{"id":{"repo_id":"durham","oai_identifier":"oai:etheses.durham.ac.uk:678"},"canonical_url":"https://search.dev.ndltd.org/etd/durham/oai:etheses.durham.ac.uk:678","repository":{"repo_id":"durham","name":"Durham University","base_url":"http://etheses.dur.ac.uk/cgi/oai2"},"display":{"title":"Synthesis and Kinetic Studies on Palladium Hydride-Initiated Vinyl Polymerisation of Functionalised Norbornenes","abstract":"Chapter I provides a summary of the vinyl polymerisation of norbornenes and their functionalised derivatives, using palladium-based initiators. The concept of photolithography is introduced along with discussion of hexafluoropropanol-(HFP) functionalised norbornene derivatives that provide the basis for the work described in this thesis. In Chapter II, the synthesis of a series of HFP-functionalised monomers of the type NB(CH2)nC(CF3)2OH (n = 1-2) and NB(CH2)nOCH2C(CF3)2OH (n = 0-6) is described. The monomers prepared differ in the number of methylene units (n) separating the HFP-functionality from the norbornene skeleton, which has previously been shown to have an influence upon polymerisation rate. The series of palladium hydride initiator complexes [Pd(H)(MeCN)(PCy3)2][X] (anion X = BF4, PF6, SbF6, I and B(C6F5)4) were also prepared with a view to determining the effect of the anion on polymerisation rate. The in-depth study of the stability and reactivity of the discrete complex [PdH(MeCN)(PCy3)2][B(C6F5)4] (Pd1388) is examined in Chapter III. The complex Pd1388 is shown to decompose in chlorinated solvents at 70 °C to form PdCl2(PCy3)2 and two further species, b and c that, despite extensive efforts, could not be identified. Both Pd1388 itself and Pd1388 in its decomposed form (i.e. the mixture of PdCl2(PCy3)2, b and c) are able to act as pro-initiator systems in the polymerisation of exo-NBCH2OCH2C(CF3)2OH (SX1). The kinetics of these polymerisation reactions are explored in detail and a kinetic model is proposed, which accurately describes the overall observed polymerisation rate. In Chapter IV the kinetic model was extended to the study of pure exo- and pure endo-HFP-functionalised norbornenes, with the model proving to be an excellent fit to experimental data for monomer consumption. An increase in the value of n is shown to produce a corresponding enhancement of polymerisation rate. An examination of the polymerisation of HFP-functionalised norbornenes using GPC as function of time is also described. High molecular weight material is formed at low conversion (<35%) with a reduction in molecular weight observed during the first 30 minutes of the reaction to yield a polymer of peak average molecular weight ~20,000 Daltons and low PDI (<1.4). In Chapter V, the kinetic model is further extended to the study of mixtures of endo- and exo-HFP-functionalised norbornenes (n = 0-6). As in the case of pure isomers, an increase in the value of n leads to an enhancement in overall polymerisation rate. Finally, the polymerisation of endo-/exo-NBCH2C(CF3)2OH (SXN4) is explored using initiators containing different counter anions (prepared in Chapter II) in order to determine the effect of the anion on polymerisation rate.","abstract_html":"Chapter I provides a summary of the vinyl polymerisation of norbornenes and their functionalised derivatives, using palladium-based initiators. The concept of photolithography is introduced along with discussion of hexafluoropropanol-(HFP) functionalised norbornene derivatives that provide the basis for the work described in this thesis. In Chapter II, the synthesis of a series of HFP-functionalised monomers of the type NB(CH2)nC(CF3)2OH (n = 1-2) and NB(CH2)nOCH2C(CF3)2OH (n = 0-6) is described. The monomers prepared differ in the number of methylene units (n) separating the HFP-functionality from the norbornene skeleton, which has previously been shown to have an influence upon polymerisation rate. The series of palladium hydride initiator complexes [Pd(H)(MeCN)(PCy3)2][X] (anion X = BF4, PF6, SbF6, I and B(C6F5)4) were also prepared with a view to determining the effect of the anion on polymerisation rate. The in-depth study of the stability and reactivity of the discrete complex [PdH(MeCN)(PCy3)2][B(C6F5)4] (Pd1388) is examined