CN106757485B - A kind of preparation method of high drawing spandex fibre - Google Patents
A kind of preparation method of high drawing spandex fibre Download PDFInfo
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- CN106757485B CN106757485B CN201611046662.8A CN201611046662A CN106757485B CN 106757485 B CN106757485 B CN 106757485B CN 201611046662 A CN201611046662 A CN 201611046662A CN 106757485 B CN106757485 B CN 106757485B
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 53
- 239000004759 spandex Substances 0.000 title claims abstract description 53
- 239000000835 fiber Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 238000000578 dry spinning Methods 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical group 0.000 claims description 4
- 230000001050 lubricating effect Effects 0.000 claims description 4
- 238000004383 yellowing Methods 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 23
- 239000002861 polymer material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 4
- 210000004177 elastic tissue Anatomy 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- 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
-
- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of preparation methods of high drawing spandex fibre, belong to field of polymer material preparing technology, high speed spinning particularly suitable for spandex fibre, include the following steps: (1) in the prepolymerization reaction stage, using diisocyanate and oligomer dihydric alcohol as base stock, isocyanate-terminated prepolymer is obtained；(2) prepolymer prepared with aprotic polar solvent dissolving step 1 obtains pre-polymer solution；(3) the mixing amine aqueous solution that chain extender and chain terminating agent form is added in the pre-polymer solution obtained to step 2, polyurethane urea solutions are obtained after aggregated reaction, the chain extender is the mixture of polyetheramine and aliphatic diamine；(4) after the spandex spinning fluid curing prepared step 3, high drawing spandex is prepared using dry spinning.
Description
Technical Field
The invention belongs to the technical field of polymer material preparation, and particularly relates to a preparation method of high-elongation spandex fibers. The spandex fiber prepared by the invention has excellent elongation performance and is particularly suitable for dry spinning at high spinning speed.
Background
Spandex is a multi-block copolymer with alternating soft and hard segments, the hard segments provide strength for the spandex fibers, and the soft segments provide elasticity for the spandex fibers. The structure of alternating soft and hard sections endows the spandex fiber with high breaking strength and elasticity, so that the spandex fiber can be widely applied to various clothing articles.
With the application of spandex in various garment materials, the market demand of spandex is increased year by year, and upstream spandex manufacturers improve the production efficiency and reduce the cost, while downstream textile manufacturers reduce the production cost so as to strengthen the market competitiveness. An effective way for upstream spandex manufacturers to reduce production cost is to increase the spinning speed of spandex fibers, but the increase in spinning speed causes deterioration of spandex physical properties (such as reduction in elongation and reduction in breaking strength); when downstream textile manufacturers weave by using spandex, the content of the spandex fiber in the fabric is reduced by improving the draft multiple of the spandex fiber in the unwinding process, so that the production cost is reduced, and yarn breakage is easily caused if the elongation of the spandex fiber is insufficient.
Aiming at the problems, a high-elongation spandex is developed, which can not only meet the requirements of spandex manufacturers on improving spinning speed and reducing production cost, but also achieve the purpose of low ammonia content of downstream textile fabrics. Chinese patent CN101736435A discloses a method for producing soft spandex, which uses polymeric polyol with molecular weight more than 3000 and side group to prepare spandex fiber with higher elongation and lower stress, but the breaking strength is obviously reduced, which can cause filament breakage in the subsequent application of spandex fiber. Chinese patent CN102154729A discloses a preparation method of spandex fiber with high elongation and high drafting, which endows the fiber with the characteristics of high elongation, high drafting and low stress by increasing the dosage of ethylenediamine relative to propylenediamine in a chain extender, but the spinning speed of the preparation method is low, only 600-750m/min, and the production cost is high.
The researches relate to a preparation method of high-elongation spandex, but all have certain defects, so that how to prepare the high-elongation spandex under the condition of high spinning speed has very important significance to upstream spandex manufacturing enterprises and downstream textile enterprises.
Disclosure of Invention
The technical problem is as follows: the invention aims to solve the defects of the prior art and provides a preparation method of high-elongation spandex fiber. The polyurethane elastic fiber prepared by the method can meet the requirement of high spinning speed of the spandex fiber and also can meet the requirement of high drafting of the spandex fiber in the using process.
The technical scheme is as follows: in order to achieve the above object, the preparation method of the high-elongation spandex fiber of the present invention comprises the following steps:
1) in the prepolymerization stage, mixing and reacting diphenylmethane-4, 4' diisocyanate and polytetrahydrofuran ether glycol to obtain isocyanate group-terminated polyurethane prepolymer;
2) dissolving the polyurethane prepolymer obtained in step 1) with an aprotic polar solvent to obtain a prepolymer solution;
3) cooling the prepolymer solution prepared in the step 2), and adding a mixed amine solution to perform chain extension reaction and chain termination reaction to form a polyurethaneurea solution;
4) adding various additives into the polyurethane urea solution prepared in the step 3), and fully and uniformly mixing to prepare a spandex spinning solution;
5) curing the prepared spandex spinning solution, and obtaining the high-elongation spandex fiber by adopting a dry spinning method.
