{"id":{"repo_id":"durham","oai_identifier":"oai:etheses.durham.ac.uk:1403"},"canonical_url":"https://search.dev.ndltd.org/etd/durham/oai:etheses.durham.ac.uk:1403","repository":{"repo_id":"durham","name":"Durham University","base_url":"http://etheses.dur.ac.uk/cgi/oai2"},"display":{"title":"Synthesis and Characterisation of Tertiary Diallylalkylammonium Ionic Liquids and Their Metathesis","abstract":"A range of new tertiary diallylalkylammonium (t-DAAA) based Ionic Liquids (ILs) were successfully synthesised in good yields with cation alkyl substituent lengths of 5, 6, 9, 10, 11, 12 and 14 carbons. The counter anions used were [Cl]¯, [HSO4]¯, [H2PO4]¯, [BF4]¯, [PF6]¯, [TFSI]¯ and [TFA]¯. The ILs physico- and electro-chemical properties were evaluated in order to draw structure-property relationships between them. The thermal stability of the t-DAAA ILs depended heavily on the nature of the anion. The t-DAAA [TFSI]¯ ILs were the most stable reported in this work with decomposition temperatures of over 300°C. The thermal stability of the t-DAAA ILs generally increases in the order [H2PO4]¯ < [Cl]¯ ≈ [TFA]¯ < [PF6]¯ < [HSO4]¯ ≈ [BF4]¯ < [TFSI]¯. The majority of the t-DAAA ILs were solid or very viscous at ambient temperature. However, the [TFSI]¯ and [TFA]¯ based ILs displayed some very low viscosities with the lowest of 58 cP reported for diallylhexylammonium [TFA]¯. The electrochemical windows of the less viscous t-DAAA ILs compared well with those reported in literature for protic ammonium and aprotic imidazolium ILs. The most stable t-DAAA ILs were those based on the [TFSI]¯ anion which demonstrated electrochemical windows of between 4.9 and 5.2 V. ii Acyclic diene metathesis (ADMET) polymerisation produced cyclic products rather than the desired polymeric materials. Diallylhexylammonium [BF4]¯ and [PF6]¯ gave 100% conversion to cyclic products, whilst the conversion decreased to 46 and 25% for the diallyhexylammonium [TFSI]¯ and [HSO4]¯; 4% for [TFA]¯ and [Cl]¯ and 0% for [H2PO4]¯. Ring closing metathesis (RCM) reactions were performed in order to improve on the conversions obtained in the ADMET reactions. However, only moderate conversions (74-54%) to cyclic products were obtained for the diallylhexylammonium [BF4]¯, [PF6]¯ and [HSO4]¯ ILs, while [Cl]¯, [H2PO4]¯ and [TFA]¯ did not undergo any reaction.","abstract_html":"A range of new tertiary diallylalkylammonium (t-DAAA) based Ionic Liquids (ILs) were successfully synthesised in good yields with cation alkyl substituent lengths of 5, 6, 9, 10, 11, 12 and 14 carbons. The counter anions used were [Cl]¯, [HSO4]¯, [H2PO4]¯, [BF4]¯, [PF6]¯, [TFSI]¯ and [TFA]¯. The ILs physico- and electro-chemical properties were evaluated in order to draw structure-property relationships between them. The thermal stability of the t-DAAA ILs depended heavily on the nature of the anion. The t-DAAA [TFSI]¯ ILs were the most stable reported in this work with decomposition temperatures of over 300°C. The thermal stability of the t-DAAA ILs generally increases in the order [H2PO4]¯ &lt; [Cl]¯ ≈ [TFA]¯ &lt; [PF6]¯ &lt; [HSO4]¯ ≈ [BF4]¯ &lt; [TFSI]¯. The majority of the t-DAAA ILs were solid or very viscous at ambient temperature. However, the [TFSI]¯ and [TFA]¯ based ILs displayed some very low viscosities with the lowest of 58 cP reported for diallylhexylammonium [TFA]¯. The electrochemical windows of the less viscous t-DAAA ILs compared well with those reported in literature for protic ammonium and aprotic imidazolium ILs. The most stable t-DAAA ILs were those based on the [TFSI]¯ anion which demonstrated electrochemical windows of between 4.9 and 5.2 V. ii Acyclic diene metathesis (ADMET) polymerisation produced cyclic products rather than the desired polymeric materials. Diallylhexylammonium [BF4]¯ and [PF6]¯ gave 100% conversion to cyclic products, whilst the conversion decreased to 46 and 25% for the diallyhexylammonium [TFSI]¯ and [HSO4]¯; 4% for [TFA]¯ and [Cl]¯ and 0% for [H2PO4]¯. Ring closing metathesis (RCM) reactions were performed in order to improve on the conversions obtained in the ADMET reactions. However, only moderate conversions (74-54%) to cyclic products were obtained for the diallylhexylammonium [BF4]¯, [PF6]¯ and [HSO4]¯ ILs, while [Cl]¯, [H2PO4]¯ and [TFA]¯ did not undergo any reaction.","abstract_has_math":false,"creators":["Dean, Barry"],"institution":"Durham University","degree_name":"PhD","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011","date_published":"2011","updated_at":"2026-07-24T02:11:28Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Dean, Barry"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011"]},{"key":"dc:date.issued","label":"Date","values":["2011"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Chemistry, Department