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Polymer Synthesis ROP Degradable polyesters/amides RAFT Wide range of monomers | Good for aqueous media
an opinionated guide... ROP of lactides and lactones
oganocatalysed alternative:
O
! Robust and well-established
RAFT agents
fragmenting/ stabilizing Best for these
Traditional RAFT
S OH
Class Notes RAFT agent monomer initiator
O
route to poly(ester)s initiating group group monomers S
O
Sn(Oct)2 O • versatile S
( )n
R’ Nu
+ Can control stereochemistry S S Z
··
Initiator
O R’
O(
O )n
OH
(meth)acrylates/ • high transfer const. R + + Int-X R
dry! with chiral catalyst R trithiocarbonates S Z
toluene
O
S S (meth)acrylamides • R-group structure
R’ OH alcohol
e.g.
R’ NH 2 primary amine (rare)
Caprolactone 110 ºC poly(caprolactone) Tolerant to presence of important
notes:
monomer initiator equiv. per
Cyclic ester- solvent initiator temperature time
O O O mechanism S • less hydrolytically
type class RAFT agent
based • Can suffer from back-biting termination reactions methacrylates/
monomers
O O O
R dithiobenzoates stable DMF AIBN methacrylate thermal 0.1- 0.2 70oC 4-6 h
Make sure you have on (at least) the following: O O
O
O
• Requires striclty anhydrous conditions to avoid initiaion
from water
S methacrylamides
• moderate trasfer const. DMF AIBN acrylate thermal 0.05 - 0.1 70oC 3-4 h
Lactide Glycolide Crown ether ester • Almost any cyclic ester structure is polymerizable
NCA-ROP S toluene AIBN methacrylate thermal 0.1- 0.2 70oC 8-12 h
Lab coat
vinyl esters/ • highly photo-labile
O R dithiocarbamates V-501/ acrylate/
S N vinyl amides • moderate dispersity H2O thermal 0.05 - 0.1 60oC 3-4 h
HN H
R O
Synthetic polypeptides; of bio- V-50 acrylamide
R’ Nu + O N
( N)
NH 2
H2O TPO acrylate photo 0.1 - 0.5 r.t. 0.5-1 h
··
R - n CO2
R’
H n logical interest
Initiator O O R
Enzymatically degradable
PET-RAFT H2O ascorbic acid/ acrylate/
Safety glasses
R’ NH 2 primary amine N-Carboxy α-amino acid poly(NCA) redox 0.5 - 1 r.t. 6-24 h
e.g.
R’ OH alcohol (rare) anhydride (NCA) (example: amine-initiated) tBu-OOH acrylamide
O O
S photo- hv PC+
S The best dispersity and chain-
H
Peptide • NCA monomers notoriously hard to handle - need to be + + end fidelity
notes:
O N Pn/R catalyst Pn/R•
inspired S
freshly-prepared and may require glove-box conditions S Z
-
S Z
O O
(PC) Compatible with Incompatible with
Methacrylates well-controlled
Gloves (latex or nitrile)
O HN HN
monomers • Several operating mechanisms can occur concurrently, M
O O complicating the reaction
• choice of blue, green, red, or near-infrared light (difficult for iniferter) O O
(Boc-protected) Lysine NCA (Benzyl-protected) Cystine NCA • Some amino acid functionalities require protection O R N
during polymer synthesis (e.g. acid, amine, thiol)
• lots of organic, inorganic, and porphyrin catalysts R OH
R OH
R R N
R R NH 2
R SH
+
O O O ( CH2 ) ( O ( CH2 ) )n Access to degradable polymers Photoiniferter-RAFT O O F thiol
Sensible waste disposal: R R R R R Cl R R
via radical polymerization Excellent for acrylates, acrylamides, and vinyl
hv
O (CH2) (CH2) R S
O
S R Br F F
O O
S esters
R R R H R N
H
alkyl flouro- thioether
Radical Ketene acetal ring-opening propagating poly(ester) Can be combined with RAFT Pn/R Pn/R• + ketone aldehyde
halide carbon 2o-amine
product S Z No additional reagents required - very simple
No chemicals/solvents down the sink
radical
to provide control •S Z
M set up
• Typically only used in combination with (e.g.) a (meth)-
R
May cause problems... R
notes:
Cyclic acetal- O Ph S acrylate monomer to provide “degradable linkages” photoiniferter xanthate + acrylate UV or purple
based
monomers O Ph
O N O S
S • Severe difficulties with reactivty ratios when used as light source trithiocarbonate + acrylate blue (or UV) OH
R S S R R H
ATRP Robust & established | Lots of ATRP variations ROMP Powerful | Grafting-through brushes
Basic ATRP Key equilibria in ATRP
Cu(0)-mediated ATRP Photo-mediated ATRP Monomers Grubbs’ catalyst
ATRP Cu(II)
monomer catalyst
initiator & ki >> kp Metalic copper (i.e. copper in the zero-oxidation state, Cu(0)) Photo-mediated ATRP (photo-ATRP) has developed so rapidly in the past norbornene
Cu(I) can be used very effectively for polymerization few years there are now a multitude of different approaches!
