CN114134596A - Method for preparing dry-spun spandex by adopting mixed solvent - Google Patents
Method for preparing dry-spun spandex by adopting mixed solvent Download PDFInfo
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- CN114134596A CN114134596A CN202210037060.5A CN202210037060A CN114134596A CN 114134596 A CN114134596 A CN 114134596A CN 202210037060 A CN202210037060 A CN 202210037060A CN 114134596 A CN114134596 A CN 114134596A
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- mixed solvent
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- spandex
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- 239000012046 mixed solvent Substances 0.000 title claims abstract description 38
- 229920002334 Spandex Polymers 0.000 title claims abstract description 33
- 239000004759 spandex Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 57
- 238000009987 spinning Methods 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 229920006306 polyurethane fiber Polymers 0.000 claims abstract description 11
- 230000003068 static effect Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000004804 winding Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- -1 polyethylene adipate Polymers 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000000578 dry spinning Methods 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical group 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 7
- 238000009940 knitting Methods 0.000 abstract description 4
- 206010024769 Local reaction Diseases 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a method for preparing dry-spun spandex by adopting a mixed solvent, which adopts one or more organic solvents with strong polarity and low boiling point to be compounded with DMAC to form the mixed solvent; dissolving the low molecular weight prepolymer controlled and generated by the retarder by using a mixed solvent to form a prepolymer dissolved solution; adding the prepolymer solution and the chain extender mixed solution into a static mixer for reaction to obtain a polyurethane urea spinning solution; and finally, the spinning solution passes through a high-temperature channel, the solvent is evaporated, and the polyurethane fiber is solidified. Through adding retarder in prepolymer reaction process, make the prepolymerization reaction stable controllable, prepolymer molecular weight is low and molecular weight distribution is more even, through the mode that chain extender and terminating agent added simultaneously, guarantees that the chain segment increases more gently, avoids appearing local reaction and leads to "gel" to produce too fast. The finished spandex fiber prepared by the method has high modulus and high breaking strength, and can meet the application requirements of different fields such as circular knitting machines, warp and weft knitting and the like.
Description
Technical Field
The invention belongs to a preparation method of dry-spun spandex, and particularly relates to a technical method for producing the dry-spun spandex by adopting a mixed solvent.
Technical Field
Most of spandex products in the market at present are produced by a dry spinning technology. The dry process is to dissolve polymer in organic solvent to prepare spinning solution, then to discharge the spinning solution from fine spinneret orifice into high temperature heat channel, to volatilize solvent, and to solidify polymer strand into fiber. Dry spinning techniques are particularly important for solvent selection. First, the solvent should be strongly polar so that it can sufficiently dissolve the high molecular weight polymer. Secondly, the boiling point of the solvent is low, so that the polymer solution is ensured to be quickly removed when passing through a high-temperature shaft, and the amount of the solvent remained in the fiber is as low as possible. Finally, the toxicity of the solvent is low, so that the harm of solvent contact to human health in the production process is reduced as much as possible. The organic solvent currently used for dry spinning spandex is typically N, N-Dimethylacetamide (DMAC). DMAC is an organic solvent with strong polarity and low toxicity, and its boiling point is relatively high, typically at 164-166 ℃. Therefore, the evaporation rate of DMAC often determines the production efficiency of dry spinning spandex.
The technological approach in recent years to upgrading and enhancing dry spandex production has generally centered around how to evaporate DMAC as rapidly as possible at high spinning speeds. Common process optimization comprises increasing spinning temperature and increasing spinning air quantity and air speed; the method also comprises the steps of modifying the channel equipment, including lengthening and widening the spinning channel, changing the air inlet plate hole structure (CN214193537U) of the channel and the like; there are also patented techniques that are addressed in the aspects of increasing the concentration of the spinning solution, changing the structure of the polymer component (CN105177755B), and the like. These technical methods improve the external conditions of evaporation of the solvent, increasing the efficiency of evaporation of the DMAC, but without altering the evaporation properties of the solvent itself. Therefore, under the existing equipment condition, the limit of the spinning speed of the dry-method spandex is close to 1100m/min, and higher breakthrough is difficult to achieve; and under the condition of high-speed spinning, the residual rate of the fiber solvent exceeds 1.0 percent, and the product quality is difficult to ensure.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a method for preparing dry-spun spandex by using a mixed solvent, and solves the technical problems that the solvent cannot be fully evaporated, the residual rate in fibers is too high, the product performance is deteriorated and the like in the efficient production process of spandex.
