Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod−Coil Block Copolymers
A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI < 1.1) were synthesized using Siegrist polycondensation and anionic polymerizations followed by “click” chemistry. Alkyne-terminated DEH-PPV and azido-terminated P...
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| Veröffentlicht in: | Macromolecules 2009-06, Vol.42 (12), p.4208-4219 |
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| creator | Ho, Chun-Chih Lee, Yi-Huan Dai, Chi-An Segalman, Rachel A Su, Wei-Fang |
| description | A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI < 1.1) were synthesized using Siegrist polycondensation and anionic polymerizations followed by “click” chemistry. Alkyne-terminated DEH-PPV and azido-terminated PMMA were synthesized first, and then the two functionalized polymers underwent 1,3-cycloaddition reaction to obtain copolymers. Both the conversion of the end-functionalization of the homopolymers and the yield of the “click” reaction were higher than 98% as determined by 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, this molecule offers new insight into the competition between rod−rod and rod−coil interactions that occurs in the system. The DEH-PPV rods are organized as a monolayer that is inclined with the lamellar normal (smectic C) for the copolymers containing low volume fraction of PMMA coil ( |
| doi_str_mv | 10.1021/ma802551v |
| format | Article |
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Alkyne-terminated DEH-PPV and azido-terminated PMMA were synthesized first, and then the two functionalized polymers underwent 1,3-cycloaddition reaction to obtain copolymers. Both the conversion of the end-functionalization of the homopolymers and the yield of the “click” reaction were higher than 98% as determined by 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, this molecule offers new insight into the competition between rod−rod and rod−coil interactions that occurs in the system. The DEH-PPV rods are organized as a monolayer that is inclined with the lamellar normal (smectic C) for the copolymers containing low volume fraction of PMMA coil (<54%). However, as the coil fraction increases, the strips containing DEH-PPV pack into hexagonal lattice. In contrast to previous work which demonstrated similar morphologies, the sequence of reversible liquid crystalline and microphase phase transitions is altered as a result of the increased block segregation. Upon heating, the low coil fraction copolymers exhibit a series of clear transitions of smectic−lamellar to amorphous−lamellar to disordered structures. In high coil fraction copolymers, the transitions between smectic−hexagonal to amorphous−hexagonal and smectic−hexagonal to disorder structures could not be clearly differentiated. The order-to-disorder temperature (ODT) decreases slowly with increasing coil fraction while the smectic-to-isotropic transition (SI) temperature stays relatively unchanged. The steady SI temperature suggests that the strong rod−rod interaction keeps the liquid crystalline rod in the nanodomain structure regardless of the amount of coil segment in the copolymers.</description><identifier>ISSN: 0024-9297</identifier><identifier>EISSN: 1520-5835</identifier><identifier>DOI: 10.1021/ma802551v</identifier><identifier>CODEN: MAMOBX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Applied sciences ; Exact sciences and technology ; Organic polymers ; Physicochemistry of polymers ; Polymers with particular structures ; Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><ispartof>Macromolecules, 2009-06, Vol.42 (12), p.4208-4219</ispartof><rights>Copyright © 2009 American Chemical Society</rights><rights>2009 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a355t-743c53c88ee459920a46809851355209a799b6260b9d2b7e7a798e272d3faa213</citedby><cites>FETCH-LOGICAL-a355t-743c53c88ee459920a46809851355209a799b6260b9d2b7e7a798e272d3faa213</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ma802551v$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ma802551v$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=21676969$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Ho, Chun-Chih</creatorcontrib><creatorcontrib>Lee, Yi-Huan</creatorcontrib><creatorcontrib>Dai, Chi-An</creatorcontrib><creatorcontrib>Segalman, Rachel A</creatorcontrib><creatorcontrib>Su, Wei-Fang</creatorcontrib><title>Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod−Coil Block Copolymers</title><title>Macromolecules</title><addtitle>Macromolecules</addtitle><description>A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI < 1.1) were synthesized using Siegrist polycondensation and anionic polymerizations followed by “click” chemistry. Alkyne-terminated DEH-PPV and azido-terminated PMMA were synthesized first, and then the two functionalized polymers underwent 1,3-cycloaddition reaction to obtain copolymers. Both the conversion of the end-functionalization of the homopolymers and the yield of the “click” reaction were higher than 98% as determined by 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, this molecule offers new insight into the competition between rod−rod and rod−coil interactions that occurs in the system. The DEH-PPV rods are organized as a monolayer that is inclined with the lamellar normal (smectic C) for the copolymers containing low volume fraction of PMMA coil (<54%). However, as the coil fraction increases, the strips containing DEH-PPV pack into hexagonal lattice. In contrast to previous work which demonstrated similar morphologies, the sequence of reversible liquid crystalline and microphase phase transitions is altered as a result of the increased block segregation. Upon heating, the low coil fraction copolymers exhibit a series of clear transitions of smectic−lamellar to amorphous−lamellar to disordered structures. In high coil fraction copolymers, the transitions between smectic−hexagonal to amorphous−hexagonal and smectic−hexagonal to disorder structures could not be clearly differentiated. The order-to-disorder temperature (ODT) decreases slowly with increasing coil fraction while the smectic-to-isotropic transition (SI) temperature stays relatively unchanged. The steady SI temperature suggests that the strong rod−rod interaction keeps the liquid crystalline rod in the nanodomain structure regardless of the amount of coil segment in the copolymers.