R Br + + Cu R ( )nBr R N N
N N
ratio of deactivator rate of initiation much P
normally cleaned in acid just prior 1) Using photo-redox catalysts to reduce Cu(II) to Cu(I)
Photo-ATRP
to activator higher than propagation O oxanorbornene Cl
Example Cu(0)-ATRP reaction: to use to remove oxide coating Cl Ru
strategies
2) (related) Using the Cu(II)/L complex as a kind of photo-catalyst Cl
Ru
Ph
Cl Ph N Ru
Cl
kp O
DMSO
Media:
Reducing
agents:
Pn Br + Cu(I)Br / Ln
kd
Cu(II)Br2 / Ln + Pn ●
Simple, fast, room temperature
DMSO)
alkyl halide acrylate copper
N 1.5 - 4 h
O O
Metal-free photo-
reaction Relatively poor control over initiator monomer catalyst ligand polyacrylate
aqueous { sodium ascorbate
ascorbic acid
cathodic current
Able to do in situ chain
methacrylate-type monomers 1 equiv. 100 equiv. 0.02 equiv. e.g. Me6TREN product
Robust, powerful, and tolerant
toward various functionalities
Usually requires expensive
ruthenium catalyst
ROMP
+ e- 0.12 equiv.
organic Sn(EH)2 extension -- i.e. easy multiblock/ Reaction/catalyst tends to “die” Removes need for metal
So powerful that it can easily catalyst
star polymer synthesis if running for too long -- hard to Stoichoimetric amount of cata-
Cu(II)Br2 Cu(I)Br mechano-ATRP mechano-active resuscitate! Example Photo-ATRP reaction (#3 and #4): polymerize through macro-
lyst (i.e. one per polymer chain)
OMe
catalyst monomers (i.e. grafting-through) Uses photo-redox
note: Ligand not shown Acrylamides possible when
For in situ chain extensions, O catalyst to oxidise
BaTiO3* BaTiO3 (particles) using aqueous variant
typically only very short blocks Br photo- hv O Access to conjugated polymer More stringgent reaction
vinyl ether (which
Can also be achieved by: kp
work well (DPn ≤ 20)
O
+ + catalyst O ( )nBr backbones conditions than RAFT or ATRP
acts as initiator)
Can polymerize hydrophobic O O
r.t.
BF 4
• radicals/initiators (”ICAR-ATRP”) (PC)
M
ka (e.g. tert-butyl acrylate) as well Precipitating from DMSO is a
O O
Highly reactive with typically Usually restricted to cyclic Blue LED O
+ + as hydrophilic (e.g. 2-hydroxy-
• electrochemical (“eATRP”) alkyl halide (meth)acrylate <0.1 mol%
Cu(II)Br2 / Ln Pn ●
Pn Br Cu(I)Br / Ln
kd real pain! For hydrophilic, best to fast reaction kinetics strained-ring monomers
ethyl acrylate) monomers initiator monomer poly(meth)acrylate MeO OMe
• ultrasound (”mechano-ATRP”) dialyse then freeze-dry 1 equiv. 100 equiv. product
Example Cu(0)-ATRP aqueous reaction:
Example ARGET-ATRP reaction: Note: adding salt (NaCl) might help! Iron-catalysed ATRP this complex “disproportionates” into Organic photocatalysts Inorganic ones “Grafting-through” polymerization:
Cu(II)Br2/Me6TREN and Cu0 particles
Ascorbic Although Cu is used most exten-
acid O N
sively, Fe catalysts also work. O O
O N 0.2 equiv. HO O ( )nBr H2O N
Br + O O + Cu(II)Br2 + OH
These are generally much slower;
however a recent example of
HO O
Br
+ + Cu(I)Br + N HO O ( )nBr N N
ROMP ROMP
(
HO O N O O
(
N O O ice bath
OH water ligand-free photo-ATRP using FeBr3 OH OH
O O O
RuII
IrIII
N r.t. appears promising! N 5 - 30 min N
O N N N N
6h O OH
)
FeBr3 ( )nBr
)