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«Novel Polymer Systems and Surface Modifications of Planar and Porous Substrates for Advanced Applications Dissertation zur Erlangung des Grades ...»

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Novel Polymer Systems and Surface Modifications of Planar

and Porous Substrates for Advanced Applications

Dissertation

zur Erlangung des Grades

“Doktor der Naturwissenschaften”

im Promotionsfach Chemie

am Fachbereich Chemie, Pharmazie und Geowissenschaften

der Johannes Gutenberg-Universität Mainz

Basit Yameen

geb. in

Lahore, Pakistan

Mainz, 2008

Die vorliegende Arbeit wurde in der Zeit von April 2005 bis November 2008 am Max

Planck Institut für Polymerforschung unter Betreuung von Prof. Dr. Wolfgang Knoll und Dr. Ulrich Jonas angefertigt.

Dekan: Prof. Dr. Wolfgang Hofmeister

1. Berichterstatter : Prof. Dr. Wofgang Knoll

2. Berichterstatter : Prof. Dr. Holger Frey

3. Prüfer: Prof. Dr. Karl W. Klinkhammer

4. Prüfer: Dr. habil. Heiner Detert Tag der mündlichen Prüfung : 8-12-2008 Für Lubna und Shiza Table of contents List of Abbreviations

Chapter 1

1. General Introduction

1.1. Methods of surface modification

1.1.1. Plasma treatment and plasma polymerization

1.1.2. Wet chemical surface modification

1.1.3. Polymer brush for surface modification: “Grafting-to” approach...... 15 1.1.4. Polymer brush for surface modification: “Grafting-from” approach.. 18

1.2. Aim and motivation of the present work

1.3. Materials of relevance

1.3.1. Polyether ether ketone (PEEK)

1.3.2. Cyanate ester resins

1.3.3. Solid state nano/macro-pores

1.3.3.1. Polymer membranes with Track-Etched Nanopores.................. 26 1.3.3.2. Ordered Macroporous Si/SiO2

Reference

1.4.

Chapter 2

2. Materials and methods

2.1. Materials

2.1.1. Polymer Substrates

2.1.2. Porous substrates

2.1.2.1. Fabrication of conical nanopore in PET and PI membranes....... 40 2.1.2.2. Fabrication of ordered macroporous Si membrane

2.1.3. Substances purified prior to use

2.1.4. Substances used as received

2.2. Methods

2.2.1. Thermal and mechanical analysis

2.2.2. Fourier transform infrared spectroscopy (FTIR)

2.2.3. X-ray photoelectron spectroscopy (XPS),

2.2.4. Current-voltage (I-V) measurements

2.2.5. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) 46 2.2.6. Water contact angle measurement and surface roughness................. 47 2.2.7. Atomic absorption spectroscopy (AAS)

2.2.8. Dielectric spectroscopy

References

2.3.

Chapter 3

3. Cyanate Ester Resins: Thermally Stable Adhesives for PEEK

3.1. Choice of PT-30 CEM as adhesive for PEEK

3.2. Surface activation of PEEK for adhesion improvements

3.2.1. Wet chemical surface activation

3.2.2. Plasma-assisted surface activation

3.3. Conclusions

Experimental

3.4.

3.4.1. Sample preparation

3.4.2. Wet chemical surface activation: Reduction of surface carbonyl groups to hydroxy groups (PEEK-OH)

3.4.3. Wet chemical surface activation - Transformation of surface hydroxy groups into cyanate groups (PEEK-OCN)

3.4.4. Plasma-assisted surface activation

3.4.5. Gluing and adhesion tests

References:

3.5.

Chapter 4

4. Effect of structural variations on thermal properties of aryl ether ketone based cyanate ester resins with linear and tri-arm molecular architectures

4.1. Synthesis and characterization

4.1.1. Synthesis of CEMs with linear molecular architecture

4.1.2. Synthesis of CEMs with symmetric triarm molecular architecture.... 73

4.2. Thermal properties of linear bifunctional CE resins

4.2.1. Differential scanning calorimetry

4.2.2. Thermogravimetric analysis

4.3. Thermal properties of linear multifunctional CE resin

4.3.1. Differential scanning calorimetry

4.3.2. Thermogravimetric analysis

4.4. Thermal properties of symmetric triarm CE resins

4.4.1. Differential scanning calorimetry

4.5. Electronic effect of the substituents on the reactivity of the cyanate groups

4.6. Conclusions

Experimental

4.7.

4.7.1. Synthesis of oligomeric aryl ether ketone with hydroxy end groups

4.7.2. Synthesis of linear aryl ether ketone oligomeric mixture with pendant and terminal hydroxy groups (9)

4.7.3. Synthesis of symmetrically triarmed aryl ether ketone with hydroxy end groups (17) 89 4.7.4. Synthesis of symmetrically triarmed aryl ether ketone with hydroxy end groups 1,3,5-(4hydroxyphenoxy)-4'-oxy)benzene (17), deprotection of methoxy groups

4.7.5. A general procedure for the synthesis of linear and symmetrically triarmed aryl ether ketone cyanate ester monomers (4, 5, 6, 10, 13, 18, 19, 20)

Reference

4.8.

