KR20130078585A - Poly(m-phenylene terephthal amide fiber and its manufacturing method - Google Patents
Poly(m-phenylene terephthal amide fiber and its manufacturing method Download PDFInfo
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Abstract
Description
본 발명은 폴리 메타-페닐렌테레프탈아미드 섬유 및 그의 제조방법에 관한 것으로 특히 내열성과 강도가 우수한 신규한 아라미드인 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하기 위한 제조방법에 관한 것이다.
The present invention relates to a poly meta-phenylene terephthalamide fiber and a method for producing the same, and more particularly to a manufacturing method for producing poly meta-phenylene terephthalamide fiber, which is a novel aramid having excellent heat resistance and strength.
일반적으로 폴리아미드계 합성수지는 지방족 폴리아미드와 방향족 폴리아미드로 분류된다. Generally, polyamide-based synthetic resins are classified into aliphatic polyamides and aromatic polyamides.
지방족 폴리아미드는 일반적으로 나이론이란 상표명으로, 방향족 폴리아미드는 아라미드라는 상표명으로 잘 알려져 있다. Aliphatic polyamides are generally known under the trade name Nylon, and aromatic polyamides are known under the trade name Aramid.
상기 지방족 폴리아미드. 특히 나일론 6, 그리고 나일론 6,6 등은 가장 일반적인 열가소성 엔지니어링 플라스틱으로 중요한 응용분야는로는 섬유 뿐 만 아니라 여러 분야의 성형재료로 사용되고 있다. 성형분야에 사용되는 나일론 수지는 향상된 난연성과 내충격성을 갖도록 하고 가격을 낮추고 탄성율과 같은 기계적 물성을 향상시키기 위하여 광물 또는 유리섬유로 보강하여 복합재료인 강화플라스틱(reinforced plastics)으로 제조한다. The aliphatic polyamide. Especially, nylon 6 and nylon 6,6 are the most common thermoplastic engineering plastics, and they are used not only as fibers but also as molding materials in various fields. The nylon resin used in the molding industry is made of reinforced plastics which is reinforced with mineral or glass fiber to improve mechanical properties such as elasticity and lowering the price to have improved flame retardancy and impact resistance.
1960년대 개발된 아라미드라는 방향족 폴리아미드는 지방족 폴리아미드인 나일론의 내열성을 개선시키기 위해 개발된 것으로 노멕스(Nomex), 케블라(Kevlar)와 같은 상품명으로 잘 알려져 있는 방향족 폴리아미드는 난연성 섬유직물, 타이어 코드 등의 섬유용도로 사용될 수 있는 뛰어난 내열성과 높은 인장강도를 갖는다. Aromatic polyamides, developed in the 1960s, were developed to improve the heat resistance of nylon, an aliphatic polyamide. Aromatic polyamides, well known for their trade names such as Nomex and Kevlar, And has excellent heat resistance and high tensile strength which can be used for fibers such as cord.
일반적인 지방족 폴리아미드는 아미드기사이에 지방족 탄화수소가 결합되어 있는 합성수지이나, 아라미드(aramid)는 아미드기 사이에 벤젠기가 85%의 아미드 결합이 두 개의 방향족 고리에 결합되어 있는 합성수지를 말한다. 상기 지방족 폴리아미드의 지방족 탄화수소는 열을 가하면 쉽게 분자운동이 일어나는 데 반하여, 방향족 폴리아미드의 벤젠 환은 분자쇄가 강직하고 열을 가하여도 분자가 쉽게 움직이지 않으므로 열에 안정하고 탄성률이 높아 일반 지방족 폴리아미드와는 특성에 있어서 많은 차이를 나타낸다.A general aliphatic polyamide is a synthetic resin in which an aliphatic hydrocarbon is bonded between amide groups, and aramid refers to a synthetic resin in which 85% of amide bonds of benzene groups are bonded to two aromatic rings between amide groups. The aliphatic hydrocarbon of the aliphatic polyamide easily undergoes molecular motion when heat is applied, whereas the benzene ring of the aromatic polyamide is stable to heat and has high elasticity because the molecule chains are rigid and the molecules do not easily move even when heat is applied. And there are many differences in characteristics.
상기 방향족 폴리아미드는 파라계 아라미드(para-aramid)와 메타계 아라미드(meta-aramid)로 분류되며, 파라계 아라미드는 듀폰사에서 개발된 케블라(Kevlar)가 대표적이다. 파라계 아라미드는 벤젠 고리가 파라 위치에서 아미드기와 결합된 것이다. 분자쇄가 매우 뻣뻣하고 선상구조를 가지므로 강도가 매우 높고 탄성률이 특히 높아 충격을 흡수하는 성능이 매우 우수하여 방탄복, 방탄 핼멧, 안전용 장갑이나 부츠, 소방복에 사용되며, 테니스 라켓, 보트, 하키용 스틱, 낚시 줄, 골프 클럽등의 스포츠 기구 재료로 또한 산업용으로는 FRP(Fiber Reinforced Plastic), 석면대체용 섬유등에 사용되고 있다. The aromatic polyamide is classified into a para-aramid and a meta-aramid. The para-aramid is represented by Kevlar developed by DuPont. The para-aramid is the benzene ring bound to the amide group at the para position. Since the molecular chain is very stiff and has a linear structure, it has a very high strength and a particularly high elasticity, so that it has excellent shock absorbing performance. It is used for armor, bulletproof helmet, safety gloves, boots and fire extinguisher. It is used for sports equipment such as sticks, fishing rods and golf clubs, and also for industrial use such as FRP (Fiber Reinforced Plastic) and asbestos replacement fibers.
