Block copolymers for adhesion improvement synthesized via RAFT-mediated polymerization

223 Pages·2017·6.79 MB·English

Block copolymers for adhesion improvement synthesized via
RAFT-mediated polymerization
Citation for published version (APA):
Bozovic Vukic, J. (2006). Block copolymers for adhesion improvement synthesized via RAFT-mediated
polymerization. [Phd Thesis 1 (Research TU/e / Graduation TU/e), Chemical Engineering and Chemistry].
Technische Universiteit Eindhoven. https://doi.org/10.6100/IR609508
DOI:
10.6100/IR609508
Document status and date:
Published: 01/01/2006
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Download date: 03. Jan. 2023
Block copolymers for adhesion improvement
synthesized via RAFT-mediated polymerization

Jelena Božović Vukić

Јелена Божовић Вукић
Cover: The background represents AFM picture of the copper surface. The figures
on the front side represent SAN-b-SMAh and P4VP-b-SAN block copolymers and
their interaction with the copper coating. The figure at the back side represents self-
organized block copolymers.
Created by Srdjan Kisin and Jelena Božović Vukić.
Block copolymers for adhesion improvement
synthesized via RAFT-mediated polymerization

PROEFSCHRIFT

ter verkrijging van de graad van doctor aan de
Technische Universiteit Eindhoven, op gezag van de
Rector Magnificus, prof.dr.ir. C.J. van Duijn, voor een
commissie aangewezen door het College voor
Promoties in het openbaar te verdedigen
op dinsdag 20 juni 2006 om 16.00 uur

door

Jelena Božović Vukić

geboren te Čačak, Servië
Dit proefschrift is goedgekeurd door de promotoren:

prof.dr. C.E. Koning
en
prof.dr.ir. L. Klumperman

A catalogue record is available from the Library Eindhoven University
of Technology

ISBN-10: 90-386-2688-6
ISBN-13: 978-90-386-2688-8

This project forms part of the research program of the Innovation
Oriented research Program Surface Technology (IOP-OT) #IOT01008.
To my dearest family:
to my parents, grandparents, brother and husband,
thank you for all support!

TABLE OF CONTENTS

Chapter 1 Introduction .................................................................1
1.1 Polymers and Acrylonitrile-butadiene-styrene (ABS)....................................1
1.2 Metal coating and adhesion............................................................................2
1.3 Metal coating on the ABS substrate and surface modifiers............................3
1.4 Block copolymers as Adhesion Promoting Linkers........................................4
1.5 Outline and aim of the thesis..........................................................................5
References.................................................................................................................7

Chapter 2 Homopolymers, Copolymers and Block copolymers:
Synthesis and Characterization- Theory............................................9
2.1 How to improve properties of PSTY?..........................................................10
2.2 A classification of copolymers......................................................................12
2.3 Why to go from free radical polymerization to living polymerization?.......14
2.4 Living/Controlled Radical Polymerization...................................................15
2.4.1 Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated
polymerization..........................................................................................................16
2.4.2 Block copolymers by RAFT.................................................................20
2.5 Characterization of polymers: molar mass (M) and molar mass distribution
(MMD) .......................................................................................................................22
2.5.1 Size Exclusion Chromatography (SEC)................................................22
2.5.2 Gradient Polymer Elution Chromatography (GPEC)...........................24
2.5.3 Matrix Assisted Laser Desorption/Ionization-Time Of Flight-Mass
Spectrometry (MALDI-TOF-MS)............................................................................25
2.6 Conclusions...................................................................................................27
References...............................................................................................................28

Chapter 3 Synthesis and Characterization of starting blocks
carrying a RAFT group: SAN, SMAh and P4VP..................................31
3.1 Introduction...................................................................................................32
3.2 Experimental Section....................................................................................33
3.2.1 Materials...............................................................................................33
3.2.2 Synthetic Procedures.............................................................................34
3.2.3 Analysis and Measurements.................................................................39
3.3 Results and Discussion.................................................................................40
3.3.1 MALDI-TOF-MS and end groups........................................................41
3.3.2 RAFT-functional SAN starting block...................................................43
3.3.3 RAFT-functional SMAh starting block................................................53
3.3.4 RAFT-functional P4VP starting block..................................................59
3.4 Conclusions...................................................................................................66
References...............................................................................................................68

Chapter 4 Chain extension of SAN via RAFT-mediated
polymerization.................................................................................71
4.1 Introduction...................................................................................................72
4.2 Experimental Section....................................................................................73
4.2.1 Materials...............................................................................................73
4.2.2 Synthetic Procedures.............................................................................73
4.2.3 Chain extension of low molar mass SAN.............................................74
4.2.4 Chain extension of high molar mass SAN............................................75
4.2.5 Analysis and Measurements.................................................................76
4.3 Results and Discussion.................................................................................77
4.3.1 Starting block. What is important for block copolymerization?...........77
4.3.2 Chain extension of low molar mass SAN either with STY or with STY
and MAh ...............................................................................................................80
4.3.3 Chain extension of high molar mass SAN with STY and MAh...........91
4.4 Conclusions...................................................................................................96
References...............................................................................................................97

Chapter 5 Block copolymerization in solution via RAFT-mediated
polymerization................................................................................99
5.1 Introduction.................................................................................................100
5.2 Experimental Section..................................................................................101
5.2.1 Materials.............................................................................................101
5.2.2 Synthetic Procedures...........................................................................101
5.2.3 Analysis and Measurements...............................................................105
5.3 Results and Discussion...............................................................................108
5.3.1 Chain extension of SMAh with an azeotropic mixture of STY and AN
(63:37 mol/mol)......................................................................................................108
5.3.2 SMAh-b-SAN block copolymers to be used as adhesion promoting
linkers between ABS and copper............................................................................120
5.3.3 Chain extension of P4VP with an azeotropic mixture of STY and AN....
.............................................................................................................122
5.3.4 Characterization of block copolymers by gradient polymer elution
chromatography (GPEC)........................................................................................127