CN111394821A - High-strength and high-resilience spandex fiber and preparation method thereof - Google Patents
High-strength and high-resilience spandex fiber and preparation method thereof Download PDFInfo
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- CN111394821A CN111394821A CN202010387910.5A CN202010387910A CN111394821A CN 111394821 A CN111394821 A CN 111394821A CN 202010387910 A CN202010387910 A CN 202010387910A CN 111394821 A CN111394821 A CN 111394821A
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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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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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the field of polymer chemistry, and particularly relates to a high-strength and high-resilience spandex fiber and a preparation method thereof. The preparation method comprises the following steps: reacting polyol with isocyanate to prepare prepolymer; carrying out secondary polymerization on the prepolymer and a chain extender, and adding a chain terminator to terminate the polymerization to obtain a polymer stock solution of the polyurethane urea; optionally adding an additive into the polymer stock solution of the polyurethane urea, uniformly stirring, and spinning to obtain the spandex fiber; the isocyanate is a mixture comprising a diisocyanate and a carbodiimide-modified isocyanate. The spandex fiber provided by the invention has high strength and high resilience, the strength is 1.70-2.00g/d or higher, the stress at definite elongation is 10.5-13.5cN, the elongation at break is 520 cN and 600cN or higher, and the elastic recovery rate is 93-95% or higher, so that the weaving performance of the spandex fabric in the high resilience field is greatly improved.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a high-strength and high-resilience spandex fiber and a preparation method thereof.
Background
Spandex is an elastic fiber prepared by spinning and forming a polyurethane block copolymer. Generally, spandex has an elongation at break of 500% to 700% and an elastic recovery of more than 90%, and is widely used in knitting and weaving. Certain applications (e.g., knee wraps for athletes, wrist pads, sportswear, lady corset harnesses, swimwear, etc.) require higher resilience spandex fibers in order to meet usage requirements.
Because of the incompatibility of soft and hard sections in thermodynamics, spandex usually shows a microphase separation aggregation structure, and the larger the microphase separation degree is, the better the mechanical properties of the fiber such as fatigue resistance, resilience performance and the like are. The existing methods for improving the resilience of spandex are also based on the consideration, and some of the methods achieve the purpose of improving the separation degree of soft and soft segments by improving the structure of the soft segment, such as US5981686, US5000899, US5708118 and the like; some methods adopt a mode of adding MDI for the second time to increase the physical crosslinking in the spandex prepolymer, such as Chinese patent document CN 101469463; some methods for improving physical crosslinking between hard segments by adding special chain extenders, such as chinese patent document CN 103757741B; still another method is to improve the resilience by cross-linking reaction during spinning and dyeing process, such as CN 103436983B. However, the spandex prepared in the above patent documents has problems of limited improvement of resilience, reduction of storage stability of spandex stock solution, reduction of spinning performance, and the like, to different degrees.
Therefore, there is an urgent need to develop a preparation method of spandex fiber, which has both high resilience and high strength, and simultaneously takes into account the storage stability and spinning performance of spandex stock solution.
Disclosure of Invention
The invention aims to provide a preparation method of spandex fiber, so that the prepared spandex fiber has high strength and high resilience, and simultaneously the storage stability and the spinning performance of spandex stock solution are considered.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a high-strength and high-resilience spandex fiber, comprising the steps of: reacting polyol with isocyanate to prepare prepolymer; carrying out secondary polymerization on the prepolymer and a chain extender, and adding a chain terminator to terminate the polymerization to obtain a polymer stock solution of the polyurethane urea; and (3) optionally adding an additive into the polymer stock solution of the polyurethane urea, uniformly stirring, and spinning to obtain the spandex fiber.
Preferably, in the above production method, the isocyanate is a mixture containing a diisocyanate and a carbodiimide-modified isocyanate; preferably, the carbodiimide-modified isocyanate content is from 5 to 20% by weight, preferably from 7 to 15% by weight, of the isocyanate. Preferably, in the above preparation method, the carbodiimide-modified isocyanate is carbodiimide-modified 4,4' -diphenylmethane diisocyanate (which is commercially available as liquefied MDI, e.g., produced by Wanhua chemical Co., Ltd.)
CD-MDI100L、
CD-MDI100H, Jinhui Mitsui liquefied MDI-LL, Pasteur MM103C, Bayer CD-C, MX from NPU, Hounsfield 2020, etc.).