메타계 아라미드는 듀폰사에서 개발된 노멕스(Nomex), 데이진사에서 개발된 코넥스(Conex)가 대표적이다. 메타계 아라미드는 벤젠고리가 메타 위치에서 아미드기와 결합된 것으로 강도와 신도는 보통의 나일론과 비슷하나 열에 대한 안정성이 대단히 좋으며, 다른 내열용 소재에 비하여 가볍고 땀흡수도 어느정도 가능하므로 쾌적하다는 장점을 가지고 있다. 초기에는 색상이 몇 가지로 제한되었으나, 최근에는 형광색을 포함한 다양한 색상으로 만들어지고 있다. 소방복,경주용 자동차 운전자를 위한 유니폼,우주 비행사 유니폼,작업복 등의 내열용 의복 소재로 사용 되며, 산업용으로는 고온용 필터등으로 쓰인다.Meta-based aramids are representative of Nexex developed by DuPont and Conex developed by Dejin. The meta-based aramid has a merit that the strength and elongation of the benzene ring are combined with the amide group at the meta-position, similar to ordinary nylon, but very good in heat stability, and light and sweat-absorbing compared to other heat-resistant materials. have. In the early days, the color was limited to a few, but recently it has been made in various colors including fluorescent colors. It is used as a material for heat-resistant clothing such as fire fighting suit, uniform for racing car driver, astronaut uniform, and work clothes, and it is used as high temperature filter for industrial use.
미국특허 제3,068,188호 등에 기재된 종래의 메타계 아라미드 제조방법에 따르면 극성 아미드계 용매중에 메타페닐렌디아민(m-phenylene diamine: MPD)와 이소프탈로일 클로라이드(isophthaloyl chloride: IPC)을 중합하고 중합의 부산물으니 염산을 중화하기 위해 염기성화합물을 첨가하여 메타 아라미드를 제조하였다.According to the conventional meta-aramid production method described in U.S. Patent No. 3,068,188, etc., the polymerization of metaphenylenediamine (m-phenylene diamine (MPD) and isophthaloyl chloride (IPC) in a polar amide solvent and polymerization of In order to neutralize hydrochloric acid, meta-aramid was prepared by adding a basic compound.
그러나 상기의 파라계 아라미드나 메타계 아라미드로 제조되는 섬유는 내열성이나 강도 등이 부족하여 사용상의 제약이 많아 사용상의 불편함이 있는 문제점 이있었다.
However, the fiber produced from the para-aramid or meta-aramid has a problem in that it is inconvenient in use due to its lack of heat resistance or strength and many restrictions on use.
본 발명은 상기와 같은 문제를 해결하기 위해 발명된 것을 강도와 내열성이 모두 우수한 폴리 메타-페닐렌테레프탈아미드 섬유 및 그의 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a poly meta-phenylene terephthalamide fiber excellent in both strength and heat resistance and a method for producing the same, which has been invented to solve the above problems.
또한, 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되는 폴리 메타-페닐렌테레프탈아미드 조성물을 이용한 폴리 메타-페닐렌테레프탈아미드 섬유 및 그의 제조방법을 제공하는 것을 목적으로 한다.
In addition, poly meta-phenylene terephthalamide fiber and its preparation using a poly meta-phenylene terephthalamide composition made of meta-phenylene diamine (MPD) and terephthaloyl chloride (TPC) It is an object to provide a method.
본 발명은 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되면 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)을 용매로 사용하여 형성되는 폴리 메타-페닐렌테레프탈아미드 조성물로 제조되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.The present invention is prepared from meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC) containing N-methylpyrrolidone (N-methylpyrrolidone, NMP) containing calcium chloride (CaCl 2 ) A poly meta-phenylene terephthalamide fiber, characterized in that it is made of a poly meta-phenylene terephthalamide composition formed using a solvent.
또한, 상기 염화칼슘을 포함하는 N-메틸피롤리돈에 염화칼슘이 1~5중량% 혼합되어 있는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.In addition, there is provided a poly meta-phenylene terephthalamide fiber characterized in that 1 to 5% by weight of calcium chloride is mixed with N-methylpyrrolidone containing calcium chloride.
또한, 상기 염화칼슘을 포함하는 N-메틸피롤리돈은 N-메틸피롤리돈에 염화칼슘을 혼합한 후, 질소상태에서 70~90℃, 80~140분간 교반하여 제조되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.In addition, the N-methylpyrrolidone containing calcium chloride is prepared by mixing calcium chloride with N-methylpyrrolidone and then stirring the mixture at 70 to 90 ° C. for 80 to 140 minutes in a nitrogen state. Provides phenylene terephthalamide fibers.
또한, 상기 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈에 메타-페닐렌 디아민과 테레프탈로일클로라이드는 8~20중량%가 혼합되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.In addition, meta-phenylene diamine and terephthaloyl chloride in N-methylpyrrolidone containing calcium chloride (CaCl 2 ) is a poly meta-phenylene terephthalamide fiber, characterized in that 8 to 20% by weight is mixed to provide.
또한, 상기 폴리 메타-페닐렌테레프탈아미드 조성물은, 메타-페닐렌 디아민(M-phenylene diamine, MPD)을 용매인 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)에 용해하는 용해 단계; 상기 메타-페닐렌 디아민이 용해된 N-메틸피롤리돈에 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)를 첨가하여 중합하는 중합단계; 상기 중합 후, 산화칼슘(CaO)을 첨가하여 중화하는 중화단계를 포함하여 제조되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.In addition, the poly meta-phenylene terephthalamide composition, N-methylpyrrolidone (NMP) containing meta-phenylene diamine (M-phenylene diamine, MPD) containing calcium chloride (CaCl 2 ) as a solvent Dissolution step to dissolve in; A polymerization step of polymerizing by adding terephthaloyl chloride (TPC) to N-methylpyrrolidone in which the meta-phenylene diamine is dissolved; After the polymerization, it provides a poly meta-phenylene terephthalamide fiber, characterized in that it comprises a neutralization step of neutralizing by adding calcium oxide (CaO).
