KR910004705B1 - Aromatic polyamide fiber and production thereof - Google Patents
Aromatic polyamide fiber and production thereof Download PDFInfo
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- KR910004705B1 KR910004705B1 KR1019880017954A KR880017954A KR910004705B1 KR 910004705 B1 KR910004705 B1 KR 910004705B1 KR 1019880017954 A KR1019880017954 A KR 1019880017954A KR 880017954 A KR880017954 A KR 880017954A KR 910004705 B1 KR910004705 B1 KR 910004705B1
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- solvent
- aromatic
- added
- aromatic polyamide
- polyamide fiber
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- 239000000835 fiber Substances 0.000 title claims description 24
- 239000004760 aramid Substances 0.000 title claims description 17
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- 150000001408 amides Chemical class 0.000 claims description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 150000004984 aromatic diamines Chemical class 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001879 gelation Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- -1 and then Chemical compound 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 239000012155 injection solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003313 weakening effect 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
- 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
- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyamides (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 방향족 폴리아미드 섬유와 그의 제조방법에 관한 것으로서, 더욱 상세하게는 방향족 디아민과 방향족 디에서드 클로라이드를 중합반응시킬때 그 반응을 2단계로 분리시켜서 실시하고, 중합반응에 의하여 겔화이전에 얻더진 저점도의 액정예비중합첼르 배항 및 중합촉진 혼합용매와 함께분사시킴으로서 높은 배향성과 고유정도를 갖는 방향족 폴리아미드섬유와 그의 제조방법에 관한 것이다.The present invention relates to an aromatic polyamide fiber and a method for preparing the same, and more particularly, when the aromatic diamine and aromatic die chloride are polymerized, the reaction is carried out in two stages, and is obtained before gelation by polymerization. The present invention relates to an aromatic polyamide fiber having a high orientation and intrinsic degree by spraying together with a low viscosity liquid crystal prepolymerized cell vessel and a polymerization promoting mixed solvent.
종래에는, 일본특공소 59-47,694호에서와 같이 폴리아미드를 유기용매에 용해시킨 후 물이나 알코올에 침전, 교반시켜서 펄프상 단섬유를 제조하는 방법과 미국특허 제4,511,623호에서와 같이 아미드계 용매에 3급아민을 첨가시켜 펄프상 단섬유를 제조하는 방법이 알려져 있다.Conventionally, a method for preparing pulp-like short fibers by dissolving polyamide in an organic solvent and then precipitating and stirring it in water or alcohol as in Japanese Patent Application No. 59-47,694 and an amide solvent as in US Pat. No. 4,511,623 A method for producing pulp-like short fibers by adding tertiary amines is known.
그러나, 폴릴아미드를 유기용매에 용해시킨 후 물이나 알코올에 침전, 교반시켜서 펄프상 단섬유를 제조하는 기술(일본특공소 59-47,694호)은 대체적으로 물성이 좋지 않은 것으로 나타났다. 즉, 고유점도가 높은 폴리아미드는 유기용매에서 잘 녹지 않고, 고유점도가 낮은 폴리아미드만 용해되기 때문에 제품의 물성이 낮게되는 단점이 있다. 또한, 아미드계 용매에 3급아민을 첨가하여 제조하는 기술(미국특허 제 4,511,623호)은 초기에 3급 아민을 사용하므로써 중합이 급격히 진행되어 수초내에 분자사술이 방향성이 없는 등방성겔로 형성하게 되고 이로인해 중합속도조절 및 방사가 불가능하게 되며, 또한, 3급아민을 과량첨가하는 경우에는 중합이 진행되어 겔화가 일어난 후에도 등방성의 중합체용액으로 이를 5시간이상 방치아여야 적절한 물성을 가지는 중합체를 얻을 수 있는 문제가 있다.However, the technique of preparing pulp-like short fibers by dissolving polyylamide in an organic solvent and then precipitating and stirring in water or alcohol (JP-A-59-47,694) has been found to be generally poor in physical properties. That is, a polyamide having a high intrinsic viscosity does not melt well in an organic solvent, and since only a polyamide having a low intrinsic viscosity is dissolved, there is a disadvantage in that physical properties of the product are low. In addition, the technique of preparing a tertiary amine by adding a tertiary amine (US Pat. No. 4,511,623) uses a tertiary amine in the early stage of polymerization so that the polymerization proceeds rapidly to form an aromatic isotropic gel within seconds. This makes it impossible to control the polymerization rate and to spin, and in addition, when tertiary amine is excessively added, an isotropic polymer solution is allowed to stand for at least 5 hours even after gelation occurs to obtain a polymer having proper physical properties. There is a problem that can be.
