Supporting Information
Controlling Size and Orientation of Lamellar
Microdomains in Crystalline Block Copolymers
Claudio De Rosa,* Rocco Di Girolamo, Finizia Auriemma, Giovanni Talarico, Anna Malafronte,
Carmen Scarica, Miriam Scoti.
Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Monte S.Angelo, Via Cintia, I-80126 Napoli, Italy
13C NMR measurements.
The samples of PE homopolymer and PE-b-EP block copolymers have been characterized by 13C Nuclear Magnetic Resonance Spectroscopy (13C-NMR) by using a 400 MHz Bruker Advance Spectrometer equipped with a 5mm high temperature cryoprobe. The spectra have been recorded on 50 mg/mL polymer solutions in deuterated 1,1,2,2-tetrachloroethane-d2 at 120°. The specific parameters for the measurements were as follows: 45° pulse; 2.3 s acquisition time; 5.0 s relaxation delay; 2-10K transients; 14kHz spectral width; 64K time domain data points.
The 13C-NMR spectra of the samples PE-b-EP-1 and PE-b-EP-2 are shown in Figure S1. All observed resonances have been assigned to carbon atoms belonging to constitutional sequences EE, EP, EEE, EEP, etc. (where E and P stand for ethylene and propylene units, respectively), according to ref. S1. The values of chemical shift and intensity and assignments to carbon atoms of the observed resonances are reported in Table S1. The assignments of all resonance peaks followed the
nomenclature used by Carman and WilkesS2,S3 and Cheng,S4 where primary (methyl), secondary (methylene) and tertiary (methine) carbons were denoted as P, S, and T, respectively. The position of a carbon relative to its nearest methine groups was labeled by two Greek subscripts.
20 25 30 35 40 45 H I G F E D C B δ (
ppm)
A, sample PE-b-EP-1 Sββ Pββ Sβδ Sβγ Tβδ Sδδ Tββ Tδδ Tγδ Tγγ Sγδ Sαγ+Sαδ (*) Sαβ (*) Sαα A 20 25 30 35 40 45 Sββ Pββ Sβδ Sβγ Tβδ Sδδ Tββ Tδδ Tγδ Tγγ Sγδ Sαγ+Sαδ S (*) αβ (*) δ (ppm)
B, sample PE-b-EP-2 Sαα H I G F E D C B AFigure S1. 13C NMR spectra of the samples PE-b-EP-1 (A) and PE-b-EP-2 (B) recorded at 120°C
in 1,1,2,2-tetrachloroethane-d2 solutions.
Table S1. Chemical shift (δ), intensity (area%) and assignments to carbon atoms of the resonances
observed in the 13C NMR spectra of samples PE-b-EP-1 (A) and PE-b-EP-2 (B). S, T and P stand for secondary, tertiary and primary carbon atoms, respectively.S2-S4
Carbon type Symbol used in
the area δ range
(a) Area (%)(b)
Sample PE-b-EP-1 Sample PE-b-EP-2
Sαα A 47.2-44.9 6.56 5.21 Sαγ, Sαδ B 38.8-36.9 6.89 6.81 Sαβ C 35.9-34.2 6.43 5.87 Tγγ Tγδ Tδδ D 33.9-32.7 Tγγ + Tγδ =2.71 Tδδ =1.04 Tγγ + Tγδ =2.80 Tδδ = 1.08 Tβγ Tβδ Sγγ Sγδ Sδδ E 31.4-29.2 Tβδ = 6.47 Sγγ = 0.20(c) Sγδ = 1.55 Sδδ = 45.89 Tβδ = 5.76 Sγγ = 0.31(c) Sγδ = 1.45 Sδδ = 49.98 Tββ F 28.8-27.9 3.15 2.29 Sβγ Sβδ G 27.8-26.9 Sβγ = 1.23 Sβδ = 1.96 Sβγ = 1.33 Sβδ = 2.07 Sββ H 24.9-24.2 1.58 1.66 Pββ, Pβδ, Pδδ, Pγγ I 22.5-19.5 14.32 13.39
[E] = 69 mol%d [E] = 73 mol%d
a) Chemical shifts in ppm downfield from TMS. b) Normalized to 100%. c) Due to the overlapping
of Sγγ with Tβδ ,we calculated the Sγγ by using equation Sγγ = ½(Sβδ - Sγδ). d) Concentration of ethylene units calculated according to ref. S1.
From the intensities of the observed resonances, the total ethylene concentrations of the samples have been calculated according to ref. S1. The sample PE-b-EP-2 shows an ethylene concentration higher than that of the sample PE-b-EP-1. This is mainly due to the higher intensity of the Sδδ
resonance at δ = 29.76 ppm (diagnostic of polyethylene sequences) of the sample PE-b-EP-1 (49.98% in Table S1) than that of the sample PE-b-EP-2 (45.89% in Table S1). Analogously, the ratio between constitutional sequences EEE/(PPE+EPE), calculated according to equations given in ref. S5, is 3.6 in the sample PE-b-EP-1 and increases to 4.3 in the sample PE-b-EP-2, indicating a higher concentration of long ethylene sequences in the sample PE-b-EP-2. These indicate that the
Evaluation of periodicity from AFM images.
The values of periodicity L of the lamellar nanostructures have been evaluated from the phase intensity profile of the AFM phase images of Figure 5A-C read along directions perpendicular to the lamellae. An example of phase intensity profile is shown in Figure S2 for the sample PE-b-EP-1. The values of periodicity reported in Table 2 are averaged over more than 50 different lamellae.
Figure S2. Phase intensity profile of the AFM phase image of the sample PE-b-EP-1 of Figure 5C
read along directions perpendicular to the lamellae.
References.
S1) Wang, W.-J.; Zhu, S. Structural Analysis of Ethylene/Propylene Copolymers Synthesized with a Constrained Geometry Catalyst. Macromolecules 2000, 33, 1157.
S2) Carman, C. J.; Wilkes, C. E. Monomer Sequence Distribution in Ethylene Propylene Elastomers. I. Measurement by Carbon-13 Nuclear Magnetic Resonance Spectroscopy. Rubber
Chem. Technol. 1971, 44, 781.
S3) Carman, C. J.; Harrington, R. A.; Wilkes, C. E. Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Model. Macromolecules
S4) Cheng, H. N. 13C NMR Analysis of Ethylene-Propylene Rubbers. Macromolecules 1984, 17, 1950.
S5) Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T. 13C NMR Determination of Monomer
Sequence Distribution in Ethylene-Propylene Copolymers Prepared with δ-TiCl3-A1(C2H5)2C1.
