• Title/Summary/Keyword: Polymer-supported ligand

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Ring-Opening Polymerization of $\varepsilon$-Caprolactone and Cyclohexene Oxide Initiated by Aluminum $\beta$-Ketoamino Complexes: Steric and Electronic Effect of 3-Position Substituents of the Ligands

  • Liu, Binyuan;Li, Haiqing;Ha, Chang-Sik;Kim, Il;Yan, Weidong
    • Macromolecular Research
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    • v.16 no.5
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    • pp.441-445
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    • 2008
  • A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

Oxidative Decomposition of 2, 4, 6-Trichlorophenol Catalyzed by Polymer Supported Metalloporphyins (고분자결합 금속포르피린을 촉매로 한 2, 4, 6-트리클로로페놀의 산화 분해반응)

  • Park, Hye-Ok;Lee, Bo-Young;Rhee Paeng, Insook
    • Analytical Science and Technology
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    • v.14 no.1
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    • pp.72-79
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    • 2001
  • Oxidative decomposition of 2, 4, 6-trichlorophenol(TCP) was studied in aqueous solution. Iron and manganese protoporphyrin [or tetrakis(p-carboxyphenylporphyrin)] and their polymer supported derivatives were used as catalysts, and $KHSO_5$ and tert-butyldroperoxide(TBHP) as oxidants. Metalloporphyrin itself shows very poor catalytic activity in oxidative decomposition of TCP with oxidant. However, very high catalytic activity was observed when metalloporphyrin was chemically bound to newly synthesized polymers or XAD2 resin. Additionally, it revealed much higher catalytic activity in the presence of water-soluble polymers having a electron-donating axial ligand such as pyridine and immidazole. Maleic acid and chloromaleic acid were found in the resulting solution by ESI-MS. Especially, XAD2-supported metalloporphyrins can be reused as catalysts due to insolubility to solvent, and stability against oxidant.

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Highly active and trans-1,4-specific polymerization of 1,3-butadiene catalyzed by bis(benzimidazolyl)amine chromium complexes activated with methylaluminoxane (메틸알루미녹산으로 활성화시킨 고활성 bis(benzimidazolyl)amine 크롬 착물을 이용한 부타디엔 중합에 의한 트랜스 폴리부타디엔 제조)

  • Moon, Byeong Kyu;Song, Ga Young;Zhang, Lin;Shin, Jin Young;Chang, Hyuk Chul;Shim, Sang Eun;Yun, Ju Ho;Kim, Il
    • Elastomers and Composites
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    • v.48 no.1
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    • pp.61-66
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    • 2013
  • A family of Cr(III) complexes supported on tridentate dibenzimidazolyl ligands having a general formula: $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [where Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn (3c)] have been synthesized and utilized them for the trans-1,4-specific polymerizations of 1,3-butadiene (BD), activated with methylalumoxane (MAO). The activity of BD polymerizations was sensitive to the type of ligand on the Cr metal, so that the activity decreases in the order of 3a > 3c > 3b. All the catalysts combined with MAO yielded polybutadienes with perfect trans-1,4 structure with moderate molecular weight.

Preparation of (n-BuCp)2ZrCl2 Catalyst Supported on SiO2/MgCl2 Binary Support and its Ethylene-1-hexene Copolymerization (SiO2/MgCl2 이원 담체에 담지된 (n-BuCp)2ZrCl2 합성과 에틸렌-1-헥센 공중합)

  • Carino, Ann Charise;Park, Sang Jun;Ko, Young Soo
    • Applied Chemistry for Engineering
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    • v.29 no.4
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    • pp.461-467
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    • 2018
  • In this study, $(n-BuCp)_2ZrCl_2$, was supported on $SiO_2/MgCl_2$ binary support. Before supporting the catalyst, the $SiO_2/MgCl_2$ binary support was surface treated with three different alkyl aluminum compound, namely trimethylaluminum, triethylaluminum, and ethylaluminum sesquichloride. The synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts were used for the copolymerization of ethylene and 1-hexene. Their catalytic properties and performances were analyzed through BET, XPS analysis, ICP-AES analysis, and FE-SEM. While the resulting copolymers were analyzed through DSC analysis, GPC analysis, 13C-NMR analysis, and FE-SEM. The analysis of synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts showed that the Zr content of these catalysts is relatively lower compared to that of the catalyst supported on $SiO_2$. This could be attributed to the reduction in the surface area of $SiO_2$ due to the presence of recrystallized $MgCl_2$ and alkyl aluminum. Furthermore, they exhibited a better copolymerization activity compared to that of $SiO_2$ supported catalyst, particularly the EASC-surface treated binary support, which has the highest activity of 1.9 kg PE/($mmol-Zr^*hr$) because EASC acts as a strong Lewis acid. It could also be observed that the larger the ligand of alkyl aluminum used, the rougher the particle surface of the resulting polymer.