이에 본 발명은 종래의 이와같은 문제점들을 해소시키기 위하여 방향족 디아민에 방향족 디에시드 클로라이드를 2단계로 분리시켜 중합반응시키면서 겔화이전에 형성된 지점도의 액정 예비중합체를 배향 및 중합촉진 혼합용매와 함께 분사시킴으로서 물성이 우수하고 높은 배향성과 고유점도를 갖는 방향족 폴리아미드섬유와 그의 제조방법을 제공하는데 그 목적이 있다.Therefore, the present invention is to solve the problems of the prior art by separating the aromatic die chloride from the aromatic diamine in two stages by the polymerization reaction by spraying the liquid crystal prepolymer of the branched point formed before gelation with the alignment and polymerization promoter mixed solvent An object of the present invention is to provide an aromatic polyamide fiber having excellent physical properties, high orientation and intrinsic viscosity, and a method for producing the same.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명은 방향족 폴리아미드를 제조하는데 있어서, 아미드계 용매 또는 이들의 혼합용매에 금속염을 용해시킨 후 여기에 방향족 디아민과 방향족 디에시드 클로라이드를 투입하여 중합시키되 투입하고자 하는 전체 방향족 디에시드 클로라이드에 대하여 1차로 방향족 디에시드 클로라이드 20 내지 80중량%를 투입한 다음 이로부터 생성되는 HC1몰수의 5배이하로 암모니아를 함유하는 아미드계 용매를 첨가하고, 여기에 다시 2차로 나머지 방향족 디에시드 클로라이드 20 내지 80중량%를 투입하여 중합시켜서 겔화이전에 형성되게 되는 액정상태인 지점도의 액정예비중합체 용액을 암모니아 또는 3급아민계용매 단독이나 아미드계 용매나 비양자성 용매의 혼합용매와 함께 방사 또는 압출분사시켜서 다음식(I),(II)를 반복단위로 갖는 분자사슬들의 배향성과 고유점도가 높은 방향족 폴리아미드섬유와 그의 제조방법을 그 특징으로 한다.In the present invention, in preparing an aromatic polyamide, a metal salt is dissolved in an amide solvent or a mixed solvent thereof, and then, aromatic diamine and aromatic die chloride are added thereto, followed by polymerization to 1 to the total aromatic die chloride. 20 to 80% by weight of aromatic dieside chloride was added thereto, followed by addition of an amide-based solvent containing ammonia up to 5 times the number of moles of HC1 generated therefrom, followed by 20 to 80% by weight of the remaining aromatic dieside chloride. The liquid crystal prepolymer solution in the form of a liquid crystal state, which is formed before polymerization by polymerization by adding%, is spun or extruded with ammonia or tertiary amine solvent alone or with a mixed solvent of an amide solvent or an aprotic solvent. Orientation of Molecular Chains Having Food (I) and (II) as Repeating Units And an intrinsic viscosity higher aromatic polyamide fiber and a method of manufacturing the same in its characteristics.
상기(I),(II)에서 R1, R2, R3는In (I), (II), R 1 , R 2 , R 3 are
이고, R1, R2와 R3는 서로 같거나 다를 수도 있으며, X는 H, Cl, Br, I, 페닐, 탄소수가 1∼4개인 알킬 또는 알콕시기, Y는 -CH2-, -O-,
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 아미드용매 또는 이들의 혼합용매에 금속염을 용해시킨 후 방향족 디아민과 방향족 디에시드 클로라이드를 어느정도 반응시켜서 된 점도가 낮은 액정상태의 예비중합체를 암모니아가 함유된 용매와 함께 노즐을 통해 분사 또는 방사시켜서 폴리아미드섬유를 제조하는 것으로서, 이대 상기 방향족 디에시드 클로라이드를 2단계로 분리첨가시키고 상기 암모니아가 함유된 새로운 용매의 분사속도에 의한 접촉 및 연산효과에 따라 폴리머내의 분자사슬들의 배향도를 향상시키고 높은 고유점도를 갖는 방향족 폴리아미드섬유나 펄프상 단섬유를 제조하는 것이다.The present invention is to spray or spin a low-viscosity liquid crystal state prepolymer with ammonia-containing solvent by dissolving a metal salt in an amide solvent or a mixed solvent thereof and then reacting the aromatic diamine and the aromatic dieside chloride to some extent. To prepare polyamide fibers by separating and adding the aromatic dieside chloride in two stages, and improving the orientation of molecular chains in the polymer according to the contact and computational effect by the spray rate of the new solvent containing ammonia. Aromatic polyamide fibers and pulp-like short fibers having intrinsic viscosity are produced.