또한, 상기 용해단계는 0~10℃에서 10~20분간 용해하고, 상기 중합단계는 0~10℃에서 40~80분간 중합하며, 상기 중화단계는 5~24℃에서 40~80분간 중화하는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유를 제공한다.In addition, the dissolution step is dissolved for 10 to 20 minutes at 0 ~ 10 ℃, the polymerization step is polymerized for 40 to 80 minutes at 0 ~ 10 ℃, the neutralization step is to neutralize 40 to 80 minutes at 5 ~ 24 ℃ A poly meta-phenylene terephthalamide fiber is provided.
또한, 본 발명은 폴리 메타-페닐렌테레프탈아미드 조성물을 이용하여 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하는 제조방법에 있어서, 상기 폴리 메타-페닐렌테레프탈아미드 조성물을 비양성자성 극성 용매로 용해하여 방사원액을 제조하는 방사원액제조공정; 상기 방사원액을 방사하는 방사공정; 상기 방사된 섬유에 용매를 제거하는 용매제거공정을 포함하는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법을 제공한다.In addition, the present invention is a method for producing a poly meta-phenylene terephthalamide fiber using a poly meta-phenylene terephthalamide composition, wherein the poly meta-phenylene terephthalamide composition is dissolved in an aprotic polar solvent Spinning stock solution manufacturing process for producing a spinning stock solution; Spinning step of spinning the spinning stock solution; It provides a method for producing a poly meta-phenylene terephthalamide fiber comprising a solvent removing step of removing the solvent in the spun fiber.
또한, 비양성자성 극성 용매는 헥사메틸포스포르아마이드(hexamethylphosphoramide, HMPA), N-메틸피롤리돈(N-methylpyrrolidone, NMP), 디메틸아세트아미드(N,N-dimethylacetamide, DMAC), 테트라메틸우레아(N,N,N',N'-tetramethylurea, TMU) 중 선택되는 하나인 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법을 제공한다.In addition, aprotic polar solvents are hexamethylphosphoramide (HMPA), N-methylpyrrolidone (NMP), dimethylacetamide (N, N-dimethylacetamide (DMAC), tetramethylurea ( N, N, N ', N'-tetramethylurea, TMU) provides a method for producing poly meta-phenylene terephthalamide fiber, characterized in that one selected from.
또한, 상기 폴리 메타-페닐렌테레프탈아미드 조성물은 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되면 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)을 용매로 사용하여 형성되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법을 제공한다.
In addition, the poly meta-phenylene terephthalamide composition is N-methyl containing calcium chloride (CaCl 2 ) when made of meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC) It provides a method for producing poly meta-phenylene terephthalamide fiber, characterized in that formed using pyrrolidone (N-methylpyrrolidone, NMP) as a solvent.
이하 본 발명의 바람직한 일실시예를 상세히 설명하기로 한다. 본 발명을 설명함에 있어, 관련된 공지기능 혹은 구성에 대한 구체적인 설명은 본 발명의 요지를 모호하지 않게 하기 위하여 생략한다.Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.
본 명세서에서 사용되는 정도의 용어 “약”, “실질적으로” 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. 또한 본 발명에서 사용되는 '순도'는 중량비에 따른 순도를 말한다.
The terms " about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. In addition, 'purity' used in the present invention refers to purity according to the weight ratio.
본 발명은 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되면 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)을 용매로 사용하여 형성되는 폴리 메타-페닐렌테레프탈아미드 조성물로 제조되는 폴리 메타-페닐렌테레프탈아미드 섬유에 관한 것이다.The present invention is prepared from meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC) containing N-methylpyrrolidone (N-methylpyrrolidone, NMP) containing calcium chloride (CaCl 2 ) It relates to a poly meta-phenylene terephthalamide fiber made of a poly meta-phenylene terephthalamide composition formed using a solvent.
본 발명에 사용되는 폴리 메타-페닐렌테레프탈아미드(Poly(m-phenylene terephthal amide) 조성물은 도 1에서 나타난 바와 같이 제조된다.Poly meta-phenylene terephthalamide (Poly (m-phenylene terephthal amide) composition) used in the present invention is prepared as shown in FIG.
본 발명에 사용되는 폴리 메타-페닐렌테레프탈아미드 조성물은 반응식 1과 같이 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되는 것으로 중합을 위해 사용되는 용매는 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)을 사용하는 것이다.The poly meta-phenylene terephthalamide composition used in the present invention is prepared by meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC), as shown in Scheme 1. The solvent used is N-methylpyrrolidone (NMP) containing calcium chloride (CaCl 2 ).
