WO1997003109A1 - Aromatic polyamide, optical anisotropic dope and articles and preparation for the same - Google Patents
Aromatic polyamide, optical anisotropic dope and articles and preparation for the same Download PDFInfo
- Publication number
- WO1997003109A1 WO1997003109A1 PCT/KR1996/000107 KR9600107W WO9703109A1 WO 1997003109 A1 WO1997003109 A1 WO 1997003109A1 KR 9600107 W KR9600107 W KR 9600107W WO 9703109 A1 WO9703109 A1 WO 9703109A1
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- WIPO (PCT)
- Prior art keywords
- structural formula
- aromatic
- aromatic polyamide
- optical anisotropic
- preparing
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/38—Polyamides prepared from aldehydes and polynitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
Definitions
- the present invention relates to an aromatic polyamide, in particular to a novel aromatic polyamide forming an optical anisotropic dope which is easily dissolved in a polar organic solvent and preparing thereof, an optical anisotropic aromatic polyamide dope and preparing thereof and a high modulus aromatic polyamide fibroid article prepared from the optical anisotropic aromatic polyamide dope.
- aromatic polyamide films and articles thereof are used valuably in composite materials of air craft and automobile industry, building materials and leisure and sports goods because they have a high strength, high modulus, heat resistance, abrasion resistance and insulating property. Due to such utilities, there have been developed various processes for producing aromatic polyamide fibers and preparations for the articles. In case of an optical anisotropic aromatic polyamide dope, high strength and high modulus fiber can be prepared without drawing process because polymer chains are already arranged along the axis of the fiber during extrusion spinning from the nozzle, researches for preparing thereof have been actively performed.
- Du-pont Inc. discloses an industrial process wherein polybenzamide and polyparaphenylene terephthalamide are dissolved by heating with 100 % sulfuric acid to prepare an optical anisotropic aromatic polyamide dope and high strength and high modulus aromatic polyamide fibers are prepared by extrusion spinning (U.S. patents Nos. 3,671,542 and 3,673,143) .
- U.S. patent No. 4,018,735 discloses a process wherein an aromatic polyamide prepared by incorporating 5 to 35 mole % of hetero ring unit of benzoxazol or imidazol is dissolved with sulfuric acid to produce an anisotropic aromatic dope.
- Processes disclosed in the above papers include the use of 100 % of sulfuric acid for heating and dissolving an aromatic polyamide to prepare an optical anisotropic dope of an aromatic polyamide, however the use of sulfuric acid leads to the decrease in the physical property by deteriorating the degree of polymerization during dissolving, environmental contamination and difficulty in process control.
- the first object of the present invention is to provide a novel aromatic polyamide which can be used to produce an optical anisotropic aromatic polyamide dope under easy conditions.
- the second object of the present invention is to provide an optical anisotropic aromatic polyamide dope which contains the above aromatic polyamide and does not contain sulfuric acid and a process for preparing the same.
- the third object of the present invention is to provide a high strength and high modulus aromatic polyamide fiber of which component is mainly the above novel aromatic polyamide.
- Fig. 1 is a phase transition diagram of a polymer according to the concentration of an inorganic salt and the polymer in a polar solvent;
- Fig. 2 is a phase transition diagram of a polymer according to the degree of polymerization of the polymer and the concentration of a polymer in a polar solvent;
- Fig. 3 is a phase transition diagram of a polymer according to the concentration of the polymer and the viscosity of the polymer dope.
- the present invention provides an aromatic polyamide represented by the following structural formula (I)
- R represents
- n represents an integer between 10 and
- the amount of the aromatic diamine, which forms a repeating unit of the above structural formula (I) , having a nitrile group substituted on the aromatic nucleus is at least 25 mol %, preferably 25 to 100 mol % in the total aromatic diamine.
