Reactive fluoropolymers [Elektronische Ressource] : synthesis and application / Nikolay Vladimirovich Belov

Nikolay Belov






Reactive Fluoropolymers
Synthesis and Application




















Reactive Fluoropolymers
Synthesis and Application



Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der RWTH Aachen University zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften genehmigte Dissertation

vorgelegt von

Diplom-Chemiker
Nikolay Vladimirovich Belov

aus Ivanovo, Russland


Berichter: Universitätsprofessor Dr. rer. nat. Martin Möller
Universitätsprofessor Dr. rer. nat. Uwe Beginn

Tag der mündlichen Prüfung: 22. September 2011


Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar








To my mother,
Belova Nadezhda Vasilevna














Table of contents

List of abbreviations iii

Summary vii

Zusammenfassung xv

1 Introduction 1

1.1 Combcopolymers for surface modification 1
1.2 Fluorine containing polymers 2
1.3 Content of the thesis 4
1.4 References 5

2 Literature Review 7

2.1 Free radical batch and continuous addition
polymerization in laboratory scale 7
2.2 Fluorinated compounds 8
2.2.1 Properties of fluorinated compounds 8
2.2.2 Hydrocarbon-fluorocarbon incompatibility 9
2.2.3 Polymers with fluorinated side chains 10
2.2.4 Wetting property of fluorinated compounds
and method of determination thereof 12
2.3 Unsaturated anhydrides 16
2.3.1 Maleic anhydride (MAH) physical properties 16
2.3.2 Homopolymerization of maleic anhydride 16
2.3.3 Copolymerization of maleic anhydride 17
2.3.4 Other polymerizations of maleic anhydride 19
2.3.5 Industrial applications of maleic anhydride 22
2.3.6 Itaconic anhydride (ITA) 23
2.3.7 Itaconic anhydride is a green chemistry chemical 24
2.3.8 Polymerization and applications of itaconic anhydride 26
2.3.9 Comparison of ITA with MAH 26
2.4 References 28


iTable of contents
_________________________________________________________________________________________________________________


3 Binary Copolymers of Fluorinated Methacrylates
with Maleic and Itaconic Anhydrides 33

3.1 Introduction 33
3.2 Experimental 35
3.3 Results and Discussion 50
3.4 Conclusions 101
3.5 References 104

4 Terpolymers of Aliphatic and Fluorinated Methacrylates with
Anhydride Functionalities 107

4.1 Introduction 107
4.2 Experimental 109
4.3 Results and Discussion 121
4.4 Conclusions 141
4.5 References 143

5 Application of Specifically Tailored Fluoropolymers 145

5.1 Introduction 145
5.2 Experimental 147
5.3 Results and Discussion 154
5.4 Conclusions 170
5.5 References 173

Acknowledgements 175

Curriculum Vitae 179







iiList of abbreviations and symbols

Chemicals

Ac O Acetic anhydride 2
AIBN Azobisisobutyronitrile
APTES (3-Aminopropyl)triethoxysilane
BHT 2,6-di-tert-butyl-4-methylphenol
BMC Bulk moulding compounds
BPO Benzoyl peroxide
BTHP 2,2-Bis[4-(4-trimellitimidphenoxy)phenyl]hexafluoropropane
BuMa Butylmethacrylate
CIA Citraconic anhydride
CTFE/ethylene Chlorotrifluoroethylene/ethylene copolymer
DMAc Dimethylacetamide
DMSO Dimethyl sulfoxide
DMF Dimethylformamide
ETFE Ethylene/tetrafluorethylene copolymer
EtOH Ethanol
FMA 1H,1H,2H,2H-perfluorodecyl methacrylate
Freon-113 Trichlorotrifluoroethane
FRP Fiberglass reinforced plastic
HDPE High density polyethylene
HEMA 2-hydroxyethyl methacrylate
HFX 1,3 –bis(trifluoromethyl)benzene
H NR Fluorinated amine 2 F
ITA Itaconic acid anhydride
Jeffamine M-1000 Mono amino terminated copolymers of 19 ethylene and 3 propylene oxide units
Jeffamine M-600 Mono amino terminated copolymers of 1 ethylene and 9 propylene oxide units
LaMA Laurylmethacrylate
LC polymers Liquid crystalline polymers
LDPE Low density polyethylene
MAH Maleic anhydride
MEK Methyl ethyl ketone
M Jeffamines Mono amino terminated copolymers of ethylene and propylene oxides
MMA Methyl methacrylate
NaAc Sodium acetate
PA Polyamide
iii List of Abbreviations and Symbols
_________________________________________________________________________________________________________________

PE Polyethylene
PEO Polyethylene oxide
PET Polyethylene terephthalate
PITA Poly(itaconic anhydride)
PMMA Poly(methyl methacrylate)
PTFE Poly(tetrafluoroethylene)
R MA Alkyl methacrylate H
SMA Styrene maleic anhydride copolymer
SMC Sheet moulding compounds
TEA Triethylamine
TEOS Tetraethyl orthosilicate
THF Tetrahydrofuran
UHMWPE Ultra high molecular weight polyethylene
ULDPE Ultra low density polyethylene
UP Unsaturated polyester
VLDPE Very low density polyethylene

General
AFM Atomic force microscopy
CED Cohesive energy density
Conv. Conversion
13C-NMR Carbon nuclear magnetic resonance
CTC Charge transfer complex
DLS Dynamic light scattering
DM Degree of modification
DSC Differential scanning calorimetry
ESRF European Synchrotron Radiation Facility
FRP Free radical polymerization
FT-IR Fourier transform infrared spectroscopy
FT- Raman Fourier transform Raman spectroscopy
FWHM Full width of half maximum
F Molar fraction of an X component in the copolymer x
f Molar fraction of an X component in the stock solution x
GGFY Girifalco-Good-Fowkes-Young
GPC Gel permeation chromatography
HPLC High- performance liquid chromatography
1H-NMR Proton nuclear magnetic resonance
LB films Langmuir-Blodgett films
MALDI-TOF Matrix-assisted laser desorption/ionization
n Amount of substance

ivList of Abbreviations and Symbols
_________________________________________________________________________________________________________________

NMR Nuclear magnetic resonance
PDI Polydispersity index
POM Polarizing optical microscopy
ROMP Ring-opening metathesis polymerization
RI detector Refractive index detector
r.t. Room temperature
SAXS Small angle X-ray scattering
SEC Size exclusion chromatography
SEM Scanning electron microscopy
TEM Transmission electron microscopy
TGA Thermogravimetric analysis
WAXS Wide angle X-ray scattering
UV Ultra violet
UV/VIS Ultra violet/Visible
XPS X-ray photoelectron spectroscopy
XRD X-ray difraction

Symbols
-alt- Alternating copolymer
atom % Atomic per cent
a.u. Atomic units
-b- Block
c Concentration
-co- Random copolymer
Da Dalton
h Hour
H Mixing enthalphy mix
K First dissociation constant 1
K Second dissociation constant 2
K Decomposition rate d
m Mass
M Molecular weight
M Number average molecular weight n
mol% Mole per cent
M Weight average molecular weight w
M /M Polydispersity index w n
r Reactivity ratio
R Rate of polymerization p
t Tertiary
t Time
v