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Preparation of flame-retarding poly(propylene carbonate)
Cyriac, Anish,Lee, Sang Hwan,Varghese, Jobi Kodiyan,Park, Ji Hae,Jeon, Jong Yeob,Kim, Seung Jin,Lee, Bun Yeoul Royal Society of Chemistry 2011 Green chemistry Vol.13 No.12
<P>A preparative method for a flame-retarding poly(propylene carbonate) (PPC) was demonstrated by employing diphenylphosphinic acid (Ph<SUB>2</SUB>P(O)(OH)), phenylphosphonic acid (PhP(O)(OH)<SUB>2</SUB>), or phosphoric acid (P(O)(OH)<SUB>3</SUB>) as a chain transfer agent in the immortal CO<SUB>2</SUB>/propylene oxide copolymerization catalyzed by a highly active catalyst, a cobalt(<SMALL>III</SMALL>) complex of a Salen-type ligand tethered by four quarternary ammonium salts (1). High turnover frequencies of 10 000–20 000 h<SUP>−1</SUP> (700–1300 g-polymer per g-cat·h) were maintained even in the presence of a large amount of the protic chain transfer agent ([–OH]/[1], 1600–200). Directly after the copolymerization using PhP(O)(OH)<SUB>2</SUB> as a chain transfer agent, thermoplastic polyurethane (TPU) was formed by adding a stoichiometric amount of toluene-2,4-diisocynate. The TPU also was not inflammable. Cone calorimeter studies showed that PPC itself and TPU prepared using PPC-diol emitted significantly less smoke while burning than common plastics, such as polystyrene.</P> <P>Graphic Abstract</P><P>Preparation of flame retarding polymers was demonstrated by using immortal CO<SUB>2</SUB>/propylene oxide copolymerization in the presence of phosphorous-containing chain transfer agents. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c1gc15722a'> </P>
Unusual coordination mode of tetradentate Schiff base cobalt(<small>III</small>) complexes
Cyriac, Anish,Jeon, Jong Yeob,Varghese, Jobi Kodiyan,Park, Ji Hae,Choi, Soo Young,Chung, Young Keun,Lee, Bun Yeoul The Royal Society of Chemistry 2012 Dalton Transactions Vol.41 No.5
<P>Contrary to the stereotype, Jacobsen's catalyst, chiral (salcy)Co(<SMALL>III</SMALL>)OAc adopts an unusual binding mode. The tetradentate {ONNO} ligand does not form a square plane but wraps cobalt in a <I>cis-β</I> fashion while acetate is chelating.</P> <P>Graphic Abstract</P><P>The Schiff base ligand in (salcy)Co(<SMALL>III</SMALL>)OAc does not form a square plane but wraps cobalt in a <I>cis-β</I> fashion. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2dt11871h'> </P>
Low-Energy Ionic Collisions at Molecular Solids
Cyriac, Jobin,Pradeep, T.,Kang, H.,Souda, R.,Cooks, R. G. American Chemical Society 2012 Chemical reviews Vol.112 No.10
<P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/chreay/2012/chreay.2012.112.issue-10/cr200384k/production/images/medium/cr-2011-00384k_0048.gif'></P>
Connection of polymer chains using diepoxide in CO<sub>2</sub>/propylene oxide copolymerizations
Cyriac, Anish,Lee, Sang Hwan,Lee, Bun Yeoul Royal Society of Chemistry 2011 Polymer chemistry Vol.2 No.4
<P>When a small amount of vinylcyclohexene dioxide ([diepoxide]/[cat] = 60, 0.14 w% propylene oxide) is additionally added in CO<SUB>2</SUB>/propylene oxide copolymerization catalyzed by a highly active catalyst, cobalt(<SMALL>III</SMALL>) complex of a Salen-type ligand tethered by four quaternary ammonium salts (2), some polymer chains are connected consequently resulting in an increased molecular weight of up to <I>M</I><SUB>w</SUB> = 606000 and broadened molecular weight distribution. The same chain-connecting process is also applicable in the presence of chain transfer agent, tricarballylic acid (C<SUB>3</SUB>H<SUB>5</SUB>(CO<SUB>2</SUB>H)<SUB>3</SUB>), 1,2,3,4-butanetetracarboxylic acid (C<SUB>4</SUB>H<SUB>6</SUB>(CO<SUB>2</SUB>H)<SUB>4</SUB>), or adipic acid (C<SUB>4</SUB>H<SUB>8</SUB>(CO<SUB>2</SUB>H)<SUB>2</SUB>), although a higher amount of diepoxide is needed. Gel permeation chromatography reveals multi-modal distributions along with a tail at a high molecular weight portion due to formation of the connected chains. The shape of the chain transfer agent varies the chain topology, but the rheological properties are not influenced by the topology change. The poly(propylene carbonate)-<I>block</I>-poly(ethylene glycol) copolymer, which is obtained by feeding poly(ethylene glycol)-OH as a chain transfer agent, becomes tough in the tensile properties and shows a high shear sensitivity in the rheological properties when some chains are connected using diepoxide.</P> <P>Graphic Abstract</P><P>When a small amount of dioxide is added in CO<SUB>2</SUB>/propylene oxide copolymerization, some polymer chains are consequently connected resulting in increased molecular weight and broadened molecular weight distribution. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0py00365d'> </P>
Ajitha Cyriac,Tarumay Ghoshal,Patel Ramkrushnbhai Shaileshbhai,Arun Chakraborty 한국해양과학기술원 2016 Ocean science journal Vol.51 No.1
The Bay of Bengal (BOB) is known to possess complex thermodynamics which show distinct seasonal patterns. Surface heat fluxes in the BOB are very much dependant on upper ocean heat exchanges and wind. Sensible heat flux (SHF) is also one among those fluxes that depends on air-sea temperature difference and wind. However, this study further proves that a strong relationship exists between barrier layer thickness (BLT) and SHF variability that has not been focussed on in earlier literatures. This study also investigates the seasonal as well as inter-annual variability of SHF and its relationship with BLT and sea surface temperature (SST) patterns in more detail with statistical analyses. It is found that both SST and BLT are responsible for the evolution of SHF signal in the BOB although their effects are spatially distributed. During the post monsoon period, freshwater induced enhanced BLT is more related to SHF than the summer time when effect of SST is found to be dominant. During Indian Ocean Dipole (IOD) years, the correlation between SHF and BLT in the eastern BOB is more pronounced compared to SHF and SST. The western BOB however is dominated by SST variations for the respective IOD phase which also contribute to SHF signals there. Northernmost BOB shows high standard deviation due to river discharge effects.