Chapter 5

5. Polycyanurate Thermoset Networks with High Thermal, Mechanical, and Hydrolytic Stability Based on Liquid Multifunctional Cyanate Ester Monomers with Bisphenol A and AF Units

5.1. Synthesis and characterization of bisphenol AF and bisphenol A based room temperature processable CEMs

5.1.1. FTIR monitoring of Cure kinetics of bisphenol AF and bisphenol A based CEMs

5.1.2. Thermal properties of bisphenol AF and bisphenol A based CERs..100 5.1.3. Rheological measurements of PCs derived from bisphenol AF and bisphenol A based CEMs





5.1.4. Young’s moduli and coeffecients of thermal expansion for PCs derived from bisphenol AF and bisphenol A based CEMs

5.1.5. Dielectric measurements PCs derived from bisphenol AF and bisphenol A based CEMs

5.1.6. Template assisted fabrication of polycyanurate nanorods and their hydrolytic stability

5.2. Conclusions

Experimental

5.3.

5.3.1. Synthesis of oligomeric aromatic ether with pendant methoxy and terminal hydroxy groups 1a and 1b:

5.3.2. Deprotection of pendant methoxy groups to yield 2a and 2b:

5.3.3. Synthesis of oligomeric aromatic ether with pendant and terminal cyanate groups 3a:

5.3.4. Curing of CEMs to PC thermosets:

5.3.5. Monitoring the kinetics of thermal curing of CEMs 3:

5.3.6. Template assisted fabrication of polycyanurate nanorods (PCNs) and determination of their hydrolytic stability:

References

5.4.

Chapter 6

6. Polyether ether ketone (PEEK) Surface Functionalization via Surface Initiated Atom Transfer Radical Polymerization

6.1. Immobilization of ATRP initiator and subsequent polymer brush growth by SI-ATRP

6.2. Characterization of PEEK surface modified by SI-ATRP

6.2.1. Surface topography by AFM and SEM

6.2.2. Surface chemical characterization by FTIR, XPS and Contact angle goniometry

6.3. Demonstration of properties imparted to PEEK surface by polymer brushes

6.4. Conclusions

Experimental

6.5.

6.5.1. Reduction of PEEK surface carbonyl groups to the hydroxy groups (PEEK-OH).....123 6.5.2. Immobilization of ATRP Initiator on the PEEK-OH Membrane

6.5.3. SI-ATRP on the surface of PEEK-Br membrane

6.5.4. Exploiting the surface charge: Electrostatic interaction of PEEK-PolySPM and Rhodamine 6G

6.5.5. Bio-repellency evaluation: Growth E. coli bacteria on the surface of pristine PEEK and PEEK-MeOEGMA

6.5.6. Thermally responsive switching between hydrophilicity and hydrophobicity of PEEKPolyNIPAAm: Measurement of static water contact angles above and below the LCST:.......124 Reference

6.6.

Chapter 7

7. Plasma Polymerised Polyallylamine as ad-layer for Anchoring Surface initiated polymerization initiator on polymeric (PEEK, PI, PET) Surfaces: A General Route to Polymer Surface Functionalization via SI-ATRP.......... 126

7.1. Substrate independent anchoring of ATRP initiator and subsequent SIATRP 128 7.1.1. XPS analysis

7.2. Conclusions

Experimental

7.3.

7.3.1. Deposition of plasma polymerised PAAm on polymer surface

7.3.2. Immobilization of ATRP Initiator on the PEEK-OH Membrane

7.3.3. PolyMeOEGMA brush25

Reference

7.4.

Chapter 8

8. A facile route for the preparation of azideterminated polymers. “Clicking” macromolecular building blocks on planar surfaces and nanochannels............... 136

8.1. Synthesis of the azide-terminated azo initiator.

8.2. Synthesis of azide-terminated polyelectrolytes

8.3. “Clicking” polyelectrolyte chains on planar Si surfaces

8.4. Functionalization of single conical polymer nanochannels via a “click” chemistry approach

8.5. Conclusions

8.6. Experimental Section

8.6.1. Synthesis of acyl chloride-terminated azo initiator (2)

8.6.2. Synthesis of 3-Amino-1-azide propane (4)

8.6.3. Synthesis of azide functionalized azo initiator (5)

8.6.4. Synthesis of azide-terminated polyelectrolytes

8.6.5. Click chemistry on the silicon surface

8.6.5.1. Synthesis of ethynyldimethylchlorosilane (EDMS)

Functionalization of silicon wafer with 10 and subsequent click chemistry...151 8.6.5.2.

