KR930003372B1 - Process for production of aromatic polyamide pulp - Google Patents

Process for production of aromatic polyamide pulp Download PDF

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KR930003372B1
KR930003372B1 KR1019900009381A KR900009381A KR930003372B1 KR 930003372 B1 KR930003372 B1 KR 930003372B1 KR 1019900009381 A KR1019900009381 A KR 1019900009381A KR 900009381 A KR900009381 A KR 900009381A KR 930003372 B1 KR930003372 B1 KR 930003372B1
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pulp
aromatic polyamide
aromatic
amide solvent
prepared
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KR1019900009381A
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KR920000809A (en
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류석철
최원준
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주식회사 코오롱
하기주
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)
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Abstract

polymerizing the same mol amount of aromatic diamine and aromatic diacid chloride in the mixture solution of amide solvent and inorganic salt; spinning the liquid crystalline prepolymer in pre-gelled state into polymerization acclerating precipitant contg. 0.1-90 wt.% of tert-amine per amide solvent through an irregular cross-sectional spinneret i.e. +, Y or *; drying, heat-treating at 100-300 deg.C; and finally crushing. The pulp can be rapidly produced by controlling gelation and has excellent properties.

Description

방향족 폴리아미드 펄프의 제조방법Process for producing aromatic polyamide pulp

본 발명은 물성이 우수한 방향족 폴리아미드 펄프의 제조방법에 관한 것으로서, 상세하게는 금속염을 용해시킨 아미드계 용매내에서 방향족 디아민과 방향족 디에시드클로라이드를 반응시켜서 액정예비중합체용액을 만들고, 이것을 방사장치에 유입시키고, 3급 아민이 포함된 중합촉진 침전제에 방사한 후 이를 분쇄하여 물성이 우수한 방향족 폴리아미드 펄프를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an aromatic polyamide pulp having excellent physical properties. More specifically, a liquid crystal prepolymer solution is prepared by reacting an aromatic diamine and an aromatic dieside chloride in an amide solvent in which a metal salt is dissolved. The present invention relates to a method for preparing aromatic polyamide pulp having excellent physical properties by inflow, spinning into a polymerization accelerator precipitant containing a tertiary amine, and then grinding it.

종래의 방향족 폴리아미드 펄프의 제조방법 중 일본특공 소 59-47694의 방법은 유기용매에 녹인 중합체 용액을 물이나 알코올등에 교반침전시켜 펄프상 단섬유를 얻는다고 되어 있으나 상기 방법은 저분자량의 중합체를 사용하여야만 유기용매에 용해시킬 수 있기 때문에 물성이 저하될 수 밖에 없으며, 미국특허 4,511,623는 아미드계 중합용매에 3급 아민을 첨가하여 중합하는 방법인 바, 상기 방법은 3급 아민의 과량 첨가로 인한 급격한 중합속도로 인하여 수 초내에 겔화가 일어나서 공정제어가 불가능하며 겔화가 일어나도 분자사슬들이 방향성이 없는 등방성을 나타내며, 또 우수한 물성을 가지는 폴리머를 제조하기 위해서는 5시간 이상 방치하여야 하는 단점이 있다.In the conventional method for preparing aromatic polyamide pulp, Japanese Patent Application No. 59-47694 says that pulp-like short fibers are obtained by stirring and precipitating a polymer solution dissolved in an organic solvent in water or alcohol, but the method uses a low molecular weight polymer. Since it can only be dissolved in an organic solvent, the physical properties are deteriorated, and US Pat. No. 4,511,623 is a method of polymerizing a tertiary amine by adding a tertiary amine to the amide polymerization solvent. Due to the polymerization rate, gelation occurs within a few seconds, so that process control is impossible, and even when gelation occurs, the molecular chains exhibit an isotropic property without orientation, and in order to prepare a polymer having excellent physical properties, it is required to be left for 5 hours or more.

본 발명은 상술한 바와 같은 종래의 문제점을 해결한 것인 바 이하 발명을 상세하게 설명하면 다음과 같다.The present invention solves the conventional problems as described above will be described below in detail the invention.

