Thèse présentée pour obtenir le grade de Docteur de lUniversité Louis Pasteur

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Niveau: Supérieur, Doctorat, Bac+8
Thèse présentée pour obtenir le grade de Docteur de lUniversité Louis Pasteur Strasbourg I Discipline: Chimie Physique par Marianne Gaborieau Solid-state NMR investigation of spatial and dynamic heterogeneity in acrylic pressure sensitive adhesives (PSAs) compared to model poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) Soutenue publiquement le 10 mars 2005 Membres du Jury : Directeur de Thèse: M. Bernard Meurer, Chargé de Recherche, Strasbourg Rapporteur Interne : M. Gilbert Weill, Professeur Emérite, Université Strasbourg I Rapporteur Externe : Mme Bernadette Charleux, Professeur, Université Paris VI Rapporteur Externe : M. Piotr Tekely, Directeur de Recherche, Nancy Examinateur : M. Hans Wolfgang Spiess, Professeur, Université de Mayence, Allemagne Examinateur : M. René-Paul Eustache, Ingénieur de Recherche, Arkema

  • many nice evenings

  • grade de docteur de luniversité

  • polymer physics

  • state nmr

  • nancy examinateur

  • dsc measurements

  • nmr problems

  • directeur de la recherche


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Thèse présentée pour obtenir le grade de
Docteur de l´Université Louis Pasteur
Strasbourg I

Discipline: Chimie Physique
par Marianne Gaborieau






Solid-state NMR investigation
of spatial and dynamic heterogeneity
in acrylic pressure sensitive adhesives (PSAs)
compared to model poly(n-alkyl acrylates)
and poly(n-alkyl methacrylates)









Soutenue publiquement le 10 mars 2005


Membres du Jury :

Directeur de Thèse: M. Bernard Meurer, Chargé de Recherche, Strasbourg
Rapporteur Interne : M. Gilbert Weill, Professeur Emérite, Université Strasbourg I
Rapporteur Externe : Mme Bernadette Charleux, Professeur, Université Paris VI e : M. Piotr Tekely, Directeur de Recherche, Nancy
Examinateur : M. Hans Wolfgang Spiess, Professeur, Université de Mayence, Allemagne
Examinateur : M. René-Paul Eustache, Ingénieur de Recherche, Arkema





Voici le terme d’un long périple
dans l’espace et dans le temps.

This is the end of a long travel through Space and Time.
Marc Gaborieau, Le Népal, une introduction à la connaissance du monde népalais,
Kailash éditions, Paris, 1995, p. 291






La verdadera ciencia enseña, sobre todo,
a dudar y a ser ignorante.

True science teaches, above all, to doubt and to be ignorant.
Miguel de Unamuno, Tragic sense of life, 1913










†à Marc et Catherine , Thomas, Julie et Capucine
à Patrice ...

i
ii Acknowledgements

Thanks are due to Bernard Meurer for accepting the official supervision of this work .
I would like to gratefully acknowledge Hans W. Spiess for allowing me to conduct my PhD work in his
research group at the Max Planck Institute for Polymer Research (Mainz, Germany). This was a fruitful
experience on a scientific as well as on a human point of view. I benefited from his never failing and
motivating support.
I would like to thank Manfred Wilhelm for his supervision at the beginning of this work, for his readiness
to answer my questions on various topics: science, Riesling, Pfalz...
Special thanks to Robert Graf for the never failing assistance concerning all practical spectrometer and
NMR problems, for enlightening discussions about polymer physics, for careful reading of the manuscript
and help for final corrections, as well as for many nice evenings around a good meal with Katharina ...
I am indebted to Atofina for financial support and for providing the investigated pressure sensitive
adhesive samples, to François Beaume for interesting discussions, to René-Paul Eustache, Stéphane
Lepizzéra, Françoise Cochet and Olivier Colombani for the interest they take in my project.

I am grateful to Bernadette Charleux, Gilbert Weill, and Piotr Tekely for accepting to read this manuscript
and report on this work.
Thanks are due to Nawel Khelfallah and Gilbert Weill for helping me organizing the defense.

I am very grateful to Mario Beiner from the University of Halle Wittenberg (Germany) for his invitation
and nice welcome in Halle, for numerous and fruitful disciussions. My chemist point of view of the
nanophase separation was enlightened by his physicist experience.

I would like to thank Prof. Pakula for a friendly and fruitful cooperation on local dynamics in
polyacrylates, and Stefan Kahle for numerous dielectric relaxation measurements, analysis and
explanations.