- the aromatic polyamide of the above structural formula (I) is obtained by polycondensation with an aromatic diacid halide under the condition that the amount of the aromatic diamine having a nitrile group substituted on the aromatic nucleus is at least 25 mol %, preferably 25 to 100 mol % in the total aromatic diamine.
- Both an aromatic diamine having a nitrile group substituted on the aromatic nucleus or that not having a nitrile group can be used for the aromatic diamine of the present invention, however, it is a characteristic of the present invention that the amount of the aromatic diamine having a nitrile group substituted on the aromatic nucleus is at least 25 mol %, preferably 25 to 100 mol % in the total aromatic diamine.
- Typical examples are as follows, however, the present invention is not limitatively defined by the followings as shown in the general structural formula (I) .
- Y represents Cl, Br, I, N0 2 or an alkyl or alkoxy group having 1 to 4 carbon atoms.
- Typical examples of an aromatic diacid halide which can be used in the present invention include terephthalic chloride, isophthalic chloride, naphthalic chloride and diphenyl chloride which may be unsubstituted or substituted with Cl, Br, I, NO- or an alkyl or alkoxy group having 1 to 4 carbon atoms.
- the aromatic polyamide represented by the above formula (I) is a novel high molecular weight aromatic polyamide having a intrinsic viscosity of 2.0 or higher, preferably 2 to 10, which is soluble in a polar organic solvent, and the amount of diamine component having a nitrile group substituted on the aromatic nucleus is at least 25 mol %, preferably 25 to 100 mol % in the total diamine component.
- the intrinsic viscosity can be calculated from the following formula by the measurement using an Ubbelohde viscometer and extrapolation of 5 selected dilute concentrations (in 98 % sulfuric acid at 30°C) :
- t is the time period taken for the solution to pass the viscometer
- t 0 is the time period taken for the solvent to pass the viscosmeter
- C is the concentration of the solution.
- the aromatic polyamide of the present invention can be confirmed by the absorption band of a nitrile group in the infrared spectrum at 2230 cm "1 .
- the process for producing an aromatic polyamide of the structural formula (I) to achieve the second object of _ the present invention by forming an optical anisotropic aromatic polyamide polymerization dope of which the polymerization solution shows silver-white brightness during polymerization comprises the following steps of: preparing a solvent for polymerization from an amide type organic solvent, an urea type organic solvent or a mixture thereof; adding and dissolving an aromatic diamine having a nitrile group substituted on the aromatic nucleus in the solvent for polymerization; adding pyridine as a polycondensation catalyst in the resulting solution; adding the aromatic diacid halide in the solution with vigorous stirring at 0 to 50°C; and continuing stirring for 1 to 360 minutes at the temperature to obtain a high viscous polymer solution which shows silver-white brightness during stirring.
- the process for producing an aromatic polyamide of the structural formula (I) to achieve the second object of the present invention by forming an optical anisotropic aromatic polyamide polymerization dope of which the polymerization solution shows silver- white brightness during polymerization comprises the following step ⁇ of: preparing a solvent for polymerization from an amide type organic solvent, an urea type organic solvent or a mixture thereof; adding and dissolving an aromatic diamine having a nitrile group substituted on the aromatic nucleus in the solvent for polymerization; adding the aromatic diacid halide in the solution with vigorous stirring at 0 to 50°C; keeping the gel type polymer obtained in the above step for 0 to 24 hours; adding and dissolving an inorganic alkali compound selected from the group consisting of an alkali metal such as Li 2 C0 3 , CaC0 3 , LiH, CaH 2 , LiOH, Ca(OH) 2 , Li 2 0 or CaO, carbonate of alkali earth metal, hydride, hydroxide or oxide
- the above high viscosity polymer solution is an optical anisotropic polyamide dope showing various colors through the polarized microscope, and it is easily treated to articles such as polyamide fibers having high strength and high modulus, films and pulps by spinning through a nozzle into a coagulating bath. Additionally, not containing sulfuric acid in the optical anisotropic polyamide dopes of the present invention leads to no deteriorating of degree of polymerization of polyamide and easiness in process control.
