Macromolecules with phosphorus functionalities [Elektronische Ressource] / vorgelegt von Maria Leute

Mleute

Informations

• Publié par: universitat_ulm
• Publié le: 01 janvier 2007
• Nombre de lectures: 24
• Langue: English
• Poids de l'ouvrage: 3 Mo

Extrait

Macromolecules with
Phosphorus Functionalities


Dissertation
zur Erlangung des Doktorgrades Dr. rer. nat.
der Fakultät für Naturwissenschaften
der Universität Ulm

vorgelegt von

Maria Leute
aus Ulm

2007 Macromolecules with
Phosphorus Functionalities


Calcium carbonate ‘nano pearls’, grown under the influence of polyvinylphosphonic acid.



Amtierender Dekan: Prof. Dr. K.-D. Spindler
1. Gutachter: Prof. Dr. B. Rieger
2. Gutachter: Prof. Dr. Dirk Volkmer
Tag der Promotion: 19.10.2007
II Contents
Contents ................................................................................................................................... I
Abbreviations.......................................................................................................................... III
Instruments..............................................................................................................................V

1 General Introduction .................................................................................................... 1
1.1 Phosphorus-containing polymers............................................................................. 1
1.1.1 Phosphorus in the main chain.......................................................................... 3
1.1.2 Phosphorus side groups .................................................................................. 5
1.1.3 Phosphorus in dentritic polymers ..................................................................... 5
1.2 References............................................................................................................... 7

2 Polymers with Phosphorus Side Chains...................................................................... 8
2.1 Introduction .............................................................................................................. 8
2.1.1 Overview over existing research 8
2.1.2 Polymerization techniques ............................................................................. 10
2.2 Results and Discussion.......................................................................................... 18
2.2.1 General polymerization results....................................................................... 18
2.2.2 Radical polymerization................................................................................... 20
2.2.3 Anionic Polymerization 32
2.2.4 Catalytic polymerization ................................................................................. 46
2.2.5 Conclusions.................................................................................................... 48
2.2.6 Polymer properties ......................................................................................... 49
2.3 Experimental section.............................................................................................. 53
2.3.1 Monomer synthesis........................................................................................ 53
2.3.2 Polymerization................................................................................................ 59
2.3.3 Hydrolysis of phosphonate polymers ............................................................. 63
2.3.4 Complexation ................................................................................................. 63
2.4 References............................................................................................................. 64

3 Hyperbranched Polymers with Phosphorus at the Branching Points......................... 67
3.1 Introduction ............................................................................................................ 67
3.1.1 Dendritic polymers containing phosphorus .................................................... 69
3.2 Results and Discussion.......................................................................................... 73
3.2.1 Dialkenylphosphine oxides............................................................................. 73
3.2.2 Dialkenyl phosphites ...................................................................................... 74
3.2.3 Dialkenyl-diethylamino-phosphines................................................................ 74
3.3 Experimental section.............................................................................................. 75
I 3.3.1 Monomer synthesis........................................................................................ 75
3.3.2 Polymerization................................................................................................ 83
3.3.3 Reduction of phosphine oxides ...................................................................... 84
3.4 References............................................................................................................. 85

4 Biological tests........................................................................................................... 87
4.1 Introduction ............................................................................................................ 87
4.2 Results and Discussion.......................................................................................... 88
4.2.1 Toxicity 88
4.2.2 Bone Marrow Cell development ..................................................................... 91
4.3 Experimental section.............................................................................................. 96
4.3.1 Sterilization..................................................................................................... 96
4.3.2 Cell Culturing.................................................................................................. 96
4.3.3 Unspecific Toxicity Tests................................................................................ 96
4.3.4 Bone Marrow Cell development ..................................................................... 98
4.4 References........................................................................................................... 100

Summary ............................................................................................................................. 101
Zusammenfassung .............................................................................................................. 103

Declaration.................................................................................................................................i
Acknowledgements...................................................................................................................ii


II Abbreviations
AiBN 2,2-Azo-bis-isobutyronitrile
AcOAc Acetyl acetate
ATRP Atom Transfer Radical Polymerization
b.p. Boiling point
CMC Critical Micellular Concentration (concentration at which a detergent
spontaneously forms micelles)
DBO Dibezoylperoxide
DEG Diethylene glycol
DEVP Diethylvinyl phosphonate
Diisopropylvinyl phosphonate DIVP
DMA Dimethyl acetamide
Differential Scanning Calorimetry DSC
DSM Digital Scanning Microscope
DVPO Diphenylvinyl phosphine oxide
EA Elemental Analysis
EDX Energy Dispersive X-Ray Spectroscopy
EG Ethylene glycol
FCS Fetal calf serum
FT Fourier Transformation
GM-CFS Granulocyte-Macrophage-Colony-Stimulating Factor
GPC Gel permeation chromatography
HS Horse serum
IMDM Iscove’s Modified Dulbecco’s Medium
IR Infrared spectroscopy
LDA Lithium diisopropylamide,
LTSA Lithium-bis-(trimethylsilyl)-amide
MADIX Macromolecular Design via Interchange of Xanthates
MALDI Matrix-Assisted Laser Desorption/Ionization
MEM Minimal Essential Medium
Mn Mean molecular weight of the polymer, number average
MTT 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide
mU Milli unit. One milli unit represents the amount of enzyme which converts 1
nmol of acceptor substrates to product per minute.
Mw Mean molecular weight of the polymer, weight average
n Degree of polymerization
NMP Nitroxide Mediated Polymerization
III NMR Nuclear magnetic resonance
Nu Nucleophile
PBS Phosphate Buffer Saline
PE Polyethylene
PET Polyethylene terephthalate
Poly(diisopropylvinyl phosphonate) PIVP
PP Polypropylene
PS Polystyrene
PVC Polyvinylchloride
PVPA Poly(vinyl phosphonic acid)
PVPO Poly(diphenylvinyl phosphine oxide)
RAFT Reversible Addition-Fragmentation Chain Transfer
rpm Revolutions per minute
SDS Sodium doceyl sulfate
SFRP Stable Free Radical Mediated Polymerization
TEMPO 2,2,6,6-Tetramethylpiperidyl-1-Oxyl
TGA Thermogravimetric Analysis
THF Tetrahydrofurane
TIBA Triisobutylaluminium
TMEDA Tetramethylethylenediamine
UV-VIS UltraViolet-Visible Spectroscopy
wt% weight percent
X Ethyl -α-(O-ethylxanthyl)propionate
ZIBMT Zentralinstitut für Biomedizinische Technik


NMR signals
d doublet
dd doublet of doublets
t triplet
m multiplet
q quartet

IV Instruments
• NMR: Bruker AMX 500 spectrometer; Bruker AC 400 spectrometer
• GPC: Water: Waters 717 (autosampler), Waters 600E (pump), Waters 410 RI
Refractom