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Facile Chain-End Modification of RAFT Polymers
Shelby Shankel
CCS Chemistry, UCSB
Emre Discekici
Read de Alaniz Group, Chemistry and Biochemistry
MARC U-STAR, NIH
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Importance of Modification
Br
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Importance of Modification
• Halogens allow for further functionalization of RAFT chain ends for a variety of applications
Br
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Importance of Modification
• Halogens allow for further functionalization of RAFT chain ends for a variety of applications
• Example: block copolymers
ATRP initiator
Br
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Importance of Modification
• Halogens allow for further functionalization of RAFT chain ends for a variety of applications
• Example: block copolymers• Adhesives, rubber
ATRP initiator
Br
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Importance of Modification
• Halogens allow for further functionalization of RAFT chain ends for a variety of applications
• Example: block copolymers• Adhesives, rubber• Micelles
ATRP initiator
Br
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weightsRAFT
Traditional
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity index
RAFT
Traditional
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?
![Page 12: Facile Chain-End Modification of RAFT Polymersmarc-csep.cnsi.ucsb.edu/.../scholars/files/shelbys_final_presentation.… · Bromination on Polymers + In-Hwan Lee SH n NC O O Br n NC](https://reader035.vdocument.in/reader035/viewer/2022071102/5fdc0124f67ead07ac4bca56/html5/thumbnails/12.jpg)
Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?• Tolerance of functional groups
![Page 13: Facile Chain-End Modification of RAFT Polymersmarc-csep.cnsi.ucsb.edu/.../scholars/files/shelbys_final_presentation.… · Bromination on Polymers + In-Hwan Lee SH n NC O O Br n NC](https://reader035.vdocument.in/reader035/viewer/2022071102/5fdc0124f67ead07ac4bca56/html5/thumbnails/13.jpg)
Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?• Tolerance of functional groups• Formation of complex structures
![Page 14: Facile Chain-End Modification of RAFT Polymersmarc-csep.cnsi.ucsb.edu/.../scholars/files/shelbys_final_presentation.… · Bromination on Polymers + In-Hwan Lee SH n NC O O Br n NC](https://reader035.vdocument.in/reader035/viewer/2022071102/5fdc0124f67ead07ac4bca56/html5/thumbnails/14.jpg)
Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?• Tolerance of functional groups• Formation of complex structures• High conversions
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?• Tolerance of functional groups• Formation of complex structures• High conversions• Water soluble
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Reversible Addition-Fragmentation Chain Transfer (RAFT)
Polymerization• Controlled radical polymerization
• Control of molecular weights• Narrow polydispersity
• Why RAFT?• Tolerance of functional groups• Formation of complex structures• High conversions• Water soluble• Useful in biomedical applications
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Current Challenges with RAFT
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Current Challenges with RAFT
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Current Challenges with RAFT
• Conjugation of chain end
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Current Challenges with RAFT
• Conjugation of chain end• Discoloration
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Current Challenges with RAFT
• Conjugation of chain end• Discoloration
• Poor retention of chain end
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Current Challenges with RAFT
• Conjugation of chain end• Discoloration
• Poor retention of chain end• Odor
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Current Challenges with RAFT
• Conjugation of chain end• Discoloration
• Poor retention of chain end• Odor• Toxicity
S
S
ZRR S Z
S
+
Chain Transfer Agent
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
KnownSumerlin, B. S; et al. Polym.
Chem. 2010, 1, 854-859.
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
Known UnknownSumerlin, B. S; et al. Polym.
Chem. 2010, 1, 854-859.
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
Known Unknown
Model Systems
Sumerlin, B. S; et al. Polym.
Chem. 2010, 1, 854-859.
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
Known Unknown
SH
1-Dodecanethiol
Model Systems
Sumerlin, B. S; et al. Polym.
Chem. 2010, 1, 854-859.
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Functionalize RAFT Polymer Chain Ends with Bromides
R S Z
S
R Br
R SH
Known Unknown
SH
SH
1-Adamantanethiol
1-Dodecanethiol
Model Systems
Sumerlin, B. S; et al. Polym.
Chem. 2010, 1, 854-859.
