KR910007558B1 - Manufacturing process of polyacrylonitrile hollowing fiber - Google Patents

Manufacturing process of polyacrylonitrile hollowing fiber Download PDF

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KR910007558B1
KR910007558B1 KR1019890000167A KR890000167A KR910007558B1 KR 910007558 B1 KR910007558 B1 KR 910007558B1 KR 1019890000167 A KR1019890000167 A KR 1019890000167A KR 890000167 A KR890000167 A KR 890000167A KR 910007558 B1 KR910007558 B1 KR 910007558B1
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spinneret
polyacrylonitrile
spinning
fiber
coagulation bath
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KR900011918A (en
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김우종
박세웅
김격현
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주식회사 코오롱
하기주
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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

A process for producing a polyacrylonitrile hollow fiber is characterized by dissolving a polyacrylonitrile or acrylonitile copolymer comprising at least 85 wt.% acrylonitrile in a solvent, dehydrating, wet-spining through the spinneret, drawing at 60-120 deg.C drying and heating to produce a filament. In the spinneret, the spining draft for the hollow fiber of at least 20% of hollowness ratio is pref. 250-500.

Description

폴리아크릴로니트릴 중공섬유의 제조방법Method for producing polyacrylonitrile hollow fiber

본 발명은 적어도 85중량% 이상의 아크릴로니트릴로 이루어진 폴리아크릴로니트릴 중공섬유의 제조방법에 관한 것이다.The present invention relates to a method for producing a polyacrylonitrile hollow fiber composed of at least 85% by weight or more of acrylonitrile.

더욱 상세히는 적어도 85중량% 이상의 아크릴로니트릴로 이루어진 섬유형성성 폴리아크릴로니트릴 또는 아크릴로니트릴 공중합체를 용매에 녹여 탈포 및 탈수한 다음 이것을 중공형성성 스핀너렛드를 통해 방사하고 이어서 연신, 수세, 건조 및 열처리 공정을 거쳐서 연속적으로 필라멘트를 생산할 수 있는 습식방사를 이용한 폴리아크릴로니트릴 중공섬유의 제조방법에 관한 것이다.More specifically, the fibrous polyacrylonitrile or acrylonitrile copolymer composed of at least 85% by weight of acrylonitrile is dissolved in a solvent, degassed and dehydrated, and then spun through a hollow forming spinneret, followed by stretching and washing with water. It relates to a method for producing polyacrylonitrile hollow fibers using wet spinning, which can continuously produce filaments through drying and heat treatment processes.

보통 아크릴릭 폴리머는 표준조건하에서 잘 녹지 않을 뿐만 아니라 열에 취약하기 때문에 예로부터 용융방사 대신에 폴리머를 용매에 녹여서 방사액을 만든다음 이것을 건식 또는 습식방법으로 섬유화하여서 아크릴섬유를 제조하였다. 건식방사를 이용한 폴리아크릴로니트릴 섬유의 연속적인 제조방법으로는 미국 특허 4,622,195가 있으나 이것은 제조공정이 복잡하고 각 공정마다 제조조건을 맞추기가 어려워서 바람직한 방법은 되지 못한다.Since acrylic polymers are not easily melted under standard conditions and are susceptible to heat, acrylic fibers have been prepared by dissolving polymers in a solvent instead of melt spinning to form spinning liquids, and then fiberizing them by dry or wet methods. A continuous method of producing polyacrylonitrile fibers using dry spinning is US Pat. No. 4,622,195, but this is not a preferred method because the manufacturing process is complicated and it is difficult to meet the manufacturing conditions for each process.

또한 미국 특허 4,432,923에는 건식방사를 이용한 폴리아크릴로니트릴 중공섬유의 제조장치 및 제조방법이 기재되어 있으나 중공율을 높이기 위한 구체적인 방법이 제시되어 있지 않다. 본 발명자들은 이러한 문제점을 검토하여 습식방사를 이용한 폴리아크릴로니트릴 중공섬유의 제조방법을 발명하게 되었다. 본 발명을 상세히 설명하면 다음과 같다.In addition, US Pat. No. 4,432,923 describes an apparatus and a manufacturing method of a polyacrylonitrile hollow fiber using dry spinning, but no specific method for increasing the hollow ratio is disclosed. The present inventors have studied this problem and have invented a method for producing a polyacrylonitrile hollow fiber using wet spinning. The present invention is described in detail as follows.

