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Journal of Polymer Science, Part A: Polymer Chemistry
Volumn 48, Issue 4, 2010, Pages 916-926
Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust, reusable, and environmentally benign initiating systems
Author keywords

Cationic polymerization; Heterogeneous polymerization; Living polymerization; Metal oxides; Poly(vinyl ethers)
Indexed keywords

1 ,4-DIOXANE; ACTIVE SITE; ADDED BASE; CATALYST SURFACES; CONTROLLED REACTIONS; ENVIRONMENTALLY BENIGN; ETHYL ACETATES; HETEROGENEOUS CATALYST; HETEROGENEOUS POLYMERIZATION; ISOBUTYL; LIVING CATIONIC POLYMERIZATION; METAL OXIDES; NARROW MOLECULAR WEIGHT DISTRIBUTIONS; POLY(VINYL ETHERS); POLYMERIZATION MECHANISMS; VINYL ETHERS; ZNO;
EID: 77956041757     PISSN: 0887624X     EISSN: 10990518     Source Type: Journal    
DOI: 10.1002/pola.23846     Document Type: Article
Times cited : (21)
References (57)
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    • 3 suggested that some oxidation occurred during the heat treatment, although the detailed mechanism was unclear.
    • 3 suggested that some oxidation occurred during the heat treatment, although the detailed mechanism was unclear.
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    • In the case of γ-Fe2O3, the amount of the catalyst had to be quite lower (0.3 mol, to IBVE) for the nice reactions than those used for the reactions with α-Fe2O3 and Fe3O4 2.6 mol, to IBVE, With larger amounts of γ-Fe2O3, such as 0.7 or 2.6 mol, to IBVE, the monomer conversion reached the plateau after some period and polymers with bimodal MWDs were produced. The polymers were composed of an uncontrolled higher MW part and a lower MW one deriving from long-lived species. Similar behavior was observed in polymerization with larger amounts of α-Fe 2O3.With6.5 mol% to IBVE, the reaction using α-Fe2O3 wasmuchslowerthanthatwith2. 6mol%andgavepolymers with bimodal MWDs. The results imply that the uncontrolled species were produced because of the higher activity deriving from the larger amounts of the catalysts. The smaller limi
    • 3) with larger surface area.
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    • The sharp peak shifted to the higher MW region with the progress of the reactions, which indicates the production of long-lived species even in the absence of an added base. This polymerization behavior and its mechanism are now under investigation
    • The sharp peak shifted to the higher MW region with the progress of the reactions, which indicates the production of long-lived species even in the absence of an added base. This polymerization behavior and its mechanism are now under investigation.
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    • For example, the Ga2O3 sample examined in that study (BET surface area: 21.0 m2/g) could adsorb 5.75 μmol/m2 of ammonia (see refs. 49, 50, From this value, we can calculate that the estimated amount of acidic sites of the Ga2O3 used for cationic polymerization in this study is about 0.45 mM, 0.0187 g (the used Ga2O 3) × 21.0 m2/g × 5.75 μmol/m2/5.0 mL the total of the reaction mixture, The actual amount of the active sites for cationic polymerization should be less than this estimate because the value of 5.75 μmol/m2 was obtained from the sum of all peaks showing various heats of adsorption, which correspond to different types of acidic sites with different strengths. Only a portion of the sites is considered to be active for cationic polymerization
    • 3) × 21.0 m2/g × 5.75 μmol/m2/5.0 mL (the total volume of the reaction mixture)]. The actual amount of the active sites for cationic polymerization should be less than this estimate because the value of 5.75 μmol/m2 was obtained from the sum of all peaks showing various heats of adsorption, which correspond to different types of acidic sites with different strengths. Only a portion of the sites is considered to be active for cationic polymerization.
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