1 

Supporting information

Poly(thiolactone) Homo- and Copolymers from

Maleimide Thiolactone: Synthesis and

Functionalization

Tobias Rudolph,1,2 Pieter Espeel,3 Filip E. Du Prez,3,* Felix H. Schacher1,2,*

[1] Laboratory of Organic and Macromolecular Chemistry, Friedrich Schiller University Jena,

Humboldtstr. 10, 07743 Jena, Germany

E-mail: felix.schacher@uni-jena.de

[2] Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7,

07743 Jena, Germany

[3] Polymer Chemistry Research Group, Department of Organic and Macromolecular Chemistry,

Ghent University, Krijgslaan 281 S4-bis, B-9000 Gent, Belgium

E-mail: filip.duprez@ugent.be

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2015

2 

Figure S1: Kinetic investigation of the synthesis of MITla comparing the newly formed thiolactone signal at 4.95 ppm (DMSO- d6) to trioxane as internal standard at 70 °C.

Figure S2: Comparison of FT-IR spectra for maleic anhydride (blue trace-), D,L-homocysteine thiolactone hydrochloride (black trace), and the desired maleimide thiolactone (IUPAC: 1-(2-oxotetrahdrothiophen-3-yl)-1H-pyrrole-2,5-dione; MITla, red trace).

Figure S31400, and

Figure S4

3: Enlarged Fd the maleimi

4: 1H-NMR sp

FT-IR spectride double bo

pectra of mal

rum for MITlond at 830 and

leimide thiola

3 

la and the imd 690 cm-1.

actone (MITla

mportant sign

a) and peak a

nals for: carb

assignment (C

bonyls at 1689

CDCl3, 300 M

9, C-N-C at

MHz).

Figure S5

Figure S6

5: 13C-NMR s

6: ESI-MS sp

spectrum of m

pectrum for M

maleimide thi

MITla.

4 

iolactone (MIITla) (CDCl3, 75 MHz).

5 

Figure S7: Comparison of SEC traces for the homopolymerization of MITla initiated by different amounts of TPO in solution (100 mg mL-1 DCM): 5 wt.% (dotted line), 10 wt.% (straight line), and 20 wt.% (dashed line).

Figure S8: Comparison of SEC traces for the homopolymerization of MITla initiated by different amounts of AIBN in solution (100 mg mL-1 THF): 5 wt.% (dotted line), 10 wt.% (straight line), and 20 wt.% (dashed line).

Figure S9trace) (DM

Figure S1

9: ComparisoMSO-d6 , 75 M

10: NMR spec

on of 13C-NMMHz).

ctrum for PM

MR traces for

MITlaAIBN init

6 

r MITla (bla

tiated by AIB

ack trace) and

BN in THF (C

d PMITla (1

CDCl3, 300 MH

0 wt.% TPO

Hz).

O, bulk; red

Figure S1

Figure S1

11: 13C-NMR

12: 13C-NMR

R spectrum for

R spectrum for

r PMITlaAIBN

r PMITlaAIBN

7 

N (DMSO-d6 ,

N (CDCl3, 75 M

75 MHz).

MHz).

Figure S1

Figure S1

13: COSY spe

14: HSQC NM

ectrum for PM

MR spectrum

MITlaAIBN ini

m for PMITlaA

8 

itiated via AI

AIBN initiated

BN in THF (3

via AIBN in T

300 MHz; CD

THF (300 MH

DCl3).

Hz; CDCl3).

Figure S1

Figure S1enlargem

15: DSC ther

16: Comparisment of the fin

mogram for P

son of FT-IR ngerprint regi

PMITlaTPO in

R traces for PMion (B).

9 

n the tempera

MITlaAIBN (re

ature range of

ed trace) and

f -30 to 200°C

d PMITlaTPO

C.

(black trace)

(A) and an

Figure S1P(MITla-

Figure S1

17: Comparis-alt-S)36 (dash

18: 1H-NMR

son of SEC trhed line).

spectrum for

races for P(M

r P(MITla-alt-

10 

MITla-alt-S)10

-S)23 and pea

(dotted line)

k assignment

), P(MITla-alt

t (300 MHz; C

lt-S)23 (straigh

CDCl3).

ht line), and

Figure S1

Figure S2

19: 1H-NMR

20: 1H-NMR s

spectrum for

spectrum for

r P(MITla-alt-

P(MITla-co-

11 

-S)23 and pea

-NIPAAm)23 a

k assignment

and peak assi

t (300 MHz; D

ignment (300

DMSO-d6).

