KR910004460B1 - Manufacturing process of aromatic polyamide fibers and film - Google Patents
Manufacturing process of aromatic polyamide fibers and film Download PDFInfo
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- KR910004460B1 KR910004460B1 KR1019880005923A KR880005923A KR910004460B1 KR 910004460 B1 KR910004460 B1 KR 910004460B1 KR 1019880005923 A KR1019880005923 A KR 1019880005923A KR 880005923 A KR880005923 A KR 880005923A KR 910004460 B1 KR910004460 B1 KR 910004460B1
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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
- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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
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Abstract
Description
본 발명은 방향족 폴리아미드섬유와 필름의 제조방법에 관한 것으로서, 더욱 상세하게는 방향족 디아민과 방향족 디에시드클로라이드를 중합반응시킬때 그 반응을 2단계로 분리시켜서 실시하므로서 최종섬유의 물성이 크게 향상되어지도록 하는 방향족 폴리아미드섬유와 필름의 제조방법에 관한 것이다.The present invention relates to a method for producing an aromatic polyamide fiber and a film, and more particularly, when the aromatic diamine and an aromatic dieside chloride are polymerized, the reaction is carried out in two stages, thereby greatly improving the physical properties of the final fiber. The present invention relates to an aromatic polyamide fiber and a method for producing a film.
종래, 방향족 폴리아미드섬유와 필름을 제조하는 기술로서 미국특허 제4,511,623호에는 아미드계 용매에 무기염과 피리딘을 용해시킨 후, 여기에 1몰의 파라페닐렌디아민을 용해시키고 이를 저온에서 냉각시킨 다음, 1몰의 테레프탈로일클로라이드를 일시에 투입하면서 고속으로 교반시켜 중합시키고 이를 급격히 교반하여 중합과 동시에 분자배향이 이루어진 겔(gel)상의 반응물을 분쇄하여 폴리아미드펄프상 단섬유를 제조하는 기술이 개시되어 있으나, 상기 방법을 채용하는 중합반응에서는 피리딘의 촉매효과와 약 100Kcal/mole 정도의 반응열에 의하여 급격한 반응진행에 의해 반응계가 겔화되기 때문에 이를 실제의 제조공정에 적용시키기에는 상당히 어려운 문제가 있었다.Conventionally, as a technology for producing aromatic polyamide fibers and films, US Patent No. 4,511, 623 dissolves an inorganic salt and pyridine in an amide solvent, and then dissolves 1 mole of paraphenylenediamine in it, and then cools it at a low temperature. , 1 mole of terephthaloyl chloride was added at a time and stirred at a high speed to polymerize, and then rapidly stirred to pulverize a gel-like reactant with a molecular orientation at the same time to produce polyamide pulp-like short fibers. In the polymerization reaction employing the above method, the reaction system gels due to the rapid reaction progress due to the catalytic effect of pyridine and the heat of reaction of about 100 Kcal / mole, which is difficult to apply to the actual manufacturing process. .
예컨대, 파라페닐렌디아민과 테레프탈로일클로라이드의 반응은 속도가 빠르고, 반응열이 100Kcal/mole정도로 높기 때문에 테레프탈클로라이드를 피리딘이 함유된 중합용매에 일시에 첨가시킬 경우에는 반응열에 의하여 반응속도가 증가되어 1초이내에 반응계 전체가 겔화되게 되고, 특히 촉매효과를 갖는 피리딘이 존재함으로 해서 중합반응이 더욱 빨라져 반응속도의 조절이 불가능할 뿐 아니라, 분자량분포도 지극히 넓어지게 되므로 공업상 실제로 공정화시킬 수 없는 단점이 있다.For example, the reaction of paraphenylenediamine and terephthaloyl chloride is fast and the heat of reaction is high at about 100 Kcal / mole. Therefore, when terephthal chloride is added to the polymerization solvent containing pyridine, the reaction rate is increased by the reaction heat. Within 1 second, the whole reaction system is gelled, and the presence of pyridine, which has a catalytic effect, makes the polymerization reaction even faster due to the presence of a catalytic effect, and the molecular weight distribution is extremely widened. .