The technical scheme is as follows: in order to solve the technical problems, the method for preparing dry-spun spandex by using the mixed solvent selects one or more strong-polarity low-boiling-point organic solvents to be compounded with DMAC (dimethylacetamide) to form the mixed solvent; dissolving the low molecular weight prepolymer controlled and generated by the retarder by using a mixed solvent to form a prepolymer dissolved solution; adding the prepolymer solution and the chain extender mixed solution into a static mixer for reaction to obtain a polyurethane urea spinning solution; and finally, the spinning solution passes through a high-temperature channel, the solvent is evaporated, and the polyurethane fiber is solidified.
The invention specifically comprises the following steps:
step 1, preparation of a mixed solvent: mixing a low-boiling-point organic solvent with N, N-Dimethylacetamide (DMAC) to obtain a mixed solvent;
step 2, synthesis of prepolymer solution: adding polymer dihydric alcohol and diphenylmethane diisocyanate into a reaction kettle, and simultaneously adding a retarder; stirring and reacting for 0.5-2.0 hours at 40-80 ℃ to obtain an isocyanate group (-NCO) terminated low molecular weight prepolymer; adding a mixed solvent to fully dissolve the prepolymer to obtain a prepolymer solution, and reducing the temperature of the prepolymer solution to 5-20 ℃;
step 3, preparation of spinning solution: adding the prepolymer dissolved solution and the chain extender mixed solution into a static mixer for reaction to obtain a polyurethane urea dissolved solution; adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain a polyurethane urea spinning solution;
step 4, preparing spandex finished products: and (3) passing the polyurethane urea spinning solution through a spinneret plate, passing through a 240-260-DEG hot air channel system, evaporating the solvent, solidifying to obtain polyurethane fibers, and winding into dry-spun polyurethane finished product yarn rolls through a high-speed winding machine.
Wherein the content of the first and second substances,
the low-boiling-point organic solvent is ester organic polar solvent of one or more of methyl acetate, ethyl acetate, propyl acetate or butyl acetate.
The mass ratio of the low-boiling-point organic solvent to the DMAC in the mixed solvent is 5: 95-50: 50.
the polymer diol is one or more of polyethylene glycol adipate diol, polybutylene glycol adipate diol, polycaprolactone diol, polycarbonate diol or polytetramethylene ether glycol.
The retarder is organic or inorganic acid substances, and the amount of the retarder is 0.01-0.1% of the mass of the polymer glycol.
The organic or inorganic acid substance is one or more of acetic acid, oxalic acid, malonic acid, sulfurous acid, phosphoric acid, phosphorous acid or maleic acid.
The mixed liquid of the chain extender is a mixed liquid of the chain extender, the end capping agent and DMAC.
The chain extender is one or the combination of more of ethylenediamine, propylenediamine, pentylenediamine, hexylenediamine and octylenediamine; the blocking agent is one or more of dimethylamine, diethylamine, n-propylamine, n-butylamine, isobutylamine, cyclohexylamine and dicyclohexylamine; the molar ratio of the chain extender to the end capping agent is 90: 10-99: 1.
the high-speed winding machine is set to have a winding speed of 1100-1500 m/min.
