Supporting Information

Facile Preparation of Halogen-Free Poly(ether imide) Containing

Phosphonium and Sulfonate Groups

Ke Cao,1 Benjamin J. Stovall,2 Clay B. Arrington,2 Zhen Xu,2 Timothy E. Long,1,2 Roy R. Odle,3
and Guoliang Liu1,2*
1
Macromolecules Innovation Institute (MII), 2Department of Chemistry, Virginia Tech,
Blacksburg, Virginia 24061, United States
3
SABIC, Mt. Vernon, Indiana 47620, United States

*Corresponding author: gliu1@vt.edu

Table of Contents
Simulation of 1H NMR ................................................................................................................. S1

XPS survey spectra ....................................................................................................................... S3

Selection of ions in PEIs ............................................................................................................... S4

References ..................................................................................................................................... S6
Simulation of 1H NMR

To reveal the changes in chemical shift of protons in -PhPPh3+ (Figure 1, main text), we have

performed simulations for the 1H NMR signals of two model products (Scheme S1) using the

NMR Spectrum procedure1 available in a Spartan'182 program. Note that A and B are simplified

models for PEI-PhPPh3Br and PEI-SAA-P, respectively, so that the simulations can be

conducted within a reasonable amount of time.

Table S1 summarized the chemical shifts (δH) of protons k, m, n, and p in A, as well as of

protons k', m', n', and p' in B. After replacing the bromide anion by tosylate, δH (p') was 0.4

ppm smaller than δH (p), indicating that peak p in PEI-SAA-P (Figure 1, main text) might shift to

~7.95-7.90 ppm. In contrast, both δH (m') and δH (n') were slightly larger than δH (m) and δH (n),

indicating that in PEI-SAA-P (Figure 1, main text), the peak of proton m might shift and overlap

the peaks of the PEI repeating unit at ~7.90-7.85 ppm and the peak of proton n might shift to

~7.75 ppm.

Scheme S1. Structures of model molecules A and B.

S1
Table S1. Simulated chemical shift of protons in molecules A and B.
Molecule Proton δH (ppm)
k 7.8
m 7.7
A
n 8.3
p 8.4
k' 7.8
m' 7.9
B
n' 8.5
p' 8.0

S2
XPS survey spectra

The XPS survey spectra revealed C, N, and O in PEI-PhPPh3Br, PEI-SAA-P (as-mixed), PEI-

SAA-P (mixed poly), and PEI-SAA-P (mixed EC) (Figure S1).

C 1s
Intensity (a.u.)

O 1s
O KLL O KLL
N 1s

PEI-PhPPh3Br

PEI-SAA-P (as-mixed)

PEI-SAA-P (mixed poly)

PEI-SAA-P (mixed EC)
1200 1000 800 600 400 200 0
Binding Energy (eV)

Figure S1. XPS survey spectra of PEI-PhPPh3Br, PEI-SAA-P (as-mixed), PEI-SAA-P (mixed

poly), and PEI-SAA-P (mixed EC).

S3
Selection of ions in PEIs

Using the same procedures for preparing PEI-SAA-P from PEI-PhPPh3Br and PEI-SAA-Li, PEI-

SAA-P (control) was also prepared from PEI-PhPPh3Br and PEI-SAA-K. The resultant PEI-

SAA-P (control) degraded at a lower temperature than PEI-PhPPh3Br did (Figure S2).

105

100

95

90
Weight (%)

85
PEI-PhPPh3Br
80 PEI-SAA-K
75 PEI-SAA-P (control)
70

65

60

0 200 400 600

Temperature (°C)

Figure S2. TGA thermograms of PEI-PhPPh3Br, PEI-SAA-K, and PEI-SAA-P (control) with an

Mn of 12 kDa.

S4
 In addition, simply replacing Br− by SO42− can lead to inferior thermal properties. For

example, with an Mn of 8 kDa, PEI-PhPPh3SO4 degraded at a much lower temperature than PEI-

PhPPh3Br did (Figure S3).

Figure S3. TGA thermograms of PEI-PhPPh3Br and PEI-PhPPh3SO4 with an Mn of 8 kDa.

S5
References

1. Hehre, W.; Klunzinger, P.; Deppmeier, B.; Driessen, A.; Uchida, N.; Hashimoto, M.;
Fukushi, E.; Takata, Y. Efficient Protocol for Accurately Calculating 13C Chemical Shifts of
Conformationally Flexible Natural Products: Scope, Assessment, and Limitations. J. Nat. Prod.
2019, 82 (8), 2299-2306 DOI: 10.1021/acs.jnatprod.9b00603.
2. Spartan’18, Wavefunction, Inc. Irvine, CA.

S6