또한, 일본 특개소 62-162013호에는 무기염이 함유된 아미드계 용매에 1몰의 파라페닐렌디아민을 용해시킨 후, 저온에서 50 내지 90몰%정도로 과량의 테레프탈로일클로라이드를 1차로 투입하여 평균중합도가 1.5∼15인 올리고머(oligomer)를 제조하고, 여기에 나머지 테레프탈로일클로라이드 10∼50몰%와 3∼50%의 피리딘을 동시에 투입시켜서 급격히 반응시킨 다음 분쇄시켜서 펄프상 단섬유를 제조하는 기술이 제안되어 있으나, 이러한 경우에는 먼저 1차로 올리고머상태가 형성되는데 폴리(파리-페닐렌테레탈레프이트)호모폴리머의 경우에 그때의 올리고머는 아미드계 용매에 의한 용해성이 낮으므로 침전이 형성되기 때문에 2차로 테레프탈로일클로라이드를 첨가시킨다 하더라도 반응이 실질적으로 진행되지 않게 되며, 아주 낮은 중합체 함량율에서는 용액상태의 올리고머가 유지될 수는 있으나 2차로 테레프탈로일클로라이드와 피리딘을 동시에 투입해주게 되면 이때에도 역시 순식간에 겔화가 일어나기 때문에 결국 이런 방법의 경우에도 실제로 공업화시키기에는 지극히 곤란한 점이 있었다.In addition, Japanese Patent Application Laid-Open No. 62-162013 discloses dissolving 1 mole of paraphenylenediamine in an amide solvent containing an inorganic salt, and then adding an excess amount of terephthaloyl chloride as a primary at a low temperature of about 50 to 90 mole%. An oligomer having an average degree of polymerization of 1.5 to 15 was prepared, and 10-50 mol% of the remaining terephthaloyl chloride and 3-50% of pyridine were added simultaneously to react rapidly and then pulverized to prepare pulp-like short fibers. In this case, the oligomer state is first formed. In the case of the poly (paris-phenylene terephthalate) homopolymer, the oligomer at this time has low solubility by an amide solvent, so that precipitation is formed. As a result, even if terephthaloyl chloride is added secondly, the reaction does not proceed substantially. The oligomer can be maintained, but when the womb there.Aye 2 In the chloride and pyridine to drive at the same time At this time, even there terephthalic point is also very difficult to fit a fact even if the end of this method because gelation takes place in a flash industrialization.
또한, 국내특허출원 86-4495호에 기술된 방법은 액정예비중합체상태에서 3급아민 예를 들면, 피리딘중에 작은 노즐을 통해서 분사시키는 방법이 소개되어 있으나, 이역시 중합반응을 고농도로 실시하게 되면 반응계의 반응열에 의하여 온도가 상승되기 때문에 비록 예비중합체상태까지만 반응시킨다고 하더라도 상당한 냉각비가 소요되게 되며 공정가능시간도 짧고, 10중량% 이상의 중합체를 함유하는 중합물을 얻기에는 대단히 곤란한 단점이 있다. 특히 상술한 바와 같은 종래의 방법에 의하여 제조된 고분자들은 분자량 분포가 극히 넓어서 모듈러스나 인장강도등이 상당히 낮음을 알 수 있다.In addition, the method described in Korean Patent Application No. 86-4495 introduces a method of spraying a tertiary amine, such as pyridine, through a small nozzle in a liquid crystal prepolymer state. Since the temperature is increased by the reaction heat of the reaction system, even if only reacted to the prepolymer state, a considerable cooling cost is required, and the processing time is short, and it is very difficult to obtain a polymer containing 10 wt% or more of polymer. In particular, it can be seen that the polymers prepared by the conventional method as described above have a very low molecular weight distribution and a very low modulus or tensile strength.
이에 본 발명은 종래의 이와 같은 단점을 해소하기 위하여 아라미드의 중합반응시 반응속도를 용이하게 조절할 수가 있고, 분자량의 분포도 좁혀서 중합농도와 섬유의 물성을 크게 향상시켜줄 수 있도록 하는 방향족 폴리아미드섬유와 필름의 제조방법을 제공하는데 그 목적이 있다.Therefore, the present invention can easily control the reaction rate during the polymerization reaction of aramid in order to solve the conventional disadvantages, and narrow the molecular weight distribution to greatly improve the polymerization concentration and fiber properties of the aromatic polyamide fiber and film Its purpose is to provide a method of manufacturing.
