Synthesis and characterization of alternating poly(amide urethane)s [Elektronische Ressource] / vorgelegt von Bhaskar Sharma

Sharma

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2004
• Nombre de lectures: 23
• Langue: English

Extrait

Synthesis and Characterization of Alternating
Poly(amide urethane)s




Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der Rheinisch-Westfälischen Technischen HochschuleAachen
zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften
genehmigte Dissertation


vorgelegt von

Master of Science
Bhaskar Sharma
aus Agra (Indien)


Berichter: Universitätsprofessor Dr. rer. nat. Hartwig Höcker
Universitätsprofessor Dr. rer. nat. Martin Möller


Tag der mündlichen Prüfung: 24. März 2004



Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar. ACKNOWLEDGMENTS

I would like to take this opportunity to acknowledge my heartfelt gratitude to Prof.
Dr. H. Höcker, who allowed me to carry out the PhD work at the Department of
Textile Chemistry and Macromolecular Chemistry, RWTH Aachen, from March 2001
to March 2004.

I am highly indebted to Dr. Helmut Keul, Senior Scientist at the Department of
Textile Chemistry and Macromolecular Chemistry, RWTH Aachen, for his constant
encouragement, thought provoking ideas, his ever sincere guidance and constructive
criticism for the successful completion of my PhD work.

I, indeed, would like to extend my profound sense of gratification to Prof. Dr. M.
Möller, Director of the German Wool Research Institute, Aachen, for being a co-
referee for my PhD defence and allowing me to work as a Research Associate in his
group.

Many hearty thanks go to all my colleagues working at the Department of Textile
Chemistry and Macromolecular Chemistry, RWTH Aachen, for their cooperation and
friendly discussion. In Particular, I owe my sincere thanks and gratefulness to my
colleague, Mr. Luc Ubaghs for his constructive criticism and invaluable suggestions
during the entire PhD work. Moreover, I am equally delighted to thank my other
colleagues, Dr. Thomas Fey, Dr. Peter Pilgrim, Mrs. Martina Mennicken, Mr. Günter
Prömpers and Mr. Sven Balk for their timely help.

An appreciation merely with a few words seems to be inappropriate to gratefully
acknowledge Mr. Rainer Hass for his painstaking and cordial support at laboratory
bench, particularly in hour of dire need.

I am grateful to Dr. Ton Loontjens and Dr. Rolf Van Benthem, DSM Research,
Geelen, the Netherlands, for their helpful discussions throughout the research project.
It is also proud privilege to on record my sincere thanks to Dr. Ajay Taneja, Reader of
Chemistry Department, St, John’s College, Agra, Dr. O. P. Garg, Founder of Garg
Foundation at the German Wool Research Institute, Aachen, and Dr. V. K. Naithani,
Senior Scientist at the , Aachen, for their needful
help and moral support.

The financial support of the Garg Foundation, and of DSM Research, Geelen, the
Netherlands are duly acknowledged.

Last but not the least, special thanks to all my Aachener Indian friends for their ever
lasting affection and tremendous help during the stay in Aachen.

Though, many have not been mentioned, none is forgotten.















Dedicated to my Parents





Publications:
1. Synthesis and Characterization of Alternating Poly(amide urea)s and
Poly(amide urethane urethane)s from e-Caprolactam, Diamines, and Diphenyl
carbonate or Ethylene carbonate, L. Ubaghs, B. Sharma, H. Keul, H. Höcker,
T. Loontjens, R. van Benthem, e-Polymers 2003, no. 068.

2. Synthesis and Characterization of Alternating Poly(amide urethane)s from e-
Caprolactam, Amino alcohols, and Diphenyl carbonate, B. Sharma, L.
Ubaghs, H. Keul, H. Höcker, T. Loontjens, R. van Benthem, Polymer 2004,
45, 5427.

3. Microstructure and Properties of Poly(amide urethane)s Derived from e-
Caprolactam, Amino alcohols, and Diphenyl carbonate or Ethylene carbonate:
Comparison of the Reactivity of a-Hydroxy-w-O-phenyl urethanes and a-
Hydroxy-w-O-hydroxyethyl urethanes, B. Sharma, L. Ubaghs, H. Keul, H.
Höcker, T. Loontjens, R. van Benthem, Macromol. Chem. Phys. 2004, 205,
1536.