Wherein:
the chain extender used in the chain extension reaction in the step 3) is a mixture of polyether amine and aliphatic diamine.
The polyether amine is EDR-148, and the molecular weight of the polyether amine is 148; EDR-176 having a molecular weight of 176; or EDR-192 with molecular weight of 192, and the aliphatic diamine is ethylenediamine.
The molar ratio of the polyether amine to the aliphatic diamine is 1: 9-1: 49.
The chain terminator used in the chain termination reaction in the step 3) is diethylamine, dipropylamine, ethanolamine or n-hexylamine, or a mixture thereof.
The diphenylmethane-4, 4' -diisocyanate and the polytetrahydrofuran ether glycol are mixed and react, and the molar ratio is 1.45: 1-1.95: 1.
The aprotic polar solvent is N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC).
The additives include delusterants, anti-yellowing agents, ultraviolet absorbers, antioxidants, and lubricating and unwinding agents.
Has the advantages that: the spandex fiber prepared by the method is greatly different from the conventional spandex fiber in structure and property, the soft segment part is still polyether diol, but the hard segment part introduces part of flexible chain segments, so that the regularity of the hard segment is damaged, and the hard segment also has certain flexibility, so that the prepared spandex fiber has the characteristic of high elongation.
Detailed Description
The preparation method of the high-elongation spandex fiber adopts the following technical scheme,
1) in the prepolymerization stage, mixing and reacting diphenylmethane-4, 4' diisocyanate and polytetrahydrofuran ether glycol to obtain isocyanate group-terminated polyurethane prepolymer;
2) dissolving the polyurethane prepolymer obtained in step 1) with an aprotic polar solvent to obtain a prepolymer solution;
3) cooling the prepolymer solution prepared in the step 2), and adding a mixed amine solution of a chain extender and a chain terminator to perform a chain extension reaction and a chain termination reaction to form a polyurethaneurea solution;
4) adding various additives into the polyurethane urea solution prepared in the step 3), and fully and uniformly mixing to prepare a spandex spinning solution;
5) curing the prepared spandex spinning solution, and then obtaining the high-elongation polyurethane elastic fiber by adopting a dry spinning method.
Wherein,
the molar ratio of the diphenylmethane-4, 4' -diisocyanate to the polytetrahydrofuran ether glycol in the step 1) is 1.45: 1-1.95: 1.
The aprotic polar solvent in step 2) is selected from N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC).
The chain extender in the step 3) is a mixture of polyether amine and aliphatic diamine.
Further, in the step 3), the polyether amine is EDR-148 (molecular weight 148), EDR-176 (molecular weight 176) or EDR-192 (molecular weight 192), and the aliphatic diamine is ethylenediamine.
Further, the molar ratio of the polyether amine to the aliphatic diamine in the step 3) is 1: 4-1: 49.
The chain terminator in the step 3) is diethylamine, dipropylamine, ethanolamine or n-hexylamine or a mixture thereof, preferably diethylamine.
The additive in the step 4) is a DMAC solution of a delustering agent, an anti-yellowing agent, an anti-ultraviolet absorber, an antioxidant and a lubricating and unwinding agent.
The apparent viscosity of the spandex spinning solution in the step 5) is 4000-6000 poise at 40 ℃.
The invention is described in detail below with reference to examples, which are not to be construed as limiting the invention in any way.
Example 1:
(1) 150Kg of polytetrahydrofuran ether glycol PTMG (molecular weight 1810) and 35.03Kg of diphenylmethane-4, 4 'diisocyanate are placed in a reactor and react for 120min at 86 +/-2 ℃ to obtain an isocyanate group-terminated prepolymer, wherein the molar ratio of the diphenylmethane-4, 4' diisocyanate to the polytetrahydrofuran ether glycol is 1.69: 1;
(2) adding 242.749Kg of DMAC into the prepolymer to fully dissolve the prepolymer in the DMAC to form a prepolymer solution;
(3) adding an amine mixed solution formed by dissolving 3.264Kg of ethylenediamine, 2.013Kg of EDR-148 and 0.608Kg of diethylamine in 111.817Kg of DMAC into the prepolymer solution, and carrying out chain extension reaction and chain termination reaction to obtain a polyurethane urea stock solution, wherein the concentration of the mixed amine solution is 5%, and the molar ratio of the polyether amine EDR-148 to the aliphatic ethylenediamine is 1: 4;
(4) adding a delustering agent, an anti-yellowing agent, an ultraviolet absorbent, an antioxidant and a lubricating and unwinding agent into the polyurethane urea stock solution to obtain a polyurethane spinning stock solution;
(5) after the polyurethane spinning solution is cured, the apparent viscosity at 40 ℃ is 4000poise, and the 40D high-elongation polyurethane elastic fiber is obtained by dry spinning, wherein the spinning speed is 1200m/min, and the temperature of a spinning nozzle is 264 ℃.
