Copper(I) bromide/N-(n-Octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate using carbosilane dendritic initiators. Hovestad, N., J., Van Koten, G., Bon, S., A., & Haddleton, D., M. Macromolecules, 33(11):4048-4052, ACS Publications, 2000.
Copper(I) bromide/N-(n-Octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate using carbosilane dendritic initiators [link]Website  abstract   bibtex   
The zeroth (Si(CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br)(4)), 2, and first (Si(CH2)(3)Si((CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br))(3)(4)), 3, generation of 2-bromoisobutyryl functionalized carbosilane dendrimers have been successfully applied as initiators for the copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate. The overall rate of polymerization are comparable for the two dendritic initiators studied, 2 (3.4 x 10(-5) mol L-1 s(-1)) and 3 (4.8 x 10(-5) mol L-1 s(-1)) with the benzylic model compound C6H5CH2OC(O)CMe2Br (1) showing a lower rate of polymerization for both dendritic initiators, (7.3 x 10(-5) mol L-1 s(-1)) where [initiator sites] = 1.87 x 10(-2) mol L-1. We postulate that this is caused by initial intramolecular termination. The molecular weight distribution is less than 1.3 after 3 h reaction time. Initiator 3, however, produces star-star coupling throughout the polymerization. When the dendritic periphery is partialy functionalized (statistically two and six arms of the first generation dendrimer, respectively, 4 and 5) the control of the molecular weight distribution was lost (PDI > 3) for 4 as a result of too low of a value for [initiator site], i.e., 3.12 x 10(-3) mol L-1.
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 title = {Copper(I) bromide/N-(n-Octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate using carbosilane dendritic initiators},
 type = {article},
 year = {2000},
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 pages = {4048-4052},
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 publisher = {ACS Publications},
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 abstract = {The zeroth (Si(CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br)(4)), 2, and first (Si(CH2)(3)Si((CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br))(3)(4)), 3, generation of 2-bromoisobutyryl functionalized carbosilane dendrimers have been successfully applied as initiators for the copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate. The overall rate of polymerization are comparable for the two dendritic initiators studied, 2 (3.4 x 10(-5) mol L-1 s(-1)) and 3 (4.8 x 10(-5) mol L-1 s(-1)) with the benzylic model compound C6H5CH2OC(O)CMe2Br (1) showing a lower rate of polymerization for both dendritic initiators, (7.3 x 10(-5) mol L-1 s(-1)) where [initiator sites] = 1.87 x 10(-2) mol L-1. We postulate that this is caused by initial intramolecular termination. The molecular weight distribution is less than 1.3 after 3 h reaction time. Initiator 3, however, produces star-star coupling throughout the polymerization. When the dendritic periphery is partialy functionalized (statistically two and six arms of the first generation dendrimer, respectively, 4 and 5) the control of the molecular weight distribution was lost (PDI > 3) for 4 as a result of too low of a value for [initiator site], i.e., 3.12 x 10(-3) mol L-1.},
 bibtype = {article},
 author = {Hovestad, Neldes J. and Van Koten, Gerard and Bon, Stefan A.F. and Haddleton, David M.},
 journal = {Macromolecules},
 number = {11}
}

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