in Chapter III. The complex Pd1388 is shown to decompose in chlorinated solvents at 70 °C to form PdCl2(PCy3)2 and two further species, b and c that, despite extensive efforts, could not be identified. Both Pd1388 itself and Pd1388 in its decomposed form (i.e. the mixture of PdCl2(PCy3)2, b and c) are able to act as pro-initiator systems in the polymerisation of exo-NBCH2OCH2C(CF3)2OH (SX1). The kinetics of these polymerisation reactions are explored in detail and a kinetic model is proposed, which accurately describes the overall observed polymerisation rate. In Chapter IV the kinetic model was extended to the study of pure exo- and pure endo-HFP-functionalised norbornenes, with the model proving to be an excellent fit to experimental data for monomer consumption. An increase in the value of n is shown to produce a corresponding enhancement of polymerisation rate. An examination of the polymerisation of HFP-functionalised norbornenes using GPC as function of time is also described. High molecular weight material is formed at low conversion (&lt;35%) with a reduction in molecular weight observed during the first 30 minutes of the reaction to yield a polymer of peak average molecular weight ~20,000 Daltons and low PDI (&lt;1.4). In Chapter V, the kinetic model is further extended to the study of mixtures of endo- and exo-HFP-functionalised norbornenes (n = 0-6). As in the case of pure isomers, an increase in the value of n leads to an enhancement in overall polymerisation rate. Finally, the polymerisation of endo-/exo-NBCH2C(CF3)2OH (SXN4) is explored using initiators containing different counter anions (prepared in Chapter II) in order to determine the effect of the anion on polymerisation rate.","abstract_has_math":false,"creators":["Donlon, Lynn"],"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":"2026-07-24T02:11:12Z","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":["Donlon, Lynn"]}]},{"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/678/"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://etheses.durham.ac.uk/id/eprint/678/1/Lynn_Donlon_Ph.D_Thesis_2011.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Chapter I provides a summary of the vinyl polymerisation of norbornenes and their functionalised derivatives, using palladium-based initiators. The concept of photolithography is introduced along with discussion of hexafluoropropanol-(HFP) functionalised norbornene derivatives that provide the basis for the work described in this thesis. In Chapter II, the synthesis of a series of HFP-functionalised monomers of the type NB(CH2)nC(CF3)2OH (n = 1-2) and NB(CH2)nOCH2C(CF3)2OH (n = 0-6) is described. The monomers prepared differ in the number of methylene units (n) separating the HFP-functionality from the norbornene skeleton, which has previously been shown to have an influence upon polymerisation rate. The series of palladium hydride initiator complexes [Pd(H)(MeCN)(PCy3)2][X] (anion X = BF4, PF6, SbF6, I and B(C6F5)4) were also prepared with a view to determining the effect of the anion on polymerisation rate. The in-depth study of the stability and reactivity of the discrete complex [PdH(MeCN)(PCy3)2][B(C6F5)4] (Pd1388) is examined in Chapter III. The complex Pd1388 is shown to decompose in chlorinated solvents at 70 °C to form PdCl2(PCy3)2 and two further species, b and c that, despite extensive efforts, could not be identified. Both Pd1388 itself and Pd1388 in its decomposed form (i.e. the mixture of PdCl2(PCy3)2, b and c) are able to act as pro-initiator systems in the polymerisation of exo-NBCH2OCH2C(CF3)2OH (SX1). The kinetics of these polymerisation reactions are explored in detail and a kinetic model is proposed, which accurately describes the overall observed polymerisation rate. In Chapter IV the kinetic model was extended to the study of pure exo- and pure endo-HFP-functionalised norbornenes, with the model proving to be an excellent fit to experimental data for monomer consumption. An increase in the value of n is shown to produce a corresponding enhancement of polymerisation rate. An examination of the polymerisation of HFP-functionalised norbornenes using GPC as function of time is also described. High molecular weight material is