender comprises ethylenediamine, ethanolamine and 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone or a mixture of 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid. In the preparation process of the spandex fiber, part of 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone or 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid is used as a chain extender, so that the resilience of the obtained spandex fiber is obviously improved, and the reason may be that more hydrogen bonds are generated among polyurethane molecular chains, the microcrystal area of the polyurethane fiber is increased, and active groups such as a secondary amino group and the like generate chemical crosslinking action, so that the resilience of the spandex fiber is enhanced; the prepared spandex fiber has stronger breaking strength and elongation at break, and the mechanical property of the spandex fiber is obviously improved; meanwhile, the stress relaxation rate of the spandex fiber is obviously reduced, and the use safety of the spandex fiber is effectively enhanced. The spandex fiber is prepared by combining the chlorine-resistant cross-linking agent and polyurethane, and can effectively maintain the physical properties of the fiber when used in a chlorine-containing environment, so that the spandex fiber has good chlorine resistance. Wherein, the existence of 4, 11-diamino-2- (3-methoxy propyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraketone is compounded with other components, so that the chlorine resistance of the spandex fiber is enhanced to a certain extent; the existence of the 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid obviously improves the creep resistance of the spandex fiber, so that the spandex fiber has stronger bonding capability with the non-woven fabric.
According to the specific embodiment of the invention, the molar ratio of ethylenediamine, ethanolamine and 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone or 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid in the chain extender is 5-8: 0.5-0.8: 2 to 4.
According to a specific embodiment of the present invention, the additive comprises one or a combination of titanium dioxide, an antioxidant Tinuvin 622, an antioxidant 1010, a UV stabilizer Tinuvin 234 and magnesium stearate.
According to an embodiment of the present invention, the chlorine-resistant crosslinking agent is an isocyanate group-terminated aliphatic polyester compound containing 6 to 8wt% of free isocyanate groups.
According to the specific embodiment of the invention, the raw material components of the isocyanate group-terminated aliphatic polyester compound comprise high molecular diol, isophorone diisocyanate; the molecular weight of the high molecular diol is 600-2500.
According to the specific embodiment of the invention, the molar ratio of the high molecular diol to the isophorone diisocyanate is 1: 1.1 to 1.25.
Further, a method for producing an isocyanate group-terminated aliphatic polyester compound, comprising:
respectively dissolving high-molecular diol and isophorone diisocyanate in THF to obtain a solution A and a solution B, adding the solution B into the solution A for reaction until the content of free isocyanate groups is 6-8 wt%, and stopping the reaction to obtain the isocyanate group-terminated aliphatic polyester compound.
More preferably, the raw material composition of the isocyanate group-terminated aliphatic polyester compound further comprises 2,3,4, 6-tetra-O-benzoyl- β -D-glucopyranosyl isothiocyanate, wherein the molar ratio of the 2,3,4, 6-tetra-O-benzoyl- β -D-glucopyranosyl isothiocyanate to the high molecular diol is 0.1 to 0.3: the preparation method comprises the following steps:
respectively dissolving high-molecular diol and 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate in THF to obtain a solution A and a solution B, slowly dropwise adding the solution B into the solution A, reacting for 3-5 h, then adding THF of isophorone diisocyanate to react until the content of free isocyanate groups is 6-8 wt%, and stopping the reaction to obtain the isocyanate group-terminated aliphatic polyester compound. 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate is added in the preparation process of the chlorine-resistant cross-linking agent and then compounded with polyurethane to prepare spandex fiber, so that the mechanical property of the spandex fiber can be effectively enhanced, and the breaking strength and the breaking elongation are obviously improved; and the stress relaxation rate of spandex fiber can be reduced, and the use safety of the spandex fiber is further improved. In addition, the 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate is added and compounded with other components, so that the chlorine resistance and creep resistance of the spandex fiber are obviously improved, the product quality is improved, and the application field of the spandex fiber is expanded.
