Supplementary Material for:
Supramolecular Thermoplastics and Thermoplastic Elastomer Materials with self-healing ability based on oligomeric Charged Triblock CopolymersLenny Voorhaar1,4†, Maria Mercedes Diaz2,4†, Frederic Leroux3,4, Sarah Rogers5, Artem M. Abakumov3, Gustaaf Van Tendeloo3, Guy Van Assche2, Bruno Van Mele2, Richard Hoogenboom1*
Experimental
MaterialsAcetone (99.8%), dichloromethane (DCM, 99.8%), ethyl acetate (99.7%), diethyl ether (99.8%), tetrahydofuran (99.9%), CDCl3 (99.8%), ethylene glycol (99%), 1-butanethiol (99%), 2-bromopropionic acid (99%), 4-(dimethylamino)pyridine (DMAP, 99%), carbon disulfide (99.9%) and inhibitor removers (for removing hydroquinone and monomethyl ether hydroquinone) were purchased from Sigma-Aldrich. Hydrochloric acid (HCl, 37% solution), sodium chloride (99%), sodium hydroxide (pellets, 97%) and ammonium chloride (NH4Cl, 99%) were purchased from Acros. Hexane (95%) and magnesium sulfate (MgSO4, dried) were purchased from Fisher Scientific. Methanol (99%) was purchased from Chem-Lab. Deuterated acetone (99.8%) was purchased from Euriso-top. Aluminium oxide (90 standardized) was purchased from Merck. N,N-dimethylformamide (DMF, peptide synthesis) was purchased from Biosolve. N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC) was purchased from Iris Biotech. All were used as received. N-butyl acrylate (BA, 99%), 2-(dimethylamino)ethyl acrylate (DMAEA, 98%) and 2-carboxyoxyethyl acrylate (CEA) were purchased from Sigma-Aldrich and the inhibitors were removed by passing over an aluminium oxide column (for BA) or by stirring with inhibitor removers followed by filtration (for DMAEA and CEA).
Gas Chromotography (GC)Samples were measured with GC to determine the monomer conversion. GC was performed on an Agilent 7890A system equipped with a VWR Carrier-160 hydrogen generator and an Agilent HP-5 column of 30 m length and 0.320 mm diameter. An FID detector was used and the inlet was set to 250 °C with a split injection of ratio 25:1. Hydrogen was used as carrier gas at a flow rate of 2 mL min -1. The oven temperature was increased with 20 °C min-1 from 50 °C to 120 °C, followed by a ramp of 50 °C min-1 to 300 °C.
Size Exclusion Chromotography (SEC)SEC was performed on a Agilent 1260-series HPLC system equipped with a 1260 online degasser, a 1260 ISO-pump, a 1260 automatic liquid sampler (ALS), a thermostatted column compartment (TCC) at 50 °C equipped with two PLgel 5 µm mixed-D columns in series, a 1260 diode array detector (DAD) and a 1260 refractive index detector (RID). The used eluent was DMA containing 50mM of LiCl at a flow rate of 0.593 mL min -1. The spectra were analyzed using the Agilent Chemstation software with the GPC add on. Molar mass and dispersity values were calculated against PMMA standards from polymer labs.
Nuclear Magnetic Resonance (NMR) spectroscopyNMR spectra were recorded on a Bruker Avance 300 MHz spectrometer at room temperature in deuterated solvents. The chemical shifts are given relative to TMS.
Fourier Transform Infrared (FTIR) spectroscopy FTIR was measured on a Perkin-Elmer Spectrum 1000-FTIR with Pike Miracle HATR module.
Thermogravimetric Analysis (TGA)Thermogravimetric measurements were performed to determine the degradation temperature of the synthesized polymers. Specifically, it was used as a tool to assess the molar fraction of CEA in the CEA-BA-CEA block copolymers (see Fig. S21). Since the degradation of CEA takes place in a very
1
big step at earlier temperatures than the pure BA it was possible to determine the CEA composition in the triblocks by this method. Measurements were carried out in a TA Instruments TGA Q5000IR, a ramping procedure was followed at 20 °C min -1 from 50 °C to 650 °C in air.
