• 제목/요약/키워드: Ring-opening metathesis polymerization (ROMP)

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Synthesis of Various Functional Block Copolymers via Controlled Ring Opening Metathesis Polymerization and the Subsequent Chemical Modifications

  • Kang, Min-Hyuk;Moon, Bong-Jin
    • 한국고분자학회:학술대회논문집
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    • 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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    • pp.200-200
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    • 2006
  • Several polynorbornene or poly(norbornene-7-oxide) based functional block copolymers were synthesized by ring opening metathesis polymerization (ROMP) with good molecular weight and polydispersity control. Some representative functional groups in these polymers are a nitrobenzoyl group or ferrocene. These polymers were subjected to various chemical modification reactions to give other block copolymers that contain novel functionality such as amine, diazonium salt, and diazo groups. The resulting polymers were characterized by various techniques such as GPC, NMR, UV-VIS, AFM, and cyclovotammography (CV).

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Ring-Opening Metathesis Polymerization and Hydrogenation of Ethyl-substituted Tetracyclododecene

  • Kwon, Oh-Joon;Vo, Huyen Thanh;Lee, Sul-Bee;Kim, Tae-Kyung;Kim, Hoon-Sik;Lee, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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    • pp.2737-2742
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    • 2011
  • Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

Amphiphilic Norbornene-Based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared by Living Ring Opening Metathesis Polymerization

  • Park, Su-Dong;Xu, Wentao;Chung, Chan-Hong;Kwon, Young-Hwan
    • Macromolecular Research
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    • 제16권2호
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    • pp.155-162
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    • 2008
  • We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the $RuCl_2(=CHPh)(PCY_3)_2$/$CH_2Cl_2$/$20^{\circ}C$ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a $\bar{M}_n$ vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBE-COOH-b-NBEPOSS) copolymers was confirmed by $^1H$-NMR, $^{13}C$-NMR spcctroscopy and GPC.

Synthesis and Characterization of Novel Hydrogenated Poly(norbornene bisimide)s Prepared from Ring Opening Metathesis Polymerization

  • Yoon, Kyung-Hwan;Park, Seung-Beom;Park, In-Sook;Yoon, Do-Y.
    • Bulletin of the Korean Chemical Society
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    • 제32권spc8호
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    • pp.3074-3080
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    • 2011
  • We synthesized three novel poly(norbornene bisimide)s by ring opening metathesis polymerization (ROMP) and subsequent hydrogenation. Their thermal, mechanical and optical properties were investigated with TGA, DMA, UV-Vis spectrometer, and optical reflectometer. The new polymers showed high glass transition temperatures over $260^{\circ}C$ and good thermal stability with 5% wt-loss temperature higher than $390^{\circ}C$. When solvent casted, they yielded optically transparent and dimensionally stable films with a relatively low coefficient of thermal expansion of about 50 ppm $K^{-1}$. Therefore, the bisimide moieties substantially enhanced thermal and dimensional stabilities, as compared with normal ROMP-prepared polynorbornene films. Though the water uptake was increased to 0.6 wt-%, this water uptake is still considerably lower than that for polyethersulfones (1.4 wt-%) or polyimides (2.0 wt-%). Hence, the new poly(norbornene bisimide)s may become attractive candidates for flexible substrates of optoelectronic devices such as displays and photovoltaic solar cells.

Olefin Metathesis를 이용한 황칠 Essential Oil의 경화 반응에 관한 연구 (Olefin Metathesis Curing Reaction of Essential Oils in Korean Dendropanax Lacquer)

  • 김미리;이원휘;유혜진;김종상;정인우
    • 접착 및 계면
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    • 제16권4호
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    • pp.146-151
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    • 2015
  • 황칠원액을 에탄올로 추출한 황칠의 essential oil을 올레핀 메타테시스(olefin metathesis) 반응의 하나인 ROMP(ring opening metathesis polymerization)법을 이용하여 경화 반응을 수행하였으며, 자연 경화 및 UV 광경화법의 경화 특성 및 경화된 필름의 물성에 대해서 비교 연구하였다. 경화 전후의 황칠의 조성 변화에 대해서 가스 크로마토그래피 질량분석법(GC-MS, gas chromatography mass spectrometry)을 통해 연구하였으며, ROMP법에 의해 경화된 필름의 겔 함량(gel contents, 40%)은 자연 경화(8%)나 UV 광경화법(25%)에 비해 높은 값을 보여주었다. $100^{\circ}C$의 온도 및 2 wt%의 Grubbs' catalyst 조건에서 ROMP 경화반응은 2 h 이내의 경화 반응이 완료되어 자연 경화에 비해 비교적 빠른 경화 속도를 보여주었으며, UV 광경화법에 비해 주름이 없으며 외관상 균일한 도막이 형성됨을 확인하였다. 또한 기존에 경화반응에 참여하는 것으로 알려져 있는 폴리아세틸렌계 성분 이외에 sesquiterpene류인 ${\alpha}$-selinene, ${\beta}$-selinene, ${\delta}$-cadinene 등도 ROMP 경화 반응에 참여함을 확인하였다.

