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Title

THE SYNTHESIS AND CHARACTERIZATION STRONG CATION EXCHANGE

RESINS

Abstract

In this project the synthesis and characterization of hypercrosslinked polymer in the

form of monodisperse microspheres with average diameter around at 300 m by
modified subsequently with two types of milder sulfonation agent: acetyl sulfate and
lauroyl sulfate with the different reaction timewill be carried out. Strong cation
exchange resins arise with presence of sulfonic acid functional groups will be
introduced through chemical modification reactions called as sulfonation process.
Two milder sulfonation agents of differing polarity will be used as sulfonation agents
in sulfonation reactions. 2.5 g of dried hypercrosslinked beads will be swollen in 60
mL of 1,2-dichloroethane for 6 h at 30 C will be followed by dropwise addition 15
mL of milder sulfonation reactions at different time. The final product will be
characterized by using FTIR, SEM, BET, TGA, IEC, XRF and DSC. It is expected
the good quality, satisfy specific area and moderate IEC on the final product will be

Background

produced in this project.

Sulfonic acids functional polymer beads resin, so called strong-acid cation-exchange
resins have determined in many chemical processes, such as dehydration of alcohols
to olefins or ethers, alkylation of phenols, addition of alcohols to olefins, and many
more. (Ozer O. et al., 2013). The sulfonation reaction can operate at monomer before
polymerization or during post polymerization. This reaction will be effect to the
degree of sulfonation and the final ion exchange properties of the sulfonated polymer.
Most usually during post-sulfonation process occur are lead in a homogenous way
and The polymer solubility will be limited. (Meyer M. et al., 2013). While relatively
strong sulfonation agents, such as concentrated sulfuric acid, have been used for the
sulfonation process on polymer beads. The milder sulfonation agents such as acetyl

sulfate and lauroyl sulfate have also been used efficiently for this chemical
transformation. (P.A.G. Cormack et al., 2012)
Motivation

The special of ion exchange resins is flexible alternatives in many applications

because it is less fragile, less care handling, react faster in functionalization and

application reactions, and process higher loading capacities.

The milder sulfonation agents is suitable to change the conventional sulfonation
agents which is strong agents that be reduced the side effect on the modified ion
exchange resin.

Problem
statement

The conventional sulfonation agent, sulfuric acid can create many limitations on

the reaction such as chain cleavage and unreproducible degree of sulfonation.

The conventional sulfonation agent, sulfuric acid also can cause high degradation
of resins which is undesirable instead of increasing the exchange capacities of
the resins.

Objective

To synthesize the strong cation exchange resin using different the milder

sulfonation agent at different reaction time.

To characterize the physico-chemical properties of strong cation exchange resins
using FT-IR, BET, IEC, TGA, DSC, and XRF.

Scopes

Preparation of milder sulfonation agents of acetyl sulfate.

Preparation of milder sulfonation agents of lauroyl sulfate.
Synthesis of sulfonated hypercrosslinked polymer using acetyl sulfate at different

reaction time.
Synthesis of sulfonated hypercrosslinked polymer using lauroyl sulfate at

different reaction time.

Characterization of ion-exchange capacities (IEC) in sulfonated hypercrosslinked

polymer by experimental of acid-base titration method.

Characterization of elemental analysis in sulfonated hypercrosslinked polymer

using Fourier-Transform Infrared (FT-IR).

Characterization of specific surface area

hypercrosslinked polymer by using Brunauer-Emmett-Teller (BET).

Characterization of thermal analysis for sulfonated hypercrosslinked polymer

using Thermogravimetry analysis (TGA).

Characterization of thermal analysis for sulfonated hypercrosslinked polymer

using differential scanning calorimetry (DSC).

Characterization of elemental analysis for sulfonated hypercrosslinked polymer
using Powder X-ray fluorescence (XRF).

and

pore

size

sulfonated

Characterization of structural analysis for sulfonated hypercrosslinked polymer

using Scanning Electron Microscopy (SEM).