Modulated Temperature Differential Scanning Calorimetry (MTDSC)MTDSC was used to evaluate the thermal transitions of the triblock copolymers and their mixtures. Measurements were performed in a DSC Q2000 from TA Instruments equipped with a cooling system RCS 90. Ramp experiments were done at a heating rate of 2 °C min-1 using amplitude of ±0.4 °C and a period of 80 seconds.
Dynamic Mechanical Analysis (DMA)DMA measurements were performed to evaluate the mechanical properties of the materials, these were carried out in a TA Instruments DMA Q800. Samples were film pressed and were evaluated in tension. Ramp experiments were done at 2.5 °C min-1 using a strain percentage of 0.05 and a frequency of 1Hz. The mechanical recovery of properties evaluated in DMA was performed by measuring the samples in dynamic mode in tension at 25 °C, using a strain percentage of 0.05 and a frequency of 1Hz; the recovery of properties was followed without removing the samples from the DMA and taking care that the samples were kept dry at all times to guarantee adequate measuring conditions.
Dynamic RheometryDynamic rheometry measurements were performed in a TA instruments ARG2 rheometer equipped with Electrically Heated Plates (EHP). A cone and plate geometry of 4 mm in diameter and parallel plates of 25 mm were used to measure the individual triblock copolymers. The copolymer mixtures were measured in parallel plates of 10 mm in diameter. Measurements were performed following a ramping procedure at 2 °C min-1.
Small-angle Neutron Scattering (SANS)SANS was carried out on the Sans2d small-angle diffractometer at the ISIS Pulsed Neutron Source (STFC Rutherford Appleton Laboratory, Didcot, U.K.)1. A simultaneous Q-range of 0.0045 – 0.75 Å-
1 was achieved utilizing an incident wavelength range of 1.75 – 16.5 Å and employing an instrument set up of L1 = L2 = 4 m, with the 1 m2 detector offset vertically 150 mm and sideways 50 mm. Q is defined as:
Q=4 π sin θ
2λ
where θ is the scattered angle and λ is the incident neutron wavelength. Samples were prepared in deuterated solvents, providing the necessary contrast and were contained in 1 mm path length quartz cells. Each raw scattering data set was corrected for the detector efficiencies, sample transmission and background scattering and converted to scattering cross-section data (∂Σ/∂Ω vs. Q) using the instrument-specific software. These data were placed on an absolute scale (cm -1) using the scattering from a standard sample (a solid blend of hydrogenous and perdeuterated polystyrene) in accordance with established procedures.2 SANS results are shown in Fig. S22.
HAADF-STEMUltrathin sections of 60 nm from Mixtures 1-4 were obtained by cryosectioning at -80°C using a LEICA EM UC7 microtome equipped with a FC7 cryochamber. Sections were collected on a Quantifoil grid and vapour stained with osmium tetroxide (2%) or uranylacetate (Fig. S25) for 30 minutes. Alternatively sections were stained with a 2% solution of uranyl acetate and a final rinse in ultrapure water. A 3 nm layer of amorphous carbon was deposited using a LEICA ACE600 carbon evaporator in order to increase the stability of the sections. The samples were analyzed in HAADF-STEM mode using an FEI Titan transmission electron microscope operated at 200 kV. A Fischione (model 3000) annular detector was used to acquire dark field images.
Electrical conductivity measurementsThe samples for the conductivity measurements were film pressed to a thickness of around 0.2 mm. Cuts of 1 cm length were made in the samples which were filled with graphite conductive paste to
2
improve the contact between the sample and the electrodes and to measure in a well-defined area of 1 cm². A Fluke 1587 multimeter was used to record the electrical resistance of the sample at a potential of 100 V and 250 V from which the bulk resistivity and conductivity is calculated.
Atomic Force Microscopy (AFM) measurementsAtomic force microscopy (AFM) measurements to evaluate the sealing properties were performed in an Asylum research MFP-3D Atomic force microscope equipped with an Olympus AC 160TS-R3 cantilever and a MFP-3D Cooler Heater Stage with operating temperatures between -20 to 120°C.
Assessment of recovery of propertiesThe definition used to calculate the healing efficiency of supramolecular blend Mix 3 is given by η.
η=100E ' healed
E 'initialThe setup used to measure these properties is shown in Fig. S26.