Ethylidene Norbornene/endo-Dicyclopentadiene 블렌드의 경화 거동 및 인장 특성 (Cure Behavior and Tensile Properties of Ethylidene Norbornene/endo-Dicyclopentadiene Blends)

  • 정종기;최정화;양광;박종문;김동학;김성길;이종근;오명훈;김봉석;방대석
    • 폴리머
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    • 제39권3호
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    • pp.506-513
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    • 2015
  • Ethylidene norbornene(ENB)과 endo-dicyclopentadiene(endo-DCPD) 블렌드를 $1^{st}$ generation과 $2^{nd}$ generation Grubbs 촉매 하에서 ring-opening metathesis polymerization(ROMP)으로 제조하였다. ROMP 과정을 이해하기 위하여 시차주사열분석기(DSC)로 동적 발열거동을 분석하였으며, 반응 후 만능시험기(UTM)로 인장특성을 조사하였다. 반응속도는 endo-DCPD의 양이 적을수록 그리고 $2^{nd}$ generation 촉매 하에서 더 빨라졌다. 또한 endo-DCPD를 첨가할수록 그리고 $1^{st}$ generation 촉매 시스템에서 인장탄성률과 강도는 더 높은 값을 보였으나 강인성은 감소하였다. 이와 같은 인장특성의 변화를 젤 분율 측정과 파단면 관찰을 통하여 자세히 설명하였다.

자가손상복구용 복구액의 특성 분석 (Characterization of Healing Agent Candidates for Self-healing Applications)

  • 유성;이종근;김정석
    • 한국철도학회:학술대회논문집
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    • 한국철도학회 2008년도 추계학술대회 논문집
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    • pp.1668-1673
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    • 2008
  • 고분자 복합재 구조물의 경우 일반적으로 여러 층의 단층(laminar)이 적층된 구조로 이루어져 있으며, 모재균열, 층간분리 및 섬유파단과 같은 손상이 발생되어 파단에 이르게 된다. 자가손상 복구기법은 복합소재의 열경화성 수지 내에 손상복구액을 포함하고 있는 마이크로캡슐과 촉매를 투입하여 외부의 도움 없이 손상을 치료할 수 있는 방법으로, 소재의 디자인에 있어서 새로운 페러다임을 제공할 수 있는 것으로 현재 많은 연구가 진행되고 있다. 본 연구에서는 ENB(5-ethylidene-2-norbornene)와 DCPD(dicyclopentadiene)에 대하여 DMA(dynamic mechanical analysis)와 DSC(differential scanning calorimetry)를 이용하여 특성을 분석하였다. 또한 그들의 ROMP(ring-opening metathesis polymerization)반응과의 관계를 조사하였으며, ENB와 DCPD 블렌드에 대한 복구액으로서의 특성도 조사하였다. 본 연구실에서 합성된 두 가지 다른 종류의 ROMP 경화제에 대한 실제 자가손상복구에으로서의 적용상 특성도 연구하였다.

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S-RIM을 이용한 Glass Fiber Chopped Strand Mat 강화 p-DCPD 복합재료 제작 및 수치해석을 통한 공정 시간 예측 (Manufacturing and Numerical Analysis of Glass Fiber Chopped Strand Mat Reinforced p-DCPD Composites Processed by S-RIM)

  • 유형민;엄문광;최성웅
    • 한국수소및신에너지학회논문집
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    • 제30권6호
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    • pp.629-634
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    • 2019
  • Dicyclopentadiene is a low viscosity resin which forms a poly-dicyclopentadiene rapidly through ring opening metathesis polymerization (ROMP). This poly-dicyclopentadiene has outstanding properties of low-temperature, water and impact resistances. Due to these advantages, military and offshore structures try to apply the DCPD composites by using liquid composite molding process. In this study, 14%, 38% volume fraction fiber glass strand mat reinforced p-DCPD composites processed by structural reaction injection molding (S-RIM) which has resin-catalsyt mixing head and glass fiber preform in the mold. Additionally, S-RIM numerical analysis was conducted to predict the process time depending on fiber volume fraction and mold temperature. The process time is shorter when it has the lower fiber volume fraction or the higher mold temperature. At higher mold temperature, it is necessary to set the maximum mold temperature considering the resin curing time.