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1
Zhang, Wei. « Living coordinative chain transfer polymerization of 1-alkenes ». College Park, Md. : University of Maryland, 2008. http://hdl.handle.net/1903/8897.
Résumé :
Thesis (Ph. D.)--University of Maryland, College Park, 2008.Thesis research directed by: Dept. of Chemistry and Biochemistry. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
2
Valente, Andreia. « Lanthanide based coordinative chain transfer polymerization for architecture control in (co)polymers and ruthenium catalyzed ring-opening polymerization : two aspects of atom economy in polymerization catalysis ». Thesis, Lille 1, 2010. http://www.theses.fr/2010LIL10061.
Résumé :
Le nouveau complexe Cp*La(BH4)2(THF)2 a été utilisé en combinaison avec des alkyles magnésiens et aluminiques pour la (co)polymérisation coordinative par transfert de chaîne (CCTP) du styrène et de l’isoprène. En développant ce concept nous avons obtenu la première croissance de chaîne catalysée du styrène et de l’isoprène avec contrôle de la microstructure. L’application de la CCTP à la copolymérisation statistique est une voie nouvelle et originale pour le contrôle de la composition de copolymères.Par ailleurs, une étude mécanistique a été réalisée pour la polymérisation de l’ ε-caprolactone avec des dérivés cationiques de ruthénium [(η5-C5H5)Ru(η6-arène substitué)][PF6]. Nous avons montré que la polymérisation a lieu selon un mécanisme de type monomère activé avec transfert aux alcools, avec modification de l’hapticité du ligand arèneA newly synthesized Cp*La(BH4)2(THF)2 complex in combination with magnesium or aluminum alkyls was used for the coordinative chain transfer (co)polymerization (CCTP) of styrene and isoprene. Using this concept, we have accomplished the first catalyzed chain growth like reaction of styrene and isoprene, with control of the microstructure. The application of CCTP to statistical copolymerization represents a new and original approach to tune the composition of copolymers. In addition, a mechanistic study of the ring-opening polymerization of ε-caprolactone by [(η5-C5H5)Ru(η6-substituted arene)][PF6] complexes shows that the polymerization proceeds via an activated monomer mechanism by transfer to the alcohol with a change of hapticity of the arene ligand
3
Hashmi, Obaid Hasan. « Engineering of iron-based polymerization catalysts : towards the design of original multi-structured thermoplastic (co) polymers ». Electronic Thesis or Diss., Université de Lille (2018-2021), 2021. http://www.theses.fr/2021LILUR022.
Résumé :
Une série de ligands L1-L11 à base d'iminopyridine/iminoquinoline du type 11-[(Ar)N=C(R)]-R' (Ar = 2,6-Me2-C6H3 ou 2,6-iPr2-C6H3 ou 3,5-(CF3)2-C6H3 ou C6F5, R = H ou Me et R’ = 2-C6H5N ou 2-C6H4N-5-Me ou 2-C9H7N ou 8-C9H7N) et leurs complexes de fer (II) correspondants ont été développés. Les complexes ont été entièrement caractérisés, y compris par diffraction des rayons X pour les nouveaux complexes (6-11), et leurs applications catalytiques ont été étudiées pour la polymérisation coordonnée contrôlée de l'isoprène. La modulation des propriétés stériques et électroniques au sein de cette famille de ligands/complexes s'est avérée influencer la stéréosélectivité et l'activité de la polymérisation de l'isoprène après activation avec divers cocatalyseurs. Les catalyseurs obtenus ont produit des polyisoprènes avec une excellente conversion, une activité élevée et une variété de stéréo-/régio-régularités. Certains de ces catalyseurs ont également été évalués pour la polymérisation coordinative du styrène et ont montré une bonne activité pour la formation de polystyrènes syndiotactiques enrichis. Une autre méthodologie organométallique a été utilisée pour la synthèse de ligands d'aminopyridine (rac-L1H and rac-L2H) et de leurs complexes d'amides de fer correspondants 12 ((L1)2Fe), 13Py et 14Py (LnFe[N(SiMe3)2](Py)) pour leur application dans la (co)polymérisation par ouverture de cycle de L-lactide et ε-caprolactone où les complexes 13Py et 14Py se sont avérés efficacesA series of iminopyridine-/iminoquinoline-based ligands L1-L11 of type 11-[(Ar)N=C(R)]-R’ (Ar = 2,6-Me2-C6H3 or 2,6-iPr2-C6H3 or 3,5-(CF3)2-C6H3 or C6F5, R = H or Me and R’ = 2-C6H5N or 2-C6H4N-5-Me or 2-C9H7N or 8-C9H7N) and their corresponding iron (II) complexes were developed. The complexes were fully characterized including by X-ray for new complexes (6-11) and their catalytic applications were investigated for the controlled coordinative polymerization of isoprene. The modulation of steric and electronic properties within this family of ligands/complexes has shown to influence the stereo-selectivity and activity of the polymerization of isoprene after activation with various cocatalysts. The resulting catalysts produced polyisoprenes with an excellent conversion, high activity and a variety of stereo-/regio-regularities. Some of these catalysts were also assessed for the coordinative polymerization of styrene and displayed good activity for the formation of syndiotactic enriched polystyrenes. Another organometallic methodology has been utilized for the synthesis of aminopyridine ligands (rac-L1H and rac-L2H) and their corresponding iron amide complexes 12 ((L1)2Fe), 13Py and 14Py (LnFe[N(SiMe3)2](Py)) for their application in the Ring-Opening (Co)polymerizaion of L-lactide and ε-caprolactone where the complexes 13Py and 14Py proved to be effective
4
Obenauf, Johannes [Verfasser], et Rhett [Akademischer Betreuer] Kempe. « Coordinative Chain-Transfer Polymerization of Ethylene with NCN-Ligand Stabilized Complexes of Titanium and Zirconium / Johannes Obenauf. Betreuer : Rhett Kempe ». Bayreuth : Universität Bayreuth, 2015. http://d-nb.info/1075249414/34.