- organic solvent of the present invention all organic solvents of amide or urea type can be used but it is preferable to use N-methyl-2-pyrrolidone (NMP) , N,N-dimethyl acetamide (DMAc) , hexamethyl phosphoamide (HMPA) , N,N,N' ,N'-tetramethyl urea (TM ⁇ ) , N,N-dimethyl formamide (DMF) , dimethyl sulfoxide (DMSO) or a mixture thereof.
- NMP N-methyl-2-pyrrolidone
- DMAc N,N-dimethyl acetamide
- HMPA hexamethyl phosphoamide
- TM ⁇ N,N,N' ,N'-tetramethyl urea
- DMF N,N-dimethyl formamide
- DMSO dimethyl sulfoxide
- An inorganic salt may be further added to a solvent for polymerization used in the present invention in order to increase the solubility.
- Typical examples of the inorganic salt include an alkali metal halide or an alkali earth metal halide such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr.
- An inorganic salt can be added in the solvent for polymerization by itself or as a mixture of 2 or more.
- the added amount of the inorganic salt is desirably 12 % by weight or lower based upon the weight of solvent for polymerization. The amount higher than 12 % by weight is economically disadvantageous because the desired effects of the present invention cannot be expected.
- a by-product (HCl) is produced by the reaction between an aromatic diamine and an aromatic diacid chloride in the third step of the latter process for producing an aromatic polyamide of the structural formula (I) .
- an inorganic alkali compound selected from the group consisting of an alkali metal such as Li 2 C0 3 , CaC0 3 , LiH, CaH 2 , LiOH, Ca(OH) 2 , Li 2 0 or CaO, carbonate of alkali earth metal, hydride, hydroxide or oxide is added.
- An inorganic alkali compound or a mixture comprising 2 or more of it can be added and its added amount is desirably 10 to 200 mol % of the required equivalent to neutralize the HCl.
- the second object of obtaining silver white optical anisotropic dope of the present invention can be also achieved by dissolving an aromatic polyamide of the structural formula (I) of which amount is 7 % by weight or more in a polar organic solvent having 1 % by weight or more of an inorganic salt at 0 to 100°C, preferably 20 to 70°C.
- NMP N-methyl-2-pyrrolidone
- DMAc N,N-dimethyl acetamide
- HMPA hexamethyl phosphoamide
- TM ⁇ N,N,N',N'- tetramethyl urea
- DMF dimethyl sulfoxide
- DMSO dimethyl sulfoxide
- Typical examples of the inorganic salt of the present invention include an alkali metal halide or an alkali earth metal halide such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr.
- An inorganic salt can be added by itself or as a mixture of 2 or more. It is necessary that the added amount of the inorganic salt is at least 1 % by weight, desirably 1 to 10 % by weight. An amount lower than 1 % by weight is not desirable to produce an optical anisotropic dope because the solubility of the polyamide of the structural formula (I) is decreased in the organic polar solution. An amount higher than 10 % by weight is economically disadvantageous because the solubility of polyamide is not increased by increasing the amount of the inorganic salt.
- the concentration of the polyamide in an organic polar solution for preparing an optical anisotropic dope can be changed according to the degree of polymerization of the polyamide, the viscosity of the dope or the
- the concentration of the inorganic salt in the polar organic solvent it is desirable to have at least 7 % by weight, preferably 7 to 23 % by weight of the polyamide.
- the optical property of the dope shows isotropy because of having a low amount of the polymer.
- the effects of the present invention cannot be expected because the dope is present in the state of a solid (Fig. 1) .
- the degree of polymerization of the polyamide represented by the structural formula (I) is at least 2 or more of the limiting viscosity for preparing an optical anisotropic polyamide dope of the present invention.