Has the advantages that: the invention uses the mixture of low boiling polar solvent and DMAC as the good solvent of polyurethane urea spinning solution, and utilizes the azeotropic effect formed by the two solvents in a high-temperature channel to ensure that the solvent is removed rapidly; by adding the retarder in the reaction process of the prepolymer, the prepolymerization reaction is stable and controllable, the prepolymer has low molecular weight and more uniform molecular weight distribution, and is more favorable for being dissolved in a mixed solvent; by adding the chain extender and the end capping agent simultaneously, the chain segment is ensured to grow more smoothly, and the generation of gel caused by over-quick local reaction is avoided. The polyurethane urea spinning solution prepared by the method is solidified into filaments at the speed of 1100-1500 m/min, and the residual rate of the solvent in the fibers is lower than 0.5%; the finished spandex fiber has high modulus and high breaking strength, and can meet the application requirements of different fields such as circular knitting machines, warp and weft knitting and the like.
Detailed Description
The invention specifically comprises the following 4 steps:
1) preparation of mixed solvent: and mixing the low-boiling-point organic solvent with DMAC according to a mass ratio to obtain a mixed solvent.
2) Synthesis of prepolymer solution: adding polymer dihydric alcohol and diphenylmethane diisocyanate into a reaction kettle, and simultaneously adding a retarder; stirring and reacting for 0.5-2.0 hours at 40-80 ℃ to obtain an isocyanate group (-NCO) terminated low molecular weight prepolymer; adding a mixed solvent to fully dissolve the prepolymer, and then reducing the temperature of the prepolymer solution to 5-20 ℃.
3) Preparation of spinning solution. Adding the prepolymer dissolved solution and the chain extender mixed solution into a static mixer for reaction to obtain a polyurethane urea dissolved solution; and adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain the polyurethane urea spinning solution.
4) Preparation of finished spandex. And (3) passing the spinning solution through a spinneret plate, passing the spinning solution through a 240-260-DEG hot air channel system, evaporating the solvent, solidifying the spinning solution into a polyurethane fiber, and forming a polyurethane yarn roll through a high-speed winding machine.
Wherein:
the low-boiling-point organic solvent used in the invention is an ester organic polar solvent, and can be one or a combination of methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
The mass ratio of the low-boiling-point organic solvent to the DMAC in the mixed solvent prepared by the method is 5: 95-50: 50. the polymer diol used in the present invention may be one or a combination of more of polyethylene adipate diol, polybutylene adipate diol, polycaprolactone diol, polycarbonate diol, polytetramethylene ether glycol, and the like.
The retarder used in the invention is organic or inorganic acid substances, and can be one or a combination of more of acetic acid, oxalic acid, malonic acid, sulfurous acid, phosphoric acid, phosphorous acid, maleic acid and the like; the using amount of the retarder is 0.01-0.1% of the mass ratio of the polymer glycol.
The chain extender mixed solution used in the invention is a mixed solution of a chain extender, an end capping agent and DMAC. The chain extender can be one or more of ethylenediamine, propylenediamine, pentylenediamine, hexylenediamine, octylenediamine and the like; the blocking agent can be one or more of dimethylamine, diethylamine, n-propylamine, n-butylamine, isobutylamine, cyclohexylamine, dicyclohexylamine and the like. The molar mass ratio of the chain extender to the end capping agent is 90: 10-99: 1.
the high-speed winder used in the present invention has a winding speed of 1100 to 1500 m/min.
