Synthesis and characterization of novel poly(imino ketone)s via palladium-catalyzed aryl amination [Elektronische Ressource] / by Ayman S. al-Hussaini

Mpi Für Polymerforschung

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• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2005
• Nombre de lectures: 43
• Langue: Deutsch
• Poids de l'ouvrage: 3 Mo

Extrait

Synthesis and Characterization
of
Novel Poly(imino ketone)s
Via Palladium-Catalyzed Aryl Amination
Dissertation zur Erlangung des Grades
“Doktor der Naturwissenschaften”
am Fachbereich Chemie und Pharmazie
der Johannes Gutenberg-Universität in Mainz
By
Ayman S. Al-Hussaini
geb. in Ägypten
Mainz 2005Tag der mündlichen Prüfung: Friday, 22 April 2005.
iiDie vorliegende Arbeit wurde in der Zeit von Juli 2001 bis December 2004 am
Max-Planck-Institut für Polymerforschung in Mainz unter Anleitung von Herrn
Professor Dr. K. Müllen durchgeführt.
Herrn Professor Dr. K. Müllen danke ich für seine wissenschaftliche und
persönliche Unterstützung sowie für zahlreiche motivierende Diskussionen.
iiii Table of contents
Table of contents.................................................................................................…….…(I-IX)
CHAPTER I
INTRODUCTION
1.0 Introduction..................................................................................………………………...1
1.1 Poly(arylene ether ketone)s (PEKs). …………………………………………………….1
1.1.1 Synthesis and properties of poly(arylene ether ketone)s and related materials………….1
1.1.2 Nucleophilic aromatic substitution with emphasis on important variables……………...2
1.1.2.1 Synthesis of poly(arylene ether ketone)s via nucleophilic aromatic substitution……...3
1.1.2.2 The activating group. .....................................................................................................4
1.1.2.3 The leaving group. . ...................................................................................................…5
1.1.2.4 The nucleophile. . ...................................................................................................……5
1.1.2.5 The solvent. ...................................................................................................………….6
1.2 Polyaniline (PANI) . ..................................................................................................…….7
1.2.1 Synthesis, properties and structure of polyaniline....................................................…....7
1.2.2 The concept of doping. ...................................................................................................10
1.2.3 Electronic polyaniline fibers............................................................................................11
1.3 Poly(arylene amide)s (PAAs) .........................................................................................12
1.3.1 Structure and properties of poly(arylene amide)s (PAAs). .............................................12
1.3.2 Synthesis of poly(arylene amide)s (PAAs) .................................................................…13
1.3.3 Structural modification of poly(arylene amide)s (PAAs). ..............................................15
1.4 Palladium-catalyzed arylene amination. ........................................................….……..19
1.4.1 Introduction. . ...................................................................................................………...19
1.4.2 Background and outline. .................................................................................................20
1.4. 3 N-Arylation of secondary amines. .................................................................................21
1.4.3.1 Cross-coupling of amines with aryl bromides. .......................................................….21
1.4.3.2 Cross-coupling of amines with aryl chlorides………………………………………..23
1.4.3.3 Cross-couplings of amines with aryl triflates………………………………………...24
1.4.4 N-Arylation of primary amines. ......................................................................................25
1.4.4.1 Cross-coupling of primary anilines with aryl bromides and iodides…………………25
I Table of contents
1.4.4.1.1 Catalytic cycle of Pd-amination of aryl bromides with primary amines…………..27
1.4.4.2 Cross-coupling of anilines with aryl chlorides.............................................................28
1.4.4.3 Cross-coupling of anilines with aryl sulfonates............................................................28
1.4.5 N-Arylation of ammonia surrogates..............................................................…………..29
1.4.6 N-Arylation of other nitrogen-containing substrates.......................................................29
