A Seminar Presentation

on
Styrene
Based Ion Exchanger
Prepared By:
Patel Yash Balmukundbhai
Guided By:
Prof. R. A. Sengupta
Co Guided By:
Himanshu Kohli
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Ion Exchange

An adsorption phenomenon and the mechanism of adsorption is electrostatic.

An ion exchanger consists of the polymer matrix and the functional groups that

interact with the ions.

Chemical Process in Ion Exchanger:
Substitution:

- An ion can be recovered from solution and replaced by a worthless one.

Separation:

- Ions are separated and emerge in order of their increasing affinity for the resin.
Removal:

- Ions are removed and replaced by water, thus solution is demineralized.

For Example: In Water Softening 2RNa' + Ca2+

R2Ca2+ + 2Na

FRANCOIS DE DARDEL, ROHM AND HAAS, THOMAS V. ARDEN. Ion Exchangers. Ullmans Encyclopedia of Industrial Chemistry, Sixth
Edition,Wiley ,January 2002.

How Ion Exchanger

recognised?

Discovery of ion exchange dates from the middle of the nineteenth century when

Thomson and way noticed that ammonium sulfate was transformed into calcium
sulfate after percolation through a tube filled with soil.
In 1905, Gans softened water for the first time
In 1935, Liebknecht and Smit discovered that certain types of coal could be sulfonated

to give a chemically and mechanically stable cation exchanger.

Adams and Holmes produced the first synthetic cation and anion exchangers
At present, aluminosilicates and phenol formaldehyde resins are reserved for special

applications and sulfonated coal has been replaced by sulfonated polystyrene.

In Last Decades several producers developed new manufacturing technologies aimed

at producing resins with particles of almost identical size.

FRANCOIS DE DARDEL, ROHM AND HAAS, THOMAS V. ARDEN. History of Ion Exchangers. Ullmans Encyclopedia of Industrial Chemistry,
Sixth Edition,Wiley ,January 2002

Classification of Ion
Exchanger

Based on Functional Groups:

1) Cation Ion Exchanger

2) Anion Ion Exchanger

Based on Types of Resin:

1) Inorganic:-

a) Synthetic Aluminosilicates
b) Oxide and hydrous oxides
c) Acidic salts of polyvalent metal ions
d) Heteropolyacid salts
e) Insoluble hydrated metal ferrocyanides

2) Organic:-

a)Polystyrene Matrix
b) Polyacrylic Matrix
c) Phenol formaldehyde resins
d) Polyalkylamine resins

C. E. HARLAND,Ion-Exchange Theory and Practice , The Development of Ion Exchange Resins, 2nd Edition, The Royal Society of Chemistry,
1994 (10-21)

Polystyrene Ion Exchanger

Insoluble, cross linked, long chain polymers
A micro-porous structure is responsible for the exchange of ions
High ion exchange capacity
High chemical stability
Good resistance against chemical and physical stress
Structure is stable at relatively high temperatures
Stable over the whole pH range
Reproducible
High exchange capacity
Wide applications and low cost
Main limitation: low stability towards radiations and heat

Application of ion exchange processes for the treatment of radioactive waste and management of spent ion exchangers, INTERNATIONAL ATOMIC
ENERGY AGENCY ,VIENNA, 2002 (19-21)

Development of Styrenic Ion

Exchanger
The first polystyrene-based resin was invented by d'Alelio in 1944.
McBurney produced polystyrene anion-exchange resins by chloro-methylation

and amination of the matrix in 1946. [1]

Ion exclusion chromatography has been introduced by Wheaton and

Baumann In which highly sulfonated poly(styrene-divinylbenzene) resins of

low cross-linkage is used.[2]
During 1970s and 1990s chelating ion exchangers has been developed which

are used for separation and determination of rare earths.

Solid acid zirconium sulfonated oligo-polystyrenylphosphonate-phosphate

supported on ZrO2 was prepared by Yan Sui and Xiangkai Fu.

Several nonionic styrenic polymer resins like amberlite, purolite etc. has been

developed in in last ten years.

