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      방향족 폴리히드록시아미드의 합성과 열적 고리화 거동(II) -플루오르 치환체의 영향- = Synthesis and Thermal Cyclization of Aromatic Polyhydroxyamides(II) -Effect of Fluoro-substituents-

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      https://www.riss.kr/link?id=A101372828

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      다국어 초록 (Multilingual Abstract)

      Polyhydroxyamide (PHA) was synthesized via low-temperature solution polymerization of 3,3'-dihydroxybenzidine with isophthaloyl chloride, and the derivatives of PHA containing fluoro-substituents were investigated for exploring their potential application as new thermally stable polymer material. The structural properties, solubility, and thermal cyclization of the PHA and its derivatives were characterized using FT-IR, DSC, and TGA to derive the relationship between the structure of the PHA derivatives and the thermal properties and cyclization behavior of the polymer. The PHA derivatives containing fluoro-substituents were readily soluble in a variety of solvents without LiCl, whereas the pristine PHA was soluble only in the presence of LiCl. The DSC analyses under isothermal conditions showed that the PHA derivatives exhibited a faster cyclization rate than the pristine PHA at $220^{\circ}C$ and $250^{\circ}C$. In addition, the DSC and TGA results revealed that the PHA derivatives could be cyclized into the corresponding polybenzoxazoles at lower temperatures than the pristine PHA; this could be attributed to the lower thermal activation energy of the derivatives owing to the introduction of the fluoro-substituents.
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      Polyhydroxyamide (PHA) was synthesized via low-temperature solution polymerization of 3,3'-dihydroxybenzidine with isophthaloyl chloride, and the derivatives of PHA containing fluoro-substituents were investigated for exploring their potential applica...

      Polyhydroxyamide (PHA) was synthesized via low-temperature solution polymerization of 3,3'-dihydroxybenzidine with isophthaloyl chloride, and the derivatives of PHA containing fluoro-substituents were investigated for exploring their potential application as new thermally stable polymer material. The structural properties, solubility, and thermal cyclization of the PHA and its derivatives were characterized using FT-IR, DSC, and TGA to derive the relationship between the structure of the PHA derivatives and the thermal properties and cyclization behavior of the polymer. The PHA derivatives containing fluoro-substituents were readily soluble in a variety of solvents without LiCl, whereas the pristine PHA was soluble only in the presence of LiCl. The DSC analyses under isothermal conditions showed that the PHA derivatives exhibited a faster cyclization rate than the pristine PHA at $220^{\circ}C$ and $250^{\circ}C$. In addition, the DSC and TGA results revealed that the PHA derivatives could be cyclized into the corresponding polybenzoxazoles at lower temperatures than the pristine PHA; this could be attributed to the lower thermal activation energy of the derivatives owing to the introduction of the fluoro-substituents.

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      참고문헌 (Reference)

      1 강찬솔, "폴리히드록시아미드 섬유의 제조와 열처리에 따른 구조-물성 상관관계(I) −다양한 고화조건에 따른 고화거동−" 한국섬유공학회 50 (50): 217-224, 2013

      2 백두현, "폴리벤즈옥사졸계 고성능 나노복합체 섬유에 관한 연구(I) -폴리히드록시아미드-클레이 나노복합체의 제조와 특성분석-" 한국섬유공학회 42 (42): 296-301, 2005

      3 백두현, "폴리벤즈옥사졸 전구체를 이용한 나노섬유의 제조" 한국섬유공학회 43 (43): 114-120, 2006

      4 백두현, "폴리벤족사졸 전구체를 이용한 새로운 내열성 섬유고분자의 개발(I) -PHA 유도체의 합성과 열고리화-" 한국섬유공학회 40 (40): 13-19, 2003

      5 윤종국, "퍼플로오로알킬에틸아크릴레이트 / 아크릴레이트 / 그리시딜메타크릴레이트 공중합체의 유화중합 및 그들의 표면특성" 한국청정기술학회 18 (18): 170-176, 2012

      6 백두현, "초고성능 PBO 섬유" 11 (11): 261-270, 2007

      7 지민호, "방향족 폴리히드록시아미드의 합성과 열적 고리화 거동(I) −벤젠고리 치환구조의 영향−" 한국섬유공학회 49 (49): 324-330, 2012

      8 J. H. Jang, "Thermal Cyclohydration of Aromatic Precursor Polymers to Polybenzoxazole and Polyimide; Their Thermal and Mechanical Properties" 44 (44): 63-69, 2000

      9 H. Wang, "The Evolution of Physicochemical and Gas Transport Properties of Thermally Rearranged Polyhdroxyamide(PHA)" 385 : 86-95, 2011

      10 C. Gao, "Synthesis of Precursor Flame Suppressing Polymers" 3 : 3072-3073, 1996

      1 강찬솔, "폴리히드록시아미드 섬유의 제조와 열처리에 따른 구조-물성 상관관계(I) −다양한 고화조건에 따른 고화거동−" 한국섬유공학회 50 (50): 217-224, 2013