본 발명에서는 방사원액내의 폴리머 성분으로서 적어도 85중량% 이상의 아크릴로니트릴로 이루어진 호모폴리머 또는 공중합체를 사용하였다. 본 발명에 있어서 공중합체의 성분으로서는 에틸아크릴래이트, 메틸메타아크릴레이트, 비닐아세테이트, 메타일설포내이트, 스타이렌설포내이트 등이 가능하며, 방사원액을 제조하는데 있어서 용제로서는 알킬라인티오시아내이트, 디메틸포름아마이드, 디메틸아세트아마이드, 디메틸메톡시아세트아마이드, 디메틸티오포름아마이드, 설포란, 에틸렌―1,2―비스에틸설폰, 2―하이드록시에틸메틸설폰, 디메틸설폭사이드, 테트라메틸렌설폭사이드, 오쏘, 메타, 파라페닐렌디아민, 석시노닐트릴, 말로노니트릴, 아디포니트릴, 비스베타시아노에틸에테르, 비스베타시아노에틸설파이드, 알파시아노아세트아마이드, 감마부티로락톤, 비스―4―시아노부틸설폰, N―메틸베타시아노에틸포름아마이드 등과 같은 유기 또는 무기용제가 적용가능하다.In the present invention, a homopolymer or copolymer composed of at least 85% by weight or more of acrylonitrile is used as the polymer component in the spinning stock solution. In the present invention, the component of the copolymer may be ethyl acrylate, methyl methacrylate, vinyl acetate, metayl sulfonate, styrene sulfonate, and the like. As a solvent in the production of the spinning stock solution, alkylene thiocyanate is used. , Dimethylformamide, dimethylacetamide, dimethylmethoxyacetamide, dimethylthioformamide, sulfolane, ethylene-1,2-bisethylsulfone, 2-hydroxyethylmethylsulfone, dimethyl sulfoxide, tetramethylene sulfoxide, Ortho, meta, paraphenylenediamine, succinoyltril, malononitrile, adiponitrile, bisbetacyanoethylether, bisbetacyanoethylsulfide, alphacyanoacetamide, gammabutyrolactone, bis-4 Organic or inorganic solvents such as -cyanobutylsulfone, N-methylbetacyanoethylformamide and the like are applicable.

본 발명자들은 이상과 같은 용제에 대하여 적어도 85중량% 이상의 아크릴로니트릴로 이루어진 호모폴리머 또는 공중합체가 5―50중량% 되도록 방사원액 제조 탱크내에서 균일하게 녹인 다음 탈포 및 여과 공정을 거친 후 응고욕 외부에 위치한 구금 및 스핀너렛드에 도달하게 하였다. 한편 스핀너렛드를 통과한 필라멘트의 속도는 아래의 식을 만족하도록 하였다.The inventors of the present invention dissolve uniformly in the spinning solution preparation tank so that the homopolymer or copolymer composed of at least 85% by weight or more of acrylonitrile to 5-50% by weight with respect to the solvents described above, and then undergo a defoaming and filtration process, followed by a coagulation bath. External detention and spinneret were reached. On the other hand, the speed of the filament passing through the spinneret was to satisfy the following equation.

Figure kpo00001
Figure kpo00001

Vo: 스핀너렛드를 지나는 원사의 속도V o : the speed of the yarn through the spinneret

D : 스핀너렛드의 직경D: diameter of spinneret

n : 스핀너렛드의 갯수n: number of spinneret

Qv: 폴리머 유량(부피)Q v : Polymer flow rate (volume)

아울러 본 발명에서는 아래의 식으로 정의되는 방사드래프트(

Figure kpo00002
)가 250―500이 되도록 하였다.In addition, in the present invention, the radial draft defined by the following equation (
Figure kpo00002
) Is 250-500.

Figure kpo00003
Figure kpo00003

Figure kpo00004
: 방사드래프트
Figure kpo00004
: Draft Draft

VL: 응고욕을 지난 필라멘트의 속도V L : Speed of filament past the coagulation bath

ρ : 방사원액의 밀도ρ: density of spinning solution

A : 스핀너렛드의 전체면적A: Total area of spinneret

Qm: 폴리머 유량(질량)Q m : Polymer flow rate (mass)

본 발명자들이 여러가지 중공형성용 구금을 사용하여 여러가지로 실험한 결과 중공율 20% 이상인 폴리아크릴로니트릴 중공섬유를 얻기 위해선 방사드래프트가 250―500이어야 한다는 것을 발견하였다.As a result of various experiments by the present inventors using various molds for forming hollows, the inventors have found that the spinning draft should be 250-500 to obtain polyacrylonitrile hollow fibers having a hollow ratio of 20% or more.