In a random order, I would like to express many thanks to the Spiess group and the MPI-P, in particular:

Uta Pawelzik for her kind help during the poly(n-alkyl acrylates) synthesis and an introduction to various
characterization techniques
Verona Maus for many urgent DSC measurements and friendly discussions
The "Chemielabor" team for the nice working atmosphere : Uli Jonas, the Neidhöfers, Kiki, Arancha, Diane,
Diana, Michelle, Silvia, Petra, Charles-André, etc.

iiiMichael Neidhöfer, Axel Kretschmer, Robert Graf and Ingrid Fischbach for their patient explanations of
the way of operating a spectrometer, and how to properly record NMR data
Katja Klimke and Matt Parkinson for the precious advices and experimental tricks concerning the
branching quantification
Manfred Hehn, Hans Peter Reich for the efficient technical assistance with spectrometers, for always
finding solutions to the problems arising from annoying samples, mechanics or electronics
Frank Keller for computer assistance on a French-speaking laptop with French keyboard

The unforgettable 3M team of the Massenzimmer: Mark McCormick, Matt Parkinson, Michael Pollard,
for my big progress in English language, journeys in time, Jazz-and-beer evenings, discussions about NMR
(what about that Mainz 05?) and more, and making me feel at home ... I thank them also, as well as Attila
Domján, Sheng-Shu Hou, Christian Krüger, Diana Boos, Timm Doetsch for the nice working atmosphere in
room of Massen and Zimmer
Ingrid Fischbach, Katja Klimke, Michael Neidhöfer, for a friendly time together by Bürochef and Alumni

Barbara Doerner-Stute, the good soul of the Spiess group, for her kindness, her patience, her continuous
help concerning administrative and morale things.
Corinna Kautz for successfully continuing this difficult task.

Michael Wind for providing the poly(n-alkyl methacrylates) samples together with the characterization of
the dynamic heterogeneity, and tricks for low temperature measurements.

The Spiess group and the MPI-P in general for the multicultural experience: among others Gillian from
Canada, Erli from Indonesia, Alexandra from Italy, Eva from Spain, Han-Bong from Korea/Saarland,
Grazyna from Poland, Julia form Russia/America/Israel, Shi Feng from China, Sanjay from
India/Netherlands, Yao from China, Doene, Fatma, Mehmet and Bahar from Turkey, Juana and Carlos
from Mexico, Rafa from Catalonia, Laurent and Baptiste from France, Britt from the USA, Karen and
Michael from Germany...

Frau Nanz for many urgent printing / cuting / binding


I am grateful to my parents and brother and sisters for encouraging higher studies in a field foreign to them
(“and at the end you will tell us why the adhesives stick ?”), my grandmother for many phone calls.
A very special thank goes to Patrice for his continuous and attentive help, from countless 6h train trips to
careful reading of solid-state NMR or dynamics study, and so much more ...

I would like to apologize to all the ones I did not have enough space or memory to namely thank...
iv Table of contents