5
Starks, Leonard J. « The polymerization of formaldehyde by coordination catalysis ». Diss., Georgia Institute of Technology, 1993. http://hdl.handle.net/1853/28018.
6
Tas, Huseyin. « Coordination Polymerization Of Cyclic Ethers By Metal Xanthates And Carbamates ». Master's thesis, METU, 2003. http://etd.lib.metu.edu.tr/upload/1225028/index.pdf.
Résumé :
Zinc xanthates are active catalysts in stereoregular polymerization of propylene oxide and markedly more stable than that of known classical stereoregular catalysts. But steric control of zinc xanthates is weaker. To find more effective catalyst systems the isopropyl xanthates of Cu, Pb, Ni, Fe, Al and Sn are investigated and only copper (Cu(isoPr)Xt) and tin (Sn(isoPr)Xt) isopropyl xanthates were appeared to be active, but Cu(isoPr)Xt yielded only low molecular weight product. Therefore Sn(isoPr)Xt system was investigated in detail in polymerization of propylene oxide (PO). Polymerization of PO with this catalyst produced two contrasting polymershigh molar mass, crystalline (K-polymer) and low molar mass (D-polymer). Formation of double bonds in D-polymer was thought to be due to as an anionic process. Polymerization reactions were studied by changing polymerization conditions and reacting catalyst with predetermined amount of water. It&
#8217
s found that Sn(isoPr)Xt have considerably low efficiency than that of Zn(isoPr)Xt catalyst. The yield linearly increases by increasing catalyst concentration. The propagation is competed by termination or transfer process hence overall activation energy is negative. Some mechanistic features of this system was also discussed. The catalytical activity of carbamates in this field has also been reported, without any information about catalytical efficiency and stereoregularity of the process. Therefore zinc diethyl dithiocarbamate was also studied and found as an active catalyst in stereoregular polymerization but it showed weaker efficiency in the PO polymerization than that of Zn(isoPr)Xt catalyst (about 12 times weaker).
7
Mochizuki, Shuto. « Controlled radical polymerization in designed porous materials ». Kyoto University, 2019. http://hdl.handle.net/2433/242535.
8
Noack, Cassandra, et n/a. « Studies in Coordination Chemistry ». Griffith University. School of Science, 2003. http://www4.gu.edu.au:8080/adt-root/public/adt-QGU20031030.145610.
Résumé :
The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.
9
Noack, Cassandra. « Studies in Coordination Chemistry ». Thesis, Griffith University, 2003. http://hdl.handle.net/10072/366798.
Résumé :
The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Faculty of Science
Full Text
10
Groeneman, Ryan H. « Investigating the inclusion chemistry of multi-dimensional coordiation polymers / ». free to MU campus, to others for purchase, 2000. http://wwwlib.umi.com/cr/mo/fullcit?p9999289.
11
Megrahi, Abdunnaser. « Super bulky α-diimine ligands and their coordination complexes for use as polymerization catalysts ». Thesis, University of Manchester, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.505376.
