• 제목/요약/키워드: Trimerization

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Trimerization of Isobutene over Solid Acid Catalysts: Comparison between Cation-exchange Resin and Zeolite Catalysts

  • Yoon, Ji-Woong;Jhung, Sung-Hwa;Chang, Jong-San
    • Bulletin of the Korean Chemical Society
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    • 제29권2호
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    • pp.339-341
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    • 2008
  • Catalytic trimerization of isobutene to produce triisobutenes has been performed over cation-exchange resin and zeolite catalysts. Resin catalysts have the advantage of long lifetime and high trimers selectivity even though the regeneration of an aged catalyst is not satisfactory. On the contrary, zeolite catalysts can be regenerated facilely by simple calcination in air even though the lifetime is short and trimers selectivity is low probably due to small pore size and strong acidity, respectively. It is, therefore highly desirable to develop an inorganic acid catalyst with macro- or meso-pores to show catalytic performances similar or superior to those of macroporous resin catalysts.

Effect of Butadiene in Catalytic Trimerization of Isobutene Using Commercial C4 Feeds

  • Yoon, Ji-Woong;Jhung, Sung-Hwa;Lee, Ji-Sun;Kim, Tae-Jin;Lee, Hee-Du;Chang, Jong-San
    • Bulletin of the Korean Chemical Society
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    • 제29권1호
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    • pp.57-60
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    • 2008
  • Catalytic oligomerization of isobutene to produce triisobutenes has been performed over a cation-exchange resin (Amberlyst-35) by using commercial C4 feeds. The catalytic activity in the oligomerization was retained without deactivation up to 90 h of reaction in a simulated reaction feed without butadiene, but its activity was significantly affected by the presence of butadiene in commercial C4 feeds. The isobutene conversion with time-on-stream was significantly decreased in the presence of butadiene, indicating the catalyst deactivation by butadiene. However, the stable activity for trimerization was accomplished when the oligomerization was carried out after eliminating butadiene by hydrogenation of the feeds. This work demonstrates that butadiene plays a role as a catalyst poison on the solid acid catalyst, so that its removal in the reactant feed is essential for practical application of trimerization.

Effect of Catalyst Type and NCO Index on the Synthesis and Thermal Properties of Poly(urethane-isocyanurate) Foams

  • Shin, Hye-Kyeong;Lee, Sang-Ho
    • Elastomers and Composites
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    • 제53권2호
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    • pp.86-94
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    • 2018
  • The effect of the NCO index and catalyst type on the thermal stability of poly(urethane-isocyanurate) (PUIR) foams was investigated to identify a method for enhancing the flame resistance of PUIR. PUIR foams were prepared using 4,4-diphenylmethane diisocyanate (MDI) and [(diethylene glycol)adipate]diol, which were synthesized by esterification of adipic acid and diethylene glycol. Dabco K-15, Dabco TMR-30, and Toyocat RX-5 were used as the catalysts for trimerization and gelation. The amount of urea and isocyanurate groups in PUIR was semi-quantitatively determined by normalizing their absorbance with the phenyl absorbance measured by FT-IR. The normalization data showed that Dabco TMR-30 effectively generated isocyanurate groups in PUIR. As a result, Dabco TMR-30 effectively raised the decomposition temperature and increased the 800 K and 900 K residues of the PUIR foam synthesized with an NCO index of 200.

Trimerization of Isobutene over Solid Acid Catalysts under Wide Reaction Conditions

  • Yoon, Ji-Woong;Jhung, Sung-Hwa;Kim, Tae-Jin;Lee, Hee-Du;Jang, Nak-Han;Chang, Jong-San
    • Bulletin of the Korean Chemical Society
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    • 제28권11호
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    • pp.2075-2078
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    • 2007
  • Oligomerization of isobutene has been investigated using a few solid acid catalysts in order to produce efficiently triisobutenes that are useful chemical feedstocks for heavy alkylates and neo-acids. Several reaction conditions such as space velocity and isobutene concentration are evaluated, and a few cation exchange resins with various acid capacities were compared in the reaction. High trimers selectivity and high conversion can be obtained over a catalyst containing high acid capacity at low space velocity and relatively low isobutene concentration. The stability of a catalyst for the reaction is high when the acid capacity of the catalyst is high (for example Amberlyst-35).