본 발명에서 아미드계 용매로서는 N-메틸-2-피롤리돈(NMP), N, N-디메틸아세트아미드(DMAc), 헥사메틸포스포아미드(HMPA), N, N-디메틸포름아미드(DMF), 디메틸(DMSO)N, N, N', N'-테트라메틸우레아(TMU)등을 단독 또는 이들의 혼합물을 사용할 수 있으며, 금속염으로서는 CaCl2, LiCl ,NACl, KCl등을 사용할 수 있다.As the amide solvent in the present invention, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N, N-dimethylformamide (DMF) , Dimethyl (DMSO) N, N, N ', N'- tetramethylurea (TMU), etc. may be used alone or a mixture thereof. CaCl 2 , LiCl, NACl, KCl and the like can be used as the metal salt.
이들의 중합반응을 설명하면, 먼저 상기 아미드계 단독 또는 아미드계의 혼합용매에 금속염을 용해시키되 중합용매에 대하여 금속염을 0.1 내지 20중량%로 용해시킨후 여기에 방향족 디아민과 방향족 디에서드 클로라이드를 등몰량으로 넣어서 녹인다. 이때 방향족 디아민을 먼저 투입하고 이어서 방향족 이데시드 클로라이드를 2차로 분리시키는 것이 바람직한데, 즉, 방향족 디아민을 먼저 금속염이 용해된 아미드계 용매에 투입하여 녹인다음 상기 방향족 디아민과 반응할 등몰량의 방향족 디에시드 클로라이드를 투입하고자 하는 전제 방향족 디에시드 클로라이드에 대하여 5중량% 내지 80중량%를 먼저 투입하여 반응시킨 후 다시 2차로 나머지 방향족 디에시드 클로라이드 20중량% 내지 95중량%를 넣어서 저온에서 반응시키는 것이 좋다.In describing the polymerization reaction, first, the metal salt is dissolved in the amide-based alone or a mixed solvent of the amide, but the metal salt is dissolved in 0.1 to 20% by weight with respect to the polymerization solvent, and the aromatic diamine and the aromatic die chloride are Dissolve in a molar amount. In this case, it is preferable to first add aromatic diamine, and then separate the aromatic idide chloride secondly, that is, aromatic diamine is first dissolved in an amide solvent in which a metal salt is dissolved, and then dissolved in an equimolar amount of aromatic die to react with the aromatic diamine. 5 wt% to 80 wt% is added to the total aromatic dietary chloride to which seed chloride is intended to be reacted first, and then 20 wt% to 95 wt% of the remaining aromatic dieside chloride is reacted at a low temperature. .
특히, 본 발명에 따르면, 상기 중합반응시에 예컨대, 방향족 디에시드 클로라이드를 1차로 투입시킨 후에 이를 반응시키게 되면 상기 반응용액에서 HCl이 발생하게 됨에 따라 이 HCl의 제거를 위하여 암모니아 또는 이를 함유하는 아미드계용매를 첨사시키는 것이 바람직하다.In particular, according to the present invention, for example, when aromatic diacid chloride is first introduced into the polymerization reaction, and then reacted with it, HCl is generated in the reaction solution. It is preferable to add a system solvent.