Résumé :
The TiCl4 mediated condensation of benzil with anilines followed by Li mediated cyclodehydrogenation of the resulting benzildiimines to access the superbulky a-dimine ligands Ll (N,N'-bis-(2,6-diisopropylphenyl)-phenanthrene-9, 1 O-diylidendiamine) and L2 (N-(2,6- diisopropylphenyl)-N'-(2,4,6-trimethylphenyl)-phenanthrene-9, 1 O-diylidenediamine) is described in this work. This route has been chosen among many other routes which failed to access these ligands. These ligands have been for the first time synthesized and fully characterized, including their single crystal X-ray structures. Attempts to tetrahedrally coordinate NiBr2 to the super bulky ligand Ll failed due to the axial crowding caused by the aryl substituents in the ortho position. Reducing this axial bulk at one side of the ligand from isopropyl groups to methyl groups as in ligand L2 enabled the synthesis of the tetrahedral NiBr2-complex (L2NiBr2). A failure has been also the attempt to coordinate MO(CO)4 to both these ligands. Instead, with the super bulky ligand Ll, a square planar Ni-allyl complex [(113- LINiC3~COOCH3)t. {B[C6H3(CF3)2k} could be easily accessed. These Ni-complexes have shown to be potent catalysts for ethylene polymerisation. The Ni-allyl version of ligand Ll has not been able to polymerize I-hexene. PdCh complexes (LIPdCh) and (L2PdCh) have been synthesized. Stirring of (LIPdCh) complex with Na B[C6H3(CF3)2]4 in acetonitrile afforded a good yield of the cationic chloroacetonitrile complex [LIPdCINCCH3t.{B[C6H3(CF3)2k}. This reaction with (L2PdCh) afforded also good yields not of the desired [L2PdCINCCH3t.{B[C6H3(CF3)2k} but of the dimer [(L2PdCI)2]2+.2{B[C6H3(CF3)2k}. This behaviour has precedent in the literature and might be due to the reduced bulk of this ligand as compared with Ll. [LIPdCINCCH3t.{B[C6H3(CF3)2]4-} has been successfully methylated with Sn(CH3)4 in DCM as solvent affording good yields of the methyl acetonitrile complex [LIPdCH3NCCH3t.{B[C6H3(CF3)2k}. The methylation of the dimer [(L2PdCI)2]2+.2{B[C6H3(CF3)2]4-} failed in DCM but was succesful in acetonitrile affording a good yield of [L2PdCH3NCCH3t.{B[C6H3(CF3)2]4-}. These palladium methyl acetonitrile complexes have been tested for ethylene, I-hexene and cyclopentene polymerization. Branched polyethylene and polyhexene with relatively high molecular weight have been produced by these catalysts. Catalyst [LIPdCH3NCCH3t.{B[C6H3(CF3)2]4-} was more active and produced higher molecular weight and less branched polymer than catalyst [L2PdCH3NCCH3t.{B[C6H3(CF3)2k } in the polymerization of ethylene. The opposite trend has been observed for I-hexene polymerization where catalyst [L2PdCH3NCCH3t.{B[C6H3(CF3)2k} was more active and produced higher molecular weight polymer than catalyst [LIPdCH3NCCH3t.{B[C6H3(CF3)2]4-}. Atactic polycyclopentene with much lower T g and T m than the ones reported in the literature for isotactic polycyclopentene, has been obtained with these catalysts. Tacticity was determined by 13CNMR.
12
Cleary, Brian P. « Structural aspects of bis(quadridentate)zirconium(IV) complexes. Ligand motion and ligand exchange behavior of bis(N, N'-disalicylidene-1,2-phenylenediamino)zirconium(IV) and the two new complexes bis(N, N'-disalicylidene-cis-1,2-diamino-cyclohexane)-zirconium(IV) and bis(N, N''-disalicylidene-trans-1,2-diaminocyclhexane)zirconium(IV) / ». Online version of thesis, 1989. http://hdl.handle.net/1850/11434.
13
Wheaton, Craig Andrew. « The development of cationic zinc complexes as a new class of lactide polymerization catalyst ». Thesis, Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry, 2011, 2011. http://hdl.handle.net/10133/3108.
Résumé :
The thesis outlines the development of novel cationic zinc complexes for application in lactide polymerization catalysis. These complexes were characterized spectroscopically and crystallographically, and where appropriate their efficacy as catalysts for the polymerization of lactide was evaluated.
The strongly donating, neutral chelating ligands employed in this study were prepared by installation of either one or two phosphinimine donors on a dibenzofuran backbone. An efficient synthetic methodology was then developed for the synthesis of cationic complexes of the formula [LZnE+][BAr4-], wherein E = C2H5, CH3, Ph, C6F5, OAc, OC6F5, or methyl-(D,L)-lactate, and AR = Ph, C6F5, or m-(CF3)2-C6H3. Only the cationic zinc-lactate species were found to be highly active polymerization catalysts.
Tuning of the steric and electronic properties of the ligand resulted in the discovery of zinc-lactate systems that promote rapid and well-controlled polymerization of lactide under mild conditions, marking the first well-defined cationic metal catalysts to do so.xxiv, 254 leaves : ill. ; 29 cm + 1 CD-ROM
14
Liu, Shaofeng. « Synthesis of transition metal complexes and their application for ethylene oligomerization and polymerization ». Strasbourg, 2011. http://www.theses.fr/2011STRA6062.