[반응식 1][Reaction Scheme 1]
반응식 1과 같이 구성된 본 발명에 따른 폴리 메타-페닐렌테레프탈아미드 조성물은 아미드(amide)기와 방향족환(aromatic ring)으로 구성되는 강직한 형태와 직연쇄배좌(extended chain conformation)의 화학구조식을 가지고 있다. 선형사슬을 따라 주기적으로 존재하는 아미드기는 분자간의 수소결합을 형성하여 결정화도를 증가시킨다. 따라서 본 발명의 폴리 메타-페닐렌테레프탈아미드 조성물은 결정화도가 60이상인 고결정성을 갖고 배향도가 80% 이상(섬유제조시 방사조건에 따라 90%이상)의 고배향성을 갖기 때문에 인장에 대한 기계적 성질이 우수하다. 또한 고분자사슬이 수소결합으로 연결되어 매우 면밀하게 짜여진 층을 형성하게 되며 이 수소결합에 기인한 고분자사슬 간의 강한 상호작용에 의해 고강도, 고탄성률의 물성을 가지게 된다. Poly meta-phenylene terephthalamide composition according to the present invention configured as shown in Scheme 1 has a rigid structure consisting of an amide group and an aromatic ring and a chemical formula of extended chain conformation. . Amide groups present periodically along the linear chain form hydrogen bonds between molecules to increase crystallinity. Therefore, the poly meta-phenylene terephthalamide composition of the present invention has a high crystallinity with a crystallinity of 60 or more and has a high orientation of 80% or more (90% or more depending on spinning conditions in the fabric manufacturing), so that the mechanical properties against tension great. In addition, the polymer chains are connected by hydrogen bonds to form a very tightly woven layer, and have high strength and high modulus properties due to the strong interaction between the polymer chains due to the hydrogen bonds.
상기 폴리 메타-페닐렌테레프탈아미드 조성물의 중합도를 높이기 위해 순도가 높은 메타-페닐렌 디아민과 테레프탈로일클로라이드를 사용하는 것이 바람직할 것이다. 상기 메타-페닐렌 디아민과 테레프탈로일클로라이드은 순도 99% 이상인 것을 사용하는 것이 바람직하다.In order to increase the degree of polymerization of the poly meta-phenylene terephthalamide composition, it is preferable to use high purity meta-phenylene diamine and terephthaloyl chloride. The meta-phenylene diamine and terephthaloyl chloride is preferably used having a purity of 99% or more.
상기 순도가 높은 메타-페닐렌 디아민과 테레프탈로일클로라이드를 제조하기 위해 0.1~1토르(torr)의 진공하에서 승화시켜 응축분리시키는 진송승화법으로 순도 99%이상의 메타-페닐렌 디아민과 테레프탈로일클로라이드를 제조할 수 있다.In order to prepare the high-purity meta-phenylene diamine and terephthaloyl chloride, sublimation is carried out by sublimation under vacuum of 0.1 to 1 torr, condensation separation of meta-phenylene diamine and terephthaloyl having a purity of 99% or more. Chloride can be prepared.
상기 메타-페닐렌 디아민과 테레프탈로일클로라이드의 중합은 상기 반응식 1에 나타난 바와 같이 몰비로 1대1로 반응하는 것으로 동일한 몰비로 반응시킬 수 있으나 중합의 효율 및 수득율을 높이기 위해 상기 메타-페닐렌 디아민과 테레프탈로일클로라이드은 몰비 1:0.8~1.2로 중합시킬 수 있다.The polymerization of the meta-phenylene diamine and terephthaloyl chloride can be carried out in the same molar ratio by reacting in a molar ratio of 1 to 1 as shown in Scheme 1, but in order to increase the efficiency and yield of the polymerization, the meta-phenylene Diamine and terephthaloyl chloride can be polymerized in a molar ratio of 1: 0.8 to 1.2.
본 발명에 사용되는 용매는 염화칼슘을 포함하는 N-메틸피롤리돈은 중합을 원활하게 하기 위해 N-메틸피롤리돈에 무기염인 염화칼슘을 포함하는 것으로 상기 염화칼슘이 용매인 염화칼슘을 포함하는 N-메틸피롤리돈에 1~5중량% 혼합되는 것이 바람직할 것이다. The solvent used in the present invention is N-methylpyrrolidone containing calcium chloride includes calcium chloride which is an inorganic salt in N-methylpyrrolidone to facilitate the polymerization. It would be desirable to mix 1-5% by weight in methylpyrrolidone.
상기 염화칼슘은 용매중에서 고분자의 용해도를 증가시켜 폴리 메타-페닐렌테레프탈아미드 조성물의 고형분 함량증가시킨다. The calcium chloride increases the solubility of the polymer in the solvent to increase the solids content of the poly meta-phenylene terephthalamide composition.
상기 용매인 염화칼슘을 포함하는 N-메틸피롤리돈은 N-메틸피롤리돈에 염화칼슘을 혼합한 후, 질소상태에서 70~90℃, 80~140분간 교반하여 제조할 수 있다.N-methylpyrrolidone containing calcium chloride as the solvent may be prepared by mixing calcium chloride with N-methylpyrrolidone, followed by stirring at 70 to 90 ° C. for 80 to 140 minutes in a nitrogen state.
상기 N-메틸피롤리돈은 순도 99%이상인 것을 사용하는 것이 바람직하며, 상기 메타-페닐렌 디아민과 테레프탈로일클로라이드과 같이 0.1~1토르(torr)의 진공하에서 승화시켜 응축분리시키는 진송승화법으로 순도 99%이상의 N-메틸피롤리돈을 제조할 수 있다.The N-methylpyrrolidone is preferably used having a purity of 99% or more, and is a sublimation sublimation method of condensation separation by sublimation under vacuum of 0.1 to 1 torr (torr), such as meta-phenylene diamine and terephthaloyl chloride. N-methylpyrrolidone with a purity of 99% or more can be prepared.
상기 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈에 메타-페닐렌 디아민과 테레프탈로일클로라이드는 8~20중량%가 혼합되는 것이 바람직하다. 즉 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈이 80g 일때 메타-페닐렌 디아민과 테레프탈로일클로라이드의 중량합이 8~20g 첨가될 수 있다.Meta-phenylene diamine and terephthaloyl chloride in N-methylpyrrolidone containing calcium chloride (CaCl 2 ) is preferably 8 to 20% by weight. That is, when N-methylpyrrolidone containing calcium chloride (CaCl 2 ) is 80 g, the weight sum of meta-phenylene diamine and terephthaloyl chloride may be added to 8-20 g.