Preferably, in the above preparation method, the diisocyanate is selected from at least one of 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 1,5 '-naphthalene diisocyanate, 1, 4' -phenylene diisocyanate, hexamethylene diisocyanate, 1,4 '-cyclohexane diisocyanate, 4' -dicyclohexyl diisocyanate and isophorone diisocyanate, preferably from 4,4 '-diphenylmethane diisocyanate or a mixture of 4,4' -diphenylmethane diisocyanate and other diisocyanates, more preferably from a mixture of 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate, still more preferably from 2 in an amount of 1 to 5%, a mixture of 4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in an amount of 95-99%; and/or the polyol is selected from at least one of polytetramethylene ether glycol, polypropylene glycol and polycarbonate glycol, preferably polytetramethylene ether glycol.
Preferably, in the above production method, the amount ratio of the polyol and the isocyanate is such that the blocking ratio (i.e., NCO/OH molar ratio) is from 1.0 to 2.0, preferably from 1.4 to 1.8.
Preferably, in the above preparation method, the polyol and the isocyanate are mixed at 40-50 ℃ for 1-2 hours, reacted at 70-90 ℃ for 1-2 hours, and then cooled at 35-45 ℃ for 1-2 hours to prepare a prepolymer; and/or, the secondary polymerization is carried out in a screw extrusion dynamic mixer, the polymerization reaction temperature is controlled to be 55-85 ℃, the time is 30-90 seconds, the solid content of the polymer is controlled to be 30-50%, and the polymerization viscosity is controlled to be 1000-5000 Poise.
Preferably, in the above preparation method, the chain extender is at least one selected from ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 2, 3-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine and 1, 4-cyclohexyldiamine, preferably one or a mixture of two selected from ethylenediamine and 1, 2-propylenediamine; and/or the chain terminator is selected from at least one of dimethylamine, diethylamine, di-n-butylamine, cyclohexylamine, n-pentylamine and ethanolamine; and/or the molar ratio of the chain extender to the prepolymer is 1: 1.01-1.1, preferably 1: 1.02-1.05; and/or the amount of the chain terminator added is 2 to 20 mol%, preferably 4 to 14 mol% of the amount of the chain extender added; preferably, a chain terminator is added with the chain extender.
Preferably, in the above preparation method, an additive selected from at least one of an ultraviolet screening agent, an antioxidant, a lubricant and a matting agent may be optionally added to the stock solution. The amounts of each of the above additives are those conventional in the art and known to those skilled in the art.
In the above preparation, spinning is carried out in a manner customary in the art, which is also known to the person skilled in the art.
In a second aspect, the invention provides spandex fibers prepared by the preparation method.
Preferably, the spandex fiber has a strength of 1.70-2.00g/d or more, a stress at definite elongation of 10.5-13.5cN, an elongation at break of 520 cN-600 cN or more, and an elastic recovery of 93-95% or more.
The technical scheme of the invention has the following advantages:
(1) according to the invention, researches show that the carbodiimide modified isocyanate with a specific structure is introduced into the isocyanate and the addition amount of the carbodiimide modified isocyanate is adjusted and optimized while the hard segment structure of the spandex is changed to improve the micro-phase separation degree of the soft segment and the hard segment, so that the performance of spandex products can be improved, and the stability of polymer stock solution and spinning can be ensured. On one hand, the carbodiimide modified isocyanate structure can provide higher strength and resilience in a hard segment, so that the finally prepared spandex fiber has higher strength and resilience; on the other hand, the isocyanate contains a small amount of carbodiimide modified isocyanate, the crosslinking structure of polyurethane molecules is improved through the prepolymer, the blockage of spinneret orifices in the spinning process is avoided, and the stability of the carbodiimide modified isocyanate provides good storage stability for the polymer stock solution of polyurethane urea, so that the problems of excessive crosslinking, unstable stock solution storage and the like described in other methods can be solved, and the storage stability of the polymer stock solution and the spinning stability are ensured.
(2) The spandex fiber prepared by the preparation method disclosed by the invention has high strength and high resilience, the strength is 1.70-2.00g/d or higher, the stress at definite elongation is 10.5-13.5cN, the elongation at break is 520 cN or higher, and the elastic recovery rate is 93-95% or higher, so that the weaving performance of the spandex fabric in the high resilience field is greatly improved.