Synthesis of bifunctional trithiocabonate chain transfer agent (BTCTA)2-(((Butylsulfanyl)carbonothioyl)sulfanyl)propanoic acid (PABTC) was synthesized following a previously published method3 (Fig. S1). A solution of PABTC (16.90 g, 71 mmol) and ethylene glycol (2.00 g, 32 mmol) in DCM (300 mL) was cooled in an ice bath. A solution of EDC (16.57 g, 81 mmol) and DMAP (0.79 g, 0.64 mmol) in DCM (100 mL) was added dropwise and the reaction was stirred overnight at room temperature (Fig. S2). The mixture was subsequently washed with a saturated NH4Cl solution, distilled water, 1M HCl and saturated brine, dried with MgSO4, filtered and the solvent was removed under reduced pressure. The product was then purified over a short aluminium oxide column using hexane:ethyl acetate 3:1 as eluent. The solvent was removed under reduced pressure and a 12.27 g yield (76%) of orange liquid was obtained. The structure and purity of the compound was confirmed by 1H NMR (Fig. S4), 13C NMR (Fig. S5) and FTIR(Fig. S6).
SH CS2
Br O
OHS S
SOH
O+ +
H2O, acetone, NaOH
RT overnight
Fig. S1. Synthesis of PABTC.
S
S
SO
OH
OHOH N
N N+
H
N
N
+ + +
OO
O
OS
S
SS
S
S
CH2Cl2
0 oC
Cl-
Fig. S2. Synthesis of BTCTA.
PolymerizationsThe ABA-type triblock copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization (Fig S3). Monomer conversions were determined by GC (BA and DMAEA) or NMR (CEA). First n-butyl acrylate (BA) was polymerized using the bifunctional chain transfer agent using a [BA]:[BTCTA]:[AIBN] ratio of 100:1:0.1 at 1.8 M monomer concentration in DMF at 60 °C. The polymer was purified by precipitation in a methanol and distilled water 2:1 mixture and dried under reduced pressure. It was then used as macro chain transfer agent for subsequent RAFT polymerizations. 2-(Dimethylamino)ethyl acrylate (DMAEA) was polymerized using a [DMAEA]:[BTCTA]:[AIBN] ratio of 100:1:0.1 at 1.7 M monomer concentration in DMF at 70 °C, purified by precipitation in hexane/diethyl ether mixture and dried under reduced pressure. 2-Carboxyethyl acrylate (CEA) was polymerized using a [CEA]:[BTCTA]:[AIBN] ratio of 100:1:0.05 at 0.56 M monomer concentration in DMF at 70 °C, purified by precipitation in distilled water and
3
dried under reduced pressure. Fig. S7 and S8 show the kinetic studies of the PBA homopolymer and the triblock copolymers, respectively. The monomer conversion and molecular weights are shown in Table S1. For all polymers, SEC (Fig. S9), NMR (Fig. S10-S20), TGA (Fig. S21, S23 and S24), MTDSC (Fig. S27) and rheometry (Fig. S27) were measured. MTDSC, DMA and rheometry results for all the polymer mixtures are shown in Fig. S28.
S
SS
OO
N
OO
O
OO O
OOS
S S
OO
N
- b - - b -
S
SS
OO
OH O
S
S S
OO
O OH
OO
O
OO O
OO
- b - - b -
OO
O
OS
S
SS
S
S
OO
OO
OHO
OO
N
AIBN
DMF 60oC
AIBN
DMF 70oC
n n
n n
mm
p p
Fig. S3. Synthesis of the triblock copolymers.
Reproducibility EvaluationThe synthesis method allowed the reproduction of polymers with the same properties. To evaluate this, the polymers were measured in SEC, NMR, TGA and MTDSC. In Fig. S9, Fig. S18, Fig. S19, Fig. S23 and Fig. S24 the data of polymers P3a and P3b is shown. These two polymers were synthesized separately but show very similar properties in each of the measurements, confirming that similar polymers can be synthesized reproducibly. The polymers P0a, P0b and P0c were also synthesized in separate batches, but show similar properties and are therefore considered to each have similar structure.