상기 메타-페닐렌 디아민과 테레프탈로일클로라이드가 너무 많이 혼합되면 용해가 원활이 진행되지 않아 중합도가 저하될 수 있으므로 20중량% 이하로 혼합되는 것이 바람직하다.
When the meta-phenylene diamine and terephthaloyl chloride are mixed too much, since the dissolution may not proceed smoothly and the degree of polymerization may be lowered, it is preferable to mix 20 wt% or less.
상기와 같은 본 발명에 따른 폴리 메타-페닐렌테레프탈아미드 조성물은 도 1에 나타난 바와 같이 용해단계, 중합단계, 중화단계로 제조된다.Poly meta-phenylene terephthalamide composition according to the present invention as described above is prepared in the dissolution step, polymerization step, neutralization step as shown in FIG.
상기 용해단계는 메타-페닐렌 디아민(M-phenylene diamine, MPD)을 용매인 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)에 용해하는 단계로 0~10℃에서 교반하면서 10~20분간 용해하는 것이 바람직하다.The dissolving step is a step of dissolving meta-phenylene diamine (M-phenylene diamine, MPD) in N-methylpyrrolidone (NMP) containing calcium chloride (CaCl 2 ) as a solvent, 0 ~ 10 ℃ It is preferable to dissolve for 10 to 20 minutes while stirring.
상기 중합단계는 상기 메타-페닐렌 디아민이 용해된 염화칼슘(CaCl2 )을 포함하는 N-메틸피롤리돈에 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)를 첨가하여 중합하는 단계로 0~10℃에서 교반하면서 40~80분간 중합하여 폴리 메타-페닐렌테레프탈아미드 조성물이 형성되도록 충분한 시간동안 중합한다.The polymerization step is a step of polymerizing by adding terephthaloyl chloride (TPC) to N-methylpyrrolidone including calcium chloride (CaCl 2 ) in which the meta-phenylene diamine is dissolved. The polymerization is carried out for 40 to 80 minutes with stirring for a sufficient time to form a poly meta-phenylene terephthalamide composition.
상기 메타-페닐렌 디아민과 테레프탈로일클로라이드는 부반응을 하여 온도가 상승하여 중합도가 저하될 수 있으므로 상기 용해 및 중합단계는 10℃이하의 온도에서 진행되는 것이 바람직할 것이다.Since the meta-phenylene diamine and terephthaloyl chloride may be side-reacted to increase the temperature to decrease the degree of polymerization, the dissolution and polymerization step may be performed at a temperature of 10 ° C. or less.
또한, 상기에서 설명된 바와 같이 메타-페닐렌 디아민, 테레프탈로일클로라이드 및 N-메틸피롤리돈은 중합도를 높이기 위해 순도 99%이상인 것이 바람직하다.In addition, as described above, meta-phenylene diamine, terephthaloyl chloride and N-methylpyrrolidone are preferably 99% or more in order to increase the degree of polymerization.
상기 중화단계는 중합단계에서 부산물로 발생되는 염산을 형성되는 폴리 메타-페닐렌테레프탈아미드 조성물의 안정성을 위해 중화하는 단계로 산화칼슘(CaO), 수산화칼슘(CaO2)이나 또는 수산화리튬(LiOH)등의 염기성 화합물을 첨가할 수 있으며, 본 발명에서는 산화칼슘(CaO)을 첨가하여 반응식 2와 같이 중화시킬 수 있을 것이다.The neutralization step is a neutralization step for the stability of the poly meta-phenylene terephthalamide composition to form hydrochloric acid generated as a by-product from the polymerization step, such as calcium oxide (CaO), calcium hydroxide (CaO 2 ) or lithium hydroxide (LiOH), etc. The basic compound may be added, and in the present invention, calcium oxide (CaO) may be added to neutralize the same as in Scheme 2.
[반응식 2][Reaction Scheme 2]
2HCl + CaO → CaCl2 +H2O2HCl + CaO ¡Æ CaCl 2 + H 2 O
상기 중화단계는 중합도가 저하되지 않도록 5~24℃, 40~80분간 진행하여 염산을 제거한다.The neutralization step is 5 ~ 24 ℃, 40 ~ 80 minutes to remove the hydrochloric acid so that the degree of polymerization does not decrease.
또한, 상기 중화단계 이후, 발생된 물을 제거 및 용해단계, 중합단계에서 교반으로 생성되는 기포를 제거하기 위해 일반적인 탈수, 탈포공정으로 실시할 수 있다.
In addition, after the neutralization step, the generated water can be carried out in a general dehydration, degassing process to remove the bubbles generated by stirring in the removal and dissolution step, the polymerization step.
상기와 같이 제조되는 폴리 메타-페닐렌테레프탈아미드 조성물을 이용하여 폴리 메타-페닐렌테레프탈아미드 섬유를 제조한다. The poly meta-phenylene terephthalamide fiber is prepared using the poly meta-phenylene terephthalamide composition prepared as described above.
상기 폴리 메타-페닐렌테레프탈아미드 섬유의 제조방법은 도 2에 나타난 바와 같이 방사원액제조공정, 방사공정, 용매제거공정으로 제조한다.The method for producing the poly meta-phenylene terephthalamide fiber is prepared by spinning spinning solution preparation process, spinning process, solvent removal process as shown in FIG.
