Accessing New Materials from Step-Growth...
Transcript of Accessing New Materials from Step-Growth...
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Accessing New Materials from Step-Growth
Polymerizations of Functionalized Fluorinated Alkenes
Scott T. Iacono
Professor, Department of Chemistry
Director, Chemistry Research Center
US Air Force Academy
Colorado Springs, CO
http://www.usafa.edu/df/dfe/dfer/centers/crc/
FLUOROPOLYMER 2016 – OCT 2016
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The US Air Force Academy
Colorado Springs, CO
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New multidisciplinary materials research laboratory for expanded
sponsor and collaborative capabilities
Monomer synthesis Materials processing Materials characterization
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Composites • Energetics • Organic Electronics
Laboratories for Synthetic Chemistry &
Applied Polymer and Materials Science
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USAFA–BAA-2016
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SRM resin/fiber replacement
Resins for advanced composites
SRM insulation replacement
Replace aerospace resins (ie, PMR-15) with more
tailorablity properties by tuning chemistry of
precursors from biofeedstocks.
Replace EPDM rubber insulation material with
elastomeric system for better compatibility with
propellant. Si-based system chars to SiO.
LRE seal wear resistance
Improve fluoropolymer seals under cryogenic
conditions. Development of smart membranes and
surface modifications.
Aerospace Systems Directorate Edwards AFB, CA
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Anionic polymerizations from cyclic ethers
Perfluoropolyethers (PFPEs)
Chain growth from trifluorovinyl ethers
Scheirs, J. Modern Fluoropolymers pp 435-485
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Dichotomy of fluoroalkene reactivity for accessing tailorable,
processable, high use temperature materials platforms
J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5707
Handbook of Fluoropolymer Science and Technology (Wiley) 2014, 343
Adv. Fluorine Containing Polym. 2012
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• Thermal initiated step-growth cyclopolymerization
• Catalyst & condensate free
• Stereorandom polymer – amorphous
• High thermal stability decomposition 450500 °C
Choice matrix:
• Solution processable
• High fidelity for µ-molding applications
• Tunable optical properties
• Retain optical clarity for particulate blending
J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5707
Handbook of Fluoropolymer Science and Technology (Wiley) 2014, 343
Perfluorocyclobutyl (PFCB) aryl ether polymers
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Synthesis of aryl trifluorovinyl ethers (TFVE) monomers
Intermediate strategy for functionalized monomers
J. Polym. Sci. Part A, Polym. Chem. 2010, 48, 1887
Handbook of Fluoropolymer Science and Technology (Wiley) 2014, 343
Fluoropolymers 1: Synthesis; Plenum Press: New York, 1999, pp 25
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PFCB aryl ether polymer technology
melt or solution
polymerization
thermal
activated
trifluorovinyl
ethers
intact latent
reactivity
B-stage cure for
thermoplastic or
thermoset
Substrate
compatibility
J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5707
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Chem. Commun. 2015, 51, 9220
O
F
F
F F F F F F F
O O
monomer 5
polymer 6
O O O O
2200 2100 2000 1900 1800 1700
Wavenumber ( cm -1 )
C C O O
O
O O O O
2108 cm - 1 1813 cm - 1
p olymer 9 1740 cm - 1
961 cm - 1 1738 cm - 1
1774 cm - 1
1800 1500 1200 900
Wavenumber ( cm -1 )
PFCB polymers with Meldrum’s acid possessing dual reactivity
C24
C23
C2
C1 C3
C4C5
C6O1
O2 O3
O4C7
C8
C9C11
C10O6
O5
C12
C13
C15C14
C16
C17
C18C19
C20
C21
C22
F1
F2
F3F4
F5
F5
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J. Am. Chem. Soc. 2011, 133, 17882
Mechanical scission/thermal re-mending of PFCB polymers
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Blue-Light emissive carbazole containing PFCB polymers
J. Polym. Sci. Part A: Polym. Chem. 2014, 52, 552
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Polym. Bull. 2015, 132, 41798
J. Appl. Poly. Sci. 2015, 132, 41798
Polym. Adv. Tech. 2016, DOI: 10.1002/pat.3808
PFCB PEG copolymers as blend compatiblizers
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Macro. Letters 2014, 3, 106
PFCB cyanate ester resins with low moisture uptake
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Ion viscosity = 1 / = 2o
@ f = 100 Hz
210o C150o C 250o C
Macro. Letters 2014, 3, 106
PFCB cyanate ester resins with low moisture uptake
0.56 ± 0.10% water uptake @ 85°C for 4 days
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Chambers, R. D. Synthetic Fluorine Chemistry, 1992, pp 359380
Nucleophile additions to fluorinated olefins
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Example: trifluorostyrene leads to low yield, low MW oligomers
Limitations toward anionic polymerization of fluorinated olefins
