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