상기 방사원액제조공정은 상기와 같이 제조되는 상기 폴리 메타-페닐렌테레프탈아미드 조성물을 비양성자성 극성 용매로 용해하여 방사원액을 제조하는 공정이다.The spinning stock solution manufacturing process is a process for preparing a spinning stock solution by dissolving the poly meta-phenylene terephthalamide composition prepared as described above in an aprotic polar solvent.
상기 폴리 메타-페닐렌테레프탈아미드 조성물을 용해시키는 화합물 중에 비양자성 극성 용매는 가장 효과적인 것으로 알려져 있으며, 상기 비양성자성 극성 용매는 헥사메틸포스포르아마이드(hexamethylphosphoramide, HMPA), N-메틸피롤리돈(N-methylpyrrolidone, NMP), 디메틸아세트아미드(N,N-dimethylacetamide, DMAC), 테트라메틸우레아(N,N,N',N'-tetramethylurea, TMU) 중 선택되는 하나를 사용할 수 있을 것이다.Among the compounds for dissolving the poly meta-phenylene terephthalamide composition, an aprotic polar solvent is known to be most effective, and the aprotic polar solvent is hexamethylphosphoramide (HMPA), N-methylpyrrolidone ( N-methylpyrrolidone (NMP), dimethylacetamide (N, N-dimethylacetamide (DMAC), tetramethylurea (N, N, N ', N'-tetramethylurea, TMU) may be used.
상기 방사원액 제조시 염화칼슘(CaCl2)등의 염을 추가할 수 할 수 있을 것이다.In preparing the spinning stock solution, salts such as calcium chloride (CaCl 2 ) may be added.
상기 방사공정은 상기 제조된 방사원액을 이용하여 섬유를 제조하는 공정으로 방사구금을 통해 방사원액을 압출하여 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하는 공정이다. 상기 방사공정은 일반적인 방사공정으로 실시할 수 있을 것이다.The spinning process is a process for producing fibers using the prepared spinning stock solution is a process for producing a poly meta-phenylene terephthalamide fiber by extruding the spinning stock solution through a spinneret. The spinning process may be carried out in a general spinning process.
상기 용매제거공정은 폴리 메타-페닐렌테레프탈아미드 섬유에 잔류된 극성 용매와 염화칼슘 등을 제거하는 공정으로 방사된 섬유를 고온의 가스를 이용하여 용매를 증발시켜 제거하는 건식법으로 실시할 수 있으며, 또는 방사된 섬유를 응고욕에 침시키셔 용매를 제거하는 습식법으로 실시할 수 있을 것이다.The solvent removal step is a process of removing the polar solvent and calcium chloride remaining in the poly meta-phenylene terephthalamide fiber may be carried out by a dry method to remove the spun fiber by evaporating the solvent using a hot gas, or The spun fibers may be wetted with a coagulation bath to remove the solvent.
상기와 같은 공정으로 본 발명에 따른 폴리 메타-페닐렌테레프탈아미드 섬유를 제조할 수 있다.
By the above process it can be produced a poly meta-phenylene terephthalamide fiber according to the present invention.
본 발명에 따른 폴리 메타-페닐렌테레프탈아미드 섬유는 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되는 아라미드 섬유를 제공하는 효과가 있다.Poly meta-phenylene terephthalamide fiber according to the present invention has the effect of providing aramid fibers made of meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC).
또한, 본 발명의 폴리 메타-페닐렌테레프탈아미드 섬유는 강도 및 내열성이 우수하여 다양한 산업분야에서 사용될 수 있는 효과가 있다.
In addition, the poly meta-phenylene terephthalamide fiber of the present invention is excellent in strength and heat resistance has an effect that can be used in various industrial fields.
도 1은 본 발명의 폴리 메타-페닐렌테레프탈아미드 조성물을 제조하기 위한 제조 공정도이다.
도 2는 본 발명의 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하기 위한 공정도이다.
도 3은 본 발명의 폴리 메타-페닐렌테레프탈아미드의 고유점도를 나타낸 그래프이다.1 is a manufacturing process chart for producing the poly meta-phenylene terephthalamide composition of the present invention.
2 is a process chart for producing the poly meta-phenylene terephthalamide fiber of the present invention.
3 is a graph showing the intrinsic viscosity of the poly meta-phenylene terephthalamide of the present invention.
이하 본 발명의 폴리 메타-페닐렌테레프탈아미드 조성물을 제조하기 위한 방법의 실시예를 나타내지만, 한정되는 것은 아니다.
Hereinafter, although the Example of the method for manufacturing the poly meta- phenylene terephthalamide composition of this invention is shown, it is not limited.
실시예Example
메타-페닐렌 디아민(M-phenylene diamine, MPD), 테레프탈로일클로라이드(Terephthaloyl chloride, TPC), N-메틸피롤리돈(N-methylpyrrolidone, NMP)은 진공승화하여 순도 99%인 것을 사용하였다.Meta-phenylene diamine (M-phenylene diamine, MPD), terephthaloyl chloride (TPC) and N-methylpyrrolidone (N-methylpyrrolidone, NMP) were used in a 99% purity by vacuum sublimation.
메타-페닐렌 디아민을 용매인 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈에 5℃에서 15분 동안 용해하는 용해단계를 진행하였으며, 용해단계 후, 테레프탈로일클로라이드를 첨가하여 5℃에서 60분 동안 중합하여 폴리 메타-페닐렌테레프탈아미드 조성물을 중합하여 제조하였다.A dissolution step of dissolving meta-phenylene diamine in N-methylpyrrolidone containing calcium chloride (CaCl 2 ) as a solvent for 15 minutes at 5 ° C. was carried out. After the dissolution step, terephthaloyl chloride was added to 5 ° C. It was prepared by polymerizing the poly meta-phenylene terephthalamide composition by polymerization for 60 minutes at.