Résumé :
L’oligomérisation catalytique de l’éthylène qui conduit aux α-oléfines linéaires (C4-C20) est d’un intérêt considérable dans les milieux académiques et industriels en raison de leur utilisation croissante comme comonomères, lubrifiants, surfactants, etc. Nous nous sommes particulièrement intéressés à la chimie de coordination et à la catalyse de complexes métalliques porteurs de ligands hétérotopiques pour cette réaction. Avec le ligand bis(2-picolyl) phénylphosphine (NPN), de nouveaux complexes mononucléaires neutres et cationiques du Pd(II) ont été caractérisés ainsi que le complexe dinucléaire [Pd2Cl2(μ-NPN)2](PF6)2. Les produits de réaction entre [CrCl3(NPN)] et divers cocatalyseurs ont permis d’illustrer les diverses fonctions de ces derniers. Avec TlPF6, ce complexe conduit étonnamment au nouvel adduit [CrCl3(NPN)TlPF6] qui présente des interactions inhabituelles en lien possible avec les étapes d’activation du catalyseur. Certains complexes du Ti(IV) avec des ligands de type amidate basés sur des benzimidazolyles ont une forte activité catalytique, après activation par le MAO, et une bonne stabilité dans le temps et à la température, et d’autres sont très actifs pour la polymérisation de l’éthylène et la copolymérisation éthylène/α-oléfine en présence de MAO. Ce travail sur de nouveaux complexes du Pd(II), Cr(III) et Ti(IV) a permis une meilleure compréhension de systèmes catalytiques permettant l’oligomérisation ou la polymérisation de l’éthylèneCatalytic ethylene oligomerization leading to linear α-olefins (C4-C20) has become of considerable interest in both academia and industry owing to their growing demand as comonomers, lubricants, surfactants, etc. We thus became particularly interested in the coordination chemistry and catalytic behavior of metal complexes bearing heterotopic ligands as potential catalysts for this reaction. Using the bis(2-picolyl)phenylphosphine (NPN) ligand, neutral and cationic mononuclear Pd(II) complexes have been prepared and fully characterized as well as the dinuclear complex [Pd2Cl2(μ-NPN)2](PF6)2. The products from the reaction of [CrCl3(NPN)] with various typical cocatalysts illustrated the different functions of the latter. With TlPF6, it unexpectedly led to a novel adduct [CrCl3(NPN)TlPF6] exhibiting unusual interactions involving the Tl+ cation of possible relevance to catalyst activation steps. Some Ti(IV) complexes bearing benzimidazolyl-based amidate ligands displayed after activation with MAO high catalytic activities and good stability for prolonged reaction times and elevated reaction temperature, and other exhibited good to high catalytic activities towards ethylene polymerization and ethylene/α-olefin copolymerization in the presence of MAO. This work on new Pd(II), Cr(III) and Ti(IV) complexes has provided a useful insight into catalytic systems for ethylene oligomerization or polymerization
15
Ritch, Grayson D. « Synthesis, Characterization, and Reactivity of Novel Zinc Coordination Complexes ». Kent State University Honors College / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ksuhonors1399675758.
16
Carlise, Joseph Raymond. « Poly(norbornene) supported side-chain coordination complexes : an efficient route to functionalized polymers / ». Diss., Available online, Georgia Institute of Technology, 2006, 2006. http://etd.gatech.edu/theses/available/etd-04072006-111344/.
Résumé :
Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2006.Prof. Will Rees, Committee Member ; Prof. Charles Liotta, Committee Member ; Prof. David Collard, Committee Member ; Prof. Marcus Weck, Committee Chair ; Prof. Kent Barefield, Committee Member.
17
Brodsky, Kathy-Jo. « The synthesis and characterization of bis(4-(3-(4-phenoxy)propionitrile))-N, N-disalicylidene-1,2-phenylenediamino)zirconium(IV), Zr(nitrile)₂ and the attempted synthesis of Zr(amine)₂ and coordination polymers containing Zr(dspOH)₂ / ». Online version of thesis, 1994. http://hdl.handle.net/1850/11764.
18
Lentz, Nicolas. « Metallylene-sulfur compounds : synthesis, characterization and applications in coordination and catalysis ». Thesis, Toulouse 3, 2018. http://www.theses.fr/2018TOU30274/document.
Résumé :
Ce travail présente la synthèse de ligands mixtes germylène-sulfoxyde qui ont été utilisés en chimie de coordination avec plusieurs métaux de transitions et finalement appliqués en catalyse de transfert d'hydrogène. Une seconde partie de ce travail est axée sur la synthèse de nouveaux métallylènes stabilisés par un sulfonimidamide qui ont été appliqués en catalyse de polymérisation. Le premier chapitre présente l'état de l'art des germylènes avec leurs synthèses, modes de stabilisations et finalement leur chimie de coordination et leurs applications en catalyse. Les sulfoxydes seront aussi décrits pour leur application en tant que ligands hémilabiles. Le second chapitre décrit la synthèse de ligands germylène-α-sulfoxide avec une diversité structurale (cyclohexyle, tBu, tolyle..) et avec différents degrés d'oxydation du souffre (thioéther, sulfoxyde et sulfone). La chimie de coordination a permis la synthèse de complexes bis-germylène du groupe IV, bidentes du ruthénium ainsi que monodentes du ruthénium. Le troisième chapitre présente l'extension de la méthodologie à la formation de ligands germylène-β-sulfoxide. L'influence du groupement espaçant les deux entités sur la chimie de coordination a été étudiée et montre la formation de complexes bidentates du groupe IV. La coordination du ruthénium a mené à la surprenante synthèse d'un complexe bis-ruthénium caractérisé par diffraction des rayons X. Finalement, la nouvelle architecture a permis d'obtenir des complexes de nickel (0) dont une structure avec des ligands carbonyles permettant une comparaison TEP. Le chapitre quatre présente la synthèse de nouveaux ligands, analogues des amidinates, pour la stabilisation des métallylènes avec un atome central soufré. L'effet apporté sur les métallylènes par ces nouveaux ligands sulfonimidamides a été étudié par calcul DFT. Le dernier chapitre est centré sur