이산화탄소/프로필렌 옥사이드 공중합을 통한 저분자량 폴리(프로필렌 카보네이트)-폴리(에틸렌 글리콜) 블록 공중합체의 합성
이상환(Sang Hwan Lee),Anish Cyriac,전종엽(Jong Yeob Jeon),이분열(Bun Yeoul Lee) 한국청정기술학회 2011 청정기술 Vol.17 No.3
이산화탄소/프로필렌 옥사이드 공중합을 통하여 고분자 사슬 내에 친수성기와 소수성기가 공존하는 저분자량의 블록 공중합체를 합성하였다. 고활성의 촉매를 사용한 이산화탄소/프로필렌 옥사이드 공중합 반응에 단말기로 -OH기를 갖는 폴리(에틸렌 글리콜)(PEG)을 분자량 조절제로 투입하여 블록 공중합체를 합성하였다. 단말기 한쪽 끝에만 -OH기를 갖는 폴리(에틸렌 글리콜)을 투입하였을 때는 PEG-block-PPC (폴리(프로필렌 카보네이트)) 다이블록 공중합체가 얻어지고, 단말기 양쪽 끝 모두 -OH기를 갖는 폴리(에틸렌 글리콜)을 투입하였을 때는 PPC-block-PEG-block-PPC 트리블록 공중합체가 얻어진다. 제조된 블록 공중합체는 <SUP>1</SUP>H-NMR 스펙트럼을 통하여 구조 분석을 하였고 GPC를 통하여 분자량을 측정하였다. We synthesized low molecular-weight polymers bearing hydrophobic and hydrophilic parts in a chain through CO₂/propylene oxide copolymerization. When hydrophilic poly (ethylene glycol) bearing -OH group (s) at the end group (s) was added as a chain transfer agent in the CO₂/propylene oxide copolymerization catalyzed by a highly active catalyst, block polymers were formed. If poly (ethylene glycol) (PEG) bearing -OH group only at an end was fed, PEG-block-PPC diblock copolymer was obtained. When PEG bearing -OH group at both ends was fed, PPC-block-PEG-block-PPC triblock copolymer was obtained. We confirmed formation of block copolymers by <SUP>1</SUP>H-NMR spectroscopy and GPC studies.
Park, Ji Hae,Do, Seung Hyun,Cyriac, Anish,Yun, Hoseop,Lee, Bun Yeoul Royal Society of Chemistry 2010 Dalton Transactions Vol.39 No.41
<P>Directed <I>ortho</I>-lithiation of the lithium carbamates generated from tetrahydroquinoline or tetrahydroquinaldine enables one-step preparation of thiophene-fused and tetrahydroquinoline-linked cyclopentadienes [2-R<SUP>1</SUP>-3-R<SUP>2</SUP>-4,5-dimethyl-6-(2-R<SUP>3</SUP>-2,3,4,5-tetrahydroquinolin-8-yl)-4<I>H</I>-cyclopenta[<I>b</I>]thiophene (R<SUP>1</SUP>, R<SUP>2</SUP>, R<SUP>3</SUP> = H or methyl)], from which titanium(<SMALL>IV</SMALL>) and zirconium(<SMALL>IV</SMALL>) complexes are prepared. The molecular structures of Me<SUB>2</SUB>Ti-complexes (<B>12</B>, R<SUP>1</SUP> = R<SUP>2</SUP> = Me, R<SUP>3</SUP> = H; <B>14</B>, R<SUP>1</SUP> = R<SUP>2</SUP> = R<SUP>3</SUP> = Me) and Cl<SUB>2</SUB>Zr-complex (<B>17</B>, R<SUP>1</SUP> = R<SUP>2</SUP> = Me, R<SUP>3</SUP> = H) are determined by X-ray crystallography. The Me<SUB>2</SUB>Ti-complexes, <B>14</B> and <B>15</B> (R<SUP>1</SUP> = R<SUP>3</SUP> = Me, R<SUP>2</SUP> = H) show excellent activities (62 and 54 × 10<SUP>6</SUP> g/molTi·h) in ethylene/1-octene copolymerization, even when activated with small amount of MAO (Al/Ti = 1000).</P> <P>Graphic Abstract</P><P>Half-metallocenes of thiophene-fused and tetrahydroquinoline-linked cyclopentadienyl ligands are prepared in 2 steps, one of which exhibits an excellent activity in ethylene/1-octene copolymerization. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0dt00637h'> </P>