Example 1
Mixing ethyl acetate and DMAC according to the mass ratio of 12.5/87.5 to obtain a mixed solvent; polytetramethylene ether glycol (PTMG) was reacted with diphenylmethane diisocyanate in the following 1: 2.0 mol percent of the mixture is added into a reaction kettle, and acetic acid is added as retarder, and the dosage of the retarder is 0.05 percent of the mass of the PTMG; stirring and reacting for 2.0 hours at 70 ℃ to obtain a prepolymer terminated by isocyanate group (-NCO); adding a mixed solvent to fully dissolve the prepolymer, and then reducing the temperature of the prepolymer solution to 10 ℃; adding the prepolymer dissolved solution and the mixed solution of ethylenediamine/pentamethylene diamine/n-butylamine into a static mixer for reaction (wherein the molar ratio of ethylenediamine/pentamethylene diamine/n-butylamine is 80/15/5) to obtain a polyurethane urea dissolved solution; adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain a polyurethane urea spinning solution; the spinning solution passes through a 252-degree hot air channel system, the solvent is evaporated, the spinning solution is solidified into polyurethane fiber, and the polyurethane fiber is wound into a polyurethane sample 1 at the speed of 1300 m/min.
Example 2
Mixing ethyl acetate and DMAC according to the mass ratio of 15.5/84.5 to obtain a mixed solvent; mixing polyethylene glycol adipate glycol with diphenylmethane diisocyanate according to a ratio of 1: 2.0 mol percent of the mixture is added into a reaction kettle, and phosphoric acid is added as a retarder, and the dosage of the phosphoric acid is 0.06 percent of the mass of the polyethylene glycol adipate glycol; stirring and reacting for 1.0 hour at 70 ℃ to obtain an isocyanate group (-NCO) terminated prepolymer; adding a mixed solvent to fully dissolve the prepolymer, and then reducing the temperature of the prepolymer solution to 10 ℃; adding the prepolymer solution and the mixed solution of ethylenediamine/propylenediamine/diethylamine into a static mixer for reaction (wherein the molar ratio of ethylenediamine/propylenediamine/diethylamine is 75/15/10), so as to obtain a polyurethaneurea solution; adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain a polyurethane urea spinning solution; the spinning solution passes through a 252-degree hot air channel system, the solvent is evaporated, the spinning solution is solidified into polyurethane fiber, and the polyurethane fiber is wound into a polyurethane sample 2 at the speed of 1300 m/min.
Example 3
Mixing methyl acetate and DMAC according to the mass ratio of 20/80 to obtain a mixed solvent; mixing polyethylene glycol adipate glycol with diphenylmethane diisocyanate according to a ratio of 1: 2.0 mol percent of the mixture is added into a reaction kettle, and phosphorous acid is added as a retarder, and the dosage of the phosphorous acid is 0.08 percent of the mass of the polyethylene glycol adipate glycol; stirring and reacting for 1.0 hour at 70 ℃ to obtain an isocyanate group (-NCO) terminated prepolymer; adding a mixed solvent to fully dissolve the prepolymer, and then reducing the temperature of the prepolymer solution to 10 ℃; adding the prepolymer solution and the mixed solution of ethylenediamine/propylenediamine/cyclohexylamine into a static mixer for reaction (wherein the molar ratio of ethylenediamine/propylenediamine/cyclohexylamine is 90/6/4), so as to obtain a polyurethaneurea solution; adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain a polyurethane urea spinning solution; the spinning solution passes through a 252-degree hot air channel system, the solvent is evaporated, the spinning solution is solidified into polyurethane fiber, and the polyurethane fiber is wound into a polyurethane sample 3 after 1300 m/min.
Comparative example 1
Comparative example spandex comparative sample 1 was also spun at 1300 m/min using a conventional spandex preparation method using a single DMAC as solvent, without any retarder.
Comparative example 2
Comparative example 2 was conducted in substantially the same manner as in example 1 except that ethyl acetate and DMAC were mixed in 3/97 mass ratio and spun at 1300 m/min to give comparative spandex sample 3.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that ethyl acetate and DMAC are mixed in 60/40 mass ratios and spun at 1300 m/min to give comparative spandex sample 4.
Comparative example 4
Comparative example 4 was prepared in substantially the same manner as in example 1 except that the retarder was eliminated and spandex comparative sample 2 was spun at 1300 m/min. The performance of each sample was tested, and the specific indices are shown in the following table:
note that: modulus is the stress value required to stretch spandex to 300% elongation.