상기 중합 후, 산화칼슘(CaO)을 첨가하여 중합반응으로 생선된 산을 중화하였다. 상기 중화는 20℃에서 60분동안 진행되었다.After the polymerization, calcium oxide (CaO) was added to neutralize the acidified by the polymerization reaction. The neutralization proceeded at 20 ° C. for 60 minutes.
상기 용해,중합,중호단계는 질소하에서 교반시켜 진행하였다.The dissolution, polymerization, and curing steps were carried out by stirring under nitrogen.
상기 N-메틸피롤리돈에 염화칼슘(CaCl2)의 함량을 1중량%, 2중량%, 3중량%, 4중량%, 5중량%로 제조하였으며, 상기의 용매에 메타-페닐렌 디아민과 테레프탈로일클로라이드의 합한 중량을 10중량%, 11중량%, 12중량%, 13중량%, 14중량%, 15중량%를 상기의 용매에 각각 첨가하여 용해하여 각각 폴리 메타-페닐렌테레프탈아미드 조성물을 중합하여 제조하였다.The content of calcium chloride (CaCl 2 ) in the N-methylpyrrolidone was prepared by 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, and meta-phenylene diamine and terephthal in the solvent. 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, and 15% by weight of the loyl chloride were added to the above solvents to dissolve the poly meta-phenylene terephthalamide composition. Prepared by polymerization.
상기 메타-페닐렌 디아민과 테레프탈로일클로라이드은 몰비 1대1로 실시하였다.The meta-phenylene diamine and terephthaloyl chloride were carried out in a molar ratio of 1: 1.
◈ 고유점도 측정◈ Intrinsic viscosity measurement
상기와 같이 제조된 본 발명에 따른 폴리 메타-페닐렌테레프탈아미드 조성물의 고유점도를 측정하여 도 3에 나타내었다.Intrinsic viscosity of the poly meta-phenylene terephthalamide composition according to the present invention prepared as described above is shown in Figure 3 by measuring.
도 3은 각각의 용매 및 메타-페닐렌 디아민과 테레프탈로일클로라이드의 함량에 따른 고유점도 그래프이다.3 is an intrinsic viscosity graph according to the content of each solvent and meta-phenylene diamine and terephthaloyl chloride.
도 3에서 나타난 바와 같이 메타-페닐렌 디아민과 테레프탈로일클로라이드의 함량이 증가할수록 고유점도가 증가하였으며, 13중량%이상에서 고유점도가 감소하는 것을 알 수 있다. 또한, 염화칼슘 1중량%, 메타-페닐렌 디아민과 테레프탈로일클로라이드 함량이 13중량%인 경우에 고유점도의 최고값을 나타내었다.
As shown in FIG. 3, the intrinsic viscosity increased as the content of meta-phenylene diamine and terephthaloyl chloride increased, and the intrinsic viscosity decreased at 13 wt% or more. In addition, the maximum value of the intrinsic viscosity was shown when the calcium chloride, meta-phenylene diamine and terephthaloyl chloride content of 13% by weight.
◈ 폴리 메타-페닐렌테레프탈아미드 섬유 제조◈ Poly meta-phenylene terephthalamide fiber manufacturing
상기의 염화칼슘 1중량%, 메타-페닐렌 디아민과 테레프탈로일클로라이드 함량이 13중량%인 폴리 메타-페닐렌테레프탈아미드 조성물을 이용하여 본 발명인 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하였다. The poly meta-phenylene terephthalamide fiber of the present invention was prepared using the poly meta-phenylene terephthalamide composition having 1 wt% of calcium chloride, meta-phenylene diamine and terephthaloyl chloride content of 13 wt%.
상기 폴리 메타-페닐렌테레프탈아미드 조성물을 원심분리기를 이용하여 기포를 제거하였다.The poly meta-phenylene terephthalamide composition was bubbled using a centrifuge.
상기 폴리 메타-페닐렌테레프탈아미드 조성물을 N-메틸피롤리돈(N-methylpyrrolidone, NMP)에 용해하여 고형분 17중량%의 방사원액을 제조하였다. 상기 방사원액에 염화칼슘을 3중량% 함유하도록 되도록 첨가시켰다.The poly meta-phenylene terephthalamide composition was dissolved in N-methylpyrrolidone (NMP) to prepare a spinning stock solution having a solid content of 17% by weight. It was added to contain 3% by weight of calcium chloride in the spinning stock solution.
상기 제조된 방사원액을 130℃내외의 온도에서 원형의 방사구금으로 이용하여 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하였다.The prepared spinning stock solution was used as a circular spinneret at a temperature of about 130 ° C. to prepare poly meta-phenylene terephthalamide fibers.
상기 섬유 제조시 방사구금에서 토출되는 섬유에 220℃ 내외의 고온 질소가스를 분사하여 용매를 제거하였으며, 이후 4.5배로 연신하여 완성된 폴리 메타-페닐렌테레프탈아미드 섬유를 제조하였다. 상기 폴리 메타-페닐렌테레프탈아미드 섬유의 강도는 4.3g/de로 측정되었다. The solvent was removed by injecting hot nitrogen gas at about 220 ° C. to the fiber discharged from the spinneret when preparing the fiber, and then drawn to 4.5 times to prepare the finished poly meta-phenylene terephthalamide fiber. The strength of the poly meta-phenylene terephthalamide fiber was measured at 4.3 g / de.
Claims (9)
상기 염화칼슘을 포함하는 N-메틸피롤리돈에 염화칼슘이 1~5중량% 혼합되어 있는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유.The method of claim 1,
Poly meta-phenylene terephthalamide fiber, characterized in that 1 to 5% by weight of calcium chloride is mixed with N-methylpyrrolidone containing calcium chloride.
