京都大学 / 新制・課程博士 / 博士(工学) / 甲第25309号 / 工博第5268号 / 新制||工||2002(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大内 誠, 教授 中村 洋, 教授 田中 一生 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

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<p>Homogeneous palladium-catalyzed Heck vinylation of aryl chlorides was investigated under air using Herrmann’s palladacycle and the P(<i>t</i>-Bu)₃-liberating salt [(<i>t</i>-Bu)₃PH]BF₄. Based on the results, controlled microwave heating was utilized to accelerate model Heck reactions with aryl chlorides down to 30 min employing an electron-poor olefin and a mixture of an ionic liquid and 1,4-dioxane as solvent.</p><p>For the first time, a highly regioselective general protocol has been developed for palladium-catalyzed terminal (β-) arylation of acyclic vinyl ethers using inexpensive aryl chlorides as starting materials and the preligand [(<i>t</i>-Bu)₃PH]BF₄ as the key additive. This swift and straightforward protocol exploits non-inert conditions and controlled microwave heating to reduce handling and processing times, and aqueous DMF or environmentally friendly PEG-200 as the reaction medium. Somewhat higher selectivity for the linear β-product was observed in PEG-200. DFT calculations were performed at the B3LYP level of theory for the regioselectivity-determining insertion step in the Heck reaction following the neutral pathway. A series of <i>para</i>-substituted phenylpalladium(II) complexes was investigated in the computational study. The calculations support a ligand-driven selectivity rationale, where the electronic and steric influence of the bulky P(<i>t</i>-Bu)₃ ligand provides improved β-selectivity. The preparative methodology was used to synthesize the β-adrenergic blocking agent Betaxolol.</p><p>Highly stereoselective Pd(0)-catalyzed β-arylation and β-vinylation of a tetra-substituted cyclopentenyl ether have been accomplished using a chiral, pyrrolidine-based and substrate-bound palladium(II)-directing group under neutral reaction conditions. To the best of the author’s knowledge, this P(<i>t</i>-Bu)₃-mediated method represents the first examples of the successful utilization of aryl and vinyl chlorides in asymmetric Heck reactions. The Heck arylation products formed were hydrolyzed and isolated as the corresponding quaternary 2-aryl-2-methyl cyclopentanones in good to moderate two-step yields with excellent stereoselectivity (90-96% ee). Inclusion of vinyl triflates under neutral reaction conditions and one aryl triflate equipped with a strongly electron-withdrawing <i>para</i>-cyano substituent under cationic conditions increased the preparative usefulness of the methodology.</p><p>Furthermore, diastereoselective Heck arylation of both five- and six-membered cyclic vinyl ethers with aryl bromides, using the identical chiral auxiliary and suitable Pd sources, was performed. Arylated products from the tetra-substituted cyclopentenyl ether were also in this case hydrolyzed to the corresponding 2-aryl-2-methyl cyclopentanones with high to excellent enantioselectivity (85-94% ee). Despite low reaction rates and relatively modest yields, arylation reactions with the tri-substituted cyclohexenyl ether were found to be highly diastereoselective (94-98% de).</p><p>Thus, an attractive supplement to direct Pd(0)-catalyzed α-arylation protocols, particularly when the use of organic chlorides, aryl bromides, and milder reaction conditions are of great importance, have been developed.</p>

