• 제목/요약/키워드: Thermal cyclization

검색결과 34건 처리시간 0.026초

4차 아민이 치환된 아닐린의 고리화반응 메카니즘 및 Pyrrolo[1,2-a]benzimidazoquinone 유도체의 합성에의 응용 (Mechanistic Studies for the Cyclization of t-Amine Substituted Anilines and Their Utilization to the Synthesis of Pyrrolo[1,2-a]benzimidazoquinone Derivatives)

  • 이창희;백호진;김국진;조규욱;오경택
    • 대한화학회지
    • /
    • 제39권5호
    • /
    • pp.408-413
    • /
    • 1995
  • A few t-amine substituted anilines and amides were synthesized and cyclized to pyrrolo[1,2-a]benzimidazole by heating in various solvents having different polarity. Subsequent nitration of cyclized compound followed by reduction and oxidation of resulting amine afforded quinone such as 7 in 14% yield. The formation of imidazole moiety by thermal cyclization was independent on the solvent polarity. The regiochemistry for the nitration of 4 was unambiguously determined by chemical transformation.

  • PDF

Two-Dimensional Raman Correlation Spectroscopy Study of the Pathway for the Thermal Imidization of Poly(amic acid)

  • Han Yu, Keun-Ok;Yoo, Yang-Hyun;Rhee, John-Moon;Lee, Myong-Hoon;Yu, Soo-Chang
    • Bulletin of the Korean Chemical Society
    • /
    • 제24권3호
    • /
    • pp.357-362
    • /
    • 2003
  • The pathway producing imide ring closure during the thermal imidization of poly(amic acid) (PAA) was investigated in detail using a new analytical method, two-dimensional (2D) Raman correlation spectroscopy. The signs of the cross peaks in synchronous spectra provided evidence of the thermal imidization of PAA into PI as the heating temperature increased. The signs of the cross peaks in asynchronous spectra suggested that the imide-related modes changed prior to the amide or carboxylic mode, which indicates that cyclization occurred before the amide proton was abstracted.

Synthesis and Cyclization of Aromatic Polyhydroxyamides. 1. Model Compound Study

  • Kim, Hae-Young;Kim, Myung-Kyoon;Baik, Doo-Hyun;Simon Kantor
    • 한국섬유공학회:학술대회논문집
    • /
    • 한국섬유공학회 1998년도 가을 학술발표회논문집
    • /
    • pp.37-40
    • /
    • 1998
  • Aromatic polybenzoxazoles have been known since 1964 as a class of aromatic heterocyclic polymers that exhibit excellent thermal stability. Polyhydroxyamides (PHA), precursor polymers to PBO, can cyclize to farm stable heterocyclic polymers with the simultaneous release of small molecules, which can be expected to act as a fire quencher. (omitted)

  • PDF

Synthesis and Cyclization of Aromatic Polyhydroxyamides. 2. Polyhydroxyamides Containing Trifluoromethyl Group

  • Kim, Myung-Kyoon;Kim, Hae-Young;Baik, Doo-Hyun;Simon Kantor
    • 한국섬유공학회:학술대회논문집
    • /
    • 한국섬유공학회 1998년도 가을 학술발표회논문집
    • /
    • pp.41-44
    • /
    • 1998
  • Wholly aromatic polybenzoxazoles (PBO) are well established as high performance materials with excellent thermal stability and mechanical properties. Heterocyclic precursor polymers such as polyhydroxyamides (PHA) have been interested in the field of high performance flame retardant polymers. The PHAs can be converted to PBOs when ignited. (omitted)

  • PDF

PHA 및 PHA-PAA 공중합체의 열적 고리화 거동 (Thermal Cyclization behaviors of PHA and PHA-PAA Copolymers)

  • 이광희;김명균;백두현
    • 한국섬유공학회:학술대회논문집
    • /
    • 한국섬유공학회 2001년도 가을 학술발표회 논문집
    • /
    • pp.359-360
    • /
    • 2001
  • 헤테로고리 방향족 polybenzoxazole(PBO)은 대표적인 내열성 고분자로서, 고온에서의 열적안정성 및 내화학성, 기계적 물성, 방염성 등에서 우수한 성질을 나타낸다. 그러나 황산과 같은 강산에만 용해되기 때문에 가공성 면에서 단점을 가지고 있어 사용하는데 있어 제약이 따른단 현재 이러한 단점을 보완하기 위해 polyhydroxyamide(PHA)와 같은 전구체 고분자에 대한 연구가 많은 연구자들에 의해 진행되고 있다. (중략)

  • PDF

High Char-Yield in AN-AM Copolymer by Acidic Hydrolysis of Homopolyacrylonitrile

  • Cheng, Run;Zhou, You;Wang, Jing;Cheng, Yumin;Ryu, Seungkon;Jin, Riguang
    • Carbon letters
    • /
    • 제14권1호
    • /
    • pp.34-39
    • /
    • 2013
  • Acrylonitrile (AN)-acrylamide (AM) copolymers were prepared by nitric acidic hydrolysis of homopolyacrylonitrile. The acrylamino group increased as a function of hydrolysis time, while crystallinity decreased. Differential scanning calorimetry and a thermal gravimetric analysis indicated that the acylamino introduced by acidic hydrolysis effectively enhanced the cyclization reaction at low temperature due to the change of the cyclization reaction mechanism. Char-yield of AN-AM copolymers also gradually increased with increasing hydrolysis time. The maximum char-yield was 49.48% when hydrolized at $23^{\circ}C$ in 65% nitric acid solution for 18 h, which was 30% higher than that of non-acidic hydrolysis of homopolyacrylonitrile. Simulation of the practical process also showed an increase of char yields, where the char yields were 55.43% and 62.60% for homopolyacrylonitrile and copolyacrylonitrile, respectively, with a hydrolysis time of 13 h.

