Table Of ContentUNSATURATED POLYSULFEDES AND POLYAMINES
VIA ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION
By
JASON PORTMESS
D.
A DISSERTATION PRESENTED TOTHE GRADUATE SCHOOL OF
THE UNIVERSITY OFFLORIDA IN PARTIAL FULFILLMENT
OFTHE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1996
Thisdissertation isdedicatedto thepeople
who have always given me the love, trustandsupport
to chase life'spursuits.
-To My Family-
ACKNOWLEDGEMENTS
The title of Ph.D. would be worthless without the friendships and respect of the
people that I have worked with during my experience. Eternal gratitude must be extended
to Dr. Jim Konzelman and Dr. Dennis Smith for showing me two completely different yet
effective ways ofapproaching the art ofchemistry. Sincere thanks are also extended to the
past and present members ofthe Wagener group: Dr. Chris Marmo, Dr. Kathleen Novak,
Dr. John O'Gara, Dr. Jasson Patton, Dr. Dehui Tao, Dr. Fabio Zuluaga Sophia
Cummings, Tammy Davidson, Fernando Gomez, Lauri Jenkins, Debra Tindall, Dominick
Valenti, MarkWatson, and Shane Wolfe.
The contributions and support of these people cannot be measured, but without
their presence the realization of my scientific goals could not have been possible. Also
special thanks go to the past and present members of the Duran and Reynolds group for
providing a unique multidisciplinary environment which was essential in my scientific and
personal development.
Respects go to Don Cameron, Mike Cruskie, Peter Balanda, Troy Bergstedt, Brian
Hauser, Tim Herod, Scott Whipps, and Paul Whitley for their special friendships and
sharing ofphilosophical ideas.
Special recognition is given to Lorraine Williams for her consistent warm
personality, willingness to help disorganized students, and impeccable proficiency.
Eternal love and respect is extended to Tammy Davidson forbeing my best friend.
Without her support, understanding, and patience the completion of this degree and
manuscript would have been tremendously more difficult.
in
Finally, the most heart felt regards and respect are gratefully extended to Professor
Ken Wagener for his philosophy of learning without restriction, for possessing the
confidence in me that I didn't have formyself, and forbeing a friend and mentor.
IV
TABLE OFCONTENTS
Page
ACKNOWLEDGEMENTS
iii
ABSTRACT
viii
CHAPTERS
INTRODUCTION
1 1
History ofSulfur-Containing Polymers 2
Synthesis ofPolymonosulfides 3
Ring Opening Polymerization 3
Anionic Polymerization 3
Cationic Polymerization 5
Coordinative Ionic Polymerization 6
Condensation Polymerization. 7
Addition ofThiol to biefin .'. .1.11.....................7
Addition ofThiol to Dihalide.
..............8
History ofAmine-Containing Polymers. 9
Synthesis ofMain Chain Polyamines 9
Ring Opening Polymerization. 9
Aziridine Polymerization 10
Azetidine Polymerization. 13
Condensation Polymerization. 14
Development ofOlefin Metathesis and Catalyst Systems. 16
Traditional Catalysts for Olefin Metathesis. 16
Elucidation ofthe Olefin Metathesis Mechanism. 18
Development ofWeil-DefinedMetathesis Catalysts. 22
Olefin Metathesis Polymerization 28
Ring Opening Metathesis Polymerization (ROMP) 29
Acyclic Diene Metathesis Polymerization (ADMET) 32
2 EXPERIMENTAL. 43
Instrumentation and Analysis 43
Materials andTechniques 44
Synthesis and Characterization 46
Sulfur Containing Monomers 46
Synthesis ofBis(3-butenyl)sulfide (5) 46
Synthesis ofBis(4-pentenyl)sulfide (6) 47
Synthesis ofBis(5-hexenyl)sulfide 47
(7).