According to the specific embodiment of the invention, the molar ratio of the polyester polyol, the isocyanate and the chain extender is 3.5-6.5: 1: 0.15 to 0.4; the addition amount of the additive is 0.8-2 wt% of the total amount of the polyester polyol, the isocyanate and the chain extender; the addition amount of the chlorine-resistant cross-linking agent is 0.5-6 wt% of the polyurethane slice.
According to the specific embodiment of the invention, the elastic recovery rate of the spandex fiber is more than 94 percent; the breaking strength is more than 2.0N, the breaking elongation is more than 580 percent, and the stress relaxation rate is less than 24 percent.
The invention also aims to provide application of the spandex fiber prepared by the preparation method in preparation of diaper, wet tissue or mask products.
Compared with the prior art, the invention has the following beneficial effects:
in the preparation process of the spandex fiber, part of 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone or 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid is used as a chain extender, so that the resilience of the obtained spandex fiber is remarkably improved, and the mechanical property is remarkably improved; meanwhile, the stress relaxation rate of the spandex fiber is obviously reduced, and the use safety of the spandex fiber is effectively enhanced. Wherein, the existence of 4, 11-diamino-2- (3-methoxy propyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraketone enhances the chlorine resistance of the spandex fiber; the existence of the 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid obviously improves the creep resistance of the spandex fiber, so that the spandex fiber has stronger bonding capability with the non-woven fabric. In addition, 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate is added in the preparation process of the chlorine-resistant cross-linking agent and then compounded with polyurethane to prepare the spandex fiber, so that the mechanical property of the spandex fiber can be effectively enhanced, the stress relaxation rate is reduced, and the use safety of the spandex fiber is further improved; and the chlorine resistance and creep resistance of the spandex fiber are obviously improved, the product quality is improved, and the application field of the spandex fiber is expanded.
Therefore, the invention provides a preparation method of the high-resilience chlorine-resistant spandex fiber and application of the high-resilience chlorine-resistant spandex fiber in diaper, the spandex fiber has higher resilience and chlorine resistance, the stress relaxation rate is low, and the use safety is effectively improved; meanwhile, the mechanical property is excellent, the creep resistance is stronger, and the bonding property with the non-woven fabric is better.
Drawings
FIG. 1 shows the results of IR spectroscopy in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the polyester polyol used in the embodiment of the present invention is polytetramethylene ether glycol (PTG-2000) ordered from south kyo hui trading ltd; the high molecular weight diol used was polypropylene glycol, available from Sigma-Aldrich, having a molecular weight of 2000.
Example 1:
preparation of high-resilience chlorine-resistant spandex fiber:
heating and melting polyester polyol and isocyanate, defoaming at 85 ℃ and under the vacuum degree of-0.10 MPa respectively, mixing, adding into a double-screw extruder under the protection of nitrogen, controlling the temperature to be 123 ℃, and reacting for 40min to obtain a prepolymer;
adding a chain extender and an additive, controlling the temperature at 195 ℃, reacting for 1min, then granulating, drying, and curing at 95 ℃ to obtain polyurethane slices;
and melting the dried polyurethane slices, uniformly mixing the melted polyurethane slices with a chlorine-resistant cross-linking agent, performing melt extrusion and spinning molding, and curing at 95 ℃ for 52 hours to obtain the high-resilience chlorine-resistant spandex fiber.
Wherein the molar ratio of the polyester polyol, the isocyanate and the chain extender is 4.7: 1: 0.29; the addition amount of the additive is 1.3wt% of the total amount of the polyester polyol, the isocyanate and the chain extender; the addition amount of the chlorine-resistant cross-linking agent is 2.6wt% of the polyurethane slice; the molar ratio of ethylenediamine, ethanolamine and 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone in the chain extender is 7.1: 0.69: 3.2; the additive is titanium dioxide, an antioxidant Tinuvin 622, a UV stabilizer Tinuvin 234 and magnesium stearate, and the mass ratio of the titanium dioxide to the antioxidant Tinuvin 622 to the UV stabilizer Tinuvin 234 is 1: 1.2: 1: 0.25.
