• Title/Summary/Keyword: Acidolysis

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Interchange Reaction Kinetics and Sequence Distribution of Liquid Crystalline Poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)

  • Rhee, Do-Mook;Ha, Wan-Shik;Youk, Ji-Ho;Yoo, Dong-Il
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.86-91
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    • 2001
  • Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) [copoly(ET/CPT)] was prepared using poly(ethylene terephthalate) (PET) as a flexible spacer, terephthalic acid (TPA), and chlorohydroquinone diacetate (CHQDA). All reactions involved in the copolymerization were investigated using some model compounds: TAP was used for acidolysis, diphenylethyl terephthalate (DPET) for interchange reaction between PET chains, and 야-o-chlorophenyl terephthalate (DOCT) and di-m-chlorophenyl terephthalate (DMCT) for interchange reaction between PET and rigid rodlike segments. Activation energies obtained for the acidolysis of PET with TPA and for interchange reaction of PET with DPET, DOCT, and DMCT were 19.8 kcal/mol, 26.5 kcal/mole, and 45.9 kcal/mole, respectively. This result supports that the copolymerization proceeds through the acidolysis of PET with TPA first and subsequent polycondensation between carboxyl end group and CHQDA or acetyl end group, which is formed from the reaction of CHQDA and TPA. Also, it was found that ester-interchange reaction can be influenced by the steric hindrance. Copoly(ET/CPT)s obtained has ethylene acetate end groups formed from acetic acid hydroxy ethylene end groups and showed almost the random sequence distribution for all compositions.

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Synthesis of Lignin-phenol Copolymers Using Horseradish Peroxidase (Horseradish Peroxidase를 이용한 리그닌-페놀계 공중합물 합성)

  • 이성문;여주상;박경문;유영제
    • KSBB Journal
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    • v.15 no.1
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    • pp.22-26
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    • 2000
  • Kraft Lignin which is produced abundantly in pulp industry, was chemically degraded into small oligomers and polymerized using horseradish peroxidase. Lignin acidolysis was optimized by controlling reaction time and HCI concentration. Acidolyzed lignin was polymerized and copolymers of acidolyzed lignin and phenol or p-cresol were synthesized. 70% of kraft lignin was degraded after acidolysis. Number average molecular weight of all lignin polymers were from 8,500 to 14,000 and did not show large difference. Differential scanning calorimeter analysis showed that acidolyzed lignin did not show any melting temparature under $300^{\circ}C$, which indicates that newly synthesized lignin polymers can be used in industry under mild condition.

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폴리에틸렌테레프탈레이트/폴리카프로락톤 용융 블렌드에서 폴리카프로락톤 분자량 고 촉매 함량에 따른 에스테르 교환 반응 거동

  • 임경율;윤기종
    • Proceedings of the Korean Fiber Society Conference
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    • 1998.10a
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    • pp.5-8
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    • 1998
  • 폴리에스테르 공중합체의 합성에 이용될 수 있는 에스테르 교환 반응은 alcoholysis, acidolysis 및 transesterification 반응들에 의해 복합적으로 진행되며 이 때 각각의 반응 속도를 비교하여 보면 어느 한 쪽 분자쇄의 말단 알코올기가 다른 쪽 분자쇄의 에스테르기를 공격하는 alcoholysis 반응이 가장 빠르고 카르복실기가 에스테르를 공격하는 acidolysis 및 두 고분자 주쇄의 에스테르기 상호간에 발생하는 transesterification 반응들은 alcoholysis 반응에 비해 느린 것으로 알려져 있다. (중략)

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Modification of Palm Mid Fraction with Stearic Acid by Enzymatic Acidolysis Reaction (효소적 Acidolysis를 이용한 Stearic Acid 함유 팜중부유의 개질)