즉, 중합반응용액에 암모니아 또는 이를 함유하는 아미드계 용매를 첨가시킬 경우에는 상기 용액으로부터 발생하게 되는 HCl의 생성량의 5배이하로 첨가시키면 된다. 이로 인하여 HCl이 제거되게 되면 중합반응을 촉진시켜주게 되면서 암모니아 HCl과의 염형성으로 폴리머의 용해도를 향상시켜 주게 된다.That is, when adding ammonia or an amide solvent containing the same to the polymerization reaction, it may be added at 5 times or less of the amount of HCl generated from the solution. As a result, when the HCl is removed, it promotes the polymerization reaction and improves the solubility of the polymer by salt formation with ammonia HCl.
상기 반응결과, 중합반응이 완결되기 직전, 즉 반응 혼합물이 겔화되기 이전에 액정사태인 저점도의 액정 예비중합체 용액이 얻어지게 되며 상기 예비 중합체는 중합용매에 대하여 3중량% 내지 30중량%의 폴리머를 함유하게 된다.As a result of the reaction, a low-viscosity liquid crystal prepolymer solution, which is a liquid crystalline state, is obtained immediately before the polymerization reaction is completed, that is, before the reaction mixture is gelled. The prepolymer is a polymer of 3% by weight to 30% by weight with respect to the polymerization solvent. It will contain.
이렇게 얻어진 본 발명에 따른 액정상태의 예비중합체 용액의 분사용매로서는 암모니아 또는 3급아민 단독 또는 아미드계 용매나 비양자성 용매, 예를 들면 클로로포름이나 벤젠, 톨루엔이 혼합된 혼합용매가 사용되어지게 된다.As the injection solvent of the liquid crystal state prepolymer solution thus obtained, a mixed solvent in which ammonia or tertiary amine alone or an amide solvent or an aprotic solvent such as chloroform, benzene, and toluene is mixed is used.
본 발명에 따르면 상기 분사용매로는 암모니아나 3급아민 단독 또는 이들에 아미드계의 혼합용매 또는 비양자성 용매가 혼합된 용매가 사용되는데, 이때 암모니아가 혼합용매로 사용될 경우에는 그 함량은 혼합용매 전체에 대하여 1 내지 20중량%로 함유하는 것이 좋으며, 암모니아와 혼합되어 사용될 수 있는 아미드계 용매로서는 이미 상술한 바와같은 N-메틸-2-피롤리돈(NMP), N, N-디메틸아세트아미드(DMAc),헥사트라메틸포스포아미드(HMPA), N, N-메틸포름아미드(을), 디메틸설폭사이드(DMSO), N, N, N', N'-테트라메틸우레아(TMU) 단독 또는 이들의 혼합물이 사용될 수 있다.According to the present invention, as the injection solvent, ammonia or tertiary amine alone or a solvent in which an amide mixed solvent or an aprotic solvent is mixed therein is used. In this case, when the ammonia is used as the mixed solvent, the content of the total solvent is It is preferable to contain in an amount of 1 to 20% by weight, and as the amide solvent which can be used in admixture with ammonia, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide ( DMAc), hexatramethylphosphoamide (HMPA), N, N-methylformamide, dimethylsulfoxide (DMSO), N, N, N ', N'-tetramethylurea (TMU) alone or these Mixtures of may be used.
그리고, 3급아민용매로서는 예를들면 피리딘, 피콜린, 피리미딘, 트리에틸아민, 피라신, t-부틸아민, N, N-디메틸아닐린 중에서 선택하여 사용하는 것이 바람직하다.The tertiary amine solvent is preferably selected from, for example, pyridine, picoline, pyrimidine, triethylamine, pyrasine, t-butylamine, N, and N-dimethylaniline.
상기의 분사용매는 액정상태의 예비중합체 용액과 함께 노즐을 통해 분사되어지게 될 때 중합체용액 내부에서 생성되게 되는 HC1과 암모니아의 반응으로 HC1를 제거시키면서 중합을촉진시켜 고유점도를 향상시키는 역할을 하게 된다.The injection solvent serves to enhance the intrinsic viscosity by promoting the polymerization while removing HC1 by the reaction of HC1 and ammonia, which is generated inside the polymer solution when it is injected through the nozzle together with the liquid crystal state prepolymer solution. do.
