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

[email protected]

http://www.usafa.edu/df/dfe/dfer/centers/crc/

FLUOROPOLYMER 2016 – OCT 2016


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

4

Composites • Energetics • Organic Electronics

Laboratories for Synthetic Chemistry &

Applied Polymer and Materials Science

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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


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


• 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



Perfluorocyclobutyl (PFCB) aryl ether polymers


Synthesis of aryl trifluorovinyl ethers (TFVE) monomers

Intermediate strategy for functionalized monomers

J. Polym. Sci. Part A, Polym. Chem. 2010, 48, 1887


Fluoropolymers 1: Synthesis; Plenum Press: New York, 1999, pp 25


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



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


J. Am. Chem. Soc. 2011, 133, 17882

Mechanical scission/thermal re-mending of PFCB polymers


Blue-Light emissive carbazole containing PFCB polymers



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


Macro. Letters 2014, 3, 106

PFCB cyanate ester resins with low moisture uptake


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


Chambers, R. D. Synthetic Fluorine Chemistry, 1992, pp 359380

Nucleophile additions to fluorinated olefins


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


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


Partially fluorinated polymers from aryl trifluorovinyl ethers


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


FAVE polymerization kinetics

AB Pattern

85 ppm

J. Polym. Sci., Part A: Polym. Chem. 2011, 132, 17882


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


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


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)


Dual thermal reactivity of FAVE telechelomers

Processable

homopolymer

Crosslinked

network

Processable

homopolymer

Crosslinked

network


Chem. Commun. 2006, 46, 4844

U.S. Patent, 7,754,837 (2010)


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


J. React. Funct. Polym. 2015, 38, 93

Universal method towards functionalization of partially

fluorinated polyarylethers


Alternate route towards fluorinated aryl/alkyl ethers

R-114B2

Halon 2402

J. Fluorine Chem. 2014, 166, 60



Benzoxazine-based PFCP thermosets


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


Processble amine-based thermoplastics/sets

Polym. Chem. 2016, 7, 5799


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


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

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