Detailed Description
The spandex fiber according to the embodiment of the invention is obtained by preparing a prepolymer through the reaction of polyol and isocyanate, carrying out secondary polymerization on the prepolymer and a chain extender to obtain a polymer stock solution of polyurethane urea, adding various additives into the stock solution, uniformly stirring, and spinning.
In the present invention, the isocyanate used for the preparation of spandex fiber is a mixture comprising diisocyanate, carbodiimide-modified isocyanate. Preferably, the content of the carbodiimide-modified isocyanate is preferably 5 to 20% of the total amount of the diisocyanate and the carbodiimide-modified isocyanate.
In the present invention, specific examples of the diisocyanate include 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 1,5 '-naphthalene diisocyanate, 1, 4' -phenylene diisocyanate, hexamethylene diisocyanate, 1,4 '-cyclohexane diisocyanate, 4' -dicyclohexyl diisocyanate and isophorone diisocyanate; among these diisocyanates, 4' -diphenylmethane diisocyanate may be preferably used alone or in combination with other diisocyanates; further preferably, a mixture of 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate is used, in which case the content of 2,4 '-diphenylmethane diisocyanate is from 1 to 5% and the content of 4,4' -diphenylmethane diisocyanate is from 95 to 99%.
In the present invention, the carbodiimide-modified isocyanate is carbodiimide-modified 4,4' -diphenylmethane diisocyanate.
In addition, the polyurethane fiber provided by the invention, the polyalcohol is one or more selected from polytetramethylene ether glycol, polypropylene glycol and polycarbonate diol; the chain extender is one or more selected from ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 2, 3-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine and 1, 4-cyclohexanediamine. Preferably, the polyol is selected from polytetramethylene ether glycol, and the chain extender is selected from one or a mixture of ethylene diamine and 1, 2-propane diamine.
Example 1
The preparation method of the spandex fiber comprises the following steps: a mixture of 99 mol% of 4,4' -diphenylmethane diisocyanate and 1 mol% of 2,4' -diphenylmethane diisocyanate was mixed to obtain a diisocyanate, and a carbodiimide-modified 4,4' -diphenylmethane diisocyanate (CD-MDI produced by Wawa chemical Co., Ltd. in this example) was used as a mixed isocyanate in a mass ratio of 5 wt% and the diisocyanate in a mass ratio of 95 wt%.
A prepolymer was prepared by mixing polytetramethylene ether glycol having an average molecular weight of 1800 with the above mixed isocyanate at a Capping Ratio (CR) of 1.65, mixing at 45 ℃ for 1.5 hours, reacting at 90 ℃ for 1.5 hours with incubation, and then cooling at 40 ℃ for 1.5 hours. A mixture of ethylene diamine and 1, 2-propylene diamine in a molar ratio of 90% was used as a chain extender, diethylamine was used as a chain terminator, the molar ratio of the chain extender to the chain terminator was 10:1, and N, N-dimethylacetamide was used as a solvent to obtain a mixed amine solution of the chain extender and the chain terminator in a concentration of 7%.
The prepolymer and the mixed amine solution were subjected to secondary polymerization in a screw extrusion dynamic mixer, and the amount of the mixed amine was 1.04 in terms of the molar ratio to the prepolymer (both without solvent), followed by polymerization at 85 ℃ for 75 seconds to obtain a polyurethaneurea stock solution having a solid content of 40% by weight and a viscosity of 2800Poise (40 ℃). The polyurethane urea polymer dope obtained as above was dry-spun at a speed of 800m/min to produce a 40 denier spandex fiber.
