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SYNTHESIS OF DYNAMIC BLOCK COPOLYMERS THROUGH IRREVERSIBLE AND REVERSIBLE TAD-BASED
CLICK REACTIONS.
Bernhard De Meyer 02/10/2014
0
N
NN
O
O
R2D LCxSEC as a valuable characterization tool
We know how 1/22
We made block copolymers In less then 1 second @ ambient temperature Chemistry for dummies Without catalyst
We know how 2/22
We broke block copolymers Reversible or irreversible @ wide temperature range Back to its starting blocks
Outline 3/22
1. Who are We?
2. Click chemistry
3. 2D LCxSEC of the clicked block copolymer
4. Transclick Chemistry 5. 2D LCxSEC of the transclicked block copolymer
Who are we? 4/22
From polymer functionalization
to absolute control
Giving renewable polymers
function(ality)
Dynamic and self-healing polymeric materials
www.pcr.ugent.be
Click Chemistry 5/22
Clicking Polymers or Just Efficient Linking: What Makes the Difference?, C. Barner-Kowollik, F.E. Du Prez, P. Espeel, C.J. Hawker, T. Junkers, H. Schlaad, W. Van Camp, Angew. Chem. Int. Ed., 50, 60-62, 2011
Click Chemistry - TAD 6/22
N
NN
O
O
R 1,2,4-triazoline-3,5-dione Unique reactivity
Reaction times = seconds/hours
Distinctive red colour providing visual feedback system TAD = Red Adduct = Colourless
Cheap starting compounds and Easy Synthesis
Versatile Chemistry with TAD 7/22
IRREVERSIBLE < 20 C < 1 sec > hours
N
NN
O
O
R
N
NN
O
O
R
Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems, S. Billiet, K. De Bruycker, F. Driessen, H. Goossens, V. Van Speybroeck, J.M. Winne, F.E. Du Prez, Nat. Chem., 6(9), 815-821, 2014
+ TAD diene
Click Chemistry - TAD 8/22
O
O
n + O
O
N
NN
Br
OO
O
NH n
1:1 < 1 sec
O
O
N
NN
Br
OO
O
NH n
O
O
n
SEC of the Clicked block copolymer 9/22
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5 6
w (l
og M
(g/
mol
))
Log M (g/mol)
PS-Cp-co-PBA-TAD
THF 1ml/min 2 x Plgel 5µm MIXED-D (300 x 7,5 mm)
SEC of the Clicked block copolymer 10/22
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5 6
w (l
og M
(g/
mol
))
Log M (g/mol)
PS-Cp
PBA-Urazole
PS-Cp-co-PBA-TAD
THF 1ml/min 2 x Plgel 5µm MIXED-D (300 x 7,5 mm)
SEC of the Clicked block copolymer 11/22
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5 6
w (l
og M
(g/
mol
))
Log M (g/mol)
PS-Cp + PBA-Urazole
PS-Cp-co-PBA-TAD
THF 1ml/min 2 x Plgel 5µm MIXED-D (300 x 7,5 mm)
This is where 2D comes in 12/22
1st dimension
2nd dimension
2D LCxSEC of the clicked block copolymer 13/22
Time (min)
ELS
D s
igna
l
LC Gradient THF/MeOH 50/50 – THF/MeOH 77,5/22,5 132 min 50 µl/min 2 x ZORBAX 300 SB-C18 (4,6 x 250 mm)
PBA-ura PS-Cp
2D LCxSEC of the clicked block copolymer 14/22
PS-Cp + PBA-ura
SEC THF 5 ml/min PSS SDV HighSpeed Linear M 5µm
PS-Cp (4.000 Da)
PBA-Ura (20.000 Da)
2D LCxSEC of the clicked block copolymer 15/22
PS-Cp-co-PBA-ura
PBA – co - PS
PBA-TAD
2D LCxSEC of the clicked block copolymer 16/22
Overlay PS-Cp + PBA-Ura + PS-Cp-co-PBA-ura
TransClick Chemistry 17/22
Clicking Polymers or Just Efficient Linking: What Makes the Difference?, C. Barner-Kowollik, F.E. Du Prez, P. Espeel, C.J. Hawker, T. Junkers, H. Schlaad, W. Van Camp, Angew. Chem. Int. Ed., 50, 60-62, 2011
Reversibility if desired
Control over Kinetics
Tuneability
TransClick Chemistry 18/22
Transesterification:
Same principle with click reactions?
“TRANSCLICK”
R O
O
R2
R O
O
R2
R1 OR1 O
R O
O
R1
R2 O
Versatile Chemistry with TAD 19/22
N
NN
O
O
R
REVERSIBLE
NH
R''
R
< 20°C 25-150°C
NR''
R'
N
N NH
OO
R
Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems, S. Billiet, K. De Bruycker, F. Driessen, H. Goossens, V. Van Speybroeck, J.M. Winne, F.E. Du Prez, Nat. Chem., 6(9), 815-821, 2014
+ TAD indole
NH
R
N
O
N
R"N
ON
R
HN
O
N
R"
N
O+T+
RT
T+R"'
R"'
N
O
N
R"
N O
NH
R
+
Transclick
TransClick Chemistry
Reversible Click
20/22
cyclopentadiene
2D LCxSEC of the Transclicked block copolymer 21/22
5
10
15
20
25
30
35
40
45
Elut
ion
Tim
e(m
in)
8.5 9.5 10.5 11.5
Elution Volume (mL)8.5 9.5 10.5 11.5
Elution Volume (mL)8.5 9.5 10.5 11.5
Elution Volume (mL)
PBA-Urazole+ PS-Indole
PBA-TAD-HDEO+ PS-IndolePBA-block-PS
PS
PBA PBA-b-PS
excess PS PS
PBA
0
10
20
30
40
50
60
70
80
90
100
Nor
mal
ized
ELS
D re
spon
se
R"'
PBA-TAD-Cp + Ps-Indole
Nature Chemistry
Thank you!
22/22
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