Oligomerization State of the Plasma Membrane Proteolipid Apoprotein Purified from the Bovine Kidney, Probed by the Fluorescence Polarization

  • Chae, Quae;Nam, Sang-Rye
    • Bulletin of the Korean Chemical Society
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    • 제9권4호
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    • pp.202-206
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    • 1988
  • In order to investigate the oligomerization state of the plasma membrane proteolipid apoprotein purified from the bovine kidney, fluorescence polarization experiment was carried out in the two different solvent systems, i.e., water and organic solvent(chloroform-methanol). The molecular volumes of the proteins estimated from the Perrin equation, were to be 45,258$A^3$ and 17,608$A^3$ in water and organic solvent, respectively. These values indicate that a trimerization is possibly occurring in the aqueous environment. As an auxiliary experiment for the calculation of the molecular volume using Perrin equation, fluorescence quenching constants ($K_q$) with the quencher acrylamide and fluorescence lifetimes (${\tau}_F$) of the intrinsic fluorophore tryptophan residue were estimated in the two different solvent systems. $K_q$ in water was 18.21$M^{-1}$ and it was 46.24$M^{-1}$ in organic solvent. Fluorescence lifetimes of tryptophan residue were calculated to be 2.80 nsec. in water and 3.81 nsec. in organic solvent, respectively.

산화환원에 따른 hHSF1의 DNA binding domain의 역할 (The Role of DNA Binding Domain in hHSF1 through Redox State)

  • 김솔;황윤정;김희은;여명;김안드레;문지영;강호성;박장수
    • 생명과학회지
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    • 제16권6호
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    • pp.1052-1059
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    • 2006
  • 다양한 종류의 박테리아에서부터 사람의 세포에 이르기까지 환경적인 스트레스나 병에 의한 스트레스 혹은 스트레스가 없는 상황에서도 열충격반응(heat shock response) 유도되어진다. 열충격반응에 노출된 세포에서는 모든 단백질의 발현이 정지되는 반면, 열충격단백질(heat shock proteins: HSPs)은 발현되어 스트레스로부터 세포를 보호한다. HSF1(heat shock factor 1)이라는 HSPs 유도단백질은 열충격반응시 단량체형태에서 삼중체의 형태로 구조변화를 일으켜 heat shock element(HSE)라고 불리우는 HSP gene의 발현 promoter에 특이적으로 결합하게 되어 HSPs를 발현시킨다. Human HSF1(hHSF1)은 다섯 개의 시스테인 잔기를 가지고 있는데 이 시스테인의 thiol(-SH)기는 강한 친전자성을 띔으로 급격히 산화되거나 질산화된다. 이러한 고찰은 시스테인 잔기가 산화 환원 의존적인 황산기/이황화결합 전환을 통해 구조적인 변화를 가져온다는 사실을 의미하고 있다. 따라서 본 연구에서는 여러 가지 산화환원제를 이용하여 HSF1에 존재하는 다섯 개의 시스테인 잔기의 역할과 삼량체 형성에 관여하는 잔기에 대하여 알아보고자 하였다. 또한 이황화결합을 통한 삼량체형성의 구조적변화의 관점에서 HSF1의 구조 변화와 DNA 결합력과의 상관관계에 관하여도 알아보고자 하였다. 본 연구결과로 HSF1의 DNA binding domain은 삼량체를 형성하는 구조적인 변화를 통해서 DNA에 대한 결합력이 증가되는 것을 알 수 있었는데 이것은 삼량체가 됨으로서 HSF1의 내부에 위치해 있던 DNA binding domain이 외부로 노출 되어져 DNA에 쉽게 결합할 수 있게 된다는 사실을 시사한다.

