dc.contributor.advisor |
Jin, J |
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dc.contributor.author |
Yanaranop, Paam |
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dc.date.accessioned |
2016-11-28T20:37:13Z |
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dc.date.issued |
2016 |
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dc.identifier.uri |
http://hdl.handle.net/2292/31167 |
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dc.description |
Full text is available to authenticated members of The University of Auckland only. |
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dc.description.abstract |
Polymers of intrinsic microporosity (PIMs) are a unique class of solution processable porous materials which have rapidly developed in the past decade. Since their discovery in 2004, there has been a broad interest in many different areas of PIMs, including alternative PIM-1 synthetic route, post-synthesis modification, cross-linking, copolymers, gas separation membranes, gas sorbent materials, catalysis and much more. The research in this thesis is concerned with the development of novel PIM materials via post-synthesis modification for industrial use including molecular separation and gas storage. Specifically, this thesis is composed of three main components focusing on the syntheses of C-PIM and PIM-CONH2, and a novel method to chemically cross-link the PIM-CONH2 polymer. Recently, post-synthesis modified carboxylated PIMs (C-PIMs) have attracted considerable interest for cross-linking and gas separation. Originally in 2009, Guiver et al. reported the preparation of carboxylated PIMs via base hydrolysis. Since then, the method has become the “standard” procedure to obtain C-PIMs. However, Budd et al. later revisited the same reaction and suggested that resulting materials contain various ratios of amide to carboxylates. Recently, Shea et al. reported an alternative route to prepare the C-PIMs in acidic conditions. To further investigate Budd’s claim and prepare the pure C-PIMs, the author carried out a detailed investigation on the reaction mechanism, synthesis and characterisation of the resulting materials via both acid and base-catalysed pathways. Moreover, the pure amide PIM-1 (named as PIM-CONH2) was firstly synthesised by the post-synthesis modification method using hydrogen peroxide (H2O2) to fully confirm the amide characteristics within the PIMs material. The protocol enjoys mild reaction conditions, easy work-up procedure and high conversion yield (i.e. nearly 100% of the nitrile group converts to the corresponding amide group.) The fully-converted sample PIM-CONH2-24h possessed an apparent BET surface area of 527 m2g-1, which is among the highest ever reported in various post-synthesis modified PIM-1 materials. Another major limitation of a PIMs polymer is the decrease in separation performance over time. Cross-linking is a well-studied method to stop ageing as well as reduce plasticisation. Previously, several cross-linking methods have been reported for PIMs materials including thermal, UV, and chemical cross-linking. Herein, the author preliminarily investigated the new chemical cross-linking methods of PIM-1 and PIM-CONH2. |
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dc.publisher |
ResearchSpace@Auckland |
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dc.relation.ispartof |
Masters Thesis - University of Auckland |
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dc.relation.isreferencedby |
UoA99264895506102091 |
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dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. |
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dc.rights |
Restricted Item. Available to authenticated members of The University of Auckland. |
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dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
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dc.rights.uri |
http://creativecommons.org/licenses/by-nc-sa/3.0/nz/ |
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dc.title |
Post-synthesis Modification of Polymers of Intrinsic Microporosity (PIMs) |
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dc.type |
Thesis |
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thesis.degree.discipline |
Chemistry |
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thesis.degree.grantor |
The University of Auckland |
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thesis.degree.level |
Masters |
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dc.rights.holder |
Copyright: The author |
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pubs.elements-id |
547315 |
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pubs.record-created-at-source-date |
2016-11-29 |
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dc.identifier.wikidata |
Q112926952 |
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