the chlorine-resistant cross-linking agent is an isocyanate group-terminated aliphatic polyester compound, and the preparation steps are as follows:
according to the mol ratio of 1: 1.21 dissolving the high molecular weight diol and the isophorone diisocyanate in THF respectively to obtain a solution A and a solution B, adding the solution B into the solution A for reaction until the content of free isocyanate groups is 6.8wt%, and stopping the reaction to obtain the isocyanate group-terminated aliphatic polyester compound.
Example 2:
the preparation of the high-resilience chlorine-resistant spandex fiber is different from that of the high-resilience chlorine-resistant spandex fiber in example 1 in that:
the molar ratio of the polyester polyol, the isocyanate and the chain extender is 5.6: 1: 0.38; the addition amount of the additive is 1.6wt% of the total amount of the polyester polyol, the isocyanate and the chain extender; the addition amount of the chlorine-resistant cross-linking agent is 4.1wt% of the polyurethane slice; the molar ratio of ethylenediamine, ethanolamine and 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone in the chain extender is 7.3: 0.77: 2.1; the additive is titanium dioxide, an antioxidant Tinuvin 622, a UV stabilizer Tinuvin 234 and magnesium stearate, and the mass ratio of the titanium dioxide to the antioxidant Tinuvin 622 to the UV stabilizer Tinuvin 234 is 1: 1.2: 1: 0.25.
the chlorine-resistant crosslinker was prepared as in example 1.
Example 3:
the preparation of the high-resilience chlorine-resistant spandex fiber is different from that of the high-resilience chlorine-resistant spandex fiber in example 1 in that:
1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid is used to replace 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone.
The chlorine-resistant crosslinker was prepared as in example 1.
Example 4:
the preparation of the high-resilience chlorine-resistant spandex fiber is different from that of the high-resilience chlorine-resistant spandex fiber in example 2 in that:
1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid is used to replace 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone.
The chlorine-resistant crosslinker was prepared as in example 1.
Example 5:
a high resilience chlorine resistant spandex fiber is prepared which differs from example 1 only in that:
preparation of chlorine-resistant crosslinking agent:
according to the mol ratio of 1: 0.19 taking high molecular weight diol and 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate to be respectively dissolved in THF to obtain a solution A and a solution B, slowly adding the solution B into the solution A, mixing and reacting for 4 hours, then adding a THF solution of isophorone diisocyanate to react until the content of free isocyanate groups is 6.8wt%, and stopping the reaction to obtain the isocyanate group-terminated aliphatic polyester compound. Wherein the molar ratio of the high-molecular diol to the 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate is 1: 1.21.
example 6:
a high resilience chlorine resistant spandex fiber is prepared which differs from example 3 only in that:
preparation of chlorine-resistant crosslinking agent:
according to the mol ratio of 1: 0.19 taking high molecular weight diol and 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate to mix and react for 3 hours, then adding isophorone diisocyanate to react until the content of free isocyanate group is 7.2wt%, and stopping the reaction to obtain the aliphatic polyester compound with the blocked isocyanate group.
Example 7:
the preparation of the high-resilience chlorine-resistant spandex fiber is different from that of the high-resilience chlorine-resistant spandex fiber in example 1 in that:
4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone is not added into the chain extender.
The chlorine-resistant crosslinker was prepared as in example 5.
Comparative example 1:
the preparation of the high-resilience chlorine-resistant spandex fiber is different from that of the high-resilience chlorine-resistant spandex fiber in example 1 in that:
4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone is not added into the chain extender.
The chlorine-resistant crosslinker was prepared as in example 1.
