Synthesis of Poly(arylene ether sulfone) via

Solution Polymerization
By
Greg Miller, Josh Burton and Mohammad Tasooji

Experiment was performed 9-28-2012

Submitted 10-8-2012

Introduction
Step-growth polymers are characterized by the reaction of monomers
of functionality greater than one, in which the reaction mechanism occurs in
a step-wise manner and high molecular weights are not achieved until high
conversion; generally step-growth polymerizations are characterized by the
need to remove a small molecule by-product which shifts the equilibrium
towards the products via LeChatliers principle.
Poly(arylene ether sulfone)s (PAES) belong to an important class of
step-growth polymers known as engineering thermoplastics characterized by
excellent mechanical and thermal properties1. Poly(arylene ether sulfone)s
are of considerable interest as a component of polyelectrolyte membranes to
provide an alternative to the current benchmark, Nafion; PAES membranes
are also recently being explored as a chlorine tolerant method to purify
water2,3.
The synthesis of this polymer occurs via an aromatic nucleophilic
substitution. Resonance of the dichlorodiphenyl sulfone (DCDPS) monomer
creates a positive charge on carbon next to the chlorine ends; the negative
portion of potassium carbonate then attacks the positive carbon thereby
cleaving the chlorine, leaving a vulnerable place for the bisphenol-A (BPA) to
attack. The polymerization is performed in a solution of N,Ndimethylacetamide (DMAc) and toluene; the toluene forms an azeotrope with
the water in the system which is removed via a dean-stark trap in the first
step of the reaction, known as the azeotrope stage.

Figure 1. Reaction Scheme of Poly(arylene ether sulfone) Synthesis.

Experimental
Materials:
Recipe

Quantity

Bisphenol-A

7.9009 g

Molar
Quantity
0.035

Dichlorodiphenylsulf
one
Potassium
Carbonate
N,NDimethylacetamide

9.7635 g

0.034

5.74 g

0.042

95 mL

Toluene

48 mL

Table 1: Materials Used in Synthesis of Poly(arylene ether sulfone).

Procedure:
The DCPS, BPA and potassium carbonate were dried for 24 hours under
vacuum to remove residual water; the DMAc was also dried prior to use. The
starting amounts of monomers were calculated using the Carotherss
Equation, assuming 100% conversion, in such a way to produce 15 grams of
25,000 g/mole polymer with OH functional end groups; therefore, BPA
monomer was in slight excess, or r=0.982. The amount of potassium
carbonate was calculated to be 1.2 moles: moles of BPA; the DMAc was
calculated in such a way that the starting monomers were 20%/wt the
amount of DMAc. The amount of toluene used was approximately 50%/vol
the amount of DMAc.
The experimental setup for this lab consisted of a three-neck, 250 mL
round-bottom flask equipped with a mechanical stirrer, N2 gas inlet, DeanStark trap and condenser. A silicone oil heating bath mounted on a hot-plate
was used for this polymerization; a thermo-couple was used to control the
heat. The set-up is shown below in Figure 2.
The monomers and potassium carbonate were charged to the roundbottom flask in the amounts reported in Table 1; 95 mL DMAc and 48 mL
toluene were then added as reaction solvents. The mixture was then heated
to 140C for approximately 2 hrs until the azeotroping stage to remove water
was complete. The heat was then raised to 165C for 12 hrs; the polymeric
solution was allowed to cool. The viscous dark brown solution was diluted
with approximately 100 mL of chloroform to aid in filtering. The solution was
filtered with a Buchner vacuum funnel to remove KCl and K2CO3 salts. The
solution was then slowly added with a syringe to a 3 L mixture of
methanol/water while stirring to precipitate the solid polymer; a white
precipitate was observed to form upon addition to the MeOH/H2O mixture.
The precipitate was then vacuum-filtered; polymeric filtrate was collected
and dried under vacuum at 100C for 48 hrs. The resulting polymer was
analyzed by nuclear magnetic resonance and size exclusion chromatography.

Figure 2. Experimental Set-up for PAES Synthesis.

Results and Discussion

Calculated Yield (g)
Actual Yield (g)
Yield %
Calculated MW
(Da)
Experimental Mn
(Da)
Experimental Mw
(Da)

15
11.5
65%
25,000
15,823
20,172
1.27

Table 2. Yields and Molecular Weight of PAES.

Size Exclusion Chromatography

Number-average molecular weight (Mn), Weight-average molecular
weight (Mw) and dispersity, , of the polymeric materials were measured
using a gel permeation chromatography (GPC) system consisting of a
Waters Alliance 2690 separation module, and three Styragel HR columns (5
m bead size) connected in series. Sample concentrations were 25 mg of
polymer/ mL of solvent and the flow rate was 1.00 mL/ min. It was assumed
that 100% mass recovery from the columns was achieved. The results are
shown in Table 2. The plot of detector response vs. retention volume, Figure
3, shows a fairly Gaussian curve which indicates that the dispersity of the
polymer does not favor larger or smaller molecular weights.
The low yield percentage and lower than expected molecular weights
are attributed to the assumption that 100% of the monomer would convert
4

to polymer in the calculations using Carotherss equation. Even a conversion

of 99.9% yields very different results.

Figure 3. Detector Response vs. Retention Volume from SEC Analysis.

Nuclear Magnetic Resonance

An Agilent MR4 NMR operating at 400 MHZ was used to analyze the
PAES sample. The resulting spectra (Figure 4) is consistent with known
spectra of PAES materials; the large peak (labeled a) is consistent with the
methyl protons of BPA which indicates successful end-group attachment4.

Figure 4. NMR spectra for PAES.

Conclusions
In conclusion, Poly(arylene ether sulfone) with bisphenol-A end-groups
was successfully synthesized. The targeted molecular weight of 25,000 Da
was underachieved; this is attributed to the assumption of full conversion in
the calculation of monomer ratios. Furthermore, the percentage of yield
from monomer to polymer was 65%; this is also attributed to assumptions
made in the calculations based on Carotherss equation.

References
(1)
Wang, F. H., M.; Kim, Y. S.; Zawondzinski, T. A.; McGrath, J. E. Journal of
Membrane Science 2002, 197, 231.
(2)
Ghassemi, H. N., G.; McGrath, J. Polymer 2004, 45, 5855.
(3)
Park, H. B. F., B. D.; Zhang, Z.; Sanskir, M.; McGrath, J. E. Angew. Chem.
Int. Ed. 2008, 47, 6019.
(4)
Nolte, R. L., K.; Bauer, M.; Mulhaupt, R. J. Membrane Sci. 1993, 83,
211.