  • Jeon, Mi-Sun;Lee, Yun-Jeung;Kang, Ji-Hyun;Lee, Jeung-Hee;Lee, Ki-Teak
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.38 no.4
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    • pp.479-485
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    • 2009
  • The acidolysis was performed to produce structured lipid with palm mid fraction (PMF) and stearic acid for 7, 24, and 36 hr at $70^{\circ}C$. The reaction was catalyzed by lipozyme TLIM (immobilized lipase from Thermonyces lanuginosa, amount of 10% and 20% by weight of total substrates) in the shaking water bath. The reaction conditions for maximum incorporation of stearic acid on the structured lipid were obtained when molar ratio of PMF and stearic acid was 1:2; concentration of lipozyme TLIM was 20wt%; reaction temperature was $70^{\circ}C$; and reaction time was 36 hr. After reaction under this condition, incorporation of stearic acid in the structured lipid was obtained up to 36.3% while the major components of triacylglycerol were 1,2-dipalmitoyl-3-stearoylglycerol (PPS, 28.19 area%), 1-palmitoyl-2-oleoyl-3-stearoylglycerol (POS/PSO, 20.70 area%) and 1-palmitoyl-2,3-distearoylglycerol (PSS, 18.13 area%). However, the fatty acid composition at the sn-2 position suggested that the positional specificity of lipozyme TLIM was not observed due to the acyl migration.

Enzymatic Synthesis of Structured Lipids Containing Conjugated Linoleic Acid from Extracted Corn and Peanut Oil (추출된 옥수수유와 땅콩유로부터 Conjugated Linoleic Acid를 함유한 재구성지질의 효소적 합성 및 분석)

  • 김남숙;이기택
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.33 no.6
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    • pp.1000-1005
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    • 2004
  • Structured lipids (SLs) were synthesized by acidolysis of crude oils (corn and peanut oil) and conjugated linoleic acid (CLA) with a molar ratio of 1:3 (extracted oil:CLA) in a shaking water bath. The reaction was performed for various reaction time (1, 2, 3, 6 and 24 hr) at 55$^{\circ}C$ with 175 rpm catalyzed by sn -1,3 specific IM 60 lipase from Rhizomucor miehei. The content of the incorporated CLA increased with the prolonged reaction time, showing 7.5∼9.3 ㏖% in the synthesized SL triacylglycerol molecules from the extracted corn and peanut oil. However, total tocopherol content in SLs decreased up to about 20% compared to the content in extracted oils. Among the CLA isomers, 6.3∼7.5 ㏖% of cis 9,trans 11- and trans 10,cis 12-CLA known as physiologically active compounds are contained in corn and peanut SLs.

Reactive compatibilization of liquid crystalline polymer/ethylene-acrylic acid ionomer blends (액정 고분자/에틸렌-아크릴산 이오노머 블렌드의 반응상용화에 관한 연구)

  • Cruz, Heidy;Son, Younggon
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.16 no.5
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    • pp.3653-3659
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    • 2015
  • This paper describes the reactive compatibilization of blends of a wholly aromatic thermotropic copolyester liquid crystalline polymer (TLCP) with random copolymers of ethylene and acrylic acid (EAA) and their salts. Blends were prepared by melt mixing in an intensive batch mixer, and the formation of a graft copolymer due to acidolysis between the TLCP and the acrylic acid group of the ionomer was evaluated. Chemical reaction was assessed by torque measurement during melt mixing and by thermal analysis and morphological observation. The Na-salt of the EAA ionomers was especially effective at promoting a grafting reaction. The extent of reaction depended not only on the cation, but also composition of the ionomer and reaction time. The product of the grafting reaction between the TLCP and a sodium-neutralized ionomer proved to be an effective compatibilizer for TLCP and EAA ionomers.

Synthesis and Hydrogen-Bonded Supramolecular Assembly of trans-Dihydroxotin(IV) Tetrapyridylporphyrin Complexes

  • Jo, Hwa-Jin;Jung, Su-Hee;Kim, Hee-Joon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.12
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    • pp.1869-1873
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    • 2004
  • trans-Dihydroxo[5,10,15,20-tetrakis(n-pyridyl)porphyrinato]tin(IV) (n = 3 and 4) complexes have been synthesized and fully characterized. X-ray structural analysis of trans-dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]tin(IV) reveals that the supramolecular hydrogen bondings between the hydroxotin(IV) porphyrins and lattice water molecules form a hydrogen-bonded two-dimensional network. The hydrogen bonding mode between the tin(IV) porphyrins and the water molecules closely resembles that of the hydrogenbonded outer-sphere intermediate in the acidolysis of dihydroxotin(IV) porphyrins.