l'application de plusieurs complexes de ruthénium en catalyse de transfert d'hydrogène avec plusieurs substrats carbonylés. L'utilisation de stannylènes stabilisés par des ligands sulfonimidamides a été étudiée en catalyse de polymérisation de la ε-caprolactoneThis work concerns the synthesis of mixed germylene-sulfoxide ligands that were involved in coordination chemistry with several transition metals and finally applied in hydrogen transfer catalysis. In a second part, the synthesis of new metallylenes stabilized by a sulfonimidamide group was develop, which were applied in polymerization catalysis. The first chapter is centered on the state of the art of germylenes with their synthesis, their stabilization and finally their coordination chemistry and applications in catalysis. Sulfoxides will also be described for their potential as hemilabile ligands. The second chapter describes the synthesis of germylene-α-sulfoxide ligands as structurally tunable structures (cyclohexyl, tBu, tolyl..) and with different oxidation states of the sulfur atom (thioether, sulfoxide and sulfone). The coordination chemistry led to the formation of bis-germylene group IV complexes, bidentate-ruthenium and monodentate ruthenium complexes. The third chapter shows the extension of the methodology to the formation of germylene-β-sulfoxide ligands. The influence of the spacer between the two entities on the coordination chemistry was studied and shows the formation of bidentate group IV complexes. Coordination to ruthenium led to obtain a surprising bis-ruthenium complex characterized by X-ray diffraction analysis. Finally, the novel architecture allowed to obtain two nickel (0) complexes, one of them including carbonyl ligands permitting a TEP comparison. The fourth chapter is centered on the synthesis of new ligands, analogue of amidinate substituents for metallylene stabilization with a central sulfur atom. The effect brought to the metallylene center by the sulfonimidamide was studied by DFT calculations. The last chapter concerns the application of several ruthenium complexes in hydrogen transfer reaction with various carbonyl compounds. The use of sulfonimidamide stannylenes was also investigated in polymerization catalysis of ε-caprolactone
19
Egly, Julien. « Synthèse de complexes métalliques et leurs applications en polymérisation de polyesters, en catalyse et en photo-physique ». Thesis, Strasbourg, 2020. http://www.theses.fr/2020STRAE033.
Résumé :
Dans un projet mené en étroite collaboration avec une industrie chimique, la problématique initiale a été de développer de nouveaux catalyseurs industriels de polycondensation à base de titane pour la production de polyéthylène téréphtalate. La valorisation du TiCl3OEt, un sous-produit industriel, a permis de développer une série de catalyseurs de polycondensation. Les résultats de polymérisation indiquent que la plupart de nos systèmes catalytiques sont aussi bons voir meilleurs que les catalyseurs commerciaux. Parallèlement, nous nous sommes intéressés à la synthèse de complexes de ruthénium(II) en vue de catalyser la réaction de double déshydrogénation oxydante d’amine primaire en nitrile. Dans un premier temps, nous avons remarqué que le complexe [Ru(p-cym)Cl2]2 était capable de convertir des amines primaires en nitriles, sans ajout supplémentaire de ligand ou d’additifs. Afin d’améliorer les rendements et la sélectivité, nous avons synthétisé plusieurs complexes originaux de ruthénium(II), stabilisés par un ligand bidendate NHC-thioether. Pour finir, afin de valoriser des phosphines produites au laboratoire, nous nous sommes intéressés à la préparation de complexes de cuivre(I). La synthèse, par méchanochimie, nous a permis d’obtenir rapidement les complexes dinucléaires correspondants avec de bons rendements. Les différents complexes exhibent tous une intense photoluminescence à l’état solide avec de bons rendements quantiquesIn a project carried out in close collaboration with a chemical industry, the initial problem was to develop new titanium-based industrial polycondensation catalysts for the production of polyethylene terephthalate. The valorization of TiCl3OEt, an industrial by-product, allowed the development of a series of polycondensation catalysts. Polymerization results indicate that most of our catalyst systems are as good as or better than commercial catalysts. In parallel, we have been interested in the synthesis of ruthenium(II) complexes to catalyze the oxidative double dehydrogenation reaction of primary amine to nitrile. In a first step, we noticed that the [Ru(p-cym)Cl2]2 complex was capable of converting primary amines into nitriles, without the addition of additional ligand or additives. In order to improve yields and selectivity, we synthesized several original ruthenium(II) complexes stabilized by a bidendate NHC-thioether ligand. Finally, in order to enhance the value of phosphines produced in the laboratory, we were interested in the preparation of copper(I) complexes. The synthesis, by mechanochemistry, allowed us to quickly obtain the corresponding dinuclear complexes with good yields. The different complexes all exhibit intense solid-state photoluminescence with good quantum yields
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Pollino, Joel Matthew. « The "Universal Polymer Backbone" concept ». Diss., Available online, Georgia Institute of Technology, 2004:, 2004. http://etd.gatech.edu/theses/available/etd-11112004-143714/unrestricted/pollino%5Fjoel%5Fm%5F200412%5Fphd.pdf.pdf.
Résumé :
Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005.Weck, Marcus, Committee Chair ; Jones, Christopher, Committee Member ; Collard, David, Committee Member ; Liotta, Charles, Committee Member ; Bunz, Uwe, Committee Member. Includes bibliographical references.
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Peleška, Jan. « Kinetika koordinační polymerace 1-olefinů katalyzované diiminovými komplexy niklu ». Doctoral thesis, Vysoké učení technické v Brně. Fakulta chemická, 2012. http://www.nusl.cz/ntk/nusl-233353.