Poly (co iso-butyl vinyl ether-alt-maleic anhydride), an alternating copolymer, was synthesised. For this class of copolymers the formation of an electron-donor complex is invoked to explain their microstructure in which the two comonomers strictly alternate. Due to its polarity, this copolymer constitutes a potential additive for imparting hydrophilic properties to a hydrophobic matrix. In order to obtain narrow molecular weight polymers and study the relation between the molecular weight of this additive and its ability to migrate to the host polymer surface, chain transfer agents were introduced in the system and also the Reversible Addition-Fragmentation chain Transfer (RAFT) process was employed. Free radical polymerisation was first carried out to allow for a comparison with the RAFT process and kinetics of copolymerisation was studied by NIR-FTIR and 1H NMR spectroscopy in order to analyse the rate of reaction of each comonomer. Dibenzyl trithiobenzoate, 3-benzyl sulfanyl thiocarbonyl sulfanyl-propionic acid and dibenzyl trithiobenzoate were used as RAFT agents. Results demonstrate that only benzyl dithiobenzoate is able to control the molecular weight of this copolymer and decrease its polydispersity index; possible reasons laying behind this result are discussed. It was also found that, in particular in the presence of benzyl dithiobenzoate, poly(iso-butyl vinyl ether) forms. This is an unusual phenomenon considering that the free radical polymerisation affords alternating copolymers and that iso-butyl vinyl ether is a monomer that polymerises through the cationic process. Experiments were carried out in various solvents in an attempt to counteract this side reaction, but no appreciable correlation between the properties of the solvents and the formation of homopolymer were found. Various hypothesis are considered, however it is likely that, in the conditions adopted, the presence of the RAFT agents alters the equilibrium constant of complex formation favouring the synthesis of the homopolymer. In addition to this side???reaction also inhibition of the copolymerisation reaction was at times encountered and an investigation into this phenomenon was also conducted.

Homogeneous palladium-catalyzed Heck vinylation of aryl chlorides was investigated under air using Herrmann’s palladacycle and the P(t-Bu)3-liberating salt [(t-Bu)3PH]BF4. Based on the results, controlled microwave heating was utilized to accelerate model Heck reactions with aryl chlorides down to 30 min employing an electron-poor olefin and a mixture of an ionic liquid and 1,4-dioxane as solvent. For the first time, a highly regioselective general protocol has been developed for palladium-catalyzed terminal (β-) arylation of acyclic vinyl ethers using inexpensive aryl chlorides as starting materials and the preligand [(t-Bu)3PH]BF4 as the key additive. This swift and straightforward protocol exploits non-inert conditions and controlled microwave heating to reduce handling and processing times, and aqueous DMF or environmentally friendly PEG-200 as the reaction medium. Somewhat higher selectivity for the linear β-product was observed in PEG-200. DFT calculations were performed at the B3LYP level of theory for the regioselectivity-determining insertion step in the Heck reaction following the neutral pathway. A series of para-substituted phenylpalladium(II) complexes was investigated in the computational study. The calculations support a ligand-driven selectivity rationale, where the electronic and steric influence of the bulky P(t-Bu)3 ligand provides improved β-selectivity. The preparative methodology was used to synthesize the β-adrenergic blocking agent Betaxolol. Highly stereoselective Pd(0)-catalyzed β-arylation and β-vinylation of a tetra-substituted cyclopentenyl ether have been accomplished using a chiral, pyrrolidine-based and substrate-bound palladium(II)-directing group under neutral reaction conditions. To the best of the author’s knowledge, this P(t-Bu)3-mediated method represents the first examples of the successful utilization of aryl and vinyl chlorides in asymmetric Heck reactions. The Heck arylation products formed were hydrolyzed and isolated as the corresponding quaternary 2-aryl-2-methyl cyclopentanones in good to moderate two-step yields with excellent stereoselectivity (90-96% ee). Inclusion of vinyl triflates under neutral reaction conditions and one aryl triflate equipped with a strongly electron-withdrawing para-cyano substituent under cationic conditions increased the preparative usefulness of the methodology. Furthermore, diastereoselective Heck arylation of both five- and six-membered cyclic vinyl ethers with aryl bromides, using the identical chiral auxiliary and suitable Pd sources, was performed. Arylated products from the tetra-substituted cyclopentenyl ether were also in this case hydrolyzed to the corresponding 2-aryl-2-methyl cyclopentanones with high to excellent enantioselectivity (85-94% ee). Despite low reaction rates and relatively modest yields, arylation reactions with the tri-substituted cyclohexenyl ether were found to be highly diastereoselective (94-98% de). Thus, an attractive supplement to direct Pd(0)-catalyzed α-arylation protocols, particularly when the use of organic chlorides, aryl bromides, and milder reaction conditions are of great importance, have been developed.

Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets. To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP). The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP. The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR). The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility. In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures. Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP. / QC 20101019

<p>Microfluidic devices have long been considered an ideal tool for rapid and inexpensive chemical analysis and reactions in areas ranging from point-of-care health to national security applications. However, fabricating microfluidic devices is time consuming, difficult and above all expensive. In commercial applications many thousand units need to be sold before the development costs are recovered. The problem is compounded since most microfluidic devices do not have generalized architectures which means that each end use requires a specialized design. The microfluidics marketplace can therefore be seen as being composed of 1000’s of niche markets.</p><p>To address development costs, there is clearly a need for a versatile technology that can be used for many different applications and that enables rapid testing and optimization of new designs. This work describes such a technology: Contact Liquid Photolithographic Polymerization (CLiPP).</p><p>The thesis consists of two parts: polymerization kinetics and the fabrication of polymeric microfluidic devices via CLiPP.</p><p>The photopolymerization kinetics is evaluated for a number of monomer types, and the results are used to assess their suitability in the CLiPP process. Vinyl ether/maleate photoinitiated copolymerization is examined in detail. It is shown that the polymerization kinetics is dramatically influenced by the availability of easily abstractable hydrogens The presence of α-hydrogens adjacent to the vinyl ether functional group reduces the polymerization rate and the dependence of the polymerization rate as a function of initiation rate. Also, photoinitiated acrylate and methacrylate polymerization kinetics are presented. The kinetics results in these three monomer types are used to explain the different patterning properties of the monomer functionalities used in the CLiPP process, in which acrylates show enhanced patterning properties compared to methacrylates. The polymerization kinetics is studied with traditional tools and methods: photo Differential Scanning Calorimetry (photo-DSC), photo Fourier Transform Real Time Infrared Spectroscopy (photo-RTIR), and photo Real Time Electron Paramagnetic Spectroscopy (ESR).</p><p>The microfluidic fabrication is performed via both in-house fabricated and commercially available CLiPP-specific hardware. The patterning qualities of the structures are evaluated via Scanning Electron Microscopy (SEM) and Optical Microscopy. The finished devices are used in their intended environment and evaluated in suitable manners to assess their utility.</p><p>In this thesis, the development and design of specialized CLiPP fabrication machines, fabrication techniques and resulting microfluidic device features are presented anddiscussed. It is shown that the CLiPP scheme enables features such as 3 dimensional (3D) capabilities for minimized device footprints, a very large number of polymeric materials for optimized device components as well as facile integration of prefabricated components. Also, covalent layer adhesion and permanent surface modifications via living radical processes are demonstrated. These capabilities are exemplified in a number of examples that range from a 3D fluidic channel maze with separated fluidic streams and a device with independently moveable parts to a device constructed from multiple polymeric materials and devices with permanently modified surfaces, Also, batch processing capabilities are shown through fabrication of 400 identical undercut microstructures.</p><p>Rapid and inexpensive design evaluations, multiple materials capabilities and the ability to seamlessly incorporate prefabricated microstructures of the CLiPP process strongly encourages continued method development. The future work that remains to be addressed is divided into two parts. First, to enable novel research devices, new polymer materials with enhanced mechanical and surface properties must be developed. Also, integration of prefabricated microstructures such as sensors and actuators has to be incorporated in a reproducible and rational manner. Secondly, to enable device mass fabrication, new automated equipment is to be developed in order to utilize the full batch processing potential of CLiPP.</p>

