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Living polymerization for the introd...
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Elkins, Casey Lynn.
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Living polymerization for the introduction of tailored hydrogen bonding.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
Living polymerization for the introduction of tailored hydrogen bonding./
作者:
Elkins, Casey Lynn.
面頁冊數:
311 p.
附註:
Source: Dissertation Abstracts International, Volume: 66-05, Section: B, page: 2608.
Contained By:
Dissertation Abstracts International66-05B.
標題:
Chemistry, Polymer. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3177332
ISBN:
0542165406
Living polymerization for the introduction of tailored hydrogen bonding.
Elkins, Casey Lynn.
Living polymerization for the introduction of tailored hydrogen bonding.
- 311 p.
Source: Dissertation Abstracts International, Volume: 66-05, Section: B, page: 2608.
Thesis (Ph.D.)--Virginia Polytechnic Institute and State University, 2005.
In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polymers with good molar mass control and narrow molar mass distributions were obtained and well-defined chain end functionality was observed. There was no observed effect on the polymer microstructure from the polar functionality in the initiator, with ∼92% 1,4- and 8% 3,4-enchainment observed in each case. Further investigation of the 3-[(N-benzyl-N-methyl)amino]-1-propyllithium initiated polyisoprenes proved that facile deprotection was not possible and residual catalyst was not removable from the polymer. However, polymers initiated with 3-(t-butyldimethylsilyloxy)-1-propyllithium were quantitatively hydrogenated and deprotected under relatively mild conditions to yield hydroxyl functional macromolecules in several architectures, including linear and star-shaped. Excellent conversion from arm polymer to star polymer was observed and well-defined macromolecules were obtained. Subsequently, a series of non-functional, hydroxyl functional, and 2-ureido-4[1H]-pyrimidone (UPy) chain end functional linear and star-shaped poly(ethylene-co-propylene)s were synthesized and characterized. The melt phase properties were investigated using melt rheology and the effect of macromolecular topology and multiple hydrogen bond functionality was investigated. Linear UPy functional poly(ethylene- co-propylene)s exhibited increased viscosity and shear thinning onset at lower frequencies than non-functional polymers of similar molar mass due to interaction of the multiple hydrogen bonding groups. Star-shaped UPy functional poly(ethylene-co-propylene)s showed inhibition to terminal flow and the absence of a zero shear viscosity in melt rheological characterization, indicative of a network like structure imparted from the multiple hydrogen bonding interactions.
ISBN: 0542165406Subjects--Topical Terms:
1018428
Chemistry, Polymer.
Living polymerization for the introduction of tailored hydrogen bonding.
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Source: Dissertation Abstracts International, Volume: 66-05, Section: B, page: 2608.
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In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polymers with good molar mass control and narrow molar mass distributions were obtained and well-defined chain end functionality was observed. There was no observed effect on the polymer microstructure from the polar functionality in the initiator, with ∼92% 1,4- and 8% 3,4-enchainment observed in each case. Further investigation of the 3-[(N-benzyl-N-methyl)amino]-1-propyllithium initiated polyisoprenes proved that facile deprotection was not possible and residual catalyst was not removable from the polymer. However, polymers initiated with 3-(t-butyldimethylsilyloxy)-1-propyllithium were quantitatively hydrogenated and deprotected under relatively mild conditions to yield hydroxyl functional macromolecules in several architectures, including linear and star-shaped. Excellent conversion from arm polymer to star polymer was observed and well-defined macromolecules were obtained. Subsequently, a series of non-functional, hydroxyl functional, and 2-ureido-4[1H]-pyrimidone (UPy) chain end functional linear and star-shaped poly(ethylene-co-propylene)s were synthesized and characterized. The melt phase properties were investigated using melt rheology and the effect of macromolecular topology and multiple hydrogen bond functionality was investigated. Linear UPy functional poly(ethylene- co-propylene)s exhibited increased viscosity and shear thinning onset at lower frequencies than non-functional polymers of similar molar mass due to interaction of the multiple hydrogen bonding groups. Star-shaped UPy functional poly(ethylene-co-propylene)s showed inhibition to terminal flow and the absence of a zero shear viscosity in melt rheological characterization, indicative of a network like structure imparted from the multiple hydrogen bonding interactions.
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In addition, the living anionic polymerization of D3 was controlled using the functionalized initiators 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium. (Abstract shortened by UMI.)
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