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Setting Up the Reaction
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Setting Up the Reaction
Reactants
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Setting Up the Reaction
Reactants
R SH
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Setting Up the Reaction
Reactants
R SH
N
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Setting Up the Reaction
Reactants
PBrBr
R SH
N
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Setting Up the Reaction
Reactants
PBrBr
R SH
N
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Setting Up the Reaction
Reactants
Inert Gas
PBrBr
R SH
N
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Setting Up the Reaction
Reactants
Inert Gas
Stir PlatePBrBr
R SH
N
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Setting Up the Reaction
Reactants
Inert GasHeating Block
Stir PlatePBrBr
R SH
N
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Setting Up the Reaction
Reactants
Inert Gas
Overnight
Heating Block
Stir PlatePBrBr
R SH
N
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Purifying and Analyzing the Reaction
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Purifying and Analyzing the Reaction
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Purifying and Analyzing the Reaction
Dialysis
Start Equilibrium
Membrane
Solvent
Conc. Solution
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Purifying and Analyzing the Reaction
Dialysis
or
Precipitation
Start Equilibrium
Membrane
Solvent
Conc. Solution
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Purifying and Analyzing the Reaction
Dialysis
or
Precipitation
Remove Solvent
Overnight
Start Equilibrium
Membrane
Solvent
Conc. Solution
![Page 46: Facile Chain-End Modification of RAFT Polymersmarc-csep.cnsi.ucsb.edu/.../scholars/files/shelbys_final_presentation.… · Bromination on Polymers + In-Hwan Lee SH n NC O O Br n NC](https://reader035.vdocument.in/reader035/viewer/2022071102/5fdc0124f67ead07ac4bca56/html5/thumbnails/46.jpg)
Purifying and Analyzing the Reaction
Dialysis
or
Precipitation
Remove Solvent
Overnight
Start Equilibrium
Membrane
Solvent
Conc. Solution
![Page 47: Facile Chain-End Modification of RAFT Polymersmarc-csep.cnsi.ucsb.edu/.../scholars/files/shelbys_final_presentation.… · Bromination on Polymers + In-Hwan Lee SH n NC O O Br n NC](https://reader035.vdocument.in/reader035/viewer/2022071102/5fdc0124f67ead07ac4bca56/html5/thumbnails/47.jpg)
Purifying and Analyzing the Reaction
Dialysis
or
Precipitation
Remove Solvent
Overnight
Start Equilibrium
Membrane
Solvent
Conc. Solution
Analyze
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Purifying and Analyzing the Reaction
Dialysis
or
Precipitation
Remove Solvent
Overnight
Start Equilibrium
Membrane
Solvent
Conc. Solution
Analyze
Nuclear Magnetic Resonance (NMR)
Spectroscopy
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Model System: Dodecanethiol
SH Br
triphenylphosphine dibromidetriethylamine
DCM
Starting material
56% conversion
>99% conversion
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Model System: Dodecanethiol
SH Br
triphenylphosphine dibromidetriethylamine
DCM
Starting material
56% conversion
>99% conversion
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Model System: Dodecanethiol
SH Br
triphenylphosphine dibromidetriethylamine
DCM
Starting material
56% conversion
>99% conversion
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Model System: Dodecanethiol
SH Br
triphenylphosphine dibromidetriethylamine
DCM
*Conversion determined by 1H-NMR
Eqv. Dodecanethiol
Eqv.Triphenylphosphinedibromide
Eqv.Triethylamine
Solvent Spargedwith argon?
Temp.(℃)
Time (hr)
Conversion
1.00 3.00 3.00 DCM yes room 18 >99%
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Model System: AdamantanethiolSH
triphenylphosphine dibromidetriethylamine
DCM
Br
>99% conversion
67% conversion
Starting material
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Model System: AdamantanethiolSH
triphenylphosphine dibromidetriethylamine
DCM
Br
>99% conversion
67% conversion
Starting material
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Model System: AdamantanethiolSH
triphenylphosphine dibromidetriethylamine
DCM
Br
>99% conversion
67% conversion
Starting material
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Model System: AdamantanethiolSH
triphenylphosphine dibromidetriethylamine
DCM
Br
*All conversions determined by H-NMR
Eqv. Adamantanethiol
Eqv. Triphenylphosphinedibromide
Eqv.Triethylamine
Solvent Spargedwith argon?