      2 백두현, "폴리벤즈옥사졸계 고성능 나노복합체 섬유에 관한 연구(I) -폴리히드록시아미드-클레이 나노복합체의 제조와 특성분석-" 한국섬유공학회 42 (42): 296-301, 2005

      3 백두현, "폴리벤즈옥사졸 전구체를 이용한 나노섬유의 제조" 한국섬유공학회 43 (43): 114-120, 2006

      4 백두현, "폴리벤족사졸 전구체를 이용한 새로운 내열성 섬유고분자의 개발(I) -PHA 유도체의 합성과 열고리화-" 한국섬유공학회 40 (40): 13-19, 2003

      5 윤종국, "퍼플로오로알킬에틸아크릴레이트 / 아크릴레이트 / 그리시딜메타크릴레이트 공중합체의 유화중합 및 그들의 표면특성" 한국청정기술학회 18 (18): 170-176, 2012

      6 백두현, "초고성능 PBO 섬유" 11 (11): 261-270, 2007

      7 지민호, "방향족 폴리히드록시아미드의 합성과 열적 고리화 거동(I) −벤젠고리 치환구조의 영향−" 한국섬유공학회 49 (49): 324-330, 2012

      8 J. H. Jang, "Thermal Cyclohydration of Aromatic Precursor Polymers to Polybenzoxazole and Polyimide; Their Thermal and Mechanical Properties" 44 (44): 63-69, 2000

      9 H. Wang, "The Evolution of Physicochemical and Gas Transport Properties of Thermally Rearranged Polyhdroxyamide(PHA)" 385 : 86-95, 2011

      10 C. Gao, "Synthesis of Precursor Flame Suppressing Polymers" 3 : 3072-3073, 1996

      11 Y. J. Kim, "Synthesis of High Molecular Weight Polybenzoxazoles in Polyphosphoric Acid and Investigation of Their Hydrolytic Stability under Acidic Conditions" 17 (17): 377-401, 2005

      12 S. H. Hsiao, "Synthesis and Properties of Novel Aromatic Poly(o-hydroxyamide)s and Polybenzoxazoles Based on the Bis(ether benzoyl chloride)s from Hydroquinone and Its Methyl-tert-Butyl-, and Phenyl-Substituted Derivatives" 37 (37): 2129-2136, 1999

      13 D. H. Baik, "Synthesis and Cyclization of Aromatic Polyhydroxyamides Containing Trifluoromethyl Groups" 3 (3): 91-96, 2002

      14 E. S. Yoo, "Synthesis and Characterization of the Polyhydroxyamide/ Polymethoxyamide Family of Polymers" 15 (15): 519-535, 2003

      15 H. E. Kissinger, "Reaction Kinetics in Differential Thermal Analysis" 29 (29): 1702-1706, 1957

      16 M. E. Hunsaker, "Processing, Structure and Mechanics of Fibres of Heteroaromatic Oxazole Polymers" 33 (33): 2128-2135, 1992

      17 S. L. C. Hsu, "Preparation of Polybezoxazole Fibers via Electrospinning and Postspun Thermal Cyclization of Polyhydroxyamide" 46 (46): 8159-8169, 2008

      18 이진수, "Polyhydroxyamide/MWNT 나노복합체의 제조와 특성분석" 한국섬유공학회 47 (47): 7-14, 2010

      19 S. H. Lin, "Organo-Soluble Polyimides : Synthesis and Polymerization of 2, 2'-Bis(trifluoromethyl)-4, 4', 5, 5'-Biphenyltetracarboxylic Dianhydride" 31 (31): 2080-2086, 1998

      20 H. Zhang, "Low Flammability and Decomposition Behavior of Poly(3, 3'-dihydroxybiphenyl isophthalamide)and Its Derivatives" 36 (36): 3944-3954, 2003

      21 T. Miyazaki, "Highly Tough and Highly Transparent Soluble Polybezoxazoles(II): Effect of Solfune Group" 21 (21): 219-244, 2009

      22 S. K. Park, "Dry-jet Wet Spinning of Polyhydroxyamide Fibers" 1 (1): 92-96, 2000

      23 윤두수, "Dimethylphenoxy와 MPEG 팬던트 그룹을 갖는 폴리벤즈옥사졸 전구체의 합성 및 특성" 한국고분자학회 29 (29): 493-500, 2005

      24 M. Liu, "Chemical Modification of Single-Walled Carbon Nanotubes with Peroxytrifluoroacetic Acid" 43 (43): 1470-1478, 2005

      25 J. H. Jang, "Characterization of Two Precursor Polyblends: Polyhydroxyamide and Poly(Amic Acid)" 40 (40): 320-329, 2000

      26 H. Hsiao, "Aromatic Polybenzoxazoles Bearing Ether and Isopropylidene or Hexafluoroisopropylidene Units in the Main Chain" 199 (199): 1247-1253, 1998

      27 S. L. C. Hsu, "A Novel Positive Photosensitive Polybenzoxazole Precursor for Microelectronic Applications" 43 (43): 6746-6750, 2002

      28 S. H. Hsiao, "A New Class of Aromatic Polybenzoxazoles Containing ortho-phenylenedioxy Groups" 40 (40): 1127-1135, 2004

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