Results
Synthesis of bifunctional trithiocabonate chain transfer agent (BTCTA)
8 7 6 5 4 3 2 1 0ppm
Fig. S4. 1H NMR of BTCTA (CDCl3, 500 MHz) δ: 4.80 ppm (2H, q, -CH(CH3)-S-), 4.32 ppm (4H, s, -C(O)-O-CH2-CH2), 3.33 ppm (4H, t, -CH2-CH2-S-), 1.65 ppm (4H, m, -CH2-CH2-CH2-S-), 1.58 ppm (6H, d, CH3-CH-), 1.40 ppm (4H, m, CH3-CH2-CH2-), 0.90 ppm (6H, t, CH3-CH2-)
4
160 140 120 100 80 60 40 20 0ppm
Fig. S5. 13C APT NMR of BTCTA (CDCl3, 300 MHz) δ: 14 ppm (CH3-CH2-), 17 ppm (CH3-CH-), 22 ppm (CH3-CH2-CH2-), 30 ppm (-CH2-CH2-CH2-S-), 37 ppm (-CH2-CH2-S-), 48 ppm (-CH(CH3)-S-), 63 ppm (-C(O)-O-CH2-CH2), 171 ppm (-C(O)-O-). Signals at 77 ppm are from CDCl3.
4000 3500 3000 2500 2000 1500 1000
50
60
70
80
90
100
% T
rans
mitt
ance
cm-1
Fig. S6. FTIR spectrum of BTCTA.
Kinetic studies of polymerizations
0 50 100 150 200 250 300 350 4000.0
0.5
1.0
1.5
ln([M
] 0/[M])
Time (min)0.0 0.2 0.4 0.6 0.8 1.00
5000
10000
Mn, theoretical
Mn(g
/mol
)
Conversion
1.0
1.2
1.4
Ð
Fig. S7. Left: first order kinetic plot for RAFT polymerization of BA using [BA]:[BTCTA]:[AIBN] = 100:1:0.1, 1.8 M monomer concentration in DMF at 60 °C. Right: corresponding molecular weight and dispersity vs. conversion plot.
5
0 50 100 150 200 250 3000.0
0.2
0.4
0.6
0.8
1.0
ln([M
] 0/[M])
Time (min)0.0 0.2 0.4 0.6 0.8 1.00
5000
10000
Mn, theoretical
CEA M
n, theoretical DMAEA
Mn(g
/mol
)
Conversion
1.0
1.2
1.4
Ð
Fig. S8. Left: first order kinetic plot for RAFT polymerizations of CEA ( ) using [CEA]:[pBA]:[AIBN] = 100:1:0.05, 0.56 M monomer concentration in DMF at 70 °C; and DMAEA (□) using [DMAEA]:[pBA]:[AIBN] = 100:1:0.1, 1.7 M monomer concentration in DMF at 70 °C. Right: corresponding molecular weight and dispersity vs. conversion plots.
Details of synthesized polymers
Table S1. Details of the polymers used in this work.Polymer type Composition
(NMR after purification)
DP (from conversion in GC/NMR)
Mn theoretical (from conversion, excluding CTA)
Before purification
After purification
Yield (g)
Mn (SEC)
Đ (SEC)
Mn (SEC)
Đ (SEC)
P0a DMAEA-BA-DMAEA
45% DMAEA55% BA
34 DMAEA55 BA
2x2400 DMAEA7600 BA
10200 1.16 10500 1.20 11.79
P0b DMAEA-BA-DMAEA
39% DMAEA61% BA
30 DMAEA54 BA
2x2200 DMAEA6900 BA
8000 1.32 8000 1.32 6.18
P0c DMAEA-BA-DMAEA
37% DMAEA63% BA
34 DMAEA56 BA
2x2400 DMAEA7000 BA
10400 1.39 14100 1.23 3.23
P0d DMAEA-BA-DMAEA
40% DMAEA 60% BA
26 DMAEA53 BA
2x1900 DMAEA 6700 BA
3700 1.35 9200 1.22 3.5
P1 CEA-BA-CEA 18% CEA82% BA
14 CEA55 BA
2x1000 CEA7600 BA
5800 1.17 4600 1.33 3.74
P2a CEA-BA-CEA 24% CEA76% BA
21 CEA54 BA
2x1500 CEA6900 BA
10000 1.25 11300 1.14 2.56
P2b CEA-BA-CEA 23% CEA77% BA
16 CEA53 BA
2x1200 CEA6700 BA
4500 1.41 4400 1.42 10
P3a CEA-BA-CEA 40% CEA 60% BA
15 CEA20 BA
2x1000 CEA2600 BA
7200 1.09 7400 1.08 0.85
P3b CEA-BA-CEA 40% CEA60% BA
11 CEA16 BA
2x900 CEA 2100 BA
6500 1.11 6500 1.21 1.86
P3c CEA-BA-CEA 42% CEA58%BA
19 CEA23 BA
2x1400 CEA3000 BA
3700 1.35 6900 1.14 9
P4 CEA-BA-CEA 60% CEA40% BA
30 CEA20 BA
2x2200 CEA2600 BA
11500 1.12 11400 1.12 1.13
6
1000 10000 100000
0.0
0.5
1.0N
orm
aliz
ed re
spon
se
Molecular weight (g/mol)
PBA homopolymer P0a P1
Mn, SEC ĐPBA 5200 1.15P0a 10500 1.20P1 4600 1.35
1000 10000 100000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
pBA homopolymer P0b P2a
Mn, SEC ĐPBA 6400 1.21P0b 8000 1.32P2a 11300 1.14
1000 10000 100000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
PBA homopolymer P0c
Mn, SEC ĐPBA 7700 1.14P0c 14100 1.23