이하 본 발명을 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 무기염과 3급아민이 함유된 아미드계 용매에다 방향족 디아민을 용해시킨 후, 등몰량의 방향족 디에시드클로라이드를 2단계로 분리첨가시켜 중합을 완료시킴과 동시에 분자배향을 완료시켜 방향족 폴리아미드섬유와 필름을 제조하는데 있어서, 무기염이 용해된 아미드계 용매에다 이 용매에 대하여 0 내지 2중량%의 3급아민을 첨가시킨 다음, 방향족 디아민과 등몰량으로 방향족 디에시드클로라이드를 2단계로 분리첨가시키되 전체 방향족 디에시드클로라이드중 20 내지 49몰%을 1차로 투입하고, 2차로 나머지 방향족 디에시드클로라이드 51 내지 80몰%를 투입하여 광학적으로 이등방성인 액정예비중합체가 될 때까지 반응시킨 다음 이것을 방사도우프로 하여 3급아민이 함유된 중합촉진침전제에 방사시켜서 연속적으로 방향족 폴리아미드섬유와 필름을 제조하는 방법을 그 특징으로 한다.The present invention dissolves an aromatic diamine in an amide solvent containing an inorganic salt and a tertiary amine, and then separates and adds an equimolar amount of aromatic dieside chloride in two stages to complete the polymerization and at the same time complete the molecular orientation of the aromatic polyamine. In preparing amide fibers and films, 0 to 2% by weight of tertiary amine is added to an amide solvent in which an inorganic salt is dissolved, and then aromatic diacid chloride is added in two steps in an equimolar amount with aromatic diamine. Separately add 20 to 49 mol% of the aromatic diacid chloride first, and then add 51 to 80 mol% of the remaining aromatic dieside chloride and react until it becomes an optically anisotropic liquid crystal prepolymer. This was spun into a spinning aid and spun onto a polymerization promoter precipitate containing tertiary amine to continuously produce aromatic polyamide fibers. And a method of producing a film.
이하 본 발명을 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 아미드계 용매에 무기염을 용해시키고 여기에 상기 아미드계 용매에 대하여 3급아민을 0∼2중량%정도로 첨가시킨 용매계에 1몰의 방향족 디아민 예를들면, 파라페닐렌디아민을 용해시키고, 저온으로 냉각시킨 다음 방향족 디에시드클로라이드, 예를들면 테레프탈로일클로라이드를 상기 방향족 디아민과 등몰량으로 사용하되 먼저 전체 방향족 디에시드클로라이드에 대하여 20 내지 49몰%를 1차로 투입하고 1차로 투입된 디에시드클로라이드의 반응이 거의 완결된 상태에서 1차로 투입된 상기의 방향족 디에시드클로라이드와 상기의 방향족 디아민의 반응에 의해 생성된 반응열을 20℃ 이하의 저온에서 냉각수로 냉각시켜서 제거한 후, 여기에 나머지 방향족 디에시드클로라이드 51 내지 80몰%을 다시 투입하여 광학적으로 이등방성인 액정예비중합체가 될 때까지 반응시킨다. 이때 생성된 액정예비중합체의 고유점도는 황산 0.5g/100ml 농도로 측정하였을 때 1.0 내지 4.0이 되게 된다. 이렇게 제조된 애겅예비중합체를 노즐을 통하여 중합촉진침저너제인 3급아민중에 방사시키게 되면 이 3급아민에 의하여 상기의 액정예비중합체가 전단력을 받으면서 분자가 배향됨과 동시에 급격한 중합반응이 일어나면서 연속적으로 고분자량의 방향족 폴리아미드섬유와 필름이 제조되게 된다.In the present invention, one mole of aromatic diamine, for example, paraphenylenediamine, is dissolved in a solvent system in which an inorganic salt is dissolved in an amide solvent and a tertiary amine is added in an amount of about 0 to 2% by weight based on the amide solvent. After cooling to low temperature, aromatic dieside chloride, for example terephthaloyl chloride, is used in an equimolar amount with the aromatic diamine, but firstly, 20 to 49 mol% of the total aromatic dieside chloride is first introduced and firstly added. After the reaction of dieside chloride is almost completed, the heat of reaction generated by the reaction of the above aromatic dieside chloride and the aromatic diamine is first removed by cooling with cooling water at a low temperature of 20 ° C. or lower, and then the remaining aromatic 51-80 mol% of dieside chloride was added again to give optically anisotropic liquid crystal preparation. It is allowed to react until the polymer. At this time, the intrinsic viscosity of the produced liquid crystal prepolymer is 1.0 to 4.0 when measured at a concentration of 0.5g / 100ml sulfuric acid. When the thus prepared prepolymer is spun through a nozzle in a tertiary amine, which is a polymerization accelerator, the liquid crystal prepolymer is subjected to shearing force by the tertiary amine, and the molecules are oriented and a rapid polymerization reaction occurs continuously. High molecular weight aromatic polyamide fibers and films are produced.