Résumé de la thèse...............................................................................................ix
I. Introduction .......................................................................................................ix
A. Contexte.................................................................................................................ix
B. Présentation des échantillons ...................................................................................x
C. Démarche...............................................................................................................xi
II. Etude du branchement......................................................................................xi
A. Etat de l’art.............................................................................................................xi
13B. Quantification du branchement par RMN C ....................................................... xi
C. Détection des branches longues par SEC multi-détection .................................... xii
III. Filtre dipolaire et dynamique locale dans des polymères fondus ...............xiii
A. Présentation des échantillons étudiés................................................................... xiii
1B. Technique de diffusion de spin H nucléaire avec filtre dipolaire....................... xiv
C. Contraste dynamique dans les PnAAs et PnAMAs fondus ...................................xv
D. Sélection réelle et mécanisme de diffusion de l’aimantation.................................xv
E. Quantification de la dynamique locale................................................................. xvi
F. Interprétation des résultats .................................................................................. xvii
G. Comparaison de tous les échantillons ................................................................ xviii
IV. Conclusion générale et perspectives ............................................................xviii
V. Plan du manuscrit de thèse.............................................................................xix
Part 0: General introduction................................................................................ 1
Part 1: Literature survey and motivation 5
7-10I. Pressure sensitive adhesive materials ..........................................................7
A. Definition and applications ......................................................................................7
B. Composition.............................................................................................................8
C. Properties and testing .............................................................................................12
2D. Influence of chemical and physical factors on the adhesive properties ................16
E. Mechanism of debonding.......................................................................................20
F. Conclusion23
II. Basic principles of solid-state nuclear magnetic resonance..........................24
A. General introduction to NMR ................................................................................24
B. Introduction to solid-state NMR ............................................................................28
C. Single pulse excitation ...........................................................................................34
13D. Cross-polarization (CP) C-NMR spectra.............................................................35
E. Two-dimensional wideline separation (2D-WISE)................................................37
F. 1 H Longitudinal or spin-lattice relaxation T .........................................................39 1
G. Dipolar filter...........................................................................................................39
H. 1 81,82 H nuclear spin diffusion ..................................................................................41
94I. Nuclear Overhauser effect (NOE) .......................................................................48
III. Conclusion and strategy...................................................................................56
A. Branching...............................................................................................................56
B. Chain dynamics......................................................................................................57
C. Nanostructuring
vPart 2: Presentation and characterization of PSA and model samples ........... 59
I. Description and characterization of the industrial pressure sensitive
adhesive samples...............................................................................................61
A. Description.............................................................................................................61
B. Solid content, particle size and calorimetric properties .........................................65
C. Adhesive and mechanical properties......................................................................66
D. Chemical characterization of the samples via solid-state NMR ............................67
II. Description, synthesis and characterization of model samples....................71
A. Comparison of poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) ..............72
B. Presentation of model poly(n-alkyl methacrylate) homopolymers........................73
C. Synthesis of model poly(n-alkyl acrylate) homopolymers ....................................75
D. Characterization of the poly(n-alkyl acrylate) homopolymers ..............................76
13III. Quantification of branching in PSA samples using C NMR .....................78
A. Molecular origin of branching and crosslinking in poly(alkyl acrylates)..............79
13B. Choice of a C NMR technique to quantify branching in poly(alkyl acrylates)...84
C. Branching level quantification and discussion of the branching topology ............94
IV. Multiple-detection SEC of the model poly(n-alkyl acrylates)....................100
199,203A. Overview of the possible SEC methods ......................................................100
B. Determined molar masses ....................................................................................102
C. Investigation of branching....................................................................................103
D. Conclusion on the multiple detection SEC investigations ...................................107
V. Conclusion on samples presentation and characterization ........................108
Part 3: Using and misusing the dipolar filter, example of PEMA................. 111
I. Literature survey on nanostructuring in poly(n-alkyl methacrylates) and
poly(n-alkyl acrylates)....................................................................................113
A. Molecular dynamics and nanophase separation in poly(n-alkyl methacrylates)
5,221(Ph.D. work of Wind)113
B. Nanophase separation in poly(n-alkyl methacrylates) and poly(n-alkyl acrylates)
220(habilitation work of Beiner )............................................................................122
C. Conclusion...........................................................................................................126
II. Dynamic contrast in poly(ethyl methacrylate), PEMA ..............................127
A. 1 H static spectra....................................................................................................127
B. 2D-WISE..............................................................................................................128
C. Conclusion on the dynamic contrast ....................................................................131
1III. Monitoring the H magnetization of the more mobile parts after the dipolar
filter..................................................................................................................131
1A. New type of sample for the H nuclear spin diffusion technique with dipolar filter131
B. Changes done to data analysis .............................................................................132
C. Results obtained for poly(ethyl methacrylate) at ca T +70 K..............................136 g
IV. Investigation of the actual selection done by the dipolar filter and of the
actual subsequent transfer mechanism ........................................................138
A. Actual selection done by the dipolar filter ...........................................................139
B. Coherent or incoherent magnetization transfer ? .................................................141
C. Mathematical equations describing the magnetization decay..............................143
D. Conclusion on the actual selection and subsequent magnetization transfer ........146
V. Conclusion on use and misuse of the dipolar filter .....................................146
A. Summary of the investigation of PEMA at ca T +70 K ......................................146 g
B. Conclusion on the use and misuse of the dipolar filter ........................................147