Backbone Cyclization of Flavin Mononucleotide-Based Fluorescent Protein Increases Fluorescence and Stability

  • Tingting Lin;Yuanyuan Ge;Qing Gao;Di Zhang;Xiaofeng Chen;Yafang Hu;Jun Fan
    • Journal of Microbiology and Biotechnology
    • /
    • 제33권12호
    • /
    • pp.1681-1691
    • /
    • 2023
  • Flavin mononucleotide-binding proteins or domains emit cyan-green fluorescence under aerobic and anaerobic conditions, but relatively low fluorescence and less thermostability limit their application as reporters. In this work, we incorporated the codon-optimized fluorescent protein from Chlamydomonas reinhardtii with two different linkers independently into the redox-responsive split intein construct, overexpressed the precursors in hyperoxic Escherichia coli SHuffle T7 strain, and cyclized the target proteins in vitro in the presence of the reducing agent. Compared with the purified linear protein, the cyclic protein with the short linker displayed enhanced fluorescence. In contrast, cyclized protein with incorporation of the long linker including the myc-tag and human rhinovirus 3C protease cleavable sequence emitted slightly increased fluorescence compared with the protein linearized with the protease cleavage. The cyclic protein with the short linker also exhibited increased thermal stability and exopeptidase resistance. Moreover, induction of the target proteins in an oxygen-deficient culture rendered fluorescent E. coli BL21 (DE3) cells brighter than those overexpressing the linear construct. Thus, the cyclic reporter can hopefully be used in certain thermophilic anaerobes.

Preparation and Properties of Polybenzoxazole Copolymers Bearing Pendants and Imide Ring in the Main Chain

  • Lee, Seul Bi;Lee, Eung Jae;Choi, Jae Kon
    • Elastomers and Composites
    • /
    • 제51권3호
    • /
    • pp.195-205
    • /
    • 2016
  • A series of aromatic poly(hydroxyamide)s (PHAs) containing varying oligo(oxyethylene) substituents and 1,3-phenylene imide ring unit in the main chain were synthesized by the direct polycondensation reaction. The inherent viscosities of the PHAs exhibited in the range of 0.89~1.12 dL/g in DMAc or DMAc/LiCl solution. The PH-2~5 copolymers were easily soluble in strong aprotic solvents: DMAc, NMP, DMSO etc. and the PH-5 copolymer was soluble in less polar solvents such as m-creasol and pyridine with LiCl salt on heating. However, all PBOs were quite insoluble in other solvents, but only partially soluble in sulfuric acid. All copolymers (PH-2~5) could afford the flexible and tough films by solution casting. We identified that the PHAs were converted to the PBOs by the thermal cyclization reaction in the range of $200{\sim}380^{\circ}C$. The 10% weight loss temperatures and char yields of the PBOs were recorded in the range of $382{\sim}647^{\circ}C$ and 38.7~73.1% values at $900^{\circ}C$. The tensile strength and initial modulus of the PH-5 in the copolmers showed the highest values of 2.46 GPa and 49.55 MPa, respectively. The LOI values of the PHAs were in the range 26.6~29.0%, and increased with increasing 1,3-phenylene imide ring unit.

Dimethylphenoxy와 MPEG 팬던트 그룹을 갖는 폴리벤즈옥사졸 전구체의 합성 및 특성 (Syntheses and Characterization of PBO Precursors Containing Dimethylphenoxy and/or MPEG Pendant Groups)

  • 윤두수;최재곤;조병욱
    • 폴리머
    • /
    • 제29권5호
    • /
    • pp.493-500
    • /
    • 2005
  • Poly(ethylene glycol)methyl ether(MPEG)와 dimethylphenoxy 팬던트 그룹을 갖는 polybenzoxazoles(PBOs)의 중합 전구체인 poly(o-hydroxyamides)(PHAs)를 저온 용액 중축합에 의해서 합성하였다. 합성된 중합 전구체들의 고유점도는 $0.51\~2.31$의 값을 나타내었다. 중합전구체는 FT-IR, $1H-NMR$, DSC, 그리고 TGA를 이용하여 특성을 조사하였다. MPEG단위를 갖는 PHAs는 MPEG의 분자량이 증가할수록 용매특성이 증가하는데, 특히 분자량이 1100인 MPEG를 갖는 PHA의 경우 aprotic 용매뿐만 아니라 에탄올, 메탄올, H,0에도 용해되었으나, 열적 고리화 반응에 의해 PBOs로 전환되면 어떠한 용매에도 용해되지 않았다. 그리고 MPEG만을 갖는 중합 전구체의 경우, MPEG의 분자량이 증가할수록 고리화 반응온도는 감소함을 확인할 수 있었다.

Preparation of Polyesters Containing Enaryloxynitrile Moiety and Their Thermal Properties

  • Moon Sung-Hee;Lee Seung-Jae;Kim Jin-Bong;Gong Myoung-Seon
    • Bulletin of the Korean Chemical Society
    • /
    • 제15권12호
    • /
    • pp.1089-1093
    • /
    • 1994
  • Polyesters containing enaryloxynitriles moiety have been newly prepared from p-bis[1-[4-(3-hydroxypropyl)phenoxy]-2,2-dicyano vinyl]benzene (3) and common diols with terephthaloyl chloride. The copolyesters have a good solubility in common organic solvents as well as polar aprotic solvents. They undergo a curing reaction at around 350 $^{circ}C$ and show a 50-60${\%}$ of residual weight at 500 $^{circ}C$. The enhanced thermal stabilities were due to the intramolecular cyclization or intermolecular cross-linking reaction of the dicyanovinyl group incorporated into polyester by copolymerization.