여기서, 본 발명에서의 아미드계 용매로서는 예를들면, N-메틸-2-피롤리돈, N,N-디메틸아세트아미드 또는 헥사메틸포스포르아미드 등이 사용되고, 무기염으로서는 예를들면 염화칼슘(CaCl2), 염화리튬(LiCl), 브롬화칼륨(KBr) 또는 염화칼륨(KCl)등이 사용되며 중합용매에 대하여 4 내지 15중량%가 사용되는 것이 바람직하다.Here, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, hexamethylphosphoramide, or the like is used as the amide solvent in the present invention. For example, calcium chloride (CaCl) is used as the inorganic salt. 2 ), lithium chloride (LiCl), potassium bromide (KBr), potassium chloride (KCl) and the like are used, and 4 to 15% by weight of the polymerization solvent is preferably used.
그리고, 아미드계 용매에 대하여 0 내지 2중량%가 첨가되어지게 되는 3급아민으로는 예를 들면 피리딘, 트리에틸아민, t-부틸아민 또는 피콜린등이 사용된다.And as a tertiary amine which 0-2 weight% is added with respect to an amide solvent, pyridine, triethylamine, t-butylamine, picoline, etc. are used, for example.
그리고 중합촉진침전제로서는 상기와 같은 아미드계 용매와 3급아민의 혼합물을 사용하는 것이 바람직하다.In addition, it is preferable to use a mixture of the above-described amide solvent and tertiary amine as a polymerization accelerator precipitater.
한편, 상기의 액정예비중합체용액은 중합체의 함량율을 10중량% 이상 20중량% 이하로 하는 것이 바람직한데, 만일 액정예비중합체의 함량율을 10중량% 이하로 하게 될 경우에는 경제적으로 불리하며, 20중량% 이상으로 할 경우에는 반응물의 점도가 높아져서 액정예비중합체 도우프의 공정관리면에서 어려움이 많게 된다. 그리고 액정예비중합체를 분리하여 황산에 0.5g/100ml의 농도로 녹였을 때 점도가 1.0 내지 4.0이면 좋고, 1.5 내지 3.5이면 더욱 좋다.On the other hand, the liquid crystal prepolymer solution is preferably a polymer content of 10% by weight or more and 20% by weight or less, if the content of the liquid crystal prepolymer is 10% by weight or less, it is economically disadvantageous, If the content is 20% by weight or more, the viscosity of the reactant becomes high, which makes it difficult to control the process of the liquid crystal prepolymer dope. When the liquid crystal prepolymer is separated and dissolved in sulfuric acid at a concentration of 0.5 g / 100 ml, the viscosity may be 1.0 to 4.0, and more preferably 1.5 to 3.5.