예컨대, 본 발명에 따른 액정상태의 예비중합체를 암모니아나 3급아민 단독 또는 이들에 아미드계 용매의 혼합용매 또는 이들에 비양자성 용매가 혼합된 혼합용매돠 함께 노즐을 통하여 분사 또는 압출시키게 되면 상기 혼합용매의 분사속도에 의한 접촉 및 연신효과와 암모니아에 의한 HCl제거 효과로 인한 반응촉진 및 이로인해 생성되는 염의 폴리머용해도 증가 효과 및 기존의 용매에서는 기대할 수 없었던 수분의 활성약화로 기존의 방법에서는 단량체의 수분함량이 500ppm이하이어야 중합이 가능하던 것을 0.5%이어도 높은 고유점도를 가지는 폴리머를 제조할 수 있게 된다. 이와같은 방법에 의하여 얻어지는 본 발명에 따른 높은 고유점도를 갖는 다음 구조식(I) 및 (II)의 반복단위를 갖는 방향족 폴리아미드가 얻어지게 되는 것이다.For example, when the liquid crystal state prepolymer according to the present invention is sprayed or extruded through a nozzle together with ammonia or a tertiary amine alone or a mixed solvent of an amide solvent or a mixed solvent containing an aprotic solvent therein, the mixing is performed. Due to the contact and stretching effect by the spraying rate of the solvent and the HCl removal effect by the ammonia, the reaction of the monomer and the increase of the polymer solubility of the salts generated by the solvent and the weakening of the water activity, which was not expected in the conventional solvent, have been achieved. It is possible to prepare a polymer having a high intrinsic viscosity even if 0.5% of the water content can be polymerized when the water content is 500 ppm or less. Aromatic polyamides having repeating units of the following structural formulas (I) and (II) having a high intrinsic viscosity according to the present invention obtained by such a method are obtained.
상기식(I),(II)에서 R1, R2, R3는In formulas (I) and (II), R 1 , R 2 , and R 3 are
이고, R1, R2와 R3는 서로 같거나 다를 수도 있으며, X는 H, Cl, Br, I, 페닐, 탄소수가 1∼4개인 알킬 또는 알콕시기,R 1 , R 2 and R 3 may be the same as or different from each other, X is H, Cl, Br, I, phenyl, an alkyl or alkoxy group having 1 to 4 carbon atoms,
Y는 -CH2-, -O-,
이와같은 방법으로 얻어진 본 발명에 따른 방향족 폴리아미드섬유는 다음 관계식에 의하여 계산할 수 있다는 고유점도의 측정결과 4.0이상을 나타내었다.The aromatic polyamide fibers according to the present invention obtained in such a manner showed more than 4.0 as a result of measuring the intrinsic viscosity, which can be calculated by the following relationship.
여기서 C는 중합체용액의 농도(95∼98% 황산 25ml에 중합체 0.125g을 용해시킨 용액의 농도)이고, 상대점도 nrel는 30℃의 온도에서 모세관 점도계로 측정되어지는 용액과 용매사이의 유동시간의 비율이며, 용매는 95∼98%의 농황산이다.Where C is the concentration of the polymer solution (the concentration of the solution in which 0.125 g of the polymer is dissolved in 25 ml of 95-98% sulfuric acid), and the relative viscosity nrel is the flow time between the solution and the solvent measured with a capillary viscometer at a temperature of 30 ° C. The solvent is 95 to 98% concentrated sulfuric acid.
이하 본 발명을 다음 실시예에 의거하여 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail based on the following examples.
[실시예 1]Example 1
반응기를 질소기류로 충분히 정화시켜 수분을 제거한 후 중합용매로서 NMP 350ml를 넣고 80℃로 승온시켜 CaCl215g을 넣어 완전히 용해시킨다.After purifying the reactor sufficiently with a nitrogen stream to remove water, 350 ml of NMP was added as a polymerization solvent, the temperature was raised to 80 ° C, and 15 g of CaCl 2 was completely dissolved.