Test example 1:
1. characterization of the Infrared Spectrum
The Fourier transform infrared spectrum analyzer manufactured by Bruker company of Germany is used at 4000-500 cm-1And (3) carrying out structural characterization on the sample in the wave number range, standing and humidifying the spandex sample for 4 hours according to the national standard requirements, and then testing by using a transmission method. Wherein the test wave number range is 4000-500 cm-1Scanning frequency 32, resolution 8cm-1。
The above tests were carried out on the novel polyurethanes prepared in comparative example 1 and examples 1,3 and 5, and the results are shown in FIG. 1. From the analysis in the figure, it is found that 1709cm in the IR spectra of the spandex fibers obtained in examples 1 and 3, compared with the IR spectra of the spandex fibers obtained in comparative example 1 and example 3-1The intensity of a characteristic absorption peak with C = O appears nearby and is obviously enhanced; in the infrared spectrum of the spandex fiber prepared in the example 1, the infrared spectrum is 1650-1580 cm-1The intensity of the vibration characteristic absorption peak of the benzene ring skeleton appearing in the range is obviously enhanced; example 3 the infrared spectrum of the spandex fiber prepared in the method is 3000-2800 cm-1The intensity of the characteristic absorption peak of methylene appeared in the range is obviously enhanced. In addition, the IR spectrum of the spandex fiber obtained in example 5 was 1293cm, as compared with the IR spectrum of the spandex fiber obtained in example 1-1A characteristic absorption peak of S = C appears nearby, and the characteristic absorption peak is 1650-1580 cm-1The absorption peak intensity of the benzene ring skeleton vibration characteristic appeared in the range is enhanced, and is 1211cm-1The characteristic absorption peak intensity of C-O in ester groups appears nearby and is obviously enhanced; the above results indicate that spandex fibers were successfully prepared in examples 1,3, and 5.
2. Breaking Strength and elongation at Break test
The breaking strength and breaking elongation of spandex are tested according to the requirements of national standard FZ/T50006-2013 stretch performance test method of spandex filament, 10 parallel tests are carried out on each group of samples, and the average value of the results is taken.
The results of the above tests on spandex prepared in comparative example 1 and examples 1 to 7 are shown in table 1:
TABLE 1 breaking Strength and elongation at Break test results
| Sample (I) | Breaking strength/N | Elongation at break/% |
| Comparative example 1 | 1.36 | 661.43 |
| Example 1 | 2.24 | 693.72 |
| Example 2 | 2.03 | 687.46 |
| Example 3 | 2.15 | 691.25 |
| Example 4 | 2.32 | 699.90 |
| Example 5 | 3.05 | 719.83 |
| Example 6 | 3.11 | 713.77 |
| Example 7 | 2.06 | 689.51 |
From the analysis in table 1, it can be seen that the breaking strength and the breaking elongation of the spandex prepared in examples 1 and 3 are both significantly higher than those of comparative example 1, indicating that the addition of 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone or 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid in the chain extender for preparing spandex can effectively enhance the breaking strength and the breaking elongation of the spandex fiber and improve the mechanical properties of the spandex fiber. The effect of example 5 is better than that of example 1, the effect of example 6 is better than that of example 3, and the effect of example 7 is better than that of comparative example 1, which shows that the existence of 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate in the chlorine-resistant crosslinking agent for preparing the spandex can obviously enhance the mechanical property of the spandex fiber by being compounded with other components.
3. Spandex elastic recovery test
According to the requirements of national standard FZ/T5007-2012 'elasticity experiment method for spandex filaments', the 300% recovery rate of 24h of spandex samples is tested, and the average value is taken after each group of samples are tested for 10 times.
4. Stress relaxation Rate test
And testing the stress relaxation rate of the spandex samples according to the requirements of national standard FZ/T5007-2012 'spandex filament elasticity test method', and testing each group of samples for 10 times to obtain an average value.