of"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["Durham University"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://etheses.durham.ac.uk/id/eprint/1403/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A range of new tertiary diallylalkylammonium (t-DAAA) based Ionic Liquids (ILs) were successfully synthesised in good yields with cation alkyl substituent lengths of 5, 6, 9, 10, 11, 12 and 14 carbons. The counter anions used were [Cl]¯, [HSO4]¯, [H2PO4]¯, [BF4]¯, [PF6]¯, [TFSI]¯ and [TFA]¯. The ILs physico- and electro-chemical properties were evaluated in order to draw structure-property relationships between them. The thermal stability of the t-DAAA ILs depended heavily on the nature of the anion. The t-DAAA [TFSI]¯ ILs were the most stable reported in this work with decomposition temperatures of over 300°C. The thermal stability of the t-DAAA ILs generally increases in the order [H2PO4]¯ < [Cl]¯ ≈ [TFA]¯ < [PF6]¯ < [HSO4]¯ ≈ [BF4]¯ < [TFSI]¯. The majority of the t-DAAA ILs were solid or very viscous at ambient temperature. However, the [TFSI]¯ and [TFA]¯ based ILs displayed some very low viscosities with the lowest of 58 cP reported for diallylhexylammonium [TFA]¯. The electrochemical windows of the less viscous t-DAAA ILs compared well with those reported in literature for protic ammonium and aprotic imidazolium ILs. The most stable t-DAAA ILs were those based on the [TFSI]¯ anion which demonstrated electrochemical windows of between 4.9 and 5.2 V. ii Acyclic diene metathesis (ADMET) polymerisation produced cyclic products rather than the desired polymeric materials. Diallylhexylammonium [BF4]¯ and [PF6]¯ gave 100% conversion to cyclic products, whilst the conversion decreased to 46 and 25% for the diallyhexylammonium [TFSI]¯ and [HSO4]¯; 4% for [TFA]¯ and [Cl]¯ and 0% for [H2PO4]¯. Ring closing metathesis (RCM) reactions were performed in order to improve on the conversions obtained in the ADMET reactions. However, only moderate conversions (74-54%) to cyclic products were obtained for the diallylhexylammonium [BF4]¯, [PF6]¯ and [HSO4]¯ ILs, while [Cl]¯, [H2PO4]¯ and [TFA]¯ did not undergo any reaction."]},{"key":"dc:title","label":"Title","values":["Synthesis and Characterisation of Tertiary Diallylalkylammonium Ionic Liquids and Their Metathesis"]}]}],"canonical_facts":{"dc:creator":["Dean, Barry"],"dc:date":["2011"],"dc:date.issued":["2011"],"dc:description.abstract":["A range of new tertiary diallylalkylammonium (t-DAAA) based Ionic Liquids (ILs) were successfully synthesised in good yields with cation alkyl substituent lengths of 5, 6, 9, 10, 11, 12 and 14 carbons. The counter anions used were [Cl]¯, [HSO4]¯, [H2PO4]¯, [BF4]¯, [PF6]¯, [TFSI]¯ and [TFA]¯. The ILs physico- and electro-chemical properties were evaluated in order to draw structure-property relationships between them. The thermal stability of the t-DAAA ILs depended heavily on the nature of the anion. The t-DAAA [TFSI]¯ ILs were the most stable reported in this work with decomposition temperatures of over 300°C. The thermal stability of the t-DAAA ILs generally increases in the order [H2PO4]¯ < [Cl]¯ ≈ [TFA]¯ < [PF6]¯ < [HSO4]¯ ≈ [BF4]¯ < [TFSI]¯. The majority of the t-DAAA ILs were solid or very viscous at ambient temperature. However, the [TFSI]¯ and [TFA]¯ based ILs displayed some very low viscosities with the lowest of 58 cP reported for diallylhexylammonium [TFA]¯. The electrochemical windows of the less viscous t-DAAA ILs compared well with those reported in literature for protic ammonium and aprotic imidazolium ILs. The most stable t-DAAA ILs were those based on the [TFSI]¯ anion which demonstrated electrochemical windows of between 4.9 and 5.2 V. ii Acyclic diene metathesis (ADMET) polymerisation produced cyclic products rather than the desired polymeric materials. Diallylhexylammonium [BF4]¯ and [PF6]¯ gave 100% conversion to cyclic products, whilst the conversion decreased to 46 and 25% for the diallyhexylammonium [TFSI]¯ and [HSO4]¯; 4% for [TFA]¯ and [Cl]¯ and 0% for [H2PO4]¯. Ring closing metathesis (RCM) reactions were performed in order to improve on the conversions obtained in the ADMET reactions. However, only moderate conversions (74-54%) to cyclic products were obtained for the diallylhexylammonium [BF4]¯, [PF6]¯ and [HSO4]¯ ILs, while [Cl]¯, [H2PO4]¯ and [TFA]¯ did not undergo any reaction."],"dc:publisher.department":["Chemistry, Department of"],"dc:publisher.institution":["Durham University"],"dc:relation.isreferencedby":["https://etheses.durham.ac.uk/id/eprint/1403/"],"dc:title":["Synthesis and Characterisation of Tertiary Diallylalkylammonium Ionic Liquids and Their Metathesis"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-24T02:11:28Z"}