- an optical anisotropic dope of the present invention can not be obtained though the concentration of the polyamide is increased in an organic polar solvent (Fig. 2) . Further, the viscosity of the dope with the content of the polymer in it also has heavy effects on the optical property of the dope.
- Fig. 1 is an isotropic and anisotropic phase transition diagram according to the concentration of the polymer and DMAc-LiCl when the aromatic polyamide of structural formula (I) of the present invention is dissolved in the DMAc-LiCl solution.
- the optical isotropy is shown in the dope because the solubility of the polyamide is decreased or the dope is present in the state of a solid.
- the concentration of the polymer is 7 to 23 % by weight in the polar organic solvent, the optical anisotropy is shown in the dope.
- Fig. 2 is an isotropic and anisotropic phase transition diagram according to the intrinsic viscosity of the degree of polymerization of the aromatic polyamide represented by the structural formula (I) of the present invention and the concentration of LiCl is 4 % by weight of the DMAc. As shown in Fig. 2, even with the concentration of the polymer higher than 7 % by weight, the concentration at which the dope shows the optical anisotropic, if the degree of polymerization is lower than 2 of intrinsic viscosity, the optical anisotropy is not shown in the dope.
- Fig. 3 is a diagram in which the concentration (the concentration of LiCl is 4 % by weight of the DMAc) of the aromatic polyamide represented by the structural formula (I) and the viscosity of the dope are shown.
- the optical anisotropy is shown at certain concentration (from 10 to 20 % by weight), wherein the viscosity of the dope is lower than that of the dope showing isotropy.
- the present invention provides the aromatic polyamide fiber, pulp or articles of film which forms repeating unit represented by the following structural formula (I) :
- R represents an aromatic diamine such as
- CN X wherein an amount of the aromatic diamine having a nitrile group substituted on the aromatic nucleus is at least 25 mol % of the total aromatic diamine; and X represents H, Cl, Br, I, N0 2 or an alkoxy group having 1 to 4 carbon atoms, n represents an integer between 10 and
- the aromatic polyamide fiber which forms the repeating unit represented by the structural formula (I) has a high strength and high modulus property (the tensile strength is 10 g/d or more and the tensile modulus is 450 g/d) .
- the aromatic polyamide fiber, pulp or article of film of the present invention is produced by spinning, coagulating, washing and drying as follows: an optical anisotropic polyamide dope having an aromatic polyamide of the above structural formula (I) which is obtained by polycondensation with an aromatic diacid halide monomer under the condition that an amount of the aromatic diamine having a nitrile group substituted on the aromatic nucleus is at least 25 mol %, preferably 25 to 100 mol % in the total aromatic diamine in the solvent for polymerization adding the inorganic salt such as an alkali metal halide or an alkali earth metal halide to the polar organic solvent including an amide type organic solvent, an urea type organic solvent or a mixture thereof with pyridine catalyst at 0 to 50°C; an optical anisotropic polyamide dope having an aromatic polyamide of the above structural formula (I) obtained by adding an inorganic salt such as an alkali metal halide or an alkali earth metal halide to the gel type polymer which
- the solid was recrystallized by soxlet and the liquid was treated with the activated carbon, filtered, an separated by repeated recrystallization by soxlet.
- the separated solid was dried in a vacuum oven to obtain 60.5 g of the raw material (yield was 83.7 %) .
- the melting point of the obtained raw material was 250 to 251°C.
- the light yellow-scalelike crystal was filtered and dried in a vacuum oven at 80°C.
- the light yellow-scalelike crystal was extracted again by soxlet with acetone and treated with the activated carbon.
- Optical anisotropic dopes were prepared by the same method as EXAMPLE 2 except the amounts of the monomer and the additive. they are listed in the following Table 1.
- Components Comp. & Prop. Prop, of of dope dur. Pol. polymeriza.
- TPC DACYB LiCl(g) (g/ pyri ⁇ DMAc Cone. Cone. Opt. Int.