Bulk Cyclization ofDiallysulfide (4) 47
Solution Cyclization ofDiallysulfide (4)
to 2,5-Dihydrothiophene (8) 48
Synthesis ofPoly(thio-3-hexene-1,6-diylj (9). 48
Synthesis ofPoly(thio-4-octene-l,8-diyl) (10). 48
Synthesis ofPoly(thio-5-decene-1,10-diyl) (11) 49
Synthesis ofPoly[(thio-5-decene- 10-diyl)-co-
1,
(1-octenylene)] (12). 49
Attempted Metathesis ofMonomers4-7
with Ruthenium Catalyst 50
BulkCyclization ofDiallydisuifide (i3). Z~"Z"/.....50
Solution Cyclization ofDiallydisulfide (13) 51
Synthesis ofBis(5-hexenyl)disulfide (15) 51
Attempted metathesis ofBis(5-hexenyl)disuifide (15) 51
Synthesis of2-Propenylthiophene (16) 52
Attempted Metathesis of2-Propenylthiophene (16). 52
Amine Containing Model Compounds, Monomers, and Polymers 53
Attempted BulkMetathesis ofDiallylamine (17)
with Catalyst1 and 2 53
NMR
Solution Reaction ofDialiylamine (17) with
Molybdenum Catalyst 2 53
Attempted Copolymerization of 17 and ,9-Decadiene
1
with Catalyst 2 53
Synthesis of4-Dodecylaminobenzaidehyde (18) 53
Synthesis of4-(Prop-l-ene)-N-Dodecylaniline 54
(19).
Synthesis of4-(Prop-1-ene)-N,N-Dimethylaniline (20) 55
Synthesis of4,4'-Bis(dodecylamino)stilbene (21) 55
Synthesis of4,4'-Bis(dimethylamino)stilbene (22) 55
Synthesis ofN,N-Diallylaniline (23). Z"!""Z""56
Synthesis ofN,N-Dibutenylaniline (24). 56
Synthesis ofN,N-Dipentenylaniline (25) 57
Synthesis of l-Phenyl-3-pyrroline (26). 57
Synthesis ofPoly(N-phenylamino-3-hexene-i,6-diyi) (27) 57
Synthesis ofPoly(N-phenylamino-4-octene-l,8-diyl) (28) 58
Synthesis ofPoly[(N-phenylamino-4-octene-l,8-diyl)-
co-(l-octenylene)] (29) 59
Synthesis ofN-methyl-2-propenyipyrrole (30) 59
Attempted metathesis ofN-methyl-2-propenylpyrroie (30) 60
Attempted Polymerization of 1,9-Decadiene in the
Presence ofAniline. 61
Formation ofCyclic Monomer (31) 61
Formation ofCyclic Monomer (32) and Cyclic
Dimer(33a-c) 61
Attempted Polymerizations ofMonomers 23-25
with Ruthenium Catalyst 3 61
Synthesis ofN,N-Diallylmethylamine (34). 62
Synthesis ofN,N-Dibutenylmethylamine (35) 62
AttemptedBulk Cyclization ofN,N-Diallylmethyiamine (34) 62
Attempted Solution Cyclization ofN,N-Diallylmethylamine (34). .62
Attempted Polymerization ofN,N-Dibutenylmethylamine (35) 63
Synthesis ofN,N-Diallyl-tert-butylamine (36) 63
Attempted BulkCyclization ofN,N-Diallyl-^rr-butylamine (36)....63
Solution Cyclization ofN,N-DiaUyl-teA?-butylamine (36) 63
Synthesis ofN,N-Diallylbenzylamine (37) ^64
Synthesis ofN,N-Dipentenylbenzylamine (38). 64
VI
Attempted Bulk Cyclization ofN,N-Diallylbenzylamine (37) 64
Attempted Solution Cyclization ofN,N-Diallylbenzylamine 64
(37)...
Attempted Polymerization ofN,N-Dipentenylbenzylamine (38) 65
Attempted Metathesis ofMonomers 34-38
with Ruthenium Catalyst 3 65
3 DESIGN AND SYNTHESIS OF UNSATURATED
POLYSULFIDES
67
Historical Review ofSulfide Metathesis 69
Monosulfide Structure and Reactivity Relationships
forADMET. 71
ADMET
Sulfide Cyclization. 73
ADMET
Polymerization ofPolymonosulfides. 75
Polysulfide Thermal Properties 80
ADMET
Attempted Cyclization and Polymerization
ofDisulfide Monomers 84
Model Studies forPolythiophenes viaADMOTZZ"Z!ZZZ!ZZ'"Z 87
Conclusions 88
4 UNSATURATED AROMATIC AND ALIPHATIC AMINES
FOR ACYCLIC DIENEMETATHESIS (ADMET)
POLYMERIZATION. 89
Historical Review ofAmineMetathesis 89
Aromatic AmineModel Compound Structure
and Reactivity Relationships 92
Aromatic Amine MonomerSynthesis 98
Metathesis ofAromatic Monomers 99
Ring Closing Metathesis Cyclization. 99
Synthesis ofUnsaturated Main Chain Polyamines. 101
PolymerAnalysis and Characterization 102
Polyamine Thermal Properties 107
Postcondensation Cyclization Reactions. 110
Aliphatic Amine MonomerStructure Reactivity
Relationships. 113
Conclusions 121
REFERENCES
122
BIOGRAPHICAL SKETCH.