MHz; CDCl3

3).

Figure S2dot) for tof the cop

Figure S2and PMI

21: A) Time the copolymerpolymerizatio

22: ComparisTlaTPO (blue l

vs. styrene mrization of Mon of MITla a

son of DSC tlines) in the s

monomer convMITla and styrand styrene u

races for P(Msecond (straig

12 

version plot drene; B) compsing RAFT.

MITla-alt-S)23

ght lines) and

determined bparison of SE

3 (black lines)third (dashed

by NMR (blaEC traces for

), P(MITla-cod lines) heatin

ck square) anthe kinetic in

o-NIPAAm)23

ng run.

 

nd GC (red nvestigation

3 (red lines)

Figure S2modificat

Figure S2butylami

23: Comparition via n-but

24: HSQC Nne and peak

ison of NMR tylamine and

NMR spectra assignment (3

spectra for methyl acryl

for PMITlaA

300 MHz; CD

13 

PMITlaAIBN blate (300 MHz

AIBN,DM initiateDCl3).

before (blackz; CDCl3).

ed via AIBN

k trace) and

in CHCl3 by

after (red tr

y methyl acry

ace) double

ylate and n-

Figure S2double m

Figure S2modificat

25: Comparismodification vi

26: Comparistion via n-but

son of NMR tia n-butylami

son of NMR ttylamine and

traces for P(Mine and meth

traces for P(Mmethyl acryl

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MITla-co-NIPhyl acrylate (3

MITla-alt-S)3

late (300 MHz

PAAm)23 befo300 MHz; CD

6 before (blacz; CDCl3).

ore (black traDCl3).

ck trace) and

ace) and after

d after (red tr

r (red trace)

race) double

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Figure S27: Comparison of 13C-NMR traces for PMITlaAIBN,DM (blue trace), P(MITla-co-NIPAAm)23DM (red

trace), and P(MITla-alt-S)36DM (black trace); inset shows the signal at 58 ppm.

 

Figure S28: Comparison of SEC traces for the double modification by methyl acrylate and n-butylamine for P(MITla-alt-S)36 in different solvents: pristine P(MITla-alt-S)36 (dashed line), in THF (black line), in dioxane (red line), chloroform (blue line), DMF (blue line).

 

Table S1(25 mg m

Solve

DMF

THF

Dioxa

Chlorof

a) Db) S

Figure S2for P(MIDMF (blusignals ar

: Double modmL-1).

ent Reac

Tim

F 4

F 4

ane 4

form 4

Degree of funSEC (DMAC/

29: CompariITla-alt-S)36 iue line) (75 Mre still observ

dification of P

ction

me [h]

Fuad

48

48

48

48

nctionalization/LiCl): PS-ca

son of 13C-NMn different so

MHz; CDCl3)ved).

P(MITla-co-S

urther educddition afte

24 h

24 h

24 h

24 h

n is estimatedalib.

MR spectra olvents: in T); (As polyme

16 

S)36 by n-buty

ct er fu

d via 1H-NMR

for double mTHF (black liners were only

lamine and m

Estimated unctionaliz

40

60

50

60

R (300 MHz; C

modification bne), in dioxa

y precipitated

methyl acrylat

degree of zation [%]a

0

0

0

0

CDCl3)

by methyl acrne (red line),

d once before

te at differen

Mnb

mol

19 6

18 6

16 6

15 0

rylate and n-, chloroform measuring N

t conditions

[g l-1]

Ðb

600 1.55

600 1.37

600 1.30

000 1.29

-butylamine (blue line),

NMR, educt

Figure Smodificat

Figure S3trace) mo

S30: Compartion by methy

31: Compariodification by

rison of FT-yl acrylate an

ison of FT-IRy methyl acry

-IR spectra nd n-butylami

R spectra forylate and n-bu

17 

for PMITlaA

ine.

r P(MITla-coutylamine.

AIBN before (

o-NIPAAm)23

(black trace)

3 before (blac

 

) and after

ck trace) and

(red trace)

 

d after (red

18 

 

Figure S32: Comparison of FT-IR spectra for P(MITla-co-S)36 before (black trace) and after (red trace) modification by methyl acrylate and n-butylamine.