Temp.(℃)
Time (hr)
Conversion
1.00 5.00 5.00 DCM yes 45 5 100%
1.00 5.00 5.00 DCM yes room 5 85%
1.00 10.00 10.00 DCM yes 45 26 100%
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Bromination on Polymers
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Bromination on Polymers
In-Hwan Lee
Polystyrene
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Bromination on Polymers
In-Hwan Lee
Polystyrene
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
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Bromination on Polymers
In-Hwan Lee
Polystyrene
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC
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Bromination on Polymers
+In-Hwan Lee
Polystyrene
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC NC
n-1
2:1
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Bromination on Polymers
+In-Hwan Lee
Polystyrene
Poly(methyl acrylate)
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC NC
n-1
2:1
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Bromination on Polymers
+In-Hwan Lee
Polystyrene
Poly(methyl acrylate)
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC
S
S
SC12H25
n
NCO
SHn
NCOOhexylamine (25 eq.)
tributylphosphine (5 eq.)
DCMroom temp
O
NC
n-1
2:1
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Bromination on Polymers
+In-Hwan Lee
SHn
NCOO
Brn
NCOO
triphenylphosphine dibromide (10 eq.)triethylamine (10 eq.)
DCMroom temp
Polystyrene
Poly(methyl acrylate)
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC
S
S
SC12H25
n
NCO
SHn
NCOOhexylamine (25 eq.)
tributylphosphine (5 eq.)
DCMroom temp
O
NC
n-1
2:1
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Bromination on Polymers
+In-Hwan Lee
SHn
NCOO
Brn
NCOO
triphenylphosphine dibromide (10 eq.)triethylamine (10 eq.)
DCMroom temp
Not complete conversion
Polystyrene
Poly(methyl acrylate)
S
S
SC12H25
n
NC
hexylamine (50 eq.)tributylphosphine (5 eq.)
DCMroom temp SH
n
NC
SHn
NC
triphenylphosphine dibromide (5 eq.)
DCMroom temp Br
n
NC
S
S
SC12H25
n
NCO
SHn
NCOOhexylamine (25 eq.)
tributylphosphine (5 eq.)
DCMroom temp
O
NC
n-1
2:1
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Future Work:Further Optimization on
Polymers Systems
• Solvent• Temperature• Equivalents• Reagents
R S Z
S
R Br
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Thank you!The Read de Alaniz Group:
Javier Read de AlanizLes BurnettKyle ClarkYvonne DiazEmre DiscekiciDavid FisherJames HemmerSaemi Oh Poelma
Andrey SamoshinJamie ShaumAndre St. AmantNicolas TreatGabby HammersleyEllia LaLandon MillsJoseph Sanz
Research reported here was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Number T34GM113848
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References1. Willcock, H.; O’Reilly R. K. Polym. Chem. 2010, 1, 149-157.2. Pissuwan, D.; Boyer, C.; Gunasekaran, K.; Davis, T. P.; Bulmus, V. Biomacromolecules. 2010, 11
(2), 412–420.3. Sigma-Aldrich. RAFT: Choosing the Right Agent to Achieve Controlled Polymerization.
http://www.sigmaaldrich.com/united-states.html4. Stories of Australian Science. Star-shaped polymers boost engine performance.
http://stories.scienceinpublic.com.au/subject/plastics/.5. Carnegie Mellon: the Matyjaszewski Polymer Group. Graft Copolymers with Complex
Architecture. http://www.cmu.edu/maty/materials/Polymers_with_Specific_Architecture/densely-grafted-linear-copolymers.html.
6. Carlmark, A.; Hawker, C.; Hult, A.; Malkoch, M. Chem. Soc. Rev. 2009, 38, 352-362. 7. Cobo, I.; Li, M.; Sumerlin, B. S.; Perrier, S. Nature Materials. 2015, 14, 143–159. 8. School Work Helper. Selective Permeability of Dialysis Tubing Lab: Explained.
http://schoolworkhelper.net/selective-permeability-of-dialysis-tubing-lab-explained/.