- the optical anisotropic aromatic polyamide dope prepared in EXAMPLE 4 was extrusion-spinned into 0.5 to 2 cm of an air layer through nozzle and, at the same time, coagulated in the 20 % by weight of dimethyl acetamide aqueous solution at 5°C and then wound into a roller at a maximum speed. After being sufficiently washed with distilled water, the filament was dried in a drier at 150°C. The dried filament had a fineness of 2 denier, a tensile strength of 16 g/d, an elongation of 4.6 % and a tensile modulus of 440 g/d.
- EXAMPLE 11 EX . 6 0. 6 20 4 .8 510 EXAMPLE 12 EX.7 2. 0 18 6. 0 400 EXAMPLE 13 EX. 8 1.3 19 5.5 370
- DMAc dimethylacetamide
- DACYB 4,4' -diamino-6-cyanobenzanilide
- TPC terephthaloyl chloride
- the polymer solution was slowly stirred for an additional day.
- the anisotropy of the dope was confirmed by a polarized microscope.
- the intrinsic viscosity of the obtained aromatic polyamide was 3.8 (exam ned in the 30°C, 97 % by weight of sulfuric acid) .
- Optical anisotropic dopes were prepared by the same method as EXAMPLE 14 except the amounts of the monomer and the additive. They are listed in the following Table 3.
- Components Comp. & Prop. Prop, of of dope dur. Pol. polymeriza.
- TPC DACYB LiCl(g) (g/ pyri- DMAc Cone. Cone. Opt. Int. (g) (g) 100ml DMAc dine (ml) of of Prop. Vis.
- the optical anisotropic aromatic polyamide dope prepared in EXAMPLE 16 was extrusion-spinned into 0.5 to 2 cm of an air layer through nozzle and, at the same time, coagulated in the 20 % by weight of dimethyl acetamide aqueous solution at 5°C and then wound into a roller at a maximum speed. After being sufficiently washed with distilled water, the filament was dried in a drier at 150°C. The dried filament had a fineness of 1.0 denier, a tensile strength of 18.4 g/d, an elongation of 7.5 % and a tensile modulus of 270 g/d.
- Optical anisotropic dopes were prepared by the same method as EXAMPLE 18 except the amounts of the monomer and the additive. They are listed in the following Table 4.
- TPC Comp. of LiCl Pyri DMAc Cone. Cone. Opt. Int. (g) Arom. diamine (g) dine (ml) of of Prop. Vis. ⁇ (g/100 (ml) on. pol. DACYB DAB Mol ml (wt%) (wt%)
- optical anisotropic aromatic polyamide dope composed of DACYB 75 mol % / DAB 25 mol % of an aromatic diamine monomer which was prepared in EXAMPLE 22 was extrusion-spinned into 0.5 to 2 cm of an air layer through nozzle and, at the same time, coagulated in the
- the filament After being sufficiently washed with distilled water, the filament was dried in a drier at 150°C. The dried filament had a fineness of 1.2 denier, a tensile strength of 12 g/d, an elongation of 5 % and a tensile modulus of 500 g/d.
- the optical anisotropic aromatic polyamide dope composed of DACYB 60 mol % / DAB 40 mol % of an aromatic diamine monomer which was prepared in EXAMPLE 21 was extrusion-spinned into 0.5 to 2 cm of an air layer through nozzle and, at the same time, coagulated in the 20 % by weight of dimethyl acetamide aqueous solution at 5°C and then wound into a roller at a maximum speed. After being sufficiently washed with distilled water, the filament was dried in a drier at 150°C. The dried filament had a fineness of 1.1 denier, a tensile strength of 21 g/d, an elongation of 5 % and a tensile modulus of 500 g/d.