1.4.7 Intramolecular N-arylation reactions..............................................................………….30
CHAPTER II
2.0 Motivation and objective….…………………………………………………………….31
2.1 Motivation..................................................................................................……………….31
2.2 Objective...................................................................................................………………..34
CHAPTER III
3.0 RESULTS AND DISCUSSIONS ......................................................................................35
3.1 Part 1: Poly(imino ketone)s (PIKs) as new high-performance polymers....…….…...35
3.1.2 Synthesis of 1,4-bis(4-halobenzoyl)benzene as monomers.....………………………....35
´- Synthesis of 4,4 -bis(4-anilinobenzoyl)benzene (10) as a model compound.........………....37
- Synthesis of PIKs. ...................................................................................................………...39
- Polymer solubility................................................................................................…………...41
- Solubility of PIKs...................................................................................................….……...43
- Gel permeation chromatography (GPC) of PIKs. ...............................................…………...44
- Elemental analysis of PIKs. ..............................................................……………......……...45
-Intermolecular and intramolecular hydrogen bonding………………………………………47
-Intermolecular hydrogen bonding of PIKs……………………………...48
-Attempted dissociation and reassociation of hydrogen bonding of PIKs……………………50
- Nuclear magnetic resonance spectroscopy (NMR) of PIKs......................................……….51
-The influences of concentration and temperature on the molecular weight of PIKs………...52
-The influences of ligand on polycondensation process……………………………………...52
-The reactivity of the halogen containing monomers on polycondensation process…………54
- Intrinsic viscosity of PIKs. . ..................................................................................................55
-Thermal behavior of PIKs .................................................................…………………….…56
- Thermogravimetric analysis (TGA). .................................................................……………56
II Table of contents
- Differential scanning calorimetry (DSC). .................................................................………57
-The relation between thermal behavior, glass transition temperatures (T s) and molecularg
weights of PIKs……………………………………………………………………………….58
- Thermo-mechanical behavior.................................................................…………..………..61
-Dielectric spectroscopy of PIKs.…………………………………………………………….65
-Outlook………………………………………………………………………………………66
- X-Ray techniques.................................................................…….. …………………………70
-Instrumentation.................................................................…….. ……………………………73
- Wide-angle X-ray diffraction of PIKs………………………………………………….…...74
-Conclusions………………………………………………………………………………….79
3.2 Part 2: Novel poly(imino alcohol)s (PIAlco)s …………………………………………80
-Synthesis of 1,4-bis(4-anilino-α-hydroxy-benzhydryl)benzene (11)………………………..81
1- H-NMR spectrum of 11... . . .................................................................…………………….82
- FT-IR spectrum of compound 11..………………………………………………………….82
- UV-vis absorption spectra of compounds 11 and 12…..……………………………………83
- Nucleophilic addition of phenyllithium on PIKs.............................................……………..84
- Solubility behavior of PIAlcos…………..………………………………………………….86
- FT-IR spectroscopy of PIAlcos……………………………………………………………..86
1- H-NMR spectra of polymer PIAlcos………………………………………………………..87
- Thermal behavior of PIAlcos………..………………………………………………………88
-Thermogravimertic analysis (TGA) …………………………………………………….…..88
-Differential scanning calorimetry (DSC) ……………………………………………………89
- Wide-angle X-ray diffraction…………………………………………………………..…...91
-Dynamic mechanical measurements ………………………………………………………...91
-Conclusions…………………………………………………………………………………..93
3.3 Part 3: Poly(quinone diimine)s via elimination reaction……………………………...96
-Synthesis of 1,4-bis{(4-benzylidene-cyclohexa-2,5-dienylidene)-anilino}benzene (12)…...97
- Mechanism of the elimination reaction……………………………………………………..98
-FT-IR spectrum of 1,4-bis{(4-benzylidene-cyclohexa-2,5-dienylidene)-anilino}benzene
(12)……………………………………………………………………………………………99
-UV-vis spectrum of 1,4-bis{(4-benzylidene-cyclohexa-2,5-dienylidene)-anilino}benzene
(12)………………………………………………………………………………………..…100
III