본 발명은 아미드계 용매{N-메틸-2-피롤리돈(NMP), N,N-디메틸아세트아미드(DMAc), 헥사메틸포스포이미드(HMPA), N,N,N,N-테트라메틸우레아(TMU), N,N-디메틸포름아미드(DMF), 디메틸설폭사이드(DMSO)등}단독 또는 이들의 혼합용매에 금속염(CaCl2, LiCl, NaCl, KCl등)을 상기 용매에 대해 0.1~20wt%의 양을 용해시킨다. 여기에 방향족 디아민을 넣고 녹인 다음, 이어서 방향족 디아민과 반응할 등몰량의 방향족 디에시드 클로라이드를 투입하여 저온에서 반응시켜 이등방성(異等方性)의 액정예비중합체용액을 제조한다. 다음에 표면적을 넓혀 3급 아민의 침투효과를 증가시키고, 펄프화가 용이하도록 원형이 아닌 이형단면의 구금공을 가진 방사장치에 유입시킨 다음에, 아미드용매에 대하여 3급 아민을 0.1 내지 90wt% 만큼 함유시킨 혼합용매인 중합촉진 침전제에 방사한 후 권취와 동시에 100℃~300℃의 온도로 건조, 열처리한 후 이를 분쇄기를 사용, 분쇄시켜서 비표면적이 향상된 다음 구조식의 반복단위를 갖는 방향족 폴리아미드 펄프를 제조하는 방법에 관한 것이다.The present invention relates to amide solvents (N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethylphosphoimid (HMPA), N, N, N, N-tetramethyl Urea (TMU), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc.} alone or a mixed solvent of these metal salts (CaCl 2 , LiCl, NaCl, KCl, etc.) to 0.1 ~ Dissolve the amount of 20wt%. An aromatic diamine is added thereto to dissolve, and then an equimolar amount of aromatic dieside chloride to react with the aromatic diamine is added thereto to react at a low temperature to prepare an anisotropic liquid crystalline prepolymer solution. Then, the surface area is increased to increase the penetration effect of tertiary amines, and introduced into a spinning device having a non-circular, non-circular deformed hole to facilitate pulping, and then by 0.1 to 90 wt% of tertiary amines to the amide solvent. Aromatic polyamide pulp having the following repeating units of the following structural formula: It relates to a method of manufacturing.

Figure kpo00001
Figure kpo00001

상기 식(I), (II)에서 R1, R2, R3는In Formulas (I) and (II), R 1 , R 2 , and R 3 are

Figure kpo00002
Figure kpo00002

R1,R2와 R3는 서로 같거나 다를 수도 있다. X는 H, Cl, Br, I이거나 탄소수가 1~4의 알킬 또는 알콕시기이며, Y는

Figure kpo00003
또는
Figure kpo00004
이다.R 1 , R 2 and R 3 may be the same as or different from each other. X is H, Cl, Br, I or an alkyl or alkoxy group having 1 to 4 carbon atoms, Y is
Figure kpo00003
or
Figure kpo00004
to be.

본 발명에서 중합용매에 대한 폴리머의 함량은 5~30wt%이며, 제조된 방향족 폴리아미드의 고유점도는 4.0이상이었으며, 제조된 펄프의 비표면적은 15㎡/g이상으로서 종래의 kevlar 펄프의 비표면적 9~11㎡/g 보다 우수하였다(비표면적의 측정은 질소흡착방법인 ASTM C-699-79에 의해 측정하였다). 비표면적이 크면 다른 물질과 복합물(Composite)을 만들 때 다른 물질과의 결합력이 커져서 복합물의 강도등의 물성을 향상시킨다.In the present invention, the polymer content of the polymerization solvent is 5-30 wt%, the intrinsic viscosity of the prepared aromatic polyamide is 4.0 or more, and the specific surface area of the prepared pulp is 15 m 2 / g or more, and the specific surface area of the conventional kevlar pulp. Better than 9-11 m 2 / g (specific surface area was measured by ASTM C-699-79, a nitrogen adsorption method). When the specific surface area is large, the bonding strength with other materials increases when making a composite with other materials, thereby improving physical properties such as strength of the composite.

본 발명은 종래의 액정예비중합체를 펄프화 장치에 유입시키고 중합촉진 침전제와 동시에 압출, 분사시키는 방법에 비하여 중합촉진 침전제의 양을 현저히 줄일 수 있었으며 상술한 바와 같이 제조된 펄프의 비표면적이 종래의 방법으로 제조된 것보다 매우 우수하였다.The present invention was able to significantly reduce the amount of the polymerization accelerator precipitant as compared to the method of introducing the conventional liquid crystal prepolymer into the pulping apparatus and simultaneously extruded and sprayed with the polymerization accelerator precipitant, and the specific surface area of the pulp prepared as described above It was much better than that produced by the method.