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- Health & Medical Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96925142A EP0837896A1 (en) | 1995-07-13 | 1996-07-12 | Aromatic polyamide, optical anisotropic dope and articles and preparation for the same |
JP50569797A JP3856833B2 (en) | 1995-07-13 | 1996-07-12 | Aromatic polyamide, optically anisotropic dope and molded product, and method for producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1995/20615 | 1995-07-13 | ||
KR1019950020615A KR0171994B1 (en) | 1995-07-13 | 1995-07-13 | Aromatic polyamide, optical anisotropic dope, and its composition and its preparation process |
Publications (1)
Publication Number | Publication Date |
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WO1997003109A1 true WO1997003109A1 (en) | 1997-01-30 |
Family
ID=19420527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR1996/000107 WO1997003109A1 (en) | 1995-07-13 | 1996-07-12 | Aromatic polyamide, optical anisotropic dope and articles and preparation for the same |
Country Status (6)
Country | Link |
---|---|
US (1) | US5728799A (en) |
EP (1) | EP0837896A1 (en) |
JP (1) | JP3856833B2 (en) |
KR (1) | KR0171994B1 (en) |
CA (1) | CA2224873A1 (en) |
WO (1) | WO1997003109A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6740406B2 (en) * | 2000-12-15 | 2004-05-25 | Kimberly-Clark Worldwide, Inc. | Coated activated carbon |
WO2004099476A1 (en) * | 2003-05-08 | 2004-11-18 | Teijin Twaron B.V. | Non-fibrous polymer solution of para-aramid with high relative viscosity |
EP2998338A4 (en) * | 2013-05-13 | 2017-03-01 | Woojung Chem. Co., Ltd. | Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040166248A1 (en) * | 2000-12-15 | 2004-08-26 | Sheng-Hsin Hu | Coated activated carbon |
KR100761321B1 (en) | 2006-01-18 | 2007-10-04 | 재단법인 대구테크노파크 | High strength conductive film material, high strength conductive film and processing mtehod using that |
KR100744169B1 (en) * | 2006-10-13 | 2007-08-06 | 경북대학교 산학협력단 | Aromatic polyamide, polymerization method thereof and optical film using the same |
FR2930777B1 (en) * | 2008-05-05 | 2011-07-01 | Arkema France | PROCESS FOR SYNTHESIS OF SUPRAMOLECULAR MATERIALS |
KR101067338B1 (en) * | 2009-04-16 | 2011-09-23 | 경북대학교 산학협력단 | Molecular miscible blend of aromatic polyamide and amorphous polymer, preparing method thereof, aromatic polyamide blend fiber using the same and dyeing method of the polyamide blend fiber |
KR101587046B1 (en) * | 2013-05-07 | 2016-01-20 | 코오롱인더스트리 주식회사 | Method of manufacturing copolymerized aramid fiber |
KR102070137B1 (en) | 2013-12-30 | 2020-01-28 | 코오롱인더스트리 주식회사 | Dope-dyeing yarn of aramid copolymer and method for manufacturing the same |
CN106661774B (en) * | 2014-08-20 | 2019-06-21 | 可隆工业株式会社 | High intensity copolymerization aramid fibre and preparation method thereof |
CN107923073A (en) * | 2015-08-07 | 2018-04-17 | 可隆工业株式会社 | High resiliency is copolymerized aramid fibre |
KR102066032B1 (en) * | 2015-12-30 | 2020-01-14 | 코오롱인더스트리 주식회사 | Hollow fiber membrane and hollow fiber membrane module comprising the same |
KR102089122B1 (en) * | 2016-08-25 | 2020-03-13 | 주식회사 엘지화학 | Diamine compounds and a substrate for flexible device prepared using same |
KR101972843B1 (en) * | 2017-03-31 | 2019-04-29 | 한양대학교 산학협력단 | Method for Preparing poly(2-cyano-p-phenylene terephthalamide) Nano-fibers and Carbon Nano-fibers Derived Therefrom |
