Supporting imformation

Closed-loop recyclable fully bio-based epoxy vitrimers from ferulic acid-derived

hyperbranched epoxy resin

Liuyue Zhonga, Yanxin Haoa, Junheng Zhanga*, Fang Weia, Tingcheng Lia, Menghe Miaob,

Daohong Zhanga*
a
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei

Key Laboratory of Catalysis and Materials Science, Hubei R&D Center of Hyperbranched

Polymers Synthesis and Applications, South-Central University for Nationalities, Wuhan 430074,

China.
b
CSIRO Manufacturing, 75 Pigdons Road, Waurn Ponds, Victoria 3216, Australia

*E-mail: [email protected]; [email protected]

Characterization.

Number of Figure: 7

Figure S1. The chemical structure of FEHBP.

Figure S2. 13CNMR (a) and mass spectra (b) of FEP.

Figure S3. MALDI-TOF mass spectra of FEHBP.

Figure S4. TGA curves of epoxy vitrimers.

Figure S5. Tensile stress-strain curves (a), Plots of storage modulus (b) and tanδ curves (c) of

original and reprocessed CA/DGEBA. Stress-strain curves (d), Plots of storage modulus (e) and

tanδ curves (f) of original and reprocessed CA/FEP.

Figure S6. Photographs of CA/FEP/FEHBP in solvents before (a) and after (b) 72h at room

1
temperature.

Figure S7. Tensile stress-strain curves (a, c) and DMA (b, d) curves of original and chemically

recycled CA/DGEBA and CA/FEP.

Number of Tables: 13

Table S1. Compositions of epoxy vitrimers

Table S2. DSC characteristic parameters of epoxy vitrimers

Table S3. Swelling ratios and gel contents of epoxy vitrimers

Table S4. Mechanical properties of epoxy vitrimers

Table S5. Thermomechanical properties of epoxy vitrimers

Table S6. Thermal stability and degradation data of epoxy vitrimers under nitrogen atmosphere

Table S7. PALS data and free volume fractions of epoxy vitrimers

Table S8. Values of shape memory properties of the original and reprocessed of CA/FEP/FEHBP
Table S9. The tensile strength of original and reprocessed epoxy vitrimers

Table S10. DMA data of original and reprocessed CA/DGEBA

Table S11. Summary of DMA results of original and reprocessed CA/FEP

Table S12. Summary of DMA results of original and reprocessed CA/FEP/FEHBP

Table S13. Mechanical properties and relevant DMA data of original and chemically recycled

epoxy vitrimers

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Characterization
1
HNMR and 13
CNMR measurements were conducted on a Bruker Avance Ⅲ-400 NMR

spectrometer with d-DMSO as the solvent. Fourier transform infrared (FTIR) spectra were

collected on a Bruker Vertex 70 FTIR spectrometer with the range of 4000-500 cm-1. Gel

permeation chromatography (GPC) was measured on a Waters 1525 with Waters 2414 using

DMF as the fluent at 40oC, after calibration with standard polystyrenes. GC-MS (Thermo, Trace

1300, TSQ9000EVO triple quadrupole) coupled with TG-5MS GC column (30m×0.25mm×

0.25μm,). The temperature gradient used was as following: from 60 to 290oC at a heating rate of

8oC/min, and from 290 to 300oC at 30oC /min, finally holding for 15min. A 1μL aliquot of the

samples was introduced in splitless injection. S/SL temperature: 300 oC. The transfer line

between the GC and the TSQ 9000 was kept at 280oC. The mass spectrometer operated in the

electron impact (EI) ionization mode (+70eV) with a source temperature of 280oC in full scan

mode with a scan range of 50-650m/z. Matrix-assisted laser desorption ionization time-of-flight

(MALDI-TOF) mass spectra were performed on a Bruker MALDI-TOF system using trans-2-[3-

(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile Propanedinitrile (DCHB) as

matrix and N,N-Dimethylformamide as solvent. The epoxy values of epoxy resins were

determined by hydrochloric acid-acetone method (ASTM D1652), and the Hydroxyl values were

determined by titration using acetic anhydride acetylation (ASTM E222). Differential scanning

calorimetry (DSC) was performed on a NETZSCH DSC 214 using N2 as a purge gas at a heating

rate of 10oC/min. Thermal gravimetric analysis (TGA) was performed on a TA Instruments TGA

Q500 under a nitrogen atmosphere over a temperature range of 30-700oC at a heating rate of

10oC/min. Tensile properties were evaluated using a universal tester (INSTRON 5966, Instron,

Norwood, USA) according to ASTM D638 at a crosshead speed of 2mm/min-1. Each reported

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value was the average of at least five specimens. AFM imaging was carried out using a Bruker

Dimension Fast Scan instrument operating in tapping mode. Fast Scan A cantilevers from Bruker

were used for the experiments and the images were investigated in Nanoscope 1.5 software.

Scanning electron microscopy (SEM) was performed on a Hitachi scanning electron microscope.

The degradeproductions were measured with LC-MS/MS (Anglient 1260-6120).