본 발명에 있어서 방사드래프트가 250이하인 경우 높은 중공율을 얻을 수 없고, 방사드래프트가 500이상인경우 중공율은 높으나 지나친 인장력에 의하여 절사가 자주 일어나기 때문에 조업적인 측면에서 불리하다. 본 발명에 있어서 스핀너렛드를 통과한 필라멘트는 외기와 접한 후 용매와 물을 혼합시킨 응고욕을 지나게 된다. 본 발명에서는 스핀너렛드와 응고욕 표면사이의 거리를 5cm 이하가 되도록 하였다. 스핀너렛드가 응고욕 내부에 위치하게 되면 방사드래프트 250이상의 속도로 필라멘트를 인장하기 곤난하며, 반면에 스핀너렛드와 응고욕 표면사이의 거리가 5cm 이상인 경우에는 최종 제품의 물성이 나빠지는 불리한 점이 있다.In the present invention, if the spinning draft is 250 or less, a high hollow ratio cannot be obtained. If the spinning draft is 500 or more, the hollow ratio is high, but cutting is frequently caused by excessive tensile force, which is disadvantageous in terms of operation. In the present invention, the filament passed through the spinneret is passed through a coagulation bath in which a solvent and water are mixed after contacting the outside air. In the present invention, the distance between the spinneret and the surface of the coagulation bath is 5 cm or less. When the spinneret is located inside the coagulation bath, it is difficult to stretch the filament at a speed of more than 250 spin drafts. On the other hand, when the distance between the spinneret and the surface of the coagulation bath is 5 cm or more, the properties of the final product are deteriorated. .

본 발명에 있어서 응고욕의 성분으로서는 물, 포믹액시드, 글리세롤, 니트로벤젠, 디옥산, 사이클로헥산, 에틸렌글라이콜, 아세톤, 아세틱액시드 등이 가능하지만 방사원액 내의 용매가 10―20중량% 되도록 물에 혼합하여 사용하였다.In the present invention, as a component of the coagulation bath, water, formic acid, glycerol, nitrobenzene, dioxane, cyclohexane, ethylene glycol, acetone, acetic acid, and the like can be used. It was used by mixing in water.

다음에 응고욕을 지난 필라멘트는 연식욕내에서 60℃―120℃로 연신된 후 수세하고, 이어서 스팀내에서 열처리 및 건조하여 필라멘트로 하거나 또는 이것을 크림핑한 후 스태이플로 제조할 수 있다.Next, the filament that has passed the coagulation bath may be stretched to 60 ° C. to 120 ° C. in a soft bath, washed with water, and then heat-treated and dried in steam to form a filament, or it may be prepared in a stapled form.

이하 실시예 및 비교예에 의거하여 더욱 상세히 설명한다.It will be described in more detail based on the following Examples and Comparative Examples.

[실시예 1]Example 1

방사원액 제조 탱크내에 3,000g의 디포름아마이드를 투입한 다음 여기에 95중량%의 아크릴로니트릴과 5중량%의 비닐아세테이트로 이루어진 아크릴계 공중합체 1,000g을 80℃까지 서서히 온도를 올리면서 2시간 동안 믹싱한다.3,000 g of diformamide was added to the spinning stock solution tank, and 1,000 g of acryl-based copolymer consisting of 95% by weight of acrylonitrile and 5% by weight of vinyl acetate was gradually heated to 80 ° C for 2 hours. Mix

이후 방사원액 제조 탱크내부에 진공을 걸어 탈포한 다음 여과공정을 거쳐 표 1과 같은 제조조건으로 제조한 사의 원사물성 및 조업성을 체크하였다. 여기서 연신욕의 온도는 100℃로 하였고, 연신배율은

Figure kpo00005
으로 하였으며, 첫번째 태이크 업 상부에 분수기를 설치하여 수세를 하였으며, 스팀의 온도를 130℃로 하여 열처리 및 건조하였다. 스핀너렛드의 위치는 응고욕 표면 상부 1cm로 하였다.After the degassing by vacuum in the spinning solution production tank and then filtered through the filtration process was checked the yarn properties and operation properties of the yarn manufactured under the manufacturing conditions shown in Table 1. The temperature of the stretching bath was 100 ℃, the stretching ratio is
Figure kpo00005
A water fountain was installed at the top of the first tie-up and washed with water, and the steam was heat-treated and dried at 130 ° C. The position of the spinneret was 1 cm above the surface of the coagulation bath.