The results of the above two tests on spandex prepared in comparative example 1 and examples 1 to 7 are shown in table 2:
TABLE 2 test results of recovery and stress relaxation rates
| Sample (I) | 300% recovery/%) | Stress relaxation rate/%) |
| Comparative example 1 | 95.03 | 30.4 |
| Example 1 | 98.42 | 20.3 |
| Example 2 | 97.86 | 21.9 |
| Example 3 | 97.73 | 23.0 |
| Example 4 | 98.08 | 23.5 |
| Example 5 | 98.61 | 15.4 |
| Example 6 | 98.18 | 18.7 |
| Example 7 | 95.97 | 25.1 |
From the analysis in table 2, it can be seen that the 300% recovery rate of the spandex prepared in example 1 and example 3 is significantly higher than that of comparative example 1, and the stress relaxation rate is significantly lower than that of comparative example 1, which indicates that the addition of 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone or 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid in the chain extender for preparing spandex can effectively improve the elastic recovery rate of the spandex fiber and enhance the elasticity of the spandex fiber; and the stress relaxation rate of spandex can be reduced, and the use safety of the spandex is enhanced. The stress relaxation rate of the spandex prepared in example 5 is obviously lower than that of example 1, the effect of example 6 is better than that of example 3, and the effect of example 7 is better than that of comparative example 1, so that the existence of 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate in the chlorine-resistant cross-linking agent for preparing the spandex is shown, and the spandex material can be obviously enhanced in use safety when being compounded with other components.
Test example 2:
1. chlorine resistance test
The test method comprises the following steps: soaking a spandex sample in a sodium hypochlorite solution with the effective chlorine concentration of 150ppm, taking out after 3 hours, washing, drying at 65 ℃, dampening for 4 hours, detecting the breaking strength, and calculating the retention rate of the breaking strength to represent the chlorine resistance of the sample.
The results of the above tests on spandex prepared in comparative example 1 and examples 1 to 7 are shown in table 3:
TABLE 3 chlorine resistance test results
| Sample (I) | Retention rate of breaking strength/%) |
| Comparative example 1 | 80.5 |
| Example 1 | 87.4 |
| Example 2 | 86.3 |
| Example 3 | 81.4 |
| Example 4 | 81.2 |
| Example 5 | 99.4 |
| Example 6 | 90.6 |
| Example 7 | 88.1 |
As can be seen from the analysis in Table 3, the retention rate of breaking strength of the spandex prepared in example 1 is significantly higher than that of comparative example 1, and the addition of 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone in the chain extender for preparing spandex can improve the chlorine resistance of spandex fibers to a certain extent. The effect of example 5 is better than that of example 1, the effect of example 6 is better than that of example 3, and the effect of example 7 is better than that of comparative example 1, which shows that the chlorine resistance of the spandex fiber can be obviously enhanced by the existence of the 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate in the chlorine-resistant cross-linking agent for preparing the spandex and the combination of the four-O-benzoyl-beta-D-glucopyranosyl isothiocyanate and other components. Wherein, the effect of the example 5 is obviously better than that of the examples 1 and 7, and the effect of enhancing the chlorine resistance of the spandex fiber is better under the condition that 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetrone and 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate coexist.
2. Creep resistance test
The test method comprises the following steps: flattening and fixing the non-woven fabric adhered with the polyurethane filament on a flat plate, measuring the length of the non-woven fabric to be 200 mm, cutting off the two ends of the non-woven fabric, placing the non-woven fabric in a 45 ℃ oven, taking out the non-woven fabric after the non-woven fabric is withdrawn after 2 hours, recording the length of the sample after the sample is withdrawn, and calculating the proportion after the sample is withdrawn.