The Potential Energy Surface of BH5 and the Rate of the Hydrogen Scrambling

  • Kim, Kyung-Hyun;Kim, Yong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.24 no.6
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    • pp.763-770
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    • 2003
  • The $BH_5$ molecule, which is suggested as an intermediate of the acidolysis of $BH_4^-$, contains a weak two-electron-three-center bond and it requires extremely high-level of theories to calculate the energy and structure correctly. The structures and energies of $BH_5$ and the transition state for the hydrogen scrambling have been studied using recently developed multi-coefficient correlated quantum mechanical methods (MCCMs). The dissociation energies and the barrier heights agree very well with the previous results at the CCSD(T)/ TZ(3d1f1g, 2p1d) level. We have also calculated the potential energy curves for the dissociation of $BH_5$ to $BH_3$ and $H_2$. The lower levels of theory were unable to plot correct potential curves, whereas the MCCM methods give very good potential energy curves and requires much less computing resources than the CCSD(T)/ TZ(3d1f1g,2p1d) level. The potential energy of the $BH_5$ scrambling has been obtained by the multiconfiguration molecular mechanics algorithm (MCMM), and the rates are calculated using the variational transition state theory including multidimensional tunneling approximation. The rate constant at 300 K is 2.1 × $10^9s^{-1}$, and tunneling is very important.

Production of Lipase-catalyzed Structured Lipid from Olive Oil with Omega-3 Polyunsaturated Fatty Acids

  • Kahveci, Derya;Can, Ash;Ozcelik, Beraat
    • Food Science and Biotechnology
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    • v.18 no.1
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    • pp.79-83
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    • 2009
  • Acidolysis of olive oil with omega-3 (n-3) polyunsaturated fatty acids (PUFAs) was carried out to produce a structured lipid. Novozym $435^{(R)}$ from Candida antarctica was used as the biocatalyst. Response surface methodology (RSM) was used to determine optimum conditions for lipase-catalyzed enrichment of olive oil. Three factors, 5 levels, central composite design was used. The effects of incubation time, temperature, and substrate mole ratio on incorporation ratio (n-3 fatty acids/total fatty acids, %) were investigated. From the evaluation of response surface graphs, the optimal conditions for incorporation of long chain n-3 PUFAs into olive oil were $40-60^{\circ}C$ for temperature, 30-45 hr for reaction time, and 3:1-5:1 (n-3 fatty acids/olive oil) for substrate mole ratio. Experiments conducted under optimized conditions predicted by the model equation obtained from RSM yielded structured lipids with 50.8% n-3 PUFAs. This value agreed well with that predicted by the model. Oxidative stability tests showed that the product was more susceptible to oxidation than unmodified olive oil. Antioxidant addition improved the oxidative stability of the product.

Enzymatic Production of Structured Lipids from Capric Acid and Conjugated Linoleic Acid in Soybean Oil

  • Shin, Jung-Ah;Lee, Ki-Teak
    • Proceedings of the Korean Society of Postharvest Science and Technology of Agricultural Products Conference
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    • 2003.10a
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    • pp.164.1-164
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    • 2003
  • In this study, medium-chain fatty acid (MCFA) metabolized in the liver for quick energy and CLA exhibited biological activity were used for synthesis of structured lipids (SLs). SLs were synthesized by acidolysis of soybean oil, capric acid (C10:0) and CLA with Chirazyme L-2 lipase as biocatalysts. The effect of enzyme load (2, 4, 6, 8, 10% w/w substrates) was investigated. Production of SL (scale-up) was performed with a 1:2:2 molar ratio (oi1/C10:0/CLA) for 24 h at 55$^{\circ}C$ in a stirred batch reactor (420 rpm). The reaction was catalyzed by Chirazyme L-2 lipase (24.48g, 4% w/w substrates). The scale-up result showed that capric acid and total CLA were incorporated 4.9%, 4.1% (mole%), respectively, in soybean oil. Then, physio-chemical property and flavor characteristic of produced SL-soybean oil were analyzed. Therefore, SL-soybean oil containing C10:0 and CLA was successfully synthesized and may be beneficial in desirable food and nutritional applications.

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