WO2015088061A1 - Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse - Google Patents

Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse Download PDF

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Publication number
WO2015088061A1
WO2015088061A1 PCT/KR2013/011408 KR2013011408W WO2015088061A1 WO 2015088061 A1 WO2015088061 A1 WO 2015088061A1 KR 2013011408 W KR2013011408 W KR 2013011408W WO 2015088061 A1 WO2015088061 A1 WO 2015088061A1
Authority
WO
WIPO (PCT)
Prior art keywords
spinning
elastic yarn
yarn
chain
speed
Prior art date
Application number
PCT/KR2013/011408
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English (en)
Korean (ko)
Inventor
이재명
진중성
강연수
Original Assignee
주식회사 효성
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 효성 filed Critical 주식회사 효성
Priority to PCT/KR2013/011408 priority Critical patent/WO2015088061A1/fr
Publication of WO2015088061A1 publication Critical patent/WO2015088061A1/fr

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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
    • D01F6/58—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
    • 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
    • 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
    • D01D5/06—Wet spinning methods

Definitions

  • the present invention relates to a method for producing a high-speed spinning polyurethane urea elastic yarn, and more particularly, by mixing MDI isomers with diisocyanate and using n-butylamine as a chain stopper to improve yarn elongation, modulus By lowering, it relates to a method for producing a high-speed spinning polyurethane urea elastic yarn that can secure yarn properties and improve productivity at the same level as the existing products when applying high-speed spinning.
  • polyurethaneurea obtains a prepolymer by reacting a polyol with an excess of diisocyanate compound, and makes an elastic yarn by spinning after making a spinning stock solution of polyurethaneurea fiber through an appropriate reaction to the prepolymer.
  • the conventional polyurethane urea polymers have a problem in that productivity is improved when high-speed spinning is applied, while elongation of yarn and a sudden increase in modulus occur.
  • the present invention is to solve the above-described problems, while maintaining the productivity in high-speed spinning, while preventing the decrease in elongation of the yarn and the sudden rise of modulus, high-speed spinning polyurethane that can obtain yarn properties similar to conventional elastic yarn
  • the main object is to provide a method for producing urea elastic yarn.
  • the step of first polymerizing the polyol and diisocyanate to obtain a prepolymer Dissolving the prepolymer in an organic solvent and adding a chain extender and a chain terminator to perform secondary polymerization to obtain a spinning stock solution; And drying or wet spinning the spinning stock solution to obtain a polyurethaneurea elastic yarn;
  • the diisocyanate includes two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and the chain dissociation agent comprises n-butylamine.
  • the chain dispersing agent may include 20 to 80 mol% of n-butylamine and 20 to 80 mol% of diethylamine with respect to the total chain extender.
  • one of the organic diisocyanate may be 2,4'-diphenylmethane diisocyanate.
  • the content of 2,4'-diphenylmethane diisocyanate may be 0.1 to 10 mol% based on the total diisocyanate.
  • the step of obtaining the polyurethane urea elastic yarn may be made by dry or wet spinning having a yarn speed of 1000 m / min or more.
  • productivity and yarn elongation can be improved and high modulus can be lowered at high speed spinning applications.
  • productivity and yarn elongation can be improved and high modulus can be lowered at high speed spinning applications.
  • high modulus can be lowered at high speed spinning applications.
  • the best mode of the present invention was the elastic yarns of Examples 1-3.
  • An elastic yarn according to one embodiment of the present invention is first polymerized with a polyol to an excess of diisocyanate to obtain a prepolymer.
  • a chain extender and a chain terminator are added to the solution to perform secondary polymerization to prepare a spinning stock solution.
  • the chain extender and chain stopper may be added all at once or divided into two or more stages.
  • the spinning solution is dry or wet spinning at 1000 m / min or more yarn to produce a polyurethane urea elastic yarn.
  • the diisocyanate used in the present embodiment may include one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates.
  • one kind of the organic diisocyanate may be preferably 2,4'-MDI.
  • the 2,4'-MDI has a three-dimensional structure, the intermolecular hydrogen bonds or intramolecular hydrogen bonds in the hard segment are weakened, thereby exhibiting the same effect as that of increasing the content of the soft segment. In this way, a large number of soft domains may be formed to obtain elastic yarns having low heat resistance, improved yarn elongation, and low modulus. At this time, even if the winding speed is further increased, the elongation of the yarn can be prevented from being lowered.
  • the content of 2,4'-MDI is appropriately 10 mol% or less in the total diisocyanate. If the content of 2,4'-MDI exceeds 10 mol%, there may be a problem that the heat resistance of the yarn is sharply lowered.
  • the polyol usable in the present invention may exemplify at least one or more selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and combinations thereof, but the present invention is not limited thereto.
  • the molecular weight of the polyol may be 500 to 8000, more preferably 1200 to 3000.
  • Diamines used in the chain extender include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-di
  • 1,2-diaminopropane 1,3-diaminopropane
  • 1,4-diaminobutane 1,4-diaminobutane
  • 2,3-diaminobutane 1,5-di
  • One kind or a mixture of two or more kinds selected from aminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine and the like can be exemplified, but the present invention is not limited thereto.
  • a chain terminator is used to control the molecular weight of the polyurethane urea.
  • diethylamine is used as a conventional terminator, the postpolymerization occurs excessively during high-speed spinning, resulting in lower yarn elongation and A sudden rise in modulus can occur.