1000 10000 100000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
pBA homopolymer P0d P2b
Mn, SEC ĐPBA 5100 1.18P0d 9200 1.22P2b 4400 1.42
1000 10000 100000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
PBA homopolymer P3a P4
Mn, SEC ĐPBA 2400 1.05P3a 7400 1.08P4 11400 1.12
1000 10000 100000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
PBA homopolymer P3b
Mn, SEC ĐPBA 1400 1.15P3b 6500 1.21
1000 10000
0.0
0.5
1.0
Nor
mal
ized
resp
onse
Molecular weight (g/mol)
pBA homopolymer P3c
Mn, SEC ĐPBA 1500 1.44P3c 6900 1.22
Fig. S9. SEC traces of each of the polymers, together with the SEC traces of the PBA homopolymers that were used as macroCTAs.
7
8 7 6 5 4 3 2 1 0ppm
Fig. S10. 1H NMR of P0a (CDCl3, 300 MHz) δ: 0.93 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.36 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.59 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.27 ppm (6H, s, (CH3)2-N-CH2), 2.54 ppm (2H, m, N-CH2-CH2-O-), 4.03 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.15 ppm (2H, m, N-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S11. 1H NMR of P0b (CDCl3, 300 MHz) δ: 0.93 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.36 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.59 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.28 ppm (6H, s, (CH3)2-N-CH2), 2.56 ppm (2H, m, N-CH2-CH2-O-), 4.03 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.15 ppm (2H, m, N-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S12. 1H NMR of P0c (CDCl3, 300 MHz) δ: 0.93 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.36 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.59 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.27 ppm (6H, s, (CH3)2-N-CH2), 2.54 ppm (2H, m, N-CH2-CH2-O-), 4.03 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.15 ppm (2H, m, N-CH2-CH2-O-).
8
8 7 6 5 4 3 2 1 0ppm
Figure S13. 1H NMR of P0d (CDCl3, 300 MHz) δ: 0.93 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.36 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.59 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.27 ppm (6H, s, (CH3)2-N-CH2), 2.54 ppm (2H, m, N-CH2-CH2-O-), 4.03 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.15 ppm (2H, m, N-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S14. 1H NMR of P1 (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.71 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S15. 1H NMR of P2a (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.71 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
9
8 7 6 5 4 3 2 1 0ppm
Figure S16. 1H NMR of P2b (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.71 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S17. 1H NMR of P3a (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.72 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S18. 1H NMR of P3b (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.72 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
10
8 7 6 5 4 3 2 1 0ppm
Figure S19. 1H NMR of P3c (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.72 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
8 7 6 5 4 3 2 1 0ppm
Fig. S20. 1H NMR of P4 (acetone-d6, 300 MHz) δ: 0.97 ppm (3H, t, CH3-CH2-CH2-CH2-O-), 1.44 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 1.64 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 2.72 ppm (2H, m, C(OOH)-CH2-CH2-O-), 4.08 ppm (2H, m, CH3-CH2-CH2-CH2-O-), 4.35 ppm (2H, m, C(OOH)-CH2-CH2-O-).