Résumé :
This Ph.D. thesis is focused on kinetic study of propene and hex-1-ene coordination polymerizations initiated by complex [(2-tBuC6H4)N=C(1,8-naphtalenediyl)C=N(2-tBuC6H4)]NiBr2 activated by simple organoaluminium compounds and on product properties. In first three parts proper activators are chosen in model polymerizations. The attention is paid to the reproducibility of polymerizations and analytical methods. The fourth part is focused on propene polymerization kinetics with the aim to define optimal reaction conditions, especially polymerization temperature and time. The four part concerns also properties of polymers. The fifth and sixth parts deal with hex-1-ene polymerization kinetics conducted at various activator/initiator molar ratios and various catalytic precursor concentrations, to find out kinetic orders with respect to catalyst and cocatalyst concentration. Last part is oriented on detail mechanistic investigation of nickel diimine complexes activation process. Results of measurements in presence or absence of monomer enabled to propose new interpretation of UV-vis spectra based on concrete structures of absorbing species.
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Finne, Anna. « Novel Possibilities for Advanced Molecular Structure Design for Polymers and Networks ». Doctoral thesis, KTH, Polymerteknologi, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3623.
Résumé :
Synthetic and degradable polymers are an attractive choicein many areas, since it is possible to control the way in whichthey are manufactured; more specifically, pathways tomanipulate the architecture, the mechanical properties and thedegradation times have been identified. In this work,L-lactide, 1,5-dioxepan-2-one and ε-caprolactone were usedas monomers to synthesize polymers with different architecturesby ring-opening polymerization. By using novel initiators,triblock copolymers, functionalized linear macromonomers andstar-shaped aliphatic polyesters with well-defined structureshave been synthesized. To synthesize triblock copolymers,cyclic germanium initiators were studied. The polymerizationproceeded in a controlled manner although the reaction rateswere low. To introduce functionality into the polymer backbone,functionalized cyclic tin alkoxides were prepared and used asinitiators. During the insertion-coordination polymerization,the initiator fragment consisting mainly of a double bond wasincorporated into the polymer backbone. The double bond wasalso successfully epoxidized and this gave unique possibilitiesof synthesizing graft polymers with precise spacing. Themacromonomer technique is a very effective method for producingwell-defined graft polymers. Spirocyclic tin initiators weresynthesized and used to construct star-shaped polymers. Thestar-shaped polymers were subsequently crosslinked in apolycondensation reaction. These crosslinked structures swelledin water, and swelling tests showed that by changing thestructure of the hydrogel network, the degree of swelling canbe altered. A first evaluation of the surface characteristicsof the linear triblock copolymers was also performed. AFManalysis of the heat-treated surfaces revealed nanometer-scalefibers and tests showed that keratinocytes were able to growand proliferate on these surfaces.QC 20100602
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Hong, Xiang. « Nouveaux catalyseurs hétérogènes chiraux pour le dédoublement cinétique hydrolytique des époxydesTERMINAUX ». Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00770302.
Résumé :
L'objectif de ce travail étaient le développement de catalyseurs hétérogènes efficaces pour promouvoir des réactions asymétriques, en utilisant la polymérisation oxydante ou la formation de polymères de coordination. De nouveaux complexes de salen Co(III) chiraux modifiés par des groupements aromatiques sur les position 5, 5' ont été préparés et testés dans le dédoublement cinétique hydrolytique (HKR) des époxydes terminaux en conditions homogènes. Ces complexes ont été ensuite engagés dans les polymérisations oxydantes électrochimiques ou chimiques, et une stratégie de copolymérisation a fourni des polymères chiraux très efficaces et stables pour catalyser l'HKR dans des conditions hétérogènes. Nous avons alors cherché à préparer un catalyseur capable de catalyser deux réactions en cascade, en copolymérisant deux complexes de salen portant des métaux différents. Pendant ces études, les complexes de salen Mn ont révélé leur participation active à la réaction d'HKR des époxydes terminaux catalysée par les complexes de salen Co(III), en augmentant l'excès énantiomérique du produit de façon significative. Les études mécanistiques ont été ensuite réalisées pour tenter de comprendre le rôle des complexes de Mn dans cette réaction. De plus, des complexes de salen fonctionnalisés par le groupement pyridine ou le groupement de type acide isophtalique ont été synthétisés. Ces complexes ont été utilisés pour préparer de nouveaux réseaux de polymères de coordination poreux chiraux (collaboration avec l'équipe LCI de l'ICMMO et l'Institut Lavoisier à Versailles), qui sont ensuite testés comme catalyseurs hétérogènes dans la réaction de Henry asymétrique et la réaction d'HKR.
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Dascalescu, Diana. « Ü-Olefins Coordination Polymerization studies with single site catalysts ». Thesis, 2008. http://spectrum.library.concordia.ca/975911/1/MR45286.pdf.