Narita, T. Macromol. Rapid Commun. 2000 21, 613
Andreades, S. J. Am. Chem. Soc. 1964 86, 2003
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Commercial utility of nucleophile additions to fluorinated olefins
Feiring, A. E. et al. J. Am. Chem. Soc. 1993, 115, 8954
Feiring, A. E.; Smart, B. E. J. Am. Chem. Soc. 1994, 116, 4135
Post curing
Facile route to linear and cyclic PFPEs
Substituted HFEs
Matsukawa, Y. et al. Angew. Chem. Int. Ed. 2005, 44, 1128
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Partially fluorinated polymers from aryl trifluorovinyl ethers
Adv. Fluorine Containing Polym. 2012
Chem. Commun. 2006, 46, 4844
U.S. Patent, 7,754,837 (2010)
• Operationally simple
• High yield (> 85%)
• Mn = 1235k (PDI = 23)
• Solution processable
• Transparent, flexible films
• Tunable Tg (50160 °C)
• Td = 512632 °C (air)
• Linear, cyclic, & telechelics
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FAVE polymerization kinetics
AB Pattern
85 ppm
J. Polym. Sci., Part A: Polym. Chem. 2011, 132, 17882
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Cheatham, C. M. et al. Polym. Int. 1998 46, 320
Ea = 105 kJ/mol (Raman)
Activation energy of FAVE polymerization
50 °C omitted
due to high
deviation
PFCB solid state cure kinetics:
k = A eEa/RT
ln k = Ea/RT
Other step-growth polymerizations:
Poly(ester)s
Poly(amide)s
Poly(urethane)s
Poly(carbonate)s
Ea (kJ/mol)‡
41–188
100
31–35
77
‡Odian, G. Principles of Polymerizations pp 88
No equilibrium steps typical
of step-growth polymers
J. Polym. Sci., Part A: Polym. Chem. 2011, 132, 17882
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Org. Biomol. Chem. 2011, 9, 4842
O
F
F
F
O Ar R'ArR
M
Aryloxylation of F-alkenes with functionalized phenols
AB Pattern
85 ppm
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Dual thermal reactivity of FAVE telechelomers
Mn ~ 1.4k (PDI = 1.5)
Processable
homopolymer
Crosslinked
network
Processable
homopolymer
Crosslinked
network
Processable
homopolymer
Crosslinked
networkAdv. Fluorine Containing Polym. (Wiley) 2012
Chem. Commun. 2006, 46, 4844
U.S. Patent, 7,754,837 (2010)
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Dual thermal reactivity of FAVE telechelomers
Processable
homopolymer
Crosslinked
network
Processable
homopolymer
Crosslinked
network
Adv. Fluorine Containing Polym. 2012
Chem. Commun. 2006, 46, 4844
U.S. Patent, 7,754,837 (2010)
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Macromolecules 2008, 41, 7490
J. Mater. Chem. 2008, 18, 1970
Sens. Actuators, B 2009, 143, 1
Modular utility of FAVE polymers for light emissive materials
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J. React. Funct. Polym. 2015, 38, 93
Universal method towards functionalization of partially
fluorinated polyarylethers
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Alternate route towards fluorinated aryl/alkyl ethers
R-114B2
Halon 2402
J. Fluorine Chem. 2014, 166, 60
Macromolecules 2012, 45, 766
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Benzoxazine-based PFCP thermosets
Macromolecules 2015, 48, 6087
103
104
105
106
2.5
3.0
3.5
4.0
4.5
5.0
5.5
Die
lec
tric
Co
ns
tan
t
Frequency (Hz)
P1
P2
100 200 300 400 500 600 700 80050
60
70
80
90
100
Resid
ual
weig
ht
(%)
Temperature (oC)
P1
P2
40 60 80 100 120 140 160 180 200
Exo
therm
Temperature (oC)
40 60 80 100 120 140 160 180 200
Exo
therm
Temperature (oC)
42 oC
Tg 130 oC
After curing
Before curing
Before curing65 oC
After curing
Tg 140 oC
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Processble amine-based thermoplastics/sets
Polym. Chem. 2016, 7, 5799
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PFCP decorated SiNPs for tuneable surface Energy
Nanoscale 2016, 8, 16212
ACS Appl. Mater. Interf. 2016, 8, 12434
U. S. Patent, 62/241,454, filed, Oct 14, 2016
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Acknowledgements of contributors at AFA since 2012
Undergraduates Chemistry Research Center Team Ms. Cynthia Corley, MS - Chemist
Mr. Stephen Budy, MS (Chemist), PhD candidate SMU
Prof. Gary Balaich – Professor
Dr. Abby Jennings - Senior Scientist
Dr. Sonya Adas - NRC post-doc
Dr. Nick Godman - (NRC post-doc), AFRL/WPAFB
Dr. Jena McCollum - (NRC post-doc), U. Colorado
Dr. Endrit Shurdha (NRC post-doc), CTI, Inks
Dr. Cassie Kettwich (Post-doc), U. New Mexico
Emeline Lochmaier
Averi Richert
Bryce O’Connell
Karl Hellwig, Dental School
Adam Wilkins, Dev Engineer
Kristian Knuths, Presently: Pilot
Ford Carty, Presently: Pilot
Kelsey Dees, Presently: Pilot
Matthew Piazza, Presently: Medical Officer
John Hudgins, Presently: Chemist
Derek Barbee , Presently: Engineer
Carl Thrasher , Presently: Chemist
Eryn Avjian, Presently: Intelligence
James Neat, Presently: Pilot
Nick Clayton, Presently: Acquisitions
Yasmin Sarmiento, Presently: OSI
Russell Johnson, Presently: Pilot
Michael Duff (MS-UTD), Presently: Chemist
Olawale Lawal, Presently: Engineer
Stephen Keck, Presently: Pilot
Seth Danielson, Presently: Pilot
Bradley Kusel, Presently: Pilot
Ryan Fantasia , Presently: Pilot
Casey Hawkins, Presently: Chemist
Scott Pierson, Jr., Presently: Intelligence