이와 같은 본 발명의 방법에 의하여 단섬유를 제조하게 될 경우에는 중합용매에 대한 고분자의 중합체 함량율을 10중량% 이상 20중량% 이하까지 고농도로 하는 것과 같이 중합체 함량율을 향상시킬 수 있으므로서 자연적으로 성형제품의 결정화도를 향상시킬 수가 있어서 섬유의 물성이 향상되게 되고, 또한 액정예비중합체까지 서서히 반응시켜줌으로서 모든 분자가 고르게 성장하여 분자량의 분포가 좁은 제품을 만들 수 있기 때문에 제품의 물성향상을 기할 수 있고, 또 실제 연속 공정화 할 수 있을 정도로 중합체 함량율에 따라 2단계로 방향족 디에시드클로라이드를 투입한 후에 20분 이내 액정예비중합체를 필라멘트, 필름, 펄프상으로 제조하기에 적합한 점도에서 각각 3급아민으로 분사시켜 제품을 제조하기 때문에 공정을 자유롭게 조절할 수가 있어서 원하는 제품을 마음대로 제조할 수 있는 특징이 있다.When the short fibers are produced by the method of the present invention, the polymer content of the polymer can be improved by increasing the polymer content of the polymer to a high concentration of 10% by weight to 20% by weight. As a result, the crystallinity of the molded product can be improved, and the physical properties of the fiber can be improved. Also, by slowly reacting the liquid crystal prepolymer, all molecules can be grown evenly and a product having a narrow molecular weight distribution can be produced. After the addition of the aromatic dieside chloride in two stages according to the polymer content rate to the extent that the actual continuous process can be carried out within 20 minutes, each of the third grade at a viscosity suitable for preparing the liquid crystal prepolymer into filament, film, and pulp phases. Since the product is manufactured by spraying with amine, the process can be freely controlled. Get the desired product are features that can be produced at will.
예컨대, 본 발명은 방향족 디에시드클로라이드를 분할 첨가시키므로서 반응열을 제거시킬 수 있게 되어 아라미드 중합반응의 속도조절이 가능하면서 고농도로 액정예비중합체를 합성시킬수 있으며, 2차로 방향족 디에시드클로라이드를 첨가시킨 후 조건에 따라 겔화시간이 2분 내지 20분정도로 연장되므로 분자들이 균일한 성장을 하여 분자량의 분포를 좁힐 수 있어서 섬유의 물성을 향상시키면서 섬유제조공정을 연속적으로 실시할 수 있다.For example, the present invention can remove the heat of reaction by dividing the addition of the aromatic dieside chloride, it is possible to synthesize the liquid crystal prepolymer in a high concentration while controlling the rate of the aramid polymerization reaction, and after adding the aromatic dieside chloride second Depending on the conditions, the gelation time is extended to about 2 minutes to 20 minutes, so that the molecules can be uniformly grown to narrow the molecular weight distribution, thereby improving the physical properties of the fiber, thereby allowing the fiber manufacturing process to be carried out continuously.
따라서, 종래섬유의 결정화도는 40% 이하가 대부분이지만 본 발명에서는 30 내지 60%의 결정화도를 갖는 고강도, 고탄성의 섬유제품을 얻을 수가 있다.Therefore, although the crystallinity degree of the conventional fiber is 40% or less, the present invention can obtain a high strength, high elastic fiber product having a crystallinity of 30 to 60%.
이하 본 발명을 실시예에 의거 더욱 상세히 설명하면 다음과 같으며, 실시예에서 섬유의 물성을 나타내는 D는 Denier로 실의 굵기이고, E는 Elongation으로 신장율(%)이며, T는 Tenacity로 인장강도(g/den)이고, M은 Modulus로 초기탄성율 (g/den)이다.Hereinafter, the present invention will be described in more detail with reference to Examples, where D represents the physical properties of the fibers in Denier, the thickness of the yarn, E is the elongation (%) in Elongation, and T is the tensile strength in Tenacity. (g / den) and M is modulus of initial modulus (g / den).