0
20
40
60
80
100
120
50 150 250 350 450 550 650
Wei
ght %
T / C
BAP1P2P3aP3bP4CEA
45% CEA
100% CEA
Fig. S21. TGA measurements of the different CEA-BA-CEA triblock copolymers.
11
0.1
1
10
100
0.001 0.01 0.1 1
I / c
m-1
q / Å-1
Mix 2Mix 3Mix 4
Fig. S22. SANS measurement for the different mixtures Mix 2, Mix 3 and Mix 4.
0
20
40
60
80
100
120
50 150 250 350 450 550 650
Wei
ght (
%)
T ( C)
P3a
P3b
Fig. S23. TGA measurement for P3a and P3b
0.6
0.8
1
1.2
1.4
1.6
-80 -60 -40 -20 0 20 40 60 80
Hea
t cap
acity
( J
g-1C
-1)
T ( C)
P3a
P3b
Fig. S24. MTDSC measurement for P3a and P3b
12
mixture d nmMix 2 8.4Mix 3 9.4Mix 4 14
Fig. S25. HAADF-STEM image of Mix 1 stained with uranylacetate staining.
A
Fig. S26. Measuring set-up for recovery of mechanical properties of Mix 3 in tension mode. Transversal cut in the middle of the film indicated by the arrow.
13
Triblock DSC RheometryP0
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-1
T / � C
P0a
P0d
P0c
1E-03
1E-02
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
G',G
"/ P
a
T / ° C
G"
P0d
P0c
P0a
0
30
60
90
20 40 60 80 100
δ/ °
T / ° C
P0dP0c
P0a
P1
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-1
T / � C
P1
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
" / P
a
T / ° C
G"
P2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-1
T / � C
P2b
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
" / P
a
T / ° C
G"
P3
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-1
T / � C
P3c
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
" / P
a
T / ° C
G"
P4
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-1
T / � C
P4
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
" / P
a
T / ° C
G"
Fig S27. MTDSC and rheometry measurements of the individual triblock copolymers P0-P4.
14
Mix DSC DMA Rheometry1
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Heat
cap
acity
/ J
g-1�C
-1
T / � C
Mix 1
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
-80 -60 -40 -20 0 20 40 60 80
δ/ °
E', E
"/ M
Pa
T / °C
E"
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
"/ P
a
T / ° C
G"
2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Heat
cap
acity
/ J
g-1�C
-1
T / � C
Mix 2
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
-80 -60 -40 -20 0 20 40 60 80
δ / °E'
,E"
/ MPa
T / °C
E"
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
"/ P
a
T / ° C
G"
3
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-
1
T / � C
Mix 3
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
-80 -60 -40 -20 0 20 40 60 80
δ / °E',E
"/ M
Pa
T / °C
E"
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
"/ P
aT / ° C
G"
4
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
-80 -60 -40 -20 0 20 40 60 80
Spec
ific
Hea
t cap
acity
/ J
g-1�C
-
1
T / � C
Mix 4
0
30
60
90
1E-01
1E+00
1E+01
1E+02
1E+03
1E+04
-80 -60 -40 -20 0 20 40 60 80
δ / °E',E
"/ M
Pa
T / °C
E"
0
30
60
90
1E+00
1E+01
1E+02
1E+03
1E+04
1E+05
1E+06
1E+07
20 40 60 80 100
δ/ °
G',G
"/ P
a
T / ° C
G"
Fig S28. MTDSC, DMA and rheometry of the different mixtures P1-P4.
References:
1 Heenan, R. K., Rogers, S. E., Turner, D., Terry, A. E., Treadgold, J., & King, S. E. Small Angle Neutron Scattering Using Sans2d. Neutron News 22, 19-21 (2011).
2 Wignall, G. D. & Bates, F. S. Absolute calibration of small-angle neutron scattering data. J. Appl. Crystallogr. 20, 28-40 (1987).
3 Ferguson, C. J., Hughes, R. J., Nguyen, D., Pham, B. T. T., Gilbert, R. G., Serelis, A. K., Such, C. H., & Hawkett, B. S. Ab Initio Emulsion Polymerization by RAFT-Controlled Self-Assembly. Macromolecules 38, 2191-2204 (2005).
15