formed at low conversion (<35%) with a reduction in molecular weight observed during the first 30 minutes of the reaction to yield a polymer of peak average molecular weight ~20,000 Daltons and low PDI (<1.4). In Chapter V, the kinetic model is further extended to the study of mixtures of endo- and exo-HFP-functionalised norbornenes (n = 0-6). As in the case of pure isomers, an increase in the value of n leads to an enhancement in overall polymerisation rate. Finally, the polymerisation of endo-/exo-NBCH2C(CF3)2OH (SXN4) is explored using initiators containing different counter anions (prepared in Chapter II) in order to determine the effect of the anion on polymerisation rate."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["Synthesis and Kinetic Studies on Palladium Hydride-Initiated Vinyl Polymerisation of Functionalised Norbornenes"]}]}],"canonical_facts":{"dc:creator":["Donlon, Lynn"],"dc:date":["2011"],"dc:date.issued":["2011"],"dc:description.abstract":["Chapter I provides a summary of the vinyl polymerisation of norbornenes and their functionalised derivatives, using palladium-based initiators. The concept of photolithography is introduced along with discussion of hexafluoropropanol-(HFP) functionalised norbornene derivatives that provide the basis for the work described in this thesis. In Chapter II, the synthesis of a series of HFP-functionalised monomers of the type NB(CH2)nC(CF3)2OH (n = 1-2) and NB(CH2)nOCH2C(CF3)2OH (n = 0-6) is described. The monomers prepared differ in the number of methylene units (n) separating the HFP-functionality from the norbornene skeleton, which has previously been shown to have an influence upon polymerisation rate. The series of palladium hydride initiator complexes [Pd(H)(MeCN)(PCy3)2][X] (anion X = BF4, PF6, SbF6, I and B(C6F5)4) were also prepared with a view to determining the effect of the anion on polymerisation rate. The in-depth study of the stability and reactivity of the discrete complex [PdH(MeCN)(PCy3)2][B(C6F5)4] (Pd1388) is examined in Chapter III. The complex Pd1388 is shown to decompose in chlorinated solvents at 70 °C to form PdCl2(PCy3)2 and two further species, b and c that, despite extensive efforts, could not be identified. Both Pd1388 itself and Pd1388 in its decomposed form (i.e. the mixture of PdCl2(PCy3)2, b and c) are able to act as pro-initiator systems in the polymerisation of exo-NBCH2OCH2C(CF3)2OH (SX1). The kinetics of these polymerisation reactions are explored in detail and a kinetic model is proposed, which accurately describes the overall observed polymerisation rate. In Chapter IV the kinetic model was extended to the study of pure exo- and pure endo-HFP-functionalised norbornenes, with the model proving to be an excellent fit to experimental data for monomer consumption. An increase in the value of n is shown to produce a corresponding enhancement of polymerisation rate. An examination of the polymerisation of HFP-functionalised norbornenes using GPC as function of time is also described. High molecular weight material is formed at low conversion (<35%) with a reduction in molecular weight observed during the first 30 minutes of the reaction to yield a polymer of peak average molecular weight ~20,000 Daltons and low PDI (<1.4). In Chapter V, the kinetic model is further extended to the study of mixtures of endo- and exo-HFP-functionalised norbornenes (n = 0-6). As in the case of pure isomers, an increase in the value of n leads to an enhancement in overall polymerisation rate. Finally, the polymerisation of endo-/exo-NBCH2C(CF3)2OH (SXN4) is explored using initiators containing different counter anions (prepared in Chapter II) in order to determine the effect of the anion on polymerisation rate."],"dc:format":["text"],"dc:identifier.uri":["https://etheses.durham.ac.uk/id/eprint/678/1/Lynn_Donlon_Ph.D_Thesis_2011.pdf"],"dc:publisher.department":["Chemistry, Department of"],"dc:publisher.institution":["Durham University"],"dc:relation.isreferencedby":["https://etheses.durham.ac.uk/id/eprint/678/"],"dc:title":["Synthesis and Kinetic Studies on Palladium Hydride-Initiated Vinyl Polymerisation of Functionalised Norbornenes"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-24T02:11:12Z"}