• Title/Summary/Keyword: 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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    • v.29 no.2
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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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    • v.29 no.1
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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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    • v.53 no.2
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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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    • v.28 no.11
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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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    • v.9 no.4
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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.

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

  • Kim, Sol;Hwang, Yun-Jeong;Kim, Hee-Eun;Lu, Ming;Kim, An-D-Re;Moon, Ji-Young;Kang, Ho-Sung;Park, Jang-Su
    • Journal of Life Science
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    • v.16 no.6
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    • pp.1052-1059
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    • 2006
  • The heat shock response is induced by environmental stress, pathophysiological state and non-stress conditions and wide spread from bacteria to human. Although translations of most proteins are stopped under a heat shock response, heat shock proteins (HSPs) are produced to protect cell from stress. When heat shock response is induced, conformation of HSF1 was changed from monomer to trimer and HSF1 specifically binds to DNA, which was called a heat shock element(HSE) within the promoter of the heat shock genes. Human HSF1(hHSFl) contains five cysteine(Cys) residues. A thiol group(R-SH) of Cys is a strong nucleophile, the most readily oxidized and nitrosylated in amino acid chain. This consideration suggests that Cys residues may regulate the change of conformation and the activity of hHSF1 through a redox-dependent thiol/disulfide exchange reaction. We want to construct role of five Cys residues of hHSF by redox reagents. According to two studies, Cys residues are related to trimer formation of hHSF1. In this study, we want to demonstrate the correlation between structural change and DNA-binding activity of HSF1 through forming disulfide bond and trimerization. In this results, we could deduce that DNA binding activity of DNA binding domain wasn't affected by redox for always expose outside to easily bind to DNA. DNA binding activity of wild-type HSF's DNA binding domain was affected by conformational change, as conformational structure change (trimerization) caused DNA binding domain.

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

  • Park, Da Min;Kim, Gye-Ryeong;Lee, Ju Hyun;Cho, Deuk Hee;Kim, Geon-Joong
    • Korean Chemical Engineering Research
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    • v.51 no.3
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    • pp.394-402
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    • 2013
  • The new complex catalysts were synthesized by the reaction of titanium compounds (titanium chloride or titanium butoxide) and diamines in this work, and they showed very high catalytic activities for the cyclododecatriene (CDT) synthesis from 1,3-butadiene through trimerization. CDT synthetic reaction was performed in an autoclave reactor, and the effects of reaction temperature, type of catalyst, catalyst amount added into the system, the mole ratio of Al/Ti and immobilization method were investigated on the yield of product CDT. The titanium complex catalyst combined to diamine with 1:1 ratio showed high selectivity to CDT more than 90%. The ratio of TTT-CDT/TTC-CDT isomers in the product revealed as different values, depending on the type of diamine combined to titanium and Ti/diamine ratios. Those homogeneous complexes could be used as a heterogenized catalyst after anchoring on the supports, and the immobilized titanium catalyst retained the catalytic activities for several times in the recycled reactions without leaching. The carbon support containing titanium has exhibited superior activity to the silica support. Especially, when the titanium complex was anchored on the support which was fabricated by the hydrolysis of tripropylaminosilane itself, the resulting titanium catalyst showed the highest BD conversion and CDT selectivity.

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

  • Kwon Hyun;Kim Sang-Bum;Kim Youn Cheol
    • Polymer(Korea)
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    • v.29 no.5
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    • pp.457-462
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    • 2005
  • Polyurethane foams (PUFs) were prepared from polymeric 4,4'-diphenylmethane diisocyanate (PMDI), mixed polyol with OH value of 480, silicone surfactant, three catalysts, and hydrofluorocarbon(HFC) as blowing agent. Balance (PC-8), gelling (33LV), and trimerization (TMR-2) catalysts were used. The effect of the catalysts on the physical properties of PUF with increase of isocyanate (NCO) index and aging time was investigated. The cell size of the PUF with PC-8 and 33LV slightly increased with an increase in NCO index from 100 to 170 but compressive strength did not change significantly. In case of trimerization catalyst, the compressive strength of PUF increased from 8.75 to 1$10.5 kg_f/cm^2$ and the cell size decreased with an increase in NCO index. The compressive strength of the PUF with 33LV increased from 9.21 to $10.15 kg_f/cm^2$ with an increase in aging time. However, there was no detectable change in the compressive strength of PUF with TMR-2. A possible interpretation of the results includes an additional cross-link reaction of non-reacted MDI and FTIR spectrum illustrated the change of NCO peak.

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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    • v.9 no.1
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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.