아민-티타늄착체 촉매상에서 1,3-부타디엔의 삼량화반응에 의한 싸이클로도데카트리엔의 합성 (Synthesis of Cyclododecatriene from 1,3-Butadiene by Trimerization over Amine-Titanium Complex Catalyst)

  • 박다민;김계령;이주현;조득희;김건중
    • Korean Chemical Engineering Research
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    • 제51권3호
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    • pp.394-402
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    • 2013
  • 티타늄화합물과 티타늄부톡사이드를 각각 디아민과 결합시켜 새로운 구조의 중합촉매를 개발하였으며, 이들은 부타디엔의 삼중고리화를 통한 싸이클로도데카트리엔(CDT)의 합성반응에 대해 높은 촉매활성을 나타내었다. CDT합성반응은 고압식 액상반응기를 사용한 배취형 반응계에서 수행하였으며, 반응온도, 촉매의 종류, 촉매량, Al/Ti의 몰비 및 고정화방법 등이 생성물 CDT의 생성수율에 미치는 영향을 관찰하였다. 디아민과 4염화티타늄을 1:1로 결합시킨 촉매는 생성물 CDT에 대하여 90% 이상의 높은 선택성을 보였다. 생성된 CDT 중의 TTT/TTC 입체이성체비는 티타늄에 결합된 디아민의 종류와 Ti/디아민의 비율 등에 따라 달라졌다. 이들 균일계 착체는 담체상에 고정화시켜 사용할 수 있었으며, 티타늄 주촉매는 반응 중 추출되지 않고 활성을 유지하면서 여러 번 사용이 가능하였다. 실리카 담체보다는 탄소담체를 사용하여 티타늄화합물을 고정한 촉매가 보다 높은 활성을 보였으며, 특히 아미노실란 만을 중합시켜 제조한 담체에 티타늄을 결합시키면 BD의 전환율도 높고 CDT에 대한 선택도도 높게 나타났다.

폴리우레탄 발포체의 물성에 대한 이소시아네이트 인덱스와 노화의 영향 (Effects of Isocyanate Index and Aging on the Physical Properties of Polyurethane Foams)

  • 권현;김상범;김연철
    • 폴리머
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    • 제29권5호
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    • pp.457-462
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    • 2005
  • Polymeric 4,4'-diphenylmethane diisocyanate(PMDI), OH 값이 480인 혼합 폴리올, 실리콘 계면활성제, 세 종류의 촉매 그리고 발포제로 불화탄화수소계를 사용하여 폴리우레탄 발포체(PUF)를 제조하였다. 촉매로는 balance 촉매(PC-8), 젤 화촉매(33LV) 그리고 삼량화 촉매(TMR-2)가 이용되었으며, 이소시아네이트(NCO) 인덱스(index)와 노화시간에 따른 PUF의 물성에 대한 촉매의 영향을 조사하였다. PC-8과 33LV를 이용한 PUF의 압축강도는 NCO 인덱스에 따라 큰 변화를 보이지 않은 반면 발포셀의 크기는 약간 증가하였다. 삼량화 촉매의 경우에, PUF의 압축강도는 NCO인덱스에 따라 8.75에서 $10.5 kg_f/cm^2$으로 증가하였고 발포셀의 크기는 감소하였다. 33LV를 이용한 PUF의 압축강도는 노화시간이 증가함에 따라 9.21에서 $10.15 kg_f/cm^2$으로 증가하였으나 삼량화 촉매인 TMR-2를 이용한 경우에는 거의 변화가 나타나지 않았다. 이는 미반응 MDI에 의한 추가적인 가교반응에 의해 설명할 수 있고 FTIR의 결과로 확인하였다.

Thermal Hazard Evaluation on Self-polymerization of MDI

  • Sato, Yoshihiko;Okada, Ken;Akiyoshi, Miyako;Murayama, Satoshi;Matsunaga, Takehiro
    • International Journal of Safety
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    • 제9권1호
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    • pp.6-11
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    • 2010
  • Thermal analysis, heating test on gram scale and simulation of exothermic behavior based on kinetic analysis has been conducted in order to evaluate thermal hazards of self-polymerization of MDI. The exothermic reactions of MDI are expected to be the polymerization which forms carbodiimide and carbon dioxide, dimerization and trimerization. When MDI is kept in adiabatic condition during 1 week (10080 hours), the simulated result shows runaway reaction can occur in the case that initial temperature was more than $130^{\circ}C$. The relationship between the initial temperature (T, $^{\circ}C$) and TMR is given in a following equation. TMR=$4.493{\times}10^{-7}$ exp ($9.532{\times}10^3$/(T+273.15)) We propose that the relationship gives important criteria of handling temperature of MDl to prevent a runaway reaction.