Résumé :
Due to their unusual physical properties, perfluorocarbon (PFC) solvents have found applications as immiscible reaction medium when unstable reagents are to be used. We became interested in using a fluorous biphasic system (FBS) for the metallocene-based polymerization of Ü-olefins. Here we present a study on its potential influences on the coordination polymerization mechanism and physical properties of the polymers synthesized in such conditions. The first step of our study consisted of the design and set-up of a new polymerization reactor. Using zirconocene and methylaluminoxane (MAO), as catalytic system, preliminary tests of ethylene polymerization were carried out in order to test the system and assess process stability through the evaluation of ethylene polymerization yields and catalyst efficiency parameters (e.g., activity, turn over number, turn over frequency). Catalyst efficiency parameters were all correlated, suggesting that the presence of a PFC in the reaction medium had a limited influence on the catalyst efficiency with little impact on the kinetics of the coordination polymerization process. When ethylene--1-hexene copolymerization reactions were performed in FBS, a negative comonomer effect was observed. Catalyst efficiency parameters calculated for FBS conditions were also affected by the presence of two monomers in the reaction medium. Differential scanning calorimetry (DSC) was used to evaluate the melting temperature and the crystallinity of the synthesized polymers. The copolymers obtained in FBS were characterized by a relative higher proportion of amorphous structure compared to those synthesized in toluene only. The relative proportion of comonomer incorporated in the copolymers synthesized in FBS increased with increasing the 1-hexene concentrations. Owing to their great potential, the study of FBS for Ü-olefin polymerization and copolymerization should be pursued until they find widespread application at the plant scale
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Popenova, Svetlana. « Computational studies of substituted zirconocenium catalysts for olefin coordination polymerization ». Thesis, 2009. http://spectrum.library.concordia.ca/976350/1/MR63254.pdf.
Résumé :
Olefin coordination polymerization catalysts consisting of Group 4 metallocene dichloride have received considerable industrial interest, as they constitute a highly active and selective class of catalysts for Ü-olefin polymerization. For zirconocene dichlorides of general formula [Zr{{466} 5 -C 5 H 5-n R n } 2 Cl 2 ], the Zr atom is j 5 -coordinated to cyclopentadienyl rings that may be substituted or not (R = H, alkyl, aryl...). When reacted with an excess of co-catalyst, the zirconocenium complexes [Zr{{466} 5 -C 5 H 5-n R n } 2 Me] + responsible for the polymerization activity are formed. The catalytic performance of these catalysts is greatly influenced by electronic and steric factors due to the R substituents on the cyclopentadienyl rings. The aim of this work is to understand how the introduction of various length alkyl chains modified with Si and F atoms alters the coordination environment and the electronic properties of the active metal center, and how these changes may affect the olefin polymerization process. A combination of theoretical methods, such as density-functional theory with natural bond orbital analysis and the quantum theory of atoms in molecules, is used to explore these issues. The results of calculations for zirconocenium complexes with various substituents are reported, and the structure, energy, electron density distribution for the different species are examined, focusing on the factors that might control catalytic activity in order to identify optimal substituents. The nature of possible intramolecular interactions between substituents and the metal, as well as the influence of such interactions on catalytic performance, are also investigated.
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Sampson, Jessica. « Nuclearity and π-π Interaction Effects on Olefin Polymerization and Coordination Chemistry ». Thesis, 2019. https://thesis.library.caltech.edu/11450/13/fullthesis_JessicaSampson_20190410.pdf.
Résumé :
This thesis details work performed on the use of secondary coordination sphere effects to impact olefin polymerization activity and tacticity control and the coordination chemistry of Y, Fe, and Cu. Chapter One provides a general introduction and summary of each chapter. Chapter Two describes work in collaboration with KFUPM on nuclearity effects in Zr bisamine bisphenolate complexes. Chapter Three describes the coordination chemistry of arene-appended Y di(pyridyl) pyrrolide complexes and the olefin polymerization activity of tris(dimethylamido) Ti, Zr, and Hf di(pyridyl) pyrrolide complexes. Appendix A describes the effects of bulky trialkylsilyl, triphenylsilyl, and diphenyl(alkyl)silyl substituents on the tacticity control of monozirconium amine bis(phenolate) complexes in 1-hexene polymerization. Appendix B describes the synthesis and structures of miscellaneous dizirconium amine bis(phenolate) complexes which could not be isolated in sufficient purity for olefin polymerization tests. Appendix C describes the synthesis, electrochemistry, and reduction of mesityl-substituted di(pyridyl) NHC supported Fe complexes. Appendix D describes the preparation, solid-state structures, and electrochemistry of di(pyridyl) pyrrolide and di(pyridyl) NHC Cu(I) and Cu(II) complexes displaying π-π interactions in the solid state. Appendix E describes work towards the synthesis of di(pyridyl) guanidinate proligands and metal complexes supported by di(pyridyl) urea, monopyridyl and di(pyridyl) N-heterocyclic olefin and N-heterocyclic vinylidene ligands for use in Lewis acid assisted olefin polymerization. Appendix F includes relevant spectra.
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Chou, Kuo yao, et 周國耀. « Transmetallation reactions and their applications in the coordination polymerization studies and polymer syntheses ». Thesis, 2003. http://ndltd.ncl.edu.tw/handle/34957801722304654863.
Résumé :
碩士國立中正大學
化學工程研究所
91
Abstract Transmetallation, by definition, is related to a process that induces the exchanging of the coordinated ligands between different metal complexes (or catalysts), and hence can lead to the alternation on the geometry of catalysts and perturbation of the electronic configuration around metal centers. Utilizations of transmetallation techniques have became the commonly used methods for the generation of active catalysts in coordination polymerization chemistry. In order to explore the possible applications of transmetallation reactions, we have focused our studies on the novel transmetallation reactions involving early transition metal complex (group III, group IV metal complexes), which can serve as active catalysts to promote the polymerization of α-olefins. In the course of our studies, we have focused that a novel [Hydrotris(3,5-dimethylpyrazol-1-yl)borate titanium triisopropoxide] can be easily prepared by transmetallation reactions. Further more, the catalyst can act as an active catalyst for syndiospecific polymerization of styrene for addition polymerization of morbornene and for ring open polymerization of norbornene.
