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Dynamics and structure of benzyl eth...
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Huang, Joseph Siang Huey.
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Dynamics and structure of benzyl ether dendritic macromolecules.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
Dynamics and structure of benzyl ether dendritic macromolecules./
作者:
Huang, Joseph Siang Huey.
面頁冊數:
332 p.
附註:
Source: Dissertation Abstracts International, Volume: 64-09, Section: B, page: 4493.
Contained By:
Dissertation Abstracts International64-09B.
標題:
Engineering, Chemical. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3104243
Dynamics and structure of benzyl ether dendritic macromolecules.
Huang, Joseph Siang Huey.
Dynamics and structure of benzyl ether dendritic macromolecules.
- 332 p.
Source: Dissertation Abstracts International, Volume: 64-09, Section: B, page: 4493.
Thesis (Ph.D.)--Stanford University, 2003.
Dendrimers are perfectly branched polymers that mimic the structure of trees. The purpose of this thesis was to study the solid state behavior of the dendrimers, their exact linear analogs, and dendrimer-based block copolymers. Understanding the solid state behavior of the dendritic macromolecules will lead to more applications that take advantage of the unique structure of the dendrimers.Subjects--Topical Terms:
1018531
Engineering, Chemical.
Dynamics and structure of benzyl ether dendritic macromolecules.
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Dendrimers are perfectly branched polymers that mimic the structure of trees. The purpose of this thesis was to study the solid state behavior of the dendrimers, their exact linear analogs, and dendrimer-based block copolymers. Understanding the solid state behavior of the dendritic macromolecules will lead to more applications that take advantage of the unique structure of the dendrimers.
520
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Natural-abundance <super>13</super>C solid-state NMR was used to study the dynamics of dendritic macromolecules through T<sub>1</sub>, T<sub>1ρ </sub>, and Dipolar Rotational Spin Echo (DRSE) experiments. From the combination of experiments, it was determined that the terminal ring units of the dendrimers were undergoing 180° ring flips. The most dramatic difference observed was between the crystalline and amorphous forms of the exact linear analog, where crystallinity greatly reduced the ring motion.
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In order to understand the role dendrimers play in crystallizable block copolymers, we synthesized a library of well-defined block copolymers composed of benzyl ether dendrimer and poly(ethylene glycol). These copolymers have lower melting temperature and lower heat of fusion changes, as observed by modulated DSC, with increasing weight percentage of dendrimer content. Cross-polarized optical microscopy showed more nucleation events in the crystallization of the block copolymers as the dendrimer block(s) gets bigger. These changes in the degree of crystallinity imply that the dendrimer blocks are acting as nucleation events, and the increasing difficulty in accommodating the large dendrimers into the growing crystal. Finally, when benzyl ether dendrimer content exceeds 50–55% of the total copolymer the crystallization of PEG is severely impaired and the copolymer is amorphous.
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Lastly, to separate the effects of the monomer from those of the <italic> structure</italic> of the block copolymers, we have synthesized benzyl ether dendrimer-linear architectural copolymers where the monomer units are the same. By modulated DSC we demonstrated that the crystallization of the linear block can be impeded by the globular block in much the same way as poly(ethylene glycol). Once again, the globular dendrimer disrupted the ability of the linear block to undergo crystallization when the dendrimer content is roughly 50% or above.
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