KR102350095B1 (en) | 2018-01-03 | 2022-01-11 | 주식회사 엘지화학 | Poly(amide-imide) copolymer film and preparation method of the same |
WO2019135500A1 (en) * | 2018-01-03 | 2019-07-11 | 주식회사 엘지화학 | Aromatic poly(amide-imide) copolymer film and production method therefor |
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US4021415A (en) * | 1974-02-14 | 1977-05-03 | Chang William J H | Nitrile containing aromatic polyamide polymers |
EP0045934A1 (en) * | 1980-08-07 | 1982-02-17 | Teijin Limited | Wholly aromatic polyamide fiber and film and process for preparation thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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BE755270A (en) * | 1969-08-27 | 1971-02-25 | Sandoz Sa | NEW DERIVATIVES OF BENZO (CD) INDOLE, THEIR PREPARATION AND MEDICINAL PRODUCTS CONTAINING THESE DERIVATIVES |
US3673143A (en) * | 1970-06-24 | 1972-06-27 | Du Pont | Optically anisotropic spinning dopes of polycarbonamides |
JPS6031208B2 (en) * | 1974-07-10 | 1985-07-20 | 帝人株式会社 | polyamide solution |
-
1995
- 1995-07-13 KR KR1019950020615A patent/KR0171994B1/en not_active IP Right Cessation
- 1995-08-31 US US08/522,103 patent/US5728799A/en not_active Expired - Lifetime
-
1996
- 1996-07-12 JP JP50569797A patent/JP3856833B2/en not_active Expired - Fee Related
- 1996-07-12 WO PCT/KR1996/000107 patent/WO1997003109A1/en not_active Application Discontinuation
- 1996-07-12 CA CA002224873A patent/CA2224873A1/en not_active Withdrawn
- 1996-07-12 EP EP96925142A patent/EP0837896A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4021415A (en) * | 1974-02-14 | 1977-05-03 | Chang William J H | Nitrile containing aromatic polyamide polymers |
EP0045934A1 (en) * | 1980-08-07 | 1982-02-17 | Teijin Limited | Wholly aromatic polyamide fiber and film and process for preparation thereof |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6740406B2 (en) * | 2000-12-15 | 2004-05-25 | Kimberly-Clark Worldwide, Inc. | Coated activated carbon |
WO2004099476A1 (en) * | 2003-05-08 | 2004-11-18 | Teijin Twaron B.V. | Non-fibrous polymer solution of para-aramid with high relative viscosity |
CN100436665C (en) * | 2003-05-08 | 2008-11-26 | 帝人阿拉米德有限公司 | Non-fibrous polymer solution of para-aramid with high relative viscosity |
AU2004236347B2 (en) * | 2003-05-08 | 2009-03-05 | Teijin Aramid B.V. | Non-fibrous polymer solution of para-aramid with high relative viscosity |
US7754797B2 (en) | 2003-05-08 | 2010-07-13 | Teijin Aramid B.V. | Non-fibrous polymer solution of para-aramid with high relative viscosity |
US8415417B2 (en) | 2003-05-08 | 2013-04-09 | Teijin Aramid B.V. | Non-fibrous polymer solution of para-aramid with high relative viscosity |
EP2998338A4 (en) * | 2013-05-13 | 2017-03-01 | Woojung Chem. Co., Ltd. | Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof |
US9803054B2 (en) | 2013-05-13 | 2017-10-31 | Woojung Chem. Co., Ltd. | Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof |
US10233288B2 (en) | 2013-05-13 | 2019-03-19 | Woojung Chem Co., Ltd. | Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof |
Also Published As
Publication number | Publication date |
---|---|
EP0837896A1 (en) | 1998-04-29 |
JP3856833B2 (en) | 2006-12-13 |
KR0171994B1 (en) | 1999-03-30 |
KR970006356A (en) | 1997-02-19 |
CA2224873A1 (en) | 1997-01-30 |
US5728799A (en) | 1998-03-17 |
JPH11508938A (en) | 1999-08-03 |
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