Bio-based adenine-containing high performance polyimide

Jianghuai Hu, Zhiping Wang, Zheng Lu, Chang Chen, Meng Shi, Jianbo Wang, Erjin

Zhao, Ke Zeng*, and Gang Yang*

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science

and Engineering, Sichuan University, Chengdu 610065, P. R. China

*Corresponding author: (1) e-mail: zk_ican@sina.com (Ke Zeng); (2) e-mail:

yanggang65420@163.com (Gang Yang), Tel: +86-28-85462736, Fax +86-28-

85462736

Electronic supplementary information

Fig. S1 The 1H NMR spectra of p-NBA, p-APA and API.

Fig. S2 The Film of API

Fig. S3 Curve-resolved FT-IR spectra in the range of 3430–3300 cm-1 at different

temperatures of API film (bend 1 belongs to the free N-H stretch, bend 2 belongs to

the bonding N-H stretch, and the peak values of each band are collected in the Figure

2c).

Fig. S4 The normalized temperature-dependent IR spectra of aromatic C=C band (the

peak values at different temperatures are collected in the Figure 2C).

Table S1 Solubility of API film

Solvents m-Cresol NMP DMSO DMF DMAc THF Acetone MC Acetonitrile

Solute

mass(mg)

10.0

Solvent

volume(mL)

0.2 0.5 0.5 0.5 0.5 2.0 2.0 2.0 2.0

Solubility + + + + + - - - -

+: soluble at room temperature; -: insoluble at room temperature. MC: methylene

chloride.

Fig. S5 The simulation stracture of p-APA

NOTE: the molecular simulation was applied to calculate the stracture p-APA. The

calulation was performed with Focite calculation (Fine quality) and subsequently with

DMol 3 calculation (Task: Energy, Quality: Fine, Functional:B3LYP, Basis set: DNP,

Basis file: 3.5) with the Materials Studio 8.0.

Scheme S1 Synthesis of 6FDA-ODA-PI

Note: The 6FDA-ODA-PI and its film was prepared by the same method which

was used in the API. GPC data of 6FDA-ODA-PI: Mn=9,177, Mw=99,336,

PD=10.824. Density: 1.3746 g/cm-3

Fig. S6 the WAXD patterns of 6FDA-ODA-PI film (πstack: 5.56 Å (15.91º),

chpack: 3.92Å (22.67º)).

Table S2 Thermal and mechanical properties of API films

Atomosphere DSC DMA TGA

Tg (°C) Tg (°C) SMa

(GPa)

T5%(°C) T10%(°C) Char yield(%) at

800°C

Air 363 4.1 506 528 0

Nitrogen 350 513 535 56

Table S3 Thermal and mechanical properties of reported 6FDA-congtaining

polyimides

Polyimides DMA TGA Mechanical properties

Tg

(°C)

T5%

(°C

) N2

T5%

(°C)

Air

Char yield(%)

at 800°C

N2

tensile

strength

(MPa)

rupture

elongation

(%)

elastic

modulus

(GPa)

API 363 513 506 56 144 13 5.6

6FDA-ODA-

PIa

298(D

SC)

510 509 38

PI-458 274 520 492 54 98 7.8 3.4

PI-558 272 508 449 54 87 5.9 3.2

PI-658 273 523 511 54 85 8.7 3.1

PI-559 290 523 59 122 8.2 3.2

PI-659 241 507 60 103 5.4 3.1

PI-759 293 471 61 134 4.2 3.1

PI-859 285 484 57 108 6.1 3.1

PI-959 305 489 59 130 4.4 3.6

6FDA-ODA60 286(D

SC)

511

6FDA-PDA61 392 497 6.2 3.8

6FDA-ODA62 319

6FDA-PDA62 375Homo-

polyimide63

273 526 109 21 2.1

1b64 315(D

SC)

530 61 40 5 2.3

Co-PI-165 267 543 103 8 3.6

Co-PI-565 271 553 113 15 4.7

9e66 321 523 117 6.4 2.3

a Obtained by one-step polymerization by our laboratory, see Scheme S1.

Red: The reported value lower than the API film.

Green: The reported value higher than the API film.

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Fig. S7 DSC curves and the corresponding first derivative curves of API and 6FDA-

ODA-PI under nitrogen atmosphere

Fig. S8 TGA curve (a) and its DTG (b) of API and 6FDA-ODA PI under nitrogen and

air atmosphere

Fig. S9 The typical Tensile stress-strain curve of API film at room temperature (The

partial enlarged drawing of Figure 6)