위 용액에 p-페닐렌 디아민 26.24g을 첨가하여 10분간 교반해서 용해시킨 후 10℃의 저온에서 테레프탈로일 클로라이드 32.05g을 투입하여 10분간 반응시킨 후 암모니아 8g과 NMP 10ml의 혼합용매를 첨가하여 5분간 더 반응시킨 다음 나머지 테레프탈로일 클로라이드 17.25g을 투입하여 10℃이하의 저온에서 반응시켜 생성된 저점도 액정상태의 중합체 용액을 L/D가 0.5이고, 직경이 0.1mm인 구금을 통해 방사하고 이와 동시에 피리딘을 분사시켜 분당 40ml의 속도로 권취한 후 물로 수세, 건조하여 섬유를 제조하였다.After adding 26.24 g of p-phenylene diamine to the solution and stirring for 10 minutes to dissolve, 32.05 g of terephthaloyl chloride was added at 10 ° C. for 10 minutes to react, and then a mixed solvent of 8 g of ammonia and 10 ml of NMP was added thereto. After further reacting for 5 minutes, 17.25 g of the remaining terephthaloyl chloride was added and reacted at a low temperature of 10 ° C. or lower to spin the polymer solution in a low viscosity liquid crystal state with a L / D of 0.5 and a diameter of 0.1 mm. At the same time, the pyridine was sprayed and wound up at a rate of 40 ml per minute, washed with water and dried to prepare a fiber.
IV = 7.1IV = 7.1
D/E/T/Mi = 0.9/2/23/483D / E / T / Mi = 0.9 / 2/23/483
[실시예 2]Example 2
상기 실시예 1과 동일하게 실시하되 저점도 액정상태 중합체용액을 암모니아/NMP/클로로포름의 부피%비가 20/40/40인 혼합용매를 분사시켜서 펄프상 단섬유를 제조하였다.The pulp-like short fibers were prepared in the same manner as in Example 1 except that a low viscosity liquid crystal polymer solution was sprayed with a mixed solvent having a volume ratio of 20/40/40 of ammonia / NMP / chloroform.
IV = 6.5IV = 6.5
D/E/T/Mi = 1.2/2.5/21/472D / E / T / Mi = 1.2 / 2.5 / 21/472
[실시예 3]Example 3
반응기에 DMAc 350ml를 넣고 80℃까지 승온시킨 후 LiCl 15g을 넣어 용해시키고 p-페닐렌디아민 26.24g을 첨가하여 10분간 교반하여 용해시킨 다음 20℃의 저운에서 테레프탈로일 클로라이드 35.3g을 투입하고 반응시킨후 암모니아 10g을 첨가하여 5분간 더 반응시킨다. 위용액에 테레프탈로일 클로라이드 14.0g을 첨가하여 20℃이하의 온도에서 반응시켜 생성된 저점도 액정상태 중합체용액을 L/D가 1이고 직경이 0.5ml인 노즐을 통해 방사하고 피리딘/NMP의 부피%가 50/50인 혼합용매를 중합체 용액의 방사속도에 비해 5배이상의 속도로 분사해 펄프상 단섬유를 제조하였다.Put 350ml DMAc into the reactor, warm up to 80 ℃, add 15g of LiCl, dissolve, add 26.24g of p-phenylenediamine, stir for 10 minutes to dissolve, add 35.3g of terephthaloyl chloride at 20 ℃ After 10g of ammonia is added, the solution is further reacted for 5 minutes. 14.0 g of terephthaloyl chloride was added to the gastric solution and reacted at a temperature of 20 ° C. or lower. The low-viscosity liquid crystal polymer solution was spun through a nozzle having a L / D of 1 and a diameter of 0.5 ml and a volume of pyridine / NMP. A pulp-like short fiber was prepared by spraying a mixed solvent having a% of 50/50 at a speed of 5 times or more relative to the spinning speed of the polymer solution.
IV = 6.7IV = 6.7
D/E/T/Mi = 1.1/2.3/22/484D / E / T / Mi = 1.1 / 2.3 / 22/484
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| CN117802609A (en) * | 2024-03-01 | 2024-04-02 | 烟台泰和新材高分子新材料研究院有限公司 | Para-position aromatic polyamide fiber and preparation method and application thereof |
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| CN117802609A (en) * | 2024-03-01 | 2024-04-02 | 烟台泰和新材高分子新材料研究院有限公司 | Para-position aromatic polyamide fiber and preparation method and application thereof |
| CN117802609B (en) * | 2024-03-01 | 2024-05-31 | 烟台泰和新材高分子新材料研究院有限公司 | Para-position aromatic polyamide fiber and preparation method and application thereof |
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