131
vn
Abstract ofDissertation Presented to the Graduate School
ofthe University ofFlorida in Partial Fulfillment ofthe
Requirements forthe Degree ofDoctorofPhilosophy
UNSATURATED POLYSUFIDES AND POLYAMINES
VIA ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION
By
Jason D. Portmess
December 1996
Chairman: Professor Ken Wagener
MajorDepartment: Chemistry
The design and synthesis of unsaturated main chain polysulfides and polyamines
via acyclic diene metathesis (ADMET) polymerization is presented. A series ofsulfur and
aminodienes were designed to delineate the specific monomer structural requirements
ADMET
necessary for polymerization using Schrock's molybdenum alkylidene,
Mo=CHR(N-2,6-C6H3-/-Pr2)[OCMe(CF3)2]2 (M=W or Mo), and Grubbs' ruthenium
alkylidene, RuCl2(=CHPh)(PCy3)2, as catalytic initiators.
Diallylsulfide showed resistance to bulk metathesis, but underwent quantitative
solution cyclization when exposed to Schrock's catalyst. Extended methylene spacing
resulted in clean metathesis polymerization yielding high molecular weight unsaturated
polysulfides with good thermal stability. Efforts to polymerize disulfide monomers proved
ineffective under bulk and solution conditions. Further, sulfide and disulfide monomers
also did not demonstrate significant productive metathesis with the above ruthenium
alkylidene.
vm
N-phenyl derivatized aminodienes showed no resistance to homometathesis and in
certain cases yielded high molecularweight, perfectly linear main chain polyamines. These
polymers are the first example of a direct synthetic route to high molecular weight, main
chain polyamines. These polymers possessed glass transition temperatures below room
temperature and exhibited good thermal stability in nitrogen. Postcondensation cyclics
were also observed at elevated temperatures as a consequence ofintramolecular backbiting
reactions. As demonstrated for sulfur dienes, the ruthenium alkylidene did not produce
unsaturated polysulfides or polydisulfides.
Electronic considerations were also examined for a series of various aliphatic
substituted aminodienes. Only limited metathesis condensation was observed in these
cases, with no high yielding cyclization or polymerization observed underbulk or solution
conditions.
Complete synthesis, characterization and thermal behavior for the derived
unsaturated polysulfides and polyamines are discussed.
IX
CHAPTER
1
INTRODUCTION
Since the inception of the concept of the macromolecule in the early 1920s,
polymer chemistry has played an integral role in almost every modern day technological
advancement. Investigations in the field of polymer science have made major
contributions to the scientific boom of the last 50 years. Intensive research activities in
several laboratories around the world has succeeded in elucidating polymerization
mechanisms and developing new synthetic strategies for engineering polymeric materials
with specifically desired properties. Polymer chemists have personified the ideals of
change and adaptation, constantly searching for a new scientific methodology or
approach to meet the demands and needs ofour changing world. The quest to understand
the application of natural and synthetic macromolecules began over a century ago and
continues to be pursued vigorously today.
This dissertation is a product of the ongoing research in acyclic diene metathesis
(ADMET)
polymerization as a viable route for producing multifunctionalized linear
unsaturated polymers. The work presented herein describes the reactivity of amine and
ADMET
sulfur functionalized dienes toward polymerization. The specific monomer
structural requirements, in addition to the synthesis and characterization of their novel
unsaturated polymers, will be discussed in detail. Due to the diverse nature ofthis study,
it is appropriate to describe the historical and continuing role with which amine and
sulfur compounds play in polymer chemistry. Although the area ofADMET chemistry is
rather unique, several amine and sulfur-containing polymers have been synthesized by
traditional methods which are fairly analogous to the subject of this work, and thus will