Literature
Review

Citation

Authors

Historically, the introduction of synthetic ion exchange resin Abrams I. M. et

is developed by two treatment expert and polymer chemist is al., 1997 and Dale
B. A. Adams and E. L. Holmes on 1935 which is do the J. A. et al., 1992.
reaction of formaldehyde with phenolic or amine derivatives
to create phenol-formaldehyde structure by condensation of
resin. From the condensate resin era in early 1940, with
continue with addition polymer in late 1950, and
transforming into new adsorbents for varies of application.
A class of polymer beads such a macroporous polymer beads Wheaton R. M. et
was contained a fixed well-developed porous structure in al., 2000.
withered state, that having a wide range of applications such
as water softening, dealkalization, purification, and many
more. The benefit of the porous system is a sensitive
function of the diameter of internal pores, their division, and
morphology.
Sulfonation reaction can operate at monomer before Meyer M. et al.,
polymerization or during post-polymerization. It will affect 2013.
the degree of sulfonation and the final ion exchange
capacities of the sulfonated polymer. Most commonly during
post-sulfonation process occur are lead in a homogenous
step and it is limited by the polymer solubility. The
disadvantages use of strong sulfonation reagent is possibility
to degradation on polymer is high. Using the milder
sulfonation reagent was lead decreasing side reactions like
degradation.
Sulfonation is a widely adopted effective strategy to prepare J. Li et al., 2015.
the material will be applied in many applications such as
catalysis, metal ion removal, water softening and many
more.

Sulfonic

acid

(-SO3H)-

functionalized

hypercrosslinked polymer materials with high surface areas

are developed by self-condensation of the type rigid
monomers through FeCl3-induced Friedel-Crafts alkylation,

Methodolog
y

Materials
Acetic anyhydride (98%), anhydrous dichloromethane (99.8%), concentrated
sulfuric acid (98%), lauric acid (98%), cyclohexane (99.5%), chlorosulfonic acid
(99%), 1,2-dichloroethane (99.8%), acetone (99%) will be supplied by SigmaAldrich.
Preparation of sulfonation agent
1. Acetyl sulfate
0.405 g of acetic anhydride and 2.5 mL of anhydrous dichloromethane will be
mixed in a round-bottomed flask under nitrogen atmosphere. The flask will be placed
in an ice bath to cool the reaction mixture and 0.163 mL concentrated sulfuric acid
will be added. The flask will be removed from the ice bath and will be allowed to
equilibrate to room temperature. (P.A.G. Cormack et al, 2012).
2. Lauroyl sulfate
0.665 g of lauric acid will be dissolved in cyclohexane (30 mL) under a
nitrogen atmosphere. Chlorosulfonic acid (0.022 mL, 0.038 g, 0.323 mmol) will be
added and the mixture will be stirred at room temperature for one hour under
nitrogen atmosphere. (P.A.G. Cormack et al, 2012).
Synthesis of sulfonated hypercrosslinked polymer
1. Using acetyl sulfate
2.5 g of dried hypercrosslinked beads will be swollen in 60 mL of 1,2dichloroethane for 6 h at 30 C will be followed by dropwise addition 15 mL of
acetyl sulfate. After that, the mixture will be stirred for 1 h for complete dispersion.
The mixture will be subsequently heated to 40 C and will be maintained at this
temperature for , 1, 2, and 4 hours. The resulting beads will be separated by
filtration, washed with water and acetone and will be dried at 60 C in an oven for at
least 24 h.
2. Using lauroyl sulfate
2.5 g of dried hypercrosslinked beads will be swollen in 60 mL of 1,2dichloroethane for 6 h at 30 C will be followed by dropwise addition 15 mL of
lauroyl sulfate. After that, the mixture will be stirred for 1 h for complete dispersion.
The mixture will be subsequently heated to 50 C and will be maintained at this
temperature for 6, 12, 18, and 24 hours. The resulting beads will be separated by

filtration, washed with water and acetone and will be dried at 60 C in an oven for at
least 24 h.
Instrumentation and Characterization of sulfonated hypercrosslinked polymer
The resin samples will be determined the ion exchange capacities contents by
using acid-base titration method. In a typical procedure, 0.1 g of resin sample will be
added to 10 mL of 1.0 M NaOH solution and will have shaken for one hour at room
temperature. The mixture will be filtered and 2.0 mL of the filtrate will be titrated
with 0.1 M HCl solution using phenolphthalein as a color indicator. (Ozer O. et al.,
2013). Fourier Transform Infrared (FTIR) and F-Ray Fluorescence (XRF) will be
used for elemental analysis of the final product are supplied by Universiti Malaysia
Pahang. Thermal Gravimetric Analysis (TGA) using TGA Q-500 system and
Differential scanning calorimetry (DSC) will be used to thermal analysis of final
product. Brunauer, Emmett, and Teller (BET) using Thermo-Scientific and Liquid
Nitrogen, N2 used as adsorbate temp 77 Kelvin will be used to calculate the specific
surface area and pore size of the final product. Scanning electron microscopy (SEM)
by using unit JOEL-JSM-7800F model. This model will be conducted at conditions
2KX, 5KX, 100X and 500X to determine the structural analysis of final product.
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