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« Three-Coordinate Aluminum Alkyl Complexes for Applications in the Polymerization of Cyclic Esters ». Thesis, 2014. http://hdl.handle.net/10388/ETD-2014-05-1556.
Résumé :
Bulky 1,4-diamines 1,2-[2,4,6-(CH3)3-C6H3NH-CH2]2-C6H4 and 1,2-(2,6-iPr2C6H3NHCH2)2-C6H4 were utilized as pro-ligands for the formation of novel three-coordinate aluminum alkyl compounds with the general formula [(1,4-diamido)AlR], where R = Me or Et. The synthesis of analogous aluminum hydrides was also explored resulting in the formation of four-coordinate complexes incorporating bridging hydrides.
The three-coordinate aluminum complexes were developed as single-component catalysts in the ring opening polymerization of cyclic esters. The main focus was on caprolactone polymerization, but other monomers were explored, including lactide, butyrolactone, cis-cyclooctene, and diphenylacetylene. The mechanism of polymerization with caprolactone was also studied.
The coordination chemistry of other metals and non-metals with the 1,4-diamido ligands were also investigated. Phosphorus, boron, zinc, and zirconium were the main focus. [(1,4-diamido)PCl] complexes were successfully synthesised as precursors to the formation of cationic phosphenium species, [(1,4-diamido)P]+.
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Kuo, Chun-Hung, et 郭俊宏. « Study and Pervaporation Application of Synthesizing Functional Poly(4-methyl-1-pentene) via Complex Coordination Polymerization ». Thesis, 2003. http://ndltd.ncl.edu.tw/handle/09144363231827510138.
Résumé :
碩士中原大學
化學研究所
91
This study focuses on modifying poly(4-methyl-1-pentene) (TPX) and increasing the efficiency of this polymer membrane in separating liquids in pervaporation (PV). TPX is the common name of ploy(4-methyl-1-pentene) . First, the monomer, 4-methyl-1-pentene, was copolymerized with other diene comonomers by complex coordination polymerization and was functionalized. The aim was to increase the polarity of TPX and increase its effectiveness in separating PV. Two catalytic systems were used to prepare the copolymer. One used homogeneous metallocene catalyst (Et(Ind)2ZrCl2/MAO)to copolymerize the 4-methyl-1-pentene and 5-ethylidene-2-norbornene ( ENB ). The copolymerization was efficient, but the action as a membrane was poor. Next, the heterogeneous Ziegler-Natta catalyst system (TiCl3-AA/AlEt2Cl) was used to copolymerize the 4-methyl-1-pentene and 1,7-octadiene. The copolymerization was not excellent but was acceptable. The copolymer did not crosslink, and the ability of to act as a membrane was better. Then, the unreactive vinyl group of the comonomer unit in the TPX was epoxidized using m-chloroperoxybenic acid ( MCPBA ). Finally, methanol or lithium aluminum hydride was used to open the ring and graft the -OCH3 and -OH functional groups. Hydrochloric acid and bromine (Br2) could also be used to perform the addition reaction. Then poly(methylmethacrylate acrylonitrile) was grafted via atomic transfer radical polymerization ( ATRP ). The compound was examined by 1H-NMR ,FT-IR ,TGA and DSC were used to measure the degradation temperature (Td), the glass transition temperature (Tg) and the melt temperature (Tm). The results indicated that the functional TPX of the methanol opened ring increasing the efficiency of separation of the alcohol/water solution. The permeation rate, separation factor and PSI value on the PV, were higher.
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Roy, Suman Kumar. « C-N BOND FORMING REACTIVITY IN ANILINE AND THEIR CO-ORDINATION CHEMISTRY ». Thesis, 2019. http://hdl.handle.net/10821/8200.
Résumé :
The research has been originated from an attempt to explore direct and selective transformation of c-h bonds that are mediated either by metal coordination or by protonation of anilido substrate oxidative dimerization and polymerization reactionsThe research guide was Prof. Sreebrata Goswami of Inorganic Chemistry division under SCS [School of Chemical Science]
Research was conducted under CSIR fellowship in IACS
31
Srebro-Hooper, Monika. « Theoretical study on the ethylene polymerization processes catalyzed by half-metallocene complexes of titanium(IV) ». Praca doktorska, 2010. https://ruj.uj.edu.pl/xmlui/handle/item/53089.
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Stahlová, Sabina. « Funkcionalizované mikroporézní polymerní sítě připravené z ethynylarenů ». Doctoral thesis, 2016. http://www.nusl.cz/ntk/nusl-353418.
Résumé :
The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...
33
Slováková, Eva. « Polymerizace bifunkčních acetylenů katalyzovaná komplexy rhodia ». Master's thesis, 2011. http://www.nusl.cz/ntk/nusl-297634.
34
Slováková, Eva. « Konjugované porézní polymery odvozené od diethynylarenů řetězovou polymerizací a polycyklotrimerizací ». Doctoral thesis, 2015. http://www.nusl.cz/ntk/nusl-350048.
Résumé :
4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...