4. Synthesis and Characterization of Alternating Poly(amide urethane)s using e-
Caprolactone, Diamines, and Diphenyl Carbonate, B. Sharma, H. Keul, H.
Höcker, T. Loontjens, R. van Benthem (submitted to Polymer).

Poster presentation:
1. New polymers for powder coatings, B. Sharma, L. Ubaghs, H. Keul, H.
thHöcker, T. Loontjens, R. van Benthem at 12 Rolduc Polymer Meeting
(25.05.03-28.05.03) , Kerkrade, the Netherlands.

Table of Contents
Table of Contents

List of Abbreviations ....................................................................................................V
Summary.....................................................VII
1 Introduction............1
1.1 Powder coatings .............................................................................................1
1.1.1 Epoxy powder coatings..........................................1
1.1.2 Hybrid powder coatings.........................................3
1.1.3 Polyester powder coatings.....3
1.1.4 Acrylic powder coatings........................................5
1.1.5 UV-curable powder coatings .................................5
1.2 Polyurethanes.................................6
1.2.1 Technical polyurethanes........................................7
1.2.2 New development in polyurethane chemistry........8
1.2.3 Blocked isocyantes...............................................................................14
1.3 Alternating poly(amide urethane)s...............................................................15
2 Target and specific aims......................19
3 Results and discussion .........................................................21
3.1 Synthesis and characterization of alternating poly(amide urethane)s from e-
caprolactam, amino alcohols, and diphenyl carbonate ................................21
3.1.1 Synthesis of alternating poly(amide urethane)s in three steps from e-
........................21
3.1.1.1 Kinetic aspects of the polycondensation of a-hydroxy-w-O-phenyl-
urethanes ..........................................................................................27
3.1.1.2 Thermal properties of poly(amide urethane)s..................................28
3.1.1.3 Polycondensation of a-hydroxy-w-O-phenyl urethanes catalyzed
with Bu Sn(OCH ) : Mechanistic consideration............................32 2 3 2
3.1.1.4 Mechanistic view of the formation of a methoxy end group of
poly(amide urethane)s......................................................................33
3.1.1.5 Influence of different parameters on the polycondensation of a-
hydroxy-w-O-phenyl urethanes .......................................................35
3.1.1.6 Influence of catalyst.........................................38
3.1.1.7 Influence of temperature..................................41
I Table of Contents
3.1.1.7.1 Polycondensation of an a-hydroxy-w-O-phenyl urethane at two
temperatures...............................................................................41
3.1.1.7.2 Difference in the microstructure of poly(amide urethane)s
obtained via polycondensation at different temperatures ..........44
3.1.1.8 Polycondensation of a poly(amide urethane)s in DMPU................47
3.1.2 Polycondensation of a-hydroxy-w-amino amides with diphenyl
carbonate ..............................................................................................50
3.2 Synthesis of poly(amide urethane)s with predetermined molecular weight
and functional end groups............................................................................53
3.2.1 Synthesis of linear poly(amide urethane)s with predetermined
molecular weight and functional end groups.......53
3.2.2 Three arm star shaped poly(amide urethane)s with predetermined
molecular weight and functional end groups .......................................55
3.2.3 Synthesis of poly(amide urethanes)s with predetermined functional end
groups...................................................................57
3.2.3.1 Synthesis of poly(amide urethane)s with carboxy end groups ........57
3.2.3.2 Synthesis of poly(amide urethane)s with hydroxy end groups........59
3.2.4 Thermal properties of poly(amide urethane)s with different functional
end groups............................................................................................62
3.3 Synthesis of poly(amide urethane)s using e-caprolactam, amino alcohols,
and carbonic acid esters ...............................................................................63
3.3.1 Synthesis of poly(amide urethane)s from e-caprolactam, amino
alcohols and ethylene carbonate ..........................................................63
3.3.1.1 Comparison between the microstructure of poly(amide urethane)s 65
3.3.1.2 Comparison of thermal properties of two homologous series of
poly(amide urethane)s...............................