[3]
[1] FRANCOIS DE DARDEL, ROHM AND HAAS, THOMAS V. ARDEN. History of Ion Exchangers. Ullmans Encyclopedia of Industrial Chemistry,
Sixth Edition, Wiley ,January 2002
[2] Christian W. Klampfl , Wolfgang Buchberger. retention behavior of carboxylic acids on highly cross-linked poly(styrene-divinylbenzene)-based and
silica-based cation exchangers, Journal of Chromatography A, 770 (1997) 23-28
[3] Yan Sui , Xiangkai Fub, Preparation, characterization and application of a new type of ion exchanger and solid acid zirconium
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sulfonated

Types of Styrenic Ion

Exchanger
In manufacturing of styrenic copolymer,

predetermined amounts of styrene and

divinylbenzene are mixed together in the
organic phase tank.
Styrene is about 90-95 wt% of the

formulation
and
divinylbenzene.

other

5-10%

is

It is required to link chains of linear

polystyrene together as polymerisation

proceeds.
Divinylbenzene is referred to as a cross-

linker.
Activation of structure gives:

1) Styrenic Cation Exchange Resins

2) Styrenic Anion Exchange Resins
C. E. HARLAND,Ion-Exchange Theory and Practice , The Development of Organic Ion Exchange Resins, 2nd Edition, The Royal Society of
Chemistry, 1994 (10-21)

Styrenic Cation Exchange Resins

H2SO4

Activation of the copolymer is carried out by sulfonation of the

matrix with hot sulfuric acid.
Strongly acidic cation exchange resin is obtained
Substitution occurring within the 'styrene' nucleus only
Treatment of the sulfonic acid resin with brine or sodium hydroxide
solution gives the sodium sulfonate salt.
C. E. HARLAND,Ion-Exchange Theory and Practice , The Development of Organic Ion Exchange Resins, 2nd Edition, The Royal Society of Chemistry,
8
1994 (10-21)

Styrenic Anion Exchange

Resins
Chloromethylation.:

Friedel- Crafts reaction between the

copolymer and chloromethoxymethane

introduces chloromethyl groups.
Amination:
In
Chloromethylated
copolymer
substitution of the functional group by
reaction with various alkyl substituted
aliphatic amines takes place.
Trimethylamine, (CH3)3N, gives the
quaternary benzyltrimethylammonium
chloride
functional
group,
RCH2N( CH3)3+C- ,which is characteristic
of most Type I strongly basic anion
exchange resins.
The
equivalent
reaction
using
C.
E. HARLAND,Ion-Exchange Theory and Practice , The Development of Organic Ion Exchange Resins, 2
dimethylethanolamine,
1994 (10-21)

nd

Edition, The Royal Society of Chemistry,

Different types of Ion Exchanger

Matrix

Ionogenic Group

Specificity

StyreneDVB

Iminodiacetate --CH2-N(CH2COO )-2

Fe, Ni, Co,

Cu,Ca,Mg

StyreneDVB

Aminophosphonate CH2-NH(CH2PO3)2-

Pb, Zn,
UO22+,Ca, Mg

StyreneDVB

thiol; thiocarbamide-SH ; -CH2-SC(NH)NH2

Pt, Pd, Au,Hg

StyreneDVB

N-methylglucamine--CH2N(CH3)
[ (CHOH)4CHOH]

Properties

B, (as boric acid)

Styrenebenzyltriethylammonium--CH2N(CH2CH3)3+
Particle size
DVB
Sphericity

NO3-

Water Content
Ion Exchange Capacity
Uniformity Coefficient
C. E. HARLAND,Ion-Exchange Theory and Practice , Properties and Characterization of Ion Exchange Resins 2nd Edition, The Royal Society of
Chemistry, 1994 (49-89)
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Applications:
Effluent management
Softening of water
Separation of metal ions
Catalysis
Hydrometallurgy
Ion exchange fiber
Condensate polishing (for nuclear power plants with

boiling water reactors)

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Applications:
Nuclear separation
Water Purification
Sugar manufacturing
Pharmaceuticals
Waste Treatment
Recovery of Flavonoids

Thank You
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