  • n-butylamine is used as a chain terminator, and the n-butylamine prevents post-polymerization in the high-speed spinning process from occurring compared to conventional spinning, thereby preventing a decrease in elongation of yarn, and thus applying high-speed spinning. Even when the yarn can obtain the yarn properties similar to the elastic yarn spun from the conventional yarn, it is possible to improve the productivity.
  • the chain terminator may include a certain amount of diethylamine, it is possible to properly adjust the elongation and modulus of the yarn according to the content of the added diethylamine.
  • the component content of the chain terminator may preferably include 20 to 80 mol% of n-butylamine and 20 to 80 mol% of diethylamine, based on the total chain terminator.
  • the expression of the postpolymerization inhibitory effect may be insufficient, and when the n-butylamine is more than 80 mol%, the viscosity is suitable for spinning due to excessive inhibition of the postpolymerization. This can become impossible.
  • the steric hindrance phenol compound in order to prevent discoloration and deterioration of the physical properties of the polyurethane urea due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • the steric hindrance phenol compound in order to prevent discoloration and deterioration of the physical properties of the polyurethane urea due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably.
  • the polyurethaneurea elastic yarn of the present invention may further include additives such as titanium dioxide and magnesium stearate, antioxidants, dyeing enhancers, thermal oxidation stabilizers, antibacterial agents, light stabilizers or antistatic agents, if necessary.
  • additives such as titanium dioxide and magnesium stearate, antioxidants, dyeing enhancers, thermal oxidation stabilizers, antibacterial agents, light stabilizers or antistatic agents.
  • NCO% [100 * 2 * NCO Formula Weight * (Capping Ratio-1)] / ⁇ (Diisocyanate Molecular Weight * Capping Ratio) + Polyol Molecular Weight ⁇
  • the capping ratio is the molar ratio of diisocyanate mole ratio / polyol.
  • the measurement is performed at a sample length of 10 cm and a tensile speed of 100 cm / min.
  • the strength and elongation at break are measured, and the load on the yarn at 200% elongation is also measured at 200% modulus.
  • the ratio of the chain extender and the chain dispersant was 9.5: 1
  • the ratio of 1,2-propanediamine was 80 mol% and 20 mol%.
  • the amine used was prepared in a total concentration of 7 mol%, and dimethylacetamide was used as a solvent.
  • the spinning stock solution obtained as described above was prepared by polyurethane spinning yarn of 20 denier 1 filament at a speed of 1300 m / min by dry spinning, and the physical properties thereof are shown in Table 1 below.
  • Example 2 It was the same as Example 1 except using 60 mol% of n-butylamine and 40 mol% of diethylamine as a chain terminator.
  • the obtained spinning stock solution prepared a polyurethane urea elastic yarn of 20 denier 1 filament at a speed of 1300 m / min, and the physical properties thereof are shown in Table 1 below.
  • Example 2 Same as Example 1 except that 100 mol% of n-butylamine was used as a chain terminator and no diethylamine was used.
  • the obtained spinning stock solution prepared a polyurethane urea elastic yarn of 20 denier 1 filament at a speed of 1300 m / min, and the physical properties thereof are shown in Table 1 below.
  • the obtained spinning stock solution produced a polyurethane urea elastic yarn of 20 denia 1 filament at a speed of 1000 m / min, which is lower than that of the Example, and evaluated for physical properties thereof are shown in Table 1 below.
  • Additive composition, spinning conditions, etc. of this polymer are the same as in Example 1.
  • the obtained spinning stock solution prepared a polyurethane urea elastic yarn of 20 denier 1 filament at a speed of 1300 m / min, and the physical properties thereof are shown in Table 1 below. Additive composition, spinning conditions, etc. of this polymer are the same as in Example 1.
  • Example 1 2,4'-diphenylmethane diisocyanate content First / Second Termination Agent NCO% [%] Winding speed [m / min] Strength [g / d] Elongation [%] Maximum draw ratio 200% modulus [g]
  • Example 1 10% 20/80 2.70 1300 1.15 ⁇ 0.1 450 ⁇ 15 4.1 ⁇ 0.1 4.5 ⁇ 0.1
  • Example 2 10% 60/40 2.70 1300 1.15 ⁇ 0.1 500 ⁇ 15 4.5 ⁇ 0.1 3.8 ⁇ 0.1
  • Example 3 10% 100/0 2.70 1300 1.15 ⁇ 0.1 560 ⁇ 15 5.0 ⁇ 0.1 3.1 ⁇ 0.1 Comparative Example 1 0% 0/100 2.70 1000 1.15 ⁇ 0.1 490 ⁇ 15 4.4 ⁇ 0.1 3.7 ⁇ 0.1 Comparative Example 2 10% 0/100 2.70 1300 1.15 ⁇ 0.1 430 ⁇ 15 4.0 ⁇ 0.1 4.3 ⁇ 0.1
  • n-butylamine and diethylamine were selectively used as a chain terminator during secondary polymerization by mixing 2,4'-diphenylmethane diisocyanate, compared with Comparative Example 2 above. It can be seen that yarn properties (elongation, maximum draw ratio and modulus) are similar to those of conventional spinning (Comparative Example 1) even at high speed spinning. In addition, it can be seen that the elongation increases and the modulus decreases as the amount of diethylamine is decreased, so that the elongation and modulus of elastic yarn can be adjusted to an appropriate level by adjusting the amount of diethylamine.
  • the polyurethaneurea elastic yarns prepared in Examples 1 to 3 have improved yarn elongation and decreased modulus compared to conventional elastic yarns using only diethylamine as a chain terminator, as in Comparative Example 1. Since yarn properties similar to elastic yarns spun at ordinary yarns can be obtained, productivity improvement can be expected by using high-speed spinning.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse, comprenant les étapes consistant : à obtenir un prépolymère par polymérisation principale de polyols et diisocyanates ; à réaliser une polymérisation secondaire par dissolution du prépolymère dans un solvant organique et ajout d'un allongeur de chaîne et d'un terminateur de chaîne de façon à obtenir une solution de filature ; et à obtenir le fil élastique de polyuréthane-urée par filage à sec ou humide de la solution de filature, les diisocyanates comprenant deux ou plusieurs types de diisocyanates organiques choisis parmi des diisocyanates aromatiques, aliphatiques et alicycliques, et le terminateur de chaîne comprenant de la n-butylamine.
PCT/KR2013/011408 2013-12-10 2013-12-10 Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse WO2015088061A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2013/011408 WO2015088061A1 (fr) 2013-12-10 2013-12-10 Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse

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Application Number Priority Date Filing Date Title
PCT/KR2013/011408 WO2015088061A1 (fr) 2013-12-10 2013-12-10 Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse

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WO2015088061A1 true WO2015088061A1 (fr) 2015-06-18

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980016619A (ko) * 1996-08-29 1998-06-05 한형수 폴리우레탄계 탄성섬유의 제조방법
US20040019146A1 (en) * 2000-12-20 2004-01-29 Hiroshi Nishikawa Elastomeric polyurethane fiber with high heat-set efficiency
KR20040027882A (ko) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 개선된 스판덱스 조성물
KR20110078784A (ko) * 2009-12-31 2011-07-07 주식회사 효성 고속방사용 폴리우레탄우레아 탄성사의 제조방법
KR20120078433A (ko) * 2010-12-31 2012-07-10 주식회사 효성 강도가 우수한 스판덱스 섬유용 폴리우레탄 수지 조성물 및 이로부터 제조된 스판덱스

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980016619A (ko) * 1996-08-29 1998-06-05 한형수 폴리우레탄계 탄성섬유의 제조방법
US20040019146A1 (en) * 2000-12-20 2004-01-29 Hiroshi Nishikawa Elastomeric polyurethane fiber with high heat-set efficiency
KR20040027882A (ko) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 개선된 스판덱스 조성물
KR20110078784A (ko) * 2009-12-31 2011-07-07 주식회사 효성 고속방사용 폴리우레탄우레아 탄성사의 제조방법
KR20120078433A (ko) * 2010-12-31 2012-07-10 주식회사 효성 강도가 우수한 스판덱스 섬유용 폴리우레탄 수지 조성물 및 이로부터 제조된 스판덱스

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