vi Part 4: Nuclear Overhauser Effect investigated in model poly(n-alkyl
acrylates) using the dipolar filter........................................................... 149
I. Investigation of the dynamic contrast in model poly(n-alkyl acrylates) ...151
A. 1 H static spectra....................................................................................................151
B. 2D-WISE..............................................................................................................153
C. Conclusion on the dynamic contrast ....................................................................155
II. Investigation of NOE in the model poly(n-alkyl acrylates) using the dipolar
filter..................................................................................................................156
A. Actual selection done by the dipolar filter ...........................................................156
B. Recording and processing NOE data using the dipolar filter in PEA at T +70 K157 g
ABC. Temperature dependence of q ⋅τ for sample PEA........................................165 AB C
ABD. Temp ⋅τ for all PnAA samples...............................166 AB C
E. Conclusion on the measurement of NOE in model PnAAs .................................167
III. Interpretation of NOE results in model poly(n-alkyl acrylates)................168
A. 1 H longitudinal relaxation in model PnAAs ........................................................168
B. Relaxation processes in model PnAAs ................................................................170
IV. Conclusion on NOE in model poly(n-alkyl acrylates).................................175
A. Conclusion...........................................................................................................175
B. Outlook.................................................................................................................
Part 5: Nuclear Overhauser Effect investigated in model poly(n-alkyl
methacrylates) using the dipolar filter; comparison with acrylate models
and PSAs................................................................................................. 177
I. Investigation of the dynamic contrast in model poly(n-alkyl methacrylates)179
A. 1 H static spectra....................................................................................................179
B. 2D-WISE..............................................................................................................181
C. Conclusion on the dynamic contrast ....................................................................181
II. Investigation of NOE in the model poly(n-alkyl methacrylates) using the
dipolar filter181
A. Actual selection done by the dipolar filter ...........................................................181
B. Recording and processing NOE data using the dipolar filter in PEMA at T +67 K184 g
ABC. Temperature dependence of q ⋅τ for poly(ethyl methacrylate) samples ......186 AB C
ABD. Temp ⋅τ for model PnAMA samples.....................187 AB C
E. Discussion of the biexponential behavior observed at low temperatures ............188
F. Conclusion on the measurement of NOE in model PnAMAs..............................189
III. Interpretation of NOE results in model poly(n-alkyl methacrylates) .......190
A. 1 H longitudinal relaxation in model PnAMAs.....................................................190
B. Relaxation processes in model PnAMAs.............................................................192
IV. Comparison of model and industrial samples .............................................195
A. Comparison of all model samples........................................................................195
B. Comparison of model and industrial samples ......................................................198
V. Conclusion on NOE in model poly(n-alkyl methacrylates) and on the
comparison of all samples..............................................................................201
A. Local nanophase separation .................................................................................201
B. Local relaxation processes detected by the NOE with dipolar filter....................201
C. Comparison with industrial samples ....................................................................202



viiPart 6: General conclusion and outlook ......................................................... 203
I. General conclusion .........................................................................................205
A. Branching.............................................................................................................205
B. Nanophase separation...........................................................................................206
C. NOE with dipolar filter ........................................................................................207
D. Chain dynamics....................................................................................................207
II. Outlook............................................................................................................208
A. Branching208
B. Nanophase
C. Chain dynamics209
D. NOE with dipolar filter
E. Characterization of PSAs .....................................................................................210
Part 7: Appendices............................................................................................ 211
I. Properties of the investigated samples .........................................................213
A. Synthesis of the industrial pressure sensitive adhesive samples..........................213
B. the model poly(n-alkyl acrylates)....................................................214
C. Characterization of the first synthesized poly(n-alkyl acrylates).........................217
D. Samples storage....................................................................................................218
II. Conditions of the experiments.......................................................................219
A. DSC, TGA, SEC and solution-state NMR...........................................................219
B. Solid content and mean particle diameter of latices, casting of films..................220
C. Solid-state NMR..................................................................................................220
III. Viscoelastic properties and stereochemistry of polymers, characterization
of homogeneous networks..............................................................................235
A. Basic concepts relative to viscoelastic properties ................................................235
280-282B. Stereochemical definitions and notations relative to tacticity.....................238
C. Characterization of the crosslinking of homogeneous networks .........................240
IV. NMR spectra and SEC results ......................................................................242
A. NMR spectra of model poly(n-alkyl methacrylates)............................................242
B. odel poly(n-alkyl acrylates)....................................................253
C. NMR spectra of PSA samples..............................................................................264
D. SEC results of poly(n-alkyl acrylates) .................................................................268
V. Abbreviations and symbols ...........................................................................270
A. Investigated samples............................................................................................270
B. Monomers, polymers and other chemicals...........................................................
C. Nuclear magnetic resonance................................................................................271
D. Others...................................................................................................................272
VI. Literature references......................................................................................274


viii