[실시예 1]Example 1
수분이 제거된 질소로 치환된 반응기에 N-메틸-2-피롤리돈 250ml에 CaCl214g을 용해시키고 파라페닐렌디아민 19.55g을 용해시킨 후 10℃ 이하 저온에서 테레프탈로일클로라이드 11.011g을 투입하여 반응을 30분간 시킨 후 다시 10℃ 이하의 저온으로 냉각하고 나머지 테레프탈로일클로라이드 25.691g을 투입하여 10분간 반응시켜 광학적 비등방성 액정예비중합체를 얻어 이를 직접 1/8인치 이송관을 통해 노즐의 직경이 0.3cm이고 개수가 10개인 방사장치를 통해 N-메틸-2-피롤리돈/피리딘=1/1(부피비)인 중합촉진침전용매중에 방사하여 섬유를 제조한다.Dissolve 14 g of CaCl 2 in 250 ml of N-methyl-2-pyrrolidone, dissolve 19.55 g of paraphenylenediamine, and add 11.011 g of terephthaloyl chloride at a low temperature below 10 ° C. After the reaction was performed for 30 minutes, the mixture was cooled to a low temperature of 10 ° C. or lower and 25.691 g of the remaining terephthaloyl chloride was added and reacted for 10 minutes to obtain an optically anisotropic liquid crystal prepolymer. Fibers are produced by spinning in a polymerization accelerator for N-methyl-2-pyrrolidone / pyridine = 1/1 (volume ratio) through a 0.3 cm diameter and 10 number spinning device.
이때 액정예비중합체의 고유점도는 1.2였고 섬유제품의 고유점도는 6.2였다.At this time, the intrinsic viscosity of the liquid crystal prepolymer was 1.2 and the intrinsic viscosity of the textile product was 6.2.
[실시예 2]Example 2
실시예 1과 동일하나 단지 파라페닐렌디아민 17.89g을 N-메틸-2-피롤리돈 200ml에 CaCl220g과 피리딘 5g을 용해시킨 용액에 녹이고 테레프탈로일클로라이드를 1차로 13g 투입하여 상기와 같이 냉각시킨 후 2차로 테레프탈로일클로라이드 20.58g을 투입하여 액정예비중합체를 제조한 후 피리딘/N-메틸-2-피롤리돈=7/3(부피비)의 중합촉진침전용매중에 방사하여 실을 만든 다음 물로 씻어 1500데니아, 100필라멘트의 실을 제조한다.Same as Example 1 except that only 17.89 g of paraphenylenediamine was dissolved in a solution of 20 g of CaCl 2 and 5 g of pyridine in 200 ml of N-methyl-2-pyrrolidone, and 13 g of terephthaloyl chloride was first added as described above. After cooling, 20.58 g of terephthaloyl chloride was added secondly to prepare a liquid crystal prepolymer, which was then spun into pyridine / N-methyl-2-pyrrolidone = 7/3 (volume ratio) for the polymerization accelerator. Then, washed with water to prepare a yarn of 1500 denier, 100 filament.
물성은 D/E/T/M=1.5/8/20/514이었고 고유점도는 6.8이었다.The physical properties were D / E / T / M = 1.5 / 8/20/514 and the intrinsic viscosity was 6.8.
[비교예 1]Comparative Example 1
수분이 제거된 질소로 치환된 반응기에 N-메틸-2-피롤리돈 250ml을 투입하고 80℃까지 승온시킨 다음 CaCl210.0g을 첨가하여 완전용해시키고 파라페닐렌디아민 10.38g을 첨가하여 용해시킨 후, 30℃ 이하의 저온에서 테레프탈로일클로라이드 19.55g을 투입하고 8분정도 격렬하게 교반 반응시켜 광학적 비등방성 액정예비중합체를 얻어 이를 직접 1/8인치 이송관을 통해 노즐의 직경이 0.3cm이고 갯수가 10개인 방사장치를 통해 피리딘에 방사하여 섬유를 제조한다.250 ml of N-methyl-2-pyrrolidone was added to a reactor substituted with nitrogen from which water was removed, and the temperature was raised to 80 ° C., followed by complete dissolution by adding 10.0 g of CaCl 2 , followed by dissolution of 10.38 g of paraphenylenediamine. Thereafter, 19.55 g of terephthaloyl chloride was added at a low temperature of 30 ° C. or lower, followed by vigorous stirring for about 8 minutes to obtain an optically anisotropic liquid crystal prepolymer, and the diameter of the nozzle was 0.3 cm through a 1/8 inch transfer tube. Fibers are produced by spinning on pyridine through a 10 number spinning device.
이때 최종섬유제품의 고유점도는 3.0이다.At this time, the intrinsic viscosity of the final fiber product is 3.0.
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