Example 2:
the preparation was identical to example 1, except that the molar ratio of polyetheramine EDR-148 to aliphatic ethylenediamine in step (3) was 1:9, and the product obtained had an apparent viscosity of 4200poise at 40 ℃.
Example 3:
the preparation was as in example 1, except that the molar ratio of polyetheramine EDR-148 to aliphatic ethylenediamine in step (3) was 1:19, and the product obtained had an apparent viscosity of 4500poise at 40 ℃.
Example 4:
the preparation process is identical to example 1, except that the molar ratio of the polyetheramine EDR-148 to the aliphatic ethylenediamine in step (3) is 1:49, and the apparent viscosity of the product obtained at 40 ℃ is 4300 poise.
Example 5:
the preparation method is the same as example 1, except that the polyether amine in step (3) is EDR-176, the molar ratio of EDR-176 to aliphatic ethylenediamine is 1:9, and the apparent viscosity of the obtained product at 40 ℃ is 4800 poise.
Comparative example 1:
the preparation method is the same as that of example 1, except that ethylene diamine is used as a chain extender in the step (3), and the apparent viscosity of the obtained product at 40 ℃ is 5000 poise.
Comparative example 2:
the preparation method is the same as example 1, except that ethylene diamine is used as a chain extender in the step (3), the apparent viscosity of the obtained product at 40 ℃ is 5000poise, and the spinning speed in the step (5) is 800 m/min.
From the above examples and comparative examples, the following test data were obtained.
| Test specimen | Spinning speed/(m.min)-1) | Breaking Strength DS/g | Elongation at break/% |
| Example 1 | 1200 | 62.8 | 650.3 |
| Example 2 | 1200 | 58.5 | 620.8 |
| Example 3 | 1200 | 52.4 | 615.4 |
| Example 4 | 1200 | 52.2 | 612.1 |
| Example 5 | 1200 | 64.5 | 678.8 |
| Comparative example 1 | 1200 | 44.3 | 503.9 |
| Comparative example 2 | 800 | 53.3 | 545.7 |
Remarking: mechanical property testing method
The CMT6101 microcomputer controlled electronic universal tester (Shenzhen, New Miss Material detection Co., Ltd.) is adopted to test the tensile strength of the sample. The sample is placed for 4 hours at the constant temperature and humidity condition of 25 ℃ and 65% of relative humidity before testing; when in test, the tensile speed is 500mm/min, the length of the sample is 50mm, and the breaking strength and the breaking elongation of each sample are obtained by averaging 5 times of test.
Claims (4)
1. A preparation method of high-elongation spandex fiber is characterized by comprising the following steps:
1) in the prepolymerization stage, mixing and reacting diphenylmethane-4, 4' diisocyanate and polytetrahydrofuran ether glycol to obtain isocyanate group-terminated polyurethane prepolymer;
2) dissolving the polyurethane prepolymer obtained in step 1) with an aprotic polar solvent to obtain a prepolymer solution;
3) cooling the prepolymer solution prepared in the step 2), and adding a mixed amine solution to perform chain extension reaction and chain termination reaction to form a polyurethaneurea solution;
4) adding various additives into the polyurethane urea solution prepared in the step 3), and fully and uniformly mixing to prepare a spandex spinning solution;
5) curing the prepared spandex spinning solution, and then obtaining high-elongation spandex fibers by adopting a dry spinning method;
wherein:
the chain extender used in the chain extension reaction in the step 3) is a mixture of polyether amine and aliphatic diamine; the chain terminator used in the chain termination reaction is diethylamine, dipropylamine, ethanolamine or n-hexylamine, or a mixture thereof;
the polyether amine is EDR-148, and the molecular weight of the polyether amine is 148; EDR-176 having a molecular weight of 176; or EDR-192 with the molecular weight of 192, wherein the aliphatic diamine is ethylenediamine;
the molar ratio of the polyether amine to the aliphatic diamine is 1: 9-1: 49.
2. The method for preparing high elongation spandex fiber according to claim 1, characterized in that: the diphenylmethane-4, 4' -diisocyanate and the polytetrahydrofuran ether glycol are mixed and react, and the molar ratio is 1.45: 1-1.95: 1.
3. The method for preparing high elongation spandex fiber according to claim 1, characterized in that: the aprotic polar solvent is N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC).
4. The method for preparing high elongation spandex fiber according to claim 1, characterized in that: the additives include delusterants, anti-yellowing agents, ultraviolet absorbers, antioxidants, and lubricating and unwinding agents.
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