The term "resilience" means the recovery from elongation and the resilience (L)1-L2)/(L1-L0) 100% of the total weight; in the formula L0The original length of the sample is obtained; l is1The length of the sample after being stretched to 300% elongation; l is2The recovery length of the sample after stretching.
Claims (9)
1. A method for preparing dry spinning spandex by adopting a mixed solvent is characterized by comprising the following steps:
step 1, preparation of a mixed solvent: mixing a low-boiling-point organic solvent with N, N-Dimethylacetamide (DMAC) to obtain a mixed solvent;
step 2, synthesis of prepolymer solution: adding polymer dihydric alcohol and diphenylmethane diisocyanate into a reaction kettle, and simultaneously adding a retarder; stirring and reacting for 0.5-2.0 hours at 40-80 ℃ to obtain an isocyanate group (-NCO) terminated low molecular weight prepolymer; adding a mixed solvent to fully dissolve the prepolymer to obtain a prepolymer solution, and reducing the temperature of the prepolymer solution to 5-20 ℃;
step 3, preparation of spinning solution: adding the prepolymer dissolved solution and the chain extender mixed solution into a static mixer for reaction to obtain a polyurethane urea dissolved solution; adding a lubricant, an ultraviolet light resistant auxiliary agent and an antioxidant auxiliary agent, mixing and curing for 24 hours to obtain a polyurethane urea spinning solution;
step 4, preparing spandex finished products: and (3) passing the polyurethane urea spinning solution through a spinneret plate, passing through a 240-260-DEG hot air channel system, evaporating the solvent, solidifying to obtain polyurethane fibers, and winding into dry-spun polyurethane finished product yarn rolls through a high-speed winding machine.
2. The method for preparing dry-spun spandex using a mixed solvent according to claim 1, characterized in that the low-boiling organic solvent is an ester organic polar solvent of one or more combinations of methyl acetate, ethyl acetate, propyl acetate, or butyl acetate.
3. The method for preparing dry-spun spandex by using the mixed solvent according to claim 1, wherein the mass ratio of the low-boiling-point organic solvent to the DMAC in the mixed solvent is 5: 95-50: 50.
4. the method for preparing dry-spun spandex using a mixed solvent according to claim 1, characterized in that the polymer diol is one or a combination of polyethylene adipate diol, polybutylene adipate diol, polycaprolactone diol, polycarbonate diol, or polytetramethylene ether glycol.
5. The method for preparing dry-spun spandex by using the mixed solvent according to claim 1, wherein the retarder is an organic or inorganic acid substance, and the amount of the retarder is 0.01-0.1% of the mass of the polymer glycol.
6. The method for preparing dry-spun spandex using a mixed solvent as claimed in claim 5, characterized in that the organic or inorganic acid substance is one or more of acetic acid, oxalic acid, malonic acid, sulfurous acid, phosphoric acid, phosphorous acid or maleic acid in combination.
7. The method for preparing dry-spun spandex by using the mixed solvent according to claim 1, wherein the mixed solution of the chain extender is a mixed solution of the chain extender, the end-capping reagent and DMAC.
8. The method for preparing dry spinning spandex by using the mixed solvent according to claim 7, characterized in that the chain extender is one or more of ethylene diamine, propane diamine, pentane diamine, hexane diamine and octane diamine; the blocking agent is one or more of dimethylamine, diethylamine, n-propylamine, n-butylamine, isobutylamine, cyclohexylamine and dicyclohexylamine; the molar ratio of the chain extender to the end capping agent is 90: 10-99: 1.
9. the method for preparing dry-spun spandex using a mixed solvent according to claim 1, wherein the set winding speed of the high-speed winder is 1100 to 1500 m/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115537962A (en) * | 2022-11-03 | 2022-12-30 | 华峰化学股份有限公司 | Spandex for nylon-spandex fabric with uniform evenness and preparation method |
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