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Controlled synthesis of mesogenic st...
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Kasko, Andrea M.
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Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures.
Record Type:
Electronic resources : Monograph/item
Title/Author:
Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures./
Author:
Kasko, Andrea M.
Description:
205 p.
Notes:
Source: Dissertation Abstracts International, Volume: 65-12, Section: B, page: 6419.
Contained By:
Dissertation Abstracts International65-12B.
Subject:
Chemistry, Polymer. -
Online resource:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3156851
ISBN:
0496175300
Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures.
Kasko, Andrea M.
Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures.
- 205 p.
Source: Dissertation Abstracts International, Volume: 65-12, Section: B, page: 6419.
Thesis (Ph.D.)--The University of Akron, 2004.
The chain transfer to polymer constant, CP, for poly[11-(4 '-cyanophenyl-4'-phenoxy)undecyl acrylate] was measured using model compounds that mimic one repeat unit of polymer, and an oligomer synthesized by ATRP. The measured chain transfer constant, CP = 5.8 x 10-3, was used to calculate the extent of branching in a free-radically synthesized poly[11-(4 '-cyanophenyl-4'-phenoxy)undecyl acrylate]. The architecture is not linear, as is typically drawn in chemical schemes, but rather a mixture of linear and branched structures. This mixture of structures may be the cause of the broad phase transitions exhibited by side-chain liquid crystalline polymers typically prepared by conventional radical polymerizations.
ISBN: 0496175300Subjects--Topical Terms:
1018428
Chemistry, Polymer.
Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures.
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Controlled synthesis of mesogenic star polymers and their miscibility with polymers with other architectures.
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205 p.
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Source: Dissertation Abstracts International, Volume: 65-12, Section: B, page: 6419.
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Adviser: Coleen Pugh.
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Thesis (Ph.D.)--The University of Akron, 2004.
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The chain transfer to polymer constant, CP, for poly[11-(4 '-cyanophenyl-4'-phenoxy)undecyl acrylate] was measured using model compounds that mimic one repeat unit of polymer, and an oligomer synthesized by ATRP. The measured chain transfer constant, CP = 5.8 x 10-3, was used to calculate the extent of branching in a free-radically synthesized poly[11-(4 '-cyanophenyl-4'-phenoxy)undecyl acrylate]. The architecture is not linear, as is typically drawn in chemical schemes, but rather a mixture of linear and branched structures. This mixture of structures may be the cause of the broad phase transitions exhibited by side-chain liquid crystalline polymers typically prepared by conventional radical polymerizations.
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We synthesized tri- and hexafunctional initiators, 2,4,6-tris(4 '-methyl(2″-bromopropionate)phenoxymethyl)mesitylene and 1,2,3,4,5,6-hexa(4'-methyl (2 ″-bromopropionate)phenoxymethyl)benzene for the atom transfer radical polymerization of 11-(4'-cyanophenyl-4 ″-phenoxy)undecyl acrylate. Three-arm star polymers with 14--87 repeat units and six-arm star polymers with 3--112 repeat units, based on gel permeation chromatography relative to poly(styrene) (GPC-PSty), were obtained after fractionation. The absolute molecular weight, size and shape of these polymers, along with previously synthesized linear, three-arm star and comb poly[11-(4'-cyanophenyl-4″-phenoxy)undecyl acrylate] were characterized by light scattering in methylene chloride, tetrahydrofuran and chloroform. Methylene chloride is the best solvent for this system, causing little or no aggregation. Aggregation generally increases with increasing branching and decreasing solvent polarity. The error in GPC-PSty-determined molecular weights increases with increasing branching. Poly[11-(4' -cyanophenyl-4″-phenoxy)undecyl acrylate] prepared by a conventional radical polymerization has solution behavior intermediate to the linear and three arm star polymers.
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The thermotropic behavior of the three- and six-arm star poly[11-(4 '-cyanophenyl-4″-phenoxy)undecyl acrylate]s was analyzed by differential scanning calorimetry (DSC), and compared to that of the other architectures. The transition temperatures for both the three- and six-arm star polymers are significantly lower than those for the other architectures at low molecular weights, indicating limited miscibility of the core of the star with the mesogenic side-chain. However, the transition temperatures of both the three-arm star and six-arm star polymers extrapolate to infinite molecular weight transition temperatures comparable to the other architectures. The breadth of the phase transition of binary blends of topological isomers of poly[11-(4'-cyanophenyl-4″-phenoxy)undecyl acrylate]s varies roughly linearly with the difference in end-group density of the components.
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School code: 0003.
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3156851
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