Ring Opening Polymerization of Cyclic Esters Promoted by Phosphido-Diphosphine Pincer
Group 3 Complexes.
Ilaria D’Auria, Mina Mazzeo,* Daniela Pappalardo,#* Marina Lamberti and Claudio Pellecchia
Department of Chemistry, University of Salerno. I-84084, via Ponte don Melillo, Fisciano,
Salerno, Italy.
#
Dipartimento di Studi Geologici ed Ambientali, Università del Sannio, via dei Mulini 59/A, I-
82100, Benevento.
Supporting Information
ESI-MS spectrum of oligomer of L-lactide by 1
pag S2
1
H NMR spectrum of the PCL obtained using 1/ iPrOH=1/40 as initiator
pag S3
1
H NMR spectrum of the CL-LA block copolymer
pag S4
13
pag S5
1
H NMR spectrum of the PVL
pag S6
1
H NMR spectrum of the PBL obtained in run 26
pag S7
C NMR spectrum of the CL-LA block copolymer
Table of Ring Opening Polymerization of -CL promoted by 4
pag S8
Table of molar ratios of the end-groups in PHB samples
pag S9
S1
Figure S-1. ESI-MS spectrum of oligomer of L-lactide using 1 as initiator.
S2
Figure S-2. 1H NMR spectrum (400 MHz, CDCl3) of the PCL obtained using 1/ iPrOH=1/40 as
initiator after quenching with wet n-hexane Conditions: [-CL]0/[Y]0 =1000) in toluene at room
temperature (see run 20 , Table 3).
S3
Figure S-3. 1H NMR spectrum (400 MHz, CDCl3) of the CL-LA block copolymer.
S4
Figure S-4. 13C NMR spectrum (400 MHz, CDCl3) of the CL-LA block copolymer.
S5
Figure S-5 1H NMR Spectrum (400 MHz, CDCl3, RT) of poly(δ-valerolactone)(PVL)
(MnGPC = 20.3 kDa, Mw/Mn=1.39) synthesized with 1.
S6
Figure S-6 . 1H NMR spectrum (400 MHz, CDCl3) of the PBL obtained in run 26
S7
Table S1. Ring Opening Polymerization of -CL promoted by 4
Run
[CL]0/[I]0 Time Conv.a Mn GPCb Mn calcc PDIb
(min)
%
(x103) (x103)
29
1000
10
36
36.7
41.0
1.48
30
1000
15
63
57.9
67.3
1.51
31
1000
20
67
65.6
73.4
1.53
32
1000
25
73
76.0
83.2
1.47
33
1000
30
87
99.4
96.9
1.48
All reactions were performed with [CL]= 0.5 M in 4 mL of toluene, [CL]/4=1000 , at 20°C. [a]Conversion of ε-CL as
determined by 1H NMR spectral data. [b] Experimental Mn (in gmol -1) and Mw/Mn values determined by GPC in
THF against polystyrene standards and corrected using the Mark-Houwink factor of 0,58.
[c] Mn,calc (in gmol-1) =114,14 x ([ε-CL]/[I ]) x conversion ε-CL .
S8
Table S2. Molar ratio of the end-groups in PHB samples.a
Run
24
0.03
0
0.02
1.00
25
0.04
0.04
0.02
1.00
26
0.01
0.01
0.10
1.00
27
0.05
0
0.09
1.00
28
0.005
0.007
0.010
1.00
a
The molar ratio between the end groups was determined by 1H NMR, normalizing at 1.00 the integral of the signal of
the methine -CH(CH3)- in the main polymer chain.
S9