</description><subject>Applied sciences</subject><subject>Exact sciences and technology</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>Polymers with particular structures</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><issn>0024-9297</issn><issn>1520-5835</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNptkL1OwzAURi0EEqUw8AZekOhgsJ04iccS8SdVAlGYI8dxlBQnjuxQ1RsjM4_Ik5BQVBamI9177ifdD4BTgi8IpuSyEQmmjJH1HpgQRjFiScD2wQRjGiJOeXwIjpxbYUwIC4MJeF_6tq-Uqx0UbQGXSpdo7pxqcu2hKeGj0f68qFVfeV2pjddm41GHukq1XqtWrestZyhH3eg2PyocIaT1WvRqBp9M8fXxmZpawytt5CtMzSg3yrpjcFAK7dTJL6fg5eb6Ob1Di4fb-3S-QCJgrEdxGEgWyCRRKmScUyzCKME8YWRYU8xFzHke0QjnvKB5rOJhkCga0yIohaAkmILZNlda45xVZdbZuhHWZwRnY3XZrrrBPdu6nXBS6NKKVtZud0BJFEc84n-ekC5bmTfbDh_8k_cNbQp83g</recordid><startdate>20090623</startdate><enddate>20090623</enddate><creator>Ho, Chun-Chih</creator><creator>Lee, Yi-Huan</creator><creator>Dai, Chi-An</creator><creator>Segalman, Rachel A</creator><creator>Su, Wei-Fang</creator><general>American Chemical Society</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20090623</creationdate><title>Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod−Coil Block Copolymers</title><author>Ho, Chun-Chih ; Lee, Yi-Huan ; Dai, Chi-An ; Segalman, Rachel A ; Su, Wei-Fang</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a355t-743c53c88ee459920a46809851355209a799b6260b9d2b7e7a798e272d3faa213</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Applied sciences</topic><topic>Exact sciences and technology</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>Polymers with particular structures</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ho, Chun-Chih</creatorcontrib><creatorcontrib>Lee, Yi-Huan</creatorcontrib><creatorcontrib>Dai, Chi-An</creatorcontrib><creatorcontrib>Segalman, Rachel A</creatorcontrib><creatorcontrib>Su, Wei-Fang</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>Macromolecules</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ho, Chun-Chih</au><au>Lee, Yi-Huan</au><au>Dai, Chi-An</au><au>Segalman, Rachel A</au><au>Su, Wei-Fang</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod−Coil Block Copolymers</atitle><jtitle>Macromolecules</jtitle><addtitle>Macromolecules</addtitle><date>2009-06-23</date><risdate>2009</risdate><volume>42</volume><issue>12</issue><spage>4208</spage><epage>4219</epage><pages>4208-4219</pages><issn>0024-9297</issn><eissn>1520-5835</eissn><coden>MAMOBX</coden><abstract>A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI < 1.1) were synthesized using Siegrist polycondensation and anionic polymerizations followed by “click” chemistry. Alkyne-terminated DEH-PPV and azido-terminated PMMA were synthesized first, and then the two functionalized polymers underwent 1,3-cycloaddition reaction to obtain copolymers. Both the conversion of the end-functionalization of the homopolymers and the yield of the “click” reaction were higher than 98% as determined by 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, this molecule offers new insight into the competition between rod−rod and rod−coil interactions that occurs in the system. The DEH-PPV rods are organized as a monolayer that is inclined with the lamellar normal (smectic C) for the copolymers containing low volume fraction of PMMA coil (<54%). However, as the coil fraction increases, the strips containing DEH-PPV pack into hexagonal lattice. In contrast to previous work which demonstrated similar morphologies, the sequence of reversible liquid crystalline and microphase phase transitions is altered as a result of the increased block segregation. Upon heating, the low coil fraction copolymers exhibit a series of clear transitions of smectic−lamellar to amorphous−lamellar to disordered structures. In high coil fraction copolymers, the transitions between smectic−hexagonal to amorphous−hexagonal and smectic−hexagonal to disorder structures could not be clearly differentiated. The order-to-disorder temperature (ODT) decreases slowly with increasing coil fraction while the smectic-to-isotropic transition (SI) temperature stays relatively unchanged. The steady SI temperature suggests that the strong rod−rod interaction keeps the liquid crystalline rod in the nanodomain structure regardless of the amount of coil segment in the copolymers.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ma802551v</doi><tpages>12</tpages></addata></record> |
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| subjects | Applied sciences Exact sciences and technology Organic polymers Physicochemistry of polymers Polymers with particular structures Preparation, kinetics, thermodynamics, mechanism and catalysts |
| title | Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod−Coil Block Copolymers |
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