Positron annihilation lifetime spectroscopy (PALS) was conducted to study on a RGM-

1/APBS-2 (First Point Inc.) trap-based slow positron beam system. The free volume fraction (Fv)

can be expressed as

FV = cVI 3 (S1)

where I3 is the lifetime of the intensity, V is the total volume of a single site of free volume

or cavity, which can be calculated from τ3 (lifetime of ortho-positronium) and c is an empirical

constant, which is usually set to 0.018 ± 0.002nm−3 for polymers.

A Q800 DMA machine (TA, America) was used for tensile creep TTS, Tv and stress

relaxation tests. Dynamic mechanical analysis (DMA) was carried out at a frequency of 1Hz and

a heating rate of 10oC/min using tensile mode. The specimens were stretched by 1.0%, and the

strain was retained during the test. Stress relaxation tests were carried out using the tensile mode.

Rectangular specimens (12.0 × 6.0 × 1.0mm3) were initially aligned by preloading a 0.001N

force, followed by thermal equilibrium at each test temperature for 1min. The variation of the

relaxation modulus versus time was recorded. The tensile creep TTS test was conducted at

temperatures between 20 and 120℃ in intervals of 10℃ with dimensions of 20mm × 0.5mm ×

300μm. During the measurement of each isotherm, a constant force of 5.0MPa was applied for

5min followed by a 10min recovery period.

The crosslink density (ρ) of vitrimers were calculated as follows,

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 Ed
ρ= (S2)
3RT

where Ed is the storage modulus at rubbery states (Tg + 50℃), R is the gas constant (8.314

J/(mol·K)) and T is the Kelvin temperature of Tg + 50℃.

Shape memory cycles were performed using DMA Q800 under a control force mode. A

certain stress (σ) was applied to the sample (dumbbell shape as mentioned above) at 120oC. Then,

the sample was cooled to 60oC under the stress. The temporary shape was kept after removal of

the stress when maintaining the temperature at 60oC. The temporarily fixed sample was heated to

120oC again to recover its permanent shape under a stress-free condition, from where a next

shape memory cycle began. The shape memory behavior was evaluated by shape fixity (Rf) and

shape recovery (Rr) calculated as follows,

Rf = ( d /  dload ) 100% (S3)

Rr = ( d −  rec /  dload ) 100% (S4)

where εdload, εrec, and εd were the maximum strain under load, the recovered strain, and the

fixed strain after cooling and load removal.

Swelling ratio (SR, %) was performed by immersing the sample (around 200.00mg) in THF

and DMSO (200ml) at room temperature, 50°C or 140°C for 72h. The swelling ratio was

calculated according to the following equation,

SR ( %) = (mb − ma ) / ma 100% (S5)

where ma is the initial mass of the samples, and mb is the mass after swelling.
Gel content (GC, %) was determined by the solvent extraction method. The samples

(around 200.00mg, m1) were placed in a Soxhlet extractor with THF at 80oC for 72h. When the

extraction was completed, the samples were dried in a vacuum oven at 80oC for 72 h and

5
weighted (m2). The gel content was calculated according to the following equation,

GC ( %) = m2 / m1 100% (S6)

Figure S1. The chemical structure of FEHBP.

Figure S2. 13CNMR (a) and mass spectra (b) of FEP.

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 Figure S3. MALDI-TOF mass spectrum of FEHBP.
Table S1. Compositions of epoxy vitrimers

Samples DGEBA (g) FEP (g) CA (g) FEHBP (g)

CA/DGEBA 20.00 0.00 7.50 0.00

CA/FEP 0.00 20.00 8.00 0.00

CA/FEP-5phrFEHBP 0.00 20.00 8.00 1.40

CA/FEP-10phrFEHBP 0.00 20.00 8.00 2.80

CA/FEP-15phrFEHBP 0.00 20.00 8.00 4.20

Table S2. DSC characteristic parameters of epoxy vitrimers

Samples Ti (℃) Tp (℃) ΔH (J/g)

CA/DGEBA 78 124 196.3

CA/FEP 77 143 90.4

CA/FEP-5phrFEHBP 60 138 101.1

CA/FEP-10phrFEHBP 58 134 107.0

CA/FEP-15phrFEHBP 57 131 115.7

Ti is the initial reaction temperatures, Tp is the peak reactiontemperatures, ΔH is reaction
activation energy.

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 Table S3. Swelling ratios and gel contents of epoxy vitrimers

swelling ratios
gel
Samples
THF THF DMSO DMSO contents
(RT) (40℃) (RT) (140℃)

CA/DGEBA 9.2% 16.4% 17.1% 27.9% 97.8%

CA/FEP 11.1% 17.3% 20.3% 30.8% 95.6%

CA/FEP-10phrFEHBP 8.7% 15.8% 16.4% 26.5% 98.4%

Table S4. Mechanical properties of epoxy vitrimers

Samples Tensile strength (MPa) Toughness (MJ/m3)

CA/DGEBA 105.2 ± 2.0 2.01 ± 0.07

CA/FEP 88.0 ± 3.2 2.26 ± 0.39

CA/FEP-5phrFEHBP 117.1 ± 4.7 3.31 ± 0.32

CA/FEP-10phrFEHBP 126.4 ± 1.5 5.28 ± 0.50

CA/FEP-15phrFEHBP 111.0 ± 3.2 3.96 ± 0.28

Table S5. Thermomechanical properties of epoxy vitrimers

Samples Tg (oC) Ec (MPa) Ed (MPa) ρ (×10-3 mol/cm3)

CA/DGEBA 87 2307 3.36 0.33

CA/FEP 95 2173 3.08 0.29

CA/FEP-5phrFEHBP 93 2312 3.89 0.37

CA/FEP-10phrFEHBP 94 2593 4.48 0.44

CA/FEP-15phrFEHBP 97 2374 2.88 0.28

Ec is the modulus at 35oC, Ed is the modulus in the rubbery region at Tg + 50oC.