The results of the above tests on spandex prepared in comparative example 1 and examples 1 to 7 are shown in table 4:
TABLE 4 creep resistance test results
| Sample (I) | Post reduction ratio/%) |
| Comparative example 1 | 68.5 |
| Example 1 | 70.1 |
| Example 2 | 69.4 |
| Example 3 | 85.3 |
| Example 4 | 86.2 |
| Example 5 | 83.7 |
| Example 6 | 93.6 |
| Example 7 | 80.9 |
From the analysis in table 4, it can be seen that the ratio of the spandex prepared in example 3 after shrinking is significantly higher than that of comparative example 1, indicating that the addition of 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid in the chain extender for spandex preparation can effectively improve the creep resistance of spandex fibers and enhance the adhesion of spandex to nonwoven fabrics. The effect of example 5 is better than that of example 1, the effect of example 6 is better than that of example 3, and the effect of example 7 is better than that of comparative example 1, which shows that the creep resistance of the spandex fiber can be obviously enhanced by the existence of 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate in the chlorine-resistant crosslinking agent for preparing the spandex and the combination of the chlorine-resistant crosslinking agent with other components. The effect of example 6 is obviously better than that of examples 3 and 7, and the results show that under the condition that 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid and 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate coexist, the effect of improving the creep resistance of spandex fibers is better, and the method can be better applied to the preparation of diapers.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A preparation method of high-resilience chlorine-resistant spandex fibers comprises the following steps:
reacting polytetramethylene ether glycol with isocyanate to obtain a prepolymer;
taking the prepolymer to react with a chain extender and an additive, discharging and curing to obtain polyurethane slices;
melting the polyurethane slices, uniformly mixing the melted polyurethane slices with a chlorine-resistant cross-linking agent, and carrying out melt extrusion, spinning forming and curing to obtain the high-resilience chlorine-resistant spandex fiber;
the chain extender comprises ethylenediamine, ethanolamine and 4, 11-diamino-2- (3-methoxypropyl) -1H-naphtho [2,3-F ] isoindole-1, 3,5,10(2H) -tetraone or a mixture of 1,4,7, 10-tetraazacyclododecane-1, 7-diacetic acid;
the chlorine-resistant cross-linking agent is an isocyanate group-terminated aliphatic polyester compound containing 6-8 wt% of free isocyanate groups.
2. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the isocyanate is 4, 4' -diphenylmethane diisocyanate.
3. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the additive comprises one or more of titanium dioxide, an antioxidant Tinuvin 622, an antioxidant 1010, a UV stabilizer Tinuvin 234 and magnesium stearate.
4. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the isocyanic acid
The raw material components of the aliphatic polyester compound with the end capping of the ester group comprise high molecular diol and isophorone diisocyanate.
5. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the raw material components of the isocyanate-terminated aliphatic polyester compound also comprise 2,3,4, 6-tetra-O-benzoyl-beta-D-glucopyranosyl isothiocyanate.
6. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the mole ratio of the polytetramethylene ether glycol to the isocyanate to the chain extender is 3.5-6.5: 1: 0.15 to 0.4; the addition amount of the additive is 0.8-2 wt% of the total amount of the polytetramethylene ether glycol, the isocyanate and the chain extender; the addition amount of the chlorine-resistant cross-linking agent is 0.5-6 wt% of the polyurethane slice.
7. The preparation method of the high-resilience chlorine-resistant spandex fiber according to claim 1, characterized in that: the elastic recovery rate of the spandex fiber is more than 94 percent; the breaking strength is more than 2.0N, the breaking elongation is more than 580 percent, and the stress relaxation rate is less than 24 percent.
8. Use of the spandex fiber prepared by the preparation method of any one of claims 1 to 7 in preparation of a diaper, a wet tissue or a mask product.
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Effective date of registration: 20220704 Address after: 312000 No. 98, Huahai Road, Datang street, Zhuji City, Shaoxing City, Zhejiang Province Patentee after: ZHUJI HUAHAI SPANDEX Co.,Ltd. Patentee after: Zhuji Huahai New Material Co.,Ltd. Patentee after: Zhuji Xingwang New Material Co.,Ltd. Patentee after: Zhuji Huahai supply chain Co.,Ltd. Address before: 311899 No. 98, Huahai Road, Datang street, Zhuji City, Shaoxing City, Zhejiang Province Patentee before: ZHUJI HUAHAI SPANDEX Co.,Ltd. |