Example 2
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 5% by weight of carbodiimide-modified diisocyanate and 95% by weight of the above diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Example 3
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the isocyanate composition is produced by mixing 4,4 '-diphenylmethane diisocyanate and 5% 2,4' -diphenylmethane diisocyanate in a molar ratio of 95% to 5% to obtain a diisocyanate, and using a mixture of 5% by weight of carbodiimide-modified diisocyanate and 95% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Example 4
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 7% by weight of carbodiimide-modified diisocyanate and 93% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Example 5
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 10% by weight of carbodiimide-modified diisocyanate and 90% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Example 6
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 15% by weight of carbodiimide-modified diisocyanate and 85% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Example 7
The preparation method of the spandex fiber of the present example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 20% by weight of carbodiimide-modified diisocyanate and 80% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Comparative example 1
The preparation method of the spandex fiber of the present comparative example is different from that of example 1 only in that: diisocyanate was prepared by mixing 97% of 4,4 '-diphenylmethane diisocyanate and 3% of 2,4' -diphenylmethane diisocyanate in the molar ratio. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Comparative example 2
The preparation method of the spandex fiber of the present comparative example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 3% by weight of carbodiimide-modified diisocyanate and 97% by weight of the above diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Comparative example 3
The preparation method of the spandex fiber of the present comparative example is different from that of example 1 only in that: the diisocyanate was prepared by mixing 97% by mole of 4,4 '-diphenylmethane diisocyanate and 3% by mole of 2,4' -diphenylmethane diisocyanate, and then preparing a mixture of 30% by weight of carbodiimide-modified diisocyanate and 70% by weight of the diisocyanate as a mixed isocyanate. The remaining raw materials, reaction steps and experimental conditions were the same as in example 1.
Examples of the experiments
The spandex fibers prepared in examples 1 to 7 and comparative examples 1 to 3 were respectively tested and evaluated for their conventional mechanical properties and elastic recovery according to the following methods.
Testing the mechanical properties of spandex filaments: the measurement was carried out using a model AI7000, Taiwan high-speed railway, with a specimen length of 10cm and a tensile speed of 500 mm/min. At this time, the strength at break (DS) and elongation at break (DE) were measured, as well as the tensile force (E) to which the wire was subjected when it was drawn to 300%r)。
Elastic loop of spandex filamentThe recovery rate is that according to the standard method FZ/T50007-2012, a sample wire with the length of more than 50mm is taken by adopting an AI7000 type universal tester of Taiwan high-speed railway company, the upper end and the lower end of the sample wire are respectively clamped in an upper clamp and a lower clamp of a dynamometer, in the wire clamping process, the sample wire is straightened but not stretched, the initial distance is 50mm, the sample wire is stretched at the stretching speed of 500mm/min according to the set linear density, and the sample is L from the 0% stretching part0Is stretched to a 300% elongation L1And then returned to 0% elongation and the stretch recovery cycle 6 times, the length of the specimen stretched to the pre-tension is recorded L2。
The 300% elastic recovery is calculated according to formula (1):
in the formula:
Eri-300% elastic recovery of a single sample,%;
L1-length in millimeters (mm) at 300% elongation;
L2-the length in millimeters (mm) of the 6 th load when stretched to pre-tension;
L0length in millimeters (mm) at 0% elongation.
The arithmetic mean of the elastic recovery is calculated according to equation (2):
in the formula:
Er-average 300% elastic recovery,%;
n-number of trials.
Stopping the stretching when the elongation reaches 300%, and returning the upper holder to the initial position; the stretching was repeated until the elongation reached 300%, and the stretching was stopped, and the cycle was repeated for a total of 5 times.
Specific test results are shown in table 1.
TABLE 1 results of mechanical and fatigue Properties test of Spandex fibers prepared in examples 1-7 and comparative examples 1-3
As can be seen from the above Table 1, (1) the spandex fibers prepared in examples 1-7 have both high strength and high resilience, the strength is 1.70-2.05g/d, the stress at definite elongation is 11.2-13.2cN, the elongation at break is 535-590cN, and the elastic recovery is 93-95%, while the spandex fibers prepared in comparative examples 1-3 cannot have both high strength and high resilience;
(2) compared with the comparative example 1, the carbodiimide modified isocyanate is added into the isocyanate in the examples 1 to 7, so that the spandex fiber can obtain better strength and elastic recovery rate;
(3) in comparative example 3, the amount of carbodiimide-modified isocyanate used is preferably 5 to 20% because the elongation at break is remarkably decreased and the elastic recovery is slightly decreased when the content of carbodiimide-modified isocyanate reaches 30% as compared with examples 1 to 7.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A preparation method of high-strength and high-resilience spandex fibers is characterized by comprising the following steps: reacting polyol with isocyanate to prepare prepolymer; carrying out secondary polymerization on the prepolymer and a chain extender, and adding a chain terminator to terminate the polymerization to obtain a polymer stock solution of the polyurethane urea; and (3) optionally adding an additive into the polymer stock solution of the polyurethane urea, uniformly stirring, and spinning to obtain the spandex fiber.