8.6.6. Functionalization of the conical nanochannel inner surface with alkyne groups and subsequent click chemistry

8.6.7. Gel permeation chromatography (GPC)

References

8.7.

Chapter 9

9. Facile Large-Scale Fabrication of Proton Conducting Channels

9.1. Grafting of polyelectrolyte brush on the surface of ordered macroporous membranes via SI-ATRP

9.1.1. Characterization

9.1.2. Proton conductivity

9.2. Development of self-humidifying proton conducting channels generated by scaffolded polyelectrolyte brushes “doped” with hygroscopic monomer units.....162 9.2.1. Characterization and proton conductivity measurements..................164

9.3. SI-ATRP of 2-acrylamino-2-methylpropane sulfonate in macroporous silicon 169

9.4. Conclusions

Experimental

9.5.

9.5.1. Synthesis of initiator (1) for SI-ATRP

9.5.2. Anchoring 1 onto the surface of macroporous silica and subsequent PEB growth by SIATRP 171 9.5.3. Effective loading by weighing the macroporous silica membrane after each step of functionalization

9.5.4. Ion exchange capacity

9.5.5. Water uptake study

9.5.6. Proton Conductivity measurements

References

9.6.

10. Stimuli responsive artificially fabricated solidstate nanopores

10.1. Ionic transport through single solid state nanopore controlled with thermally nanoactuated macromolecular gate

10.1.1. Nature: The Inspiration I

10.1.2. Grafting of polyNIPAAm brush at the surface of PI membrane bearing a single conical nanopore via SI-ATRP

10.1.3. Pore dimensions

10.1.4. Thermally induced nano-actuation read by current-voltage (I-V) curve measurements

10.2. Single conical nanopores displaying pH-tunable rectifying characteristics.

Manipulating ionic transport with zwitterionic polymer brushes

10.2.1. Nature-The Inspiration II

10.2.2. Grafting of poly-L-lysine brush at the surface of PI membrane bearing a single conical nanopore via surface initiated conventional radical polymerization and current-voltage (I-V) curves measurement

10.3. Experimental Section

Functionalization of nanopore bearing PI surface with ethylenediamine............187 10.3.1.

Immobilization of ATRP initiator on the membrane:

10.3.2.

10.3.3. PolyNIPAAm brush growth

10.3.4. Anchoring 4,4′-azobis(4-cyanopentanoic acid) on the surface of PI membrane with single conical nanopore

10.3.5. Poly-L-Lysine brush growth on initiator functionalized single nanopore-containing PI membrane 188 References

10.4.

Summary and outlook

11. Summary and outlook

11.1. Polyether ether ketone-Cyanate ester resins an innate combination: A proposal 191 11.2. Surface initiated polymerization from initiator functionalized flat polymeric surfaces

11.3. Click chemistry as a new grafting-to methodology boosted up by cRP 195 11.4. Functional porous materials achieved by a combination of elements form macromolecular and materials research fields

11.5. Facile Large-Scale Fabrication of Proton Conducting Channels..........195 11.6. Mimicing the ever-versatile ever-inspiring nature: Stimuli responsive artificially fabricated solid-state nanopores

Acknowledgement

List of Publications

List of Abbreviations PEEK Polyether ether ketone CEM Cyanate ester monomer CER Cyanate ester resin PC Polycyanurate PCN Polycyanurate nanorods PET Polyethylene terephthalate PI Polyimide PAEK Polyaromatic ether ketone AEK Aryl or aromatic ether ketone AEKOM Aromatic ether ketone Oligomeric mixture PAA Polyallylamine AMPS 2-Acrylamino-2-methylpropane sulfonate MPS 3-(Methacryloyloxy)propane-1-sulfonate NIPAAm N-Isopropylacrylamide MeOEGMA Mono-methoxy terminated oligo(ethylene glycol)methacrylate BIBr 2-Bromoisobutyryl bromide.

PEL Polyelectrolyte PEG Polyethylene glycol EDA Ethylene diamine EDC N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride Glass transition temperature Tg Melting temperature Tm T5% Temperature at 5% weight loss LCST Lower critical solution temperature CA Contact angle RH Relative humidity WU Water uptake IEC Ion exchange capacity DSC Differential scanning calorimetry TGA Thermogravimetric analysis FTIR Fourier transform infrared spectroscopy ATR-IR Attenuated total reflection infrared spectroscopy AFM Atomic force microscopy XPS X-ray photoelectron spectroscopy SEM Scanning electron microscopy AAS Atomic absorption spectroscopy GPC Gel permeation chromatography SIP Surface initiated polymerization SI-ATRP Surface initiated atom transfer radical polymerization ATRP Atom transfer radical polymerization Conventional radical polymerization cRP

Chapter 1



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