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 Figure S4. TGA curve of epoxy vitrimers.

Table S6. Thermal stability and degradation data of epoxy vitrimers under nitrogen atmosphere

Samples T10% (℃) Tp (℃) Char yield at 800℃ (wt.%)

CA/DGEBA 331 414 8.80

CA/FEP 296 380 16.61

CA/FEP-5phrFEHBP 285 388 18.04

CA/FEP-10phrFEHBP 279 393 17.14

CA/FEP-15phrFEHBP 279 392 17.46

T5% the weight loss of 5% is observed and the temperature at which the degradation rate reaches
a maximum is defined as Tp.

Table S7. PALS data and free volume fractions of epoxy vitrimers

Lifetime of Free
ortho- Intensity I3 volume
Samples R (Å)
positroniumτ3 (%) fraction,Fv
(ns) (%)
CA/FEP 1.567 13.55 2.419 1.45

CA/FEP-5phrFEHBP 1.537 14.81 2.385 1.52

CA/FEP-10phrFEHBP 1.521 15.56 2.367 1.56

CA/FEP-15phrFEHBP 1.526 15.66 2.374 1.58

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 Table S8. Values of shape memory properties of the original and reprocessed of
CA/FEP/FEHBP.

Rf（%） Rr（%）
Sample
C1 C2 C3 C1 C2 C3

CA/FEP/FEHBP 95.12 94.47 94.11 99.34 99.21 98.76

Figure S5. Tensile stress-strain curves (a), Plots of storage modulus (b) and tanδ(c) of original

and reprocessed CA/DGEBA. Stress-strain curves (d), Plots of storage modulus (e) and tanδ

curves (f) of original and reprocessed CA/FEP.

Table S9. The tensile strength of original and reprocessed epoxy vitrimers

Samples CA/DGEBA CA/FEP CA/FEP/FEHBP

Original 104.9 ± 1.9 88.3 ± 4.7 126.4 ± 1.6

1st Reprocessed 100.5 ± 1.4 86.3 ± 2.5 121.3 ± 3.1

2nd Reprocessed 95.9 ± 2.9 81.8 ± 0.9 113.4 ± 2.1

3rd Reprocessed 82.6 ± 1.5 79.7 ± 2.7 111.5± 4.3

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 Table S10. Summary of DMA results of original and reprocessed CA/DGEBA

Samples Tg (oC) Ec (MPa) Ed (MPa) ρ (×10-3 mol/cm3)

Original 87 2307 3.36 0.33

1st Reprocessed 92 2762 5.07 0.49

2nd Reprocessed 99 3186 5.68 0.54

3rd Reprocessed 97 3150 5.98 0.57

Table S11. Summary of DMA results of original and reprocessed CA/FEP

Samples Tg (oC) Ec (MPa) Ed (MPa) ρ (×10-3 mol/cm3)

Original 95 2173 3.08 0.29

1st Reprocessed 98 2720 4.04 0.39

2nd Reprocessed 99 2768 4.61 0.44

3rd Reprocessed 105 2847 6.02 0.56

Table S12. Summary of DMA results of original and reprocessed CA/FEP/FEHBP

Samples Tg (oC) Ec (MPa) Ed (MPa) ρ (×10-3 mol/cm3)

Original 94 2593 4.48 0.44

1st Reprocessed 100 2634 4.55 0.58

2nd Reprocessed 97 2789 7.89 0.75

3rd Reprocessed 108 2852 13.64 1.27

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 Figure S6. Photographs of CA/FEP/FEHBP in solvents before (a) and after (b) 72h at room

temperature.

Figure S7. Tensile stress-strain curves (a, c) and DMA (b, d) curves of original and chemically

recycled CA/DGEBA and CA/FEP.

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Table S13. Mechanical properties and relevant DMA data of original and chemically recycled

epoxy vitrimers

Tensile strength Toughness Tg Ec ρ

Samples
(MPa) (MJ/m3) (℃) (MPa) (×10-3mol/cm3)

Original CA/DGEBA 105.2 2.01 87 2307 0.33

Chemically recycled DGEBA 88.6 1.57 88 2238 0.24

OriginalCA/FEP 88.0 2.23 95 2173 0.29

Chemically recycled CA/FEP 84.7 2.44 89 2163 0.26

Original CA/FEP/FEHBP 126.4 5.28 94 2593 0.44

Chemically recycled CA/FEP/FEHBP 121.5 4.80 86 2294 0.39

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