[표 1]TABLE 1

Figure kpo00006
Figure kpo00006

* 표.1에서 스핀너렛드의 단면적(A)은 스핀너렛드 전체의 단면적이며, 스핀너렛드는 아크형 슬릿 3개로 이루어진 형태의 것이다.* In Table 1, the cross-sectional area (A) of the spinneret is the cross-sectional area of the whole spinneret, and the spinneret consists of three arc-shaped slits.

[비교예 1]Comparative Example 1

실시예 1과 같이하되 토출량 및 사속을 바꾸어 제조한 결과는 표.2와 같다.As in Example 1, but produced by changing the discharge amount and yarn speed is shown in Table 2.

[표 2]TABLE 2

Figure kpo00007
Figure kpo00007

실시예 1 및 비교예 1을 비교해보면 방사드래프트(

Figure kpo00008
)의 값이 250이하인 경우 조업성은 양호하나 중공율이 저조하며 500이상인 경우 조업이 불가능하였다.Comparing Example 1 and Comparative Example 1, the radial draft (
Figure kpo00008
When the value of) is less than 250, the operation is good, but the hollow ratio is low, and when it is more than 500, the operation is impossible.

[실시예 2]Example 2

실시예 1의 표.1에서 4번(Qv:

Figure kpo00009
, A :
Figure kpo00010
, Vo:
Figure kpo00011
, VL: 500)과 동일한 조건으로 하되 스핀너렛드의 위치를 응고욕내의 수면으로부터 여러가지로 변화시켜 조업성 및 물성을 조사한 결과는 표.3과 같다.4 in Table 1 of Example 1 (Q v :
Figure kpo00009
, A:
Figure kpo00010
, V o :
Figure kpo00011
, V L : 500), but the spinneret position was varied from the surface of the coagulation bath in various ways to investigate the operability and physical properties.

[표 3]TABLE 3

Figure kpo00012
Figure kpo00012

[비교예 2]Comparative Example 2

실시예 2에 있어서 응고욕의 수면으로부터 스핀너렛드까지의 거리를 5cm 이상으로 하여 조업성 및 물성을 조사한 결과는 표.4와 같다.In Example 2, the result of having investigated the operability and the physical property by making the distance from the surface of a coagulation bath to spinneret 5 cm or more is shown in Table 4.

[표 4]TABLE 4

Figure kpo00013
Figure kpo00013

표 4로 알 수 있는 바와 같이 스핀너렛드까지의 거리가 5cm 이상일 때는 조업성 및 물성이 급격히 떨어지며 7cm 이상일 경우 절사가 매우 심하여 조업이 불가능하였다.As can be seen from Table 4, when the distance to the spinneret is 5 cm or more, the operability and physical properties are sharply dropped, and when the distance to the spinneret is 7 cm or more, the cutting is very severe and operation is impossible.

Claims (1)

적어도 85중량% 이상의 아크릴로니트릴로 이루어진 아크릴계 공중합체를 용매에 녹여서 방사원액을 만든 다음 이것을 습식방사하여서 폴리아크릴로니트릴 중공섬유를 제조함에 있어서, 스핀너렛드의 위치를 응고욕의 표면으로부터 5cm 이내에 있도록 하고, 방사 드래프트를 250―500이 되도록 하며, 또 중공율이 20% 이상이 되도록 제조함을 특징으로 하는 폴리아크릴로니트릴 중공섬유의 제조방법.In preparing a polyacrylonitrile hollow fiber by dissolving an acrylic copolymer of at least 85% by weight or more of acrylonitrile in a solvent to form a spinning solution, and then wet spinning it, the position of the spinneret is within 5 cm from the surface of the coagulation bath. Method for producing a polyacrylonitrile hollow fiber, characterized in that the spinning draft is 250-500, and the hollow ratio is 20% or more.
KR1019890000167A 1989-01-09 1989-01-09 Manufacturing process of polyacrylonitrile hollowing fiber KR910007558B1 (en)

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