2. The production method according to claim 1, characterized in that the isocyanate is a mixture comprising a diisocyanate and a carbodiimide-modified isocyanate; preferably, the carbodiimide-modified isocyanate content is from 5 to 20% by weight, preferably from 7 to 15% by weight, of the isocyanate.
3. The production method according to claim 1 or 2, characterized in that the carbodiimide-modified isocyanate is carbodiimide-modified 4,4' -diphenylmethane diisocyanate.
4. The process according to any one of claims 1 to 3, wherein the diisocyanate is at least one selected from the group consisting of 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 1,5 '-naphthalene diisocyanate, 1, 4' -phenylene diisocyanate, hexamethylene diisocyanate, 1,4 '-cyclohexane diisocyanate, 4' -dicyclohexyl diisocyanate and isophorone diisocyanate, preferably 4,4 '-diphenylmethane diisocyanate or a mixture of 4,4' -diphenylmethane diisocyanate and another diisocyanate, more preferably a mixture of 4,4 '-diphenylmethane diisocyanate and 2,4' -diphenylmethane diisocyanate, further preferably selected from the group consisting of mixtures of 1-5% 2,4 '-diphenylmethane diisocyanate and 95-99% 4,4' -diphenylmethane diisocyanate; and/or the presence of a gas in the gas,
the polyol is selected from at least one of polytetramethylene ether glycol, polypropylene glycol and polycarbonate glycol, preferably polytetramethylene ether glycol.
5. Process according to any one of claims 1 to 4, characterized in that the polyols and the isocyanates are used in such a ratio that the blocking ratio, i.e. the NCO/OH molar ratio, is between 1.0 and 2.0, preferably between 1.4 and 1.8.
6. The method according to any one of claims 1 to 5, wherein the polyol and the isocyanate are mixed at 40 to 50 ℃ for 1 to 2 hours, reacted at 70 to 90 ℃ for 1 to 2 hours, and then cooled at 35 to 45 ℃ for 1 to 2 hours to prepare a prepolymer; and/or the presence of a gas in the gas,
the secondary polymerization is carried out in a screw extrusion dynamic mixer, the polymerization reaction temperature is controlled to be 55-85 ℃, the time is 30-90 seconds, the solid content of the polymer is controlled to be 30-50%, and the polymerization viscosity is controlled to be 1000-5000 Poise.
7. The production method according to any one of claims 1 to 6, wherein the chain extender is selected from at least one of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 2, 3-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, and 1, 4-cyclohexyldiamine, preferably from one or a mixture of two of ethylenediamine and 1, 2-propylenediamine; and/or the presence of a gas in the gas,
the chain terminator is at least one selected from dimethylamine, diethylamine, di-n-butylamine, cyclohexylamine, n-pentylamine and ethanolamine; and/or the presence of a gas in the gas,
the molar ratio of the chain extender to the prepolymer is 1: 1.01-1.1, preferably 1: 1.02-1.05; and/or the presence of a gas in the gas,
the addition amount of the chain terminator is 2 to 20 mol percent of the addition amount of the chain extender, and is preferably 4 to 14 mol percent; preferably, a chain terminator is added with the chain extender; and/or the presence of a gas in the gas,
the additive is selected from at least one of an anti-ultraviolet agent, an antioxidant, a lubricant and a matting agent.
8. The spandex fiber prepared by the method of any one of claims 1-7.
9. The spandex fiber of claim 8, wherein the spandex fiber has a strength of 1.70-2.00g/d or more, a stress at definite elongation of 10.5-13.5cN, an elongation at break of 520 cN-600 cN or more, and an elastic recovery of 93-95% or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112127006A (en) * | 2020-08-25 | 2020-12-25 | 烟台泰和新材料股份有限公司 | Easy-to-dye spandex fiber and preparation method thereof |
| CN114133724A (en) * | 2022-01-17 | 2022-03-04 | 万华化学集团股份有限公司 | Polycarbonate composite material and preparation method thereof |
| CN115010896A (en) * | 2022-07-11 | 2022-09-06 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic elastomer with excellent resilience and high strength and preparation method thereof |
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| CN114133724B (en) * | 2022-01-17 | 2023-05-30 | 万华化学集团股份有限公司 | Polycarbonate composite material and preparation method thereof |
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