상기 염화칼슘을 포함하는 N-메틸피롤리돈은 N-메틸피롤리돈에 염화칼슘을 혼합한 후, 질소상태에서 70~90℃, 80~140분간 교반하여 제조되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유.The method of claim 1,
N-methylpyrrolidone containing the calcium chloride is poly meta-phenylene, characterized in that the mixture is prepared by stirring calcium chloride to N-methylpyrrolidone, 70 ~ 90 ℃, 80 ~ 140 minutes in a nitrogen state Terephthalamide fiber.
상기 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈에 메타-페닐렌 디아민과 테레프탈로일클로라이드는 8~20중량%가 혼합되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유.The method of claim 1,
The meta-phenylene diamine and terephthaloyl chloride in N-methylpyrrolidone containing calcium chloride (CaCl 2 ) is poly meta-phenylene terephthalamide fiber, characterized in that 8 to 20% by weight is mixed.
상기 폴리 메타-페닐렌테레프탈아미드 조성물은,
메타-페닐렌 디아민(M-phenylene diamine, MPD)을 용매인 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)에 용해하는 용해 단계;
상기 메타-페닐렌 디아민이 용해된 N-메틸피롤리돈에 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)를 첨가하여 중합하는 중합단계;
상기 중합 후, 산화칼슘(CaO)을 첨가하여 중화하는 중화단계를 포함하여 제조되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유.The method of claim 1,
The poly meta-phenylene terephthalamide composition,
Dissolving meta-phenylene diamine (M-phenylene diamine, MPD) in N-methylpyrrolidone (NMP) containing calcium chloride (CaCl 2 ) as a solvent;
A polymerization step of polymerizing by adding terephthaloyl chloride (TPC) to N-methylpyrrolidone in which the meta-phenylene diamine is dissolved;
After the polymerization, poly meta-phenylene terephthalamide fiber, characterized in that it comprises a neutralization step of neutralizing by adding calcium oxide (CaO).
상기 용해단계는 0~10℃에서 10~20분간 용해하고, 상기 중합단계는 0~10℃에서 40~80분간 중합하며, 상기 중화단계는 5~24℃에서 40~80분간 중화하는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유.The method of claim 5,
The dissolution step is dissolved for 10 to 20 minutes at 0 ~ 10 ℃, the polymerization step is polymerized for 40 to 80 minutes at 0 ~ 10 ℃, the neutralization step is characterized in that for 40 to 80 minutes at 5 ~ 24 ℃ Poly meta-phenylene terephthalamide fiber.
상기 폴리 메타-페닐렌테레프탈아미드 조성물을 비양성자성 극성 용매로 용해하여 방사원액을 제조하는 방사원액제조공정;
상기 방사원액을 방사하는 방사공정;
상기 방사된 섬유에 용매를 제거하는 용매제거공정을 포함하는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법.In the production method for producing a poly meta-phenylene terephthalamide fiber using a poly meta-phenylene terephthalamide composition,
A process for producing a spinning stock solution by dissolving the poly meta-phenylene terephthalamide composition in an aprotic polar solvent to prepare a spinning stock solution;
Spinning step of spinning the spinning stock solution;
Poly meta-phenylene terephthalamide fiber manufacturing method comprising a solvent removing step of removing the solvent to the spun fiber.
비양성자성 극성 용매는 헥사메틸포스포르아마이드(hexamethylphosphoramide, HMPA), N-메틸피롤리돈(N-methylpyrrolidone, NMP), 디메틸아세트아미드(N,N-dimethylacetamide, DMAC), 테트라메틸우레아(N,N,N',N'-tetramethylurea, TMU) 중 선택되는 하나인 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법.The method of claim 7, wherein
Aprotic polar solvents include hexamethylphosphoramide (HMPA), N-methylpyrrolidone (NMP), dimethylacetamide (N, N-dimethylacetamide (DMAC), tetramethylurea (N, N, N ', N'-tetramethylurea, TMU) Poly meta-phenylene terephthalamide fiber manufacturing method characterized in that one selected from.
상기 폴리 메타-페닐렌테레프탈아미드 조성물은 메타-페닐렌 디아민(M-phenylene diamine, MPD)과 테레프탈로일클로라이드(Terephthaloyl chloride, TPC)로 제조되면 염화칼슘(CaCl2)을 포함하는 N-메틸피롤리돈(N-methylpyrrolidone, NMP)을 용매로 사용하여 형성되는 것을 특징으로 하는 폴리 메타-페닐렌테레프탈아미드 섬유 제조방법.The method of claim 7, wherein
The poly meta-phenylene terephthalamide composition is N-methylpyrrole containing calcium chloride (CaCl 2 ) when made of meta-phenylene diamine (M-phenylene diamine, MPD) and terephthaloyl chloride (TPC) A method for producing a poly meta-phenylene terephthalamide fiber, characterized in that it is formed by using Don (N-methylpyrrolidone, NMP) as a solvent.
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| CN116490546A (en) * | 2021-02-24 | 2023-07-25 | 帝人株式会社 | Heat-resistant high-toughness fiber, method for producing same, and heat-resistant high-toughness film |
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| KR20170023297A (en) * | 2015-08-20 | 2017-03-03 | 주식회사 휴비스 | Aramid Paper Having Excellent Withstand Voltage and Method for Preparing the Same |
| CN116490546A (en) * | 2021-02-24 | 2023-07-25 | 帝人株式会社 | Heat-resistant high-toughness fiber, method for producing same, and heat-resistant high-toughness film |
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