Poly (co iso-butyl vinyl ether-alt-maleic anhydride), an alternating copolymer, was synthesised. For this class of copolymers the formation of an electron-donor complex is invoked to explain their microstructure in which the two comonomers strictly alternate. Due to its polarity, this copolymer constitutes a potential additive for imparting hydrophilic properties to a hydrophobic matrix. In order to obtain narrow molecular weight polymers and study the relation between the molecular weight of this additive and its ability to migrate to the host polymer surface, chain transfer agents were introduced in the system and also the Reversible Addition-Fragmentation chain Transfer (RAFT) process was employed. Free radical polymerisation was first carried out to allow for a comparison with the RAFT process and kinetics of copolymerisation was studied by NIR-FTIR and 1H NMR spectroscopy in order to analyse the rate of reaction of each comonomer. Dibenzyl trithiobenzoate, 3-benzyl sulfanyl thiocarbonyl sulfanyl-propionic acid and dibenzyl trithiobenzoate were used as RAFT agents. Results demonstrate that only benzyl dithiobenzoate is able to control the molecular weight of this copolymer and decrease its polydispersity index; possible reasons laying behind this result are discussed. It was also found that, in particular in the presence of benzyl dithiobenzoate, poly(iso-butyl vinyl ether) forms. This is an unusual phenomenon considering that the free radical polymerisation affords alternating copolymers and that iso-butyl vinyl ether is a monomer that polymerises through the cationic process. Experiments were carried out in various solvents in an attempt to counteract this side reaction, but no appreciable correlation between the properties of the solvents and the formation of homopolymer were found. Various hypothesis are considered, however it is likely that, in the conditions adopted, the presence of the RAFT agents alters the equilibrium constant of complex formation favouring the synthesis of the homopolymer. In addition to this side???reaction also inhibition of the copolymerisation reaction was at times encountered and an investigation into this phenomenon was also conducted.

Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or “grafting-onto” methodologies, which yielding in well-defined PVEs segments with control Mn(GPC) = [VE]/[initiator] and narrow MWDs.

L'objectif de cette thèse est de synthétiser de nouveaux monomères éthers vinyliques porteurs de groupements phosphonate, dans le but d'étudier leur efficacité comme retardateurs de flamme. Les produits phosphorés s'avèrent de bonnes alternatives aux retardateurs de flamme halogénés, qui présentent des problèmes environnementaux. Dans un premier temps, nous avons réalisé la synthèse des éthers vinyliques phosphonés par transéthérification de l'éthylvinyl éther en présence d'alcools phosphonés. Ensuite, nous avons choisi la copolymérisation radicalaire (A/D) afin de préparer des copolymères à base d'éthers vinyliques phosphonés et de différents accepteurs. Des études cinétiques par Infra-Rouge en temps réel et plusieurs méthodes d'analyses ont été effectuées afin de caractériser ces copolymères. Dans un second temps, nous avons réalisé des cinétiques de photocopolymérisation radicalaire du 2-vinyloxyéthylphosphonate de diméthyle avec une série de monomères accepteurs, par exemple, les maléimides avec qui ce monomère forme des complexes forts. La photopolymérisation cationique a aussi été réalisée et offre de meilleurs résultats que la photopolymérisation radicalaire. Un bilan de tous les polymères phosphonés a été réalisé dans le but de tester leurs performances en tant que retardateurs de flamme. Les caractérisations thermogravimétriques et microcalorimétriques de ces copolymères ont montré une quantité importante de résidus et des valeurs de chaleur dégagée encourageantes en vue d'une utilisation de ceux-ci en tant que retardateurs de flamme. / The aim of this work is the synthesis of new vinyl ethers monomers bearing phosphonate groups, in order to study their efficiency as flame retardants. Phosphorus products are known to be a good alternative to halogenated flame retardants, which are involved in environmental problems. Initially, the synthesis of phosphonated vinyl ethers was performed by trans-etherification of ethylvinyl ether in the presence of phosphonated alcohols. Then, the radical copolymerization (A/D) was used to prepare copolymers based on phosphonated vinyl ether and various electron-accepting monomers. Kinetic studies by real-time Infrared and several methods of analyzes were used to characterize these copolymers. In a second step, the radical photocopolymerization of 2-dimethylvinyloxyethylphosphonate was led with a series of electron-accepting monomers, for instance maleimides which form strong complexes with vinyl ethers. The cationic photopolymerization of these phosphonated vinyl ethers is also possible and affords better results than radical photopolymerization. An assessment of all phosphonated polymers was performed in order to test their performances as flame retardants. Thermogravimetric and microcalorimetric characterizations showed good amount of released residues showing that these copolymers are good candidates as flame retardants.