[실시예 1]Example 1

2ℓ의 반응기를 질소로 충분히 정화시켜 수분을 완전히 제거한후 NMP 1200ml에 염화칼슘 27.0g을 넣고 온도를 80℃까지 승온시켜 무기염을 용해시킨 다음, 1,4-페닐렌 디아민 24.5g을 넣고 10분간 용해시킨다. 상기 용액을 5℃정도로 낮춘 후 테리프탈로일 클로라이드 45.95g을 넣고 반응시켜 액정예비중합체를 제조한 후 이를 Y자형 구금을 갖는 방사장치로 이송하고 중합용매인 NMP 1000ml과 피리딘 2000ml의 혼합용 매인 중합촉진 침전제에 방사, 권취함과 동시에 권취전의 열로울러에 250℃로 건조, 열처리효과를 준 다음 펄프화장치인 refiner로 분쇄하여 펄프를 제조하였다. 이때 펄프의 고유점도는 5.3이었으며, 비표면적은 15㎡/g이었다.After fully purifying the 2 L reactor with nitrogen to completely remove moisture, 27.0 g of calcium chloride was added to 1200 ml of NMP, and the temperature was raised to 80 ° C. to dissolve inorganic salts. Then, 24.5 g of 1,4-phenylene diamine was added and dissolved for 10 minutes. Let's do it. After the solution was lowered to about 5 ° C., 45.95 g of terephthaloyl chloride was added to react to prepare a liquid crystal prepolymer, which was then transferred to a spinning device having a Y-shaped mold, and polymerization of a mixed solvent of NMP 1000 ml, which is a polymerization solvent, and 2000 ml of pyridine, was carried out. The pulp was prepared by spinning and winding the accelerated precipitant, drying and heat-treating at 250 ° C. to the heat roller before winding, and then pulverizing with a refiner, a pulping apparatus. At this time, the intrinsic viscosity of the pulp was 5.3, and the specific surface area was 15 m 2 / g.

[실시예 2]Example 2

실시예 1과 같이 제조한 액정예비중합체를 +자형 구금을 갖는 방사장치로 이송하고 중합용매인 NMP 1500ml과 피리딘 1500ml의 혼합용매인 중합촉진 침전제에 방사, 권취함과 동시에 권취전의 열로울러에서 250℃로 건조, 열처리효과를 준 다음 펄프화장치인 refiner로 분쇄하여 펄프를 제조하였다. 이때 펄프의 고유점도는 5.8이었으며, 비표면적은 17㎡/g이었다.The liquid crystal prepolymer prepared as in Example 1 was transferred to a spinning device having a + -shaped cap and spun on a polymerization accelerator precipitant, which is a mixed solvent of NMP 1500ml and pyridine 1500ml as a polymerization solvent, and at the same time 250 ° C in a thermal roller before winding. The pulp was prepared by drying, giving a heat treatment effect and then pulverizing with a refiner, a pulping apparatus. At this time, the intrinsic viscosity of the pulp was 5.8, and the specific surface area was 17 m 2 / g.

[실시예 3]Example 3

실시예 2와 같이 제조하되

Figure kpo00005
형 방사구금을 사용하였다. 이때 펄프의 고유점도는 6.1이었으며, 비표면적은 18㎡/g이었다.Prepared as in Example 2
Figure kpo00005
Type spinnerets were used. The intrinsic viscosity of the pulp was 6.1, and the specific surface area was 18 m 2 / g.

[실시예 4]Example 4

실시예 1과 같이 제조하되 +자형 구금을 갖는 방사장치로 이송하고 중합용매인 NMP 500ml과 피리딘 2500ml의 혼합용매인 중합촉진 침전제에 방사, 권취함과 동시에 권취전의 열로울러에서 100℃로 건조, 열처리효과를 준 다음 펄프화장치인 refiner로 분쇄하여 펄프를 제조하였다. 이때 펄프의 고유점도는 5.6이었으며, 비표면적은 16㎡/g이었다.Prepared as in Example 1, but transferred to a spinning device having a + -shaped detention, spinning and winding in a polymerization accelerator precipitant, a mixed solvent of NMP 500ml and pyridine 2500ml as a polymerization solvent, and drying at 100 ° C. in a heat roller before winding and heat treatment. After the effect was pulverized with a refiner, a pulping apparatus, pulp was prepared. At this time, the intrinsic viscosity of the pulp was 5.6, and the specific surface area was 16 m 2 / g.

[실시예 5]Example 5

실시예 3과 같이 제조하되 열로울러의 온도가 300℃인 것을 사용하였다. 이때 펄프의 고유점도는 6.1이었으며, 비표면적은 17㎡/g이었다.Prepared as in Example 3, but the temperature of the thermal roller was used as 300 ℃. The intrinsic viscosity of the pulp was 6.1, and the specific surface area was 17 m 2 / g.

[비교실시예 1]Comparative Example 1

실시예 3과 같이 제조하되 물 3000ml의 응고욕에 방사, 권취함과 동시에 권취전의 열로울러에서 250℃로 건조, 열처리효과를 준 다음 펄프화장치인 refiner로 분쇄하여 펄프를 제조하였다. 이때 펄프의 고유점도는 2.5이었으며, 비표면적은 9㎡/g이었다.Prepared in the same manner as in Example 3, spinning and winding in a coagulation bath of 3000ml of water, and dried at 250 ℃ in the heat roller before the winding, giving a heat treatment effect and then pulverized in a refiner, a pulping apparatus to prepare a pulp. The intrinsic viscosity of the pulp was 2.5, and the specific surface area was 9 m 2 / g.

[비교실시예 2]Comparative Example 2

비교실시예 1과 같이 제조하되 중합용매인 NMP 3000ml의 중합촉진 침전제에 방사하였다. 이때 펄프의 고유점도는 3.1이었으며, 비표면적은 8㎡/g이었다.Prepared as in Comparative Example 1, but was spun into a polymerization accelerator precipitant of NMP 3000ml as a polymerization solvent. At this time, the intrinsic viscosity of the pulp was 3.1 and the specific surface area was 8 m 2 / g.

[비교실시예 3]Comparative Example 3

비교실시예 1과 같이 제조하되 열로울러는 90℃의 것을 사용하였다. 이때 펄프의 고유점도는 2.1이었으며, 비표면적은 9㎡/g이었다.Prepared as in Comparative Example 1, but the heat roller was used at 90 ℃. The intrinsic viscosity of the pulp was 2.1, and the specific surface area was 9 m 2 / g.

[비교실시예 4]Comparative Example 4

비교실시예 3과 같이 제조하되 피리딘 3000ml의 응고욕에 방사하였다. 이때 펄프의 고유점도는 5.6이었으며, 비표면적은 10㎡/g이었다.Prepared as in Comparative Example 3, but spun in a coagulation bath of 3000ml of pyridine. The intrinsic viscosity of the pulp was 5.6, and the specific surface area was 10 m 2 / g.

Claims (2)

아미드계용매와 무기염으로 된 혼합용액 내에서 등몰량의 방향족 디아민과 방향족 디에시드 클로라이드를 중합시키고, 이를 방사구금을 통하여 방사한 후 분쇄하여 방향족 폴리아미드 펄프를 제조함에 있어서, 겔화되기 전의 액정예비중합체를 이형단면구금을 통해 아미드용매에 대하여 3급 아민이 0.1 내지 90wt% 함유된 중합촉진 침전제로 방사하며, 분쇄하기 전에 100℃ 내지 300℃의 온도로 건조, 열처리함을 특징으로 하는 방향족 폴리아미드 펄프의 제조방법.In the mixed solution of an amide solvent and an inorganic salt, an equimolar amount of aromatic diamine and an aromatic dieside chloride are polymerized and spun through a spinneret, followed by grinding to prepare an aromatic polyamide pulp. An aromatic polyamide characterized in that the polymer is spun through a release cross-section into a polymerization accelerator precipitant containing 0.1 to 90 wt% of a tertiary amine relative to the amide solvent, and dried and heat-treated at a temperature of 100 ° C to 300 ° C before grinding. Method for producing pulp. 제 1 항에 있어서, 이형단면구금의 형상은 +자형, Y자형, 또는
Figure kpo00006
형임을 특징으로 하는 방향족 폴리아미드 펄프의 제조방법.The shape of the deformed cross section detention according to claim 1, wherein the shape of the deformed cross section is formed in the shape of +
Figure kpo00006
Process for producing aromatic polyamide pulp, characterized in that the form.
KR1019900009381A 1990-06-25 1990-06-25 Process for production of aromatic polyamide pulp KR930003372B1 (en)

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