Chapter 1: Introduction

1.1. History and Background

Polysulfones comprise a class of engineering thermoplastics with high thermal, oxidative, and
hydrolytic stability and good resistance to aqueous mineral acids, alkali, salt solutions, oils, and
greases. Their high biocompatibility and ability to be sterilized by a variety of techniques make
them highly suitable for medical applications. Polysulfones also have high permeability and
permselectivity that make them attract part of the main backbone repeat unit.
The polymers are transparent, mechanically tough and rigid, and exhibit high glass transition
temperatures and excellent thermal oxidative resistance. They are also known for their resistance
against hydrolysis and against acidic or basic attack, as well as for their easy process ability and
great stability that allows melt processing at temperatures up to 400C. This combination of
features coupled with case of fabrication has won polysulfones a wide and increasingly
diversified range of applications. A key structural feature of these polymers that distinguishes
them from other aromatic polymers is the presence of the paralinked diarylsulfone grouping:

There are three polyarylsulfones that have grown to be of commercial interest today. These are
known by the following common generic designations and acronyms:

Polysulfone (PSF)
Polyethersulfone (PES)
Polyphenylsulfone (PPSF)

Polysulfone (PSE) has the following repeat unit structure:

Its glass transition temperature is 185. Polyethersulfone (PES) was first introduced commercially
by Imperial Chemical industries, Ltd. It has a T1 of 220C and the following repeat unit
structure:

Polyphenylsulfone (PPSF) is distinguished by the presence of the biphenyl linkages in its

backbone, its repeat unit structure being:

It is a somewhat unique member of the polysulfone family. While having the same T as that of
PES, this polymer exhibits super toughness characteristics which are similar to those well known
for bisphenol-A polycarbonate. The polymer is the most notched impact-resistant amorphous
plastic in its temperature class that is produced commercially.
Handbook of Thermoplastics by Olagoke Olabisi

The first commercial polysulfone (Table 1-I) was introduced in 1965 by Union Carbide. This
material, now known as Udel, has a continuous-use temperature of 150C and a maximum-use
temperature of 170C, and it can be fabricated easily by injection molding in conventional
machines. In 1967, Minnesota Mining and Manufacturing (3M) introduced Astrel 360 (Table 1II), an especially high-performance thermoplastic, which requires specialized equipment with
extra heating and pressure capabilities for processing. ICIs polyether sulfones, introduced in
1972Victrex (Table 1-III) and polyethersulfone 720P (Table 1-IV)are intermediate in
performance and processing. In the late 1970s, Union Carbide introduced Radel (Table 1-V),
which has a higher level of toughness. Note that all of the commercial materials mentioned in
Table 1 may be described as polysulfones, polyarylsulfones, polyether sulfones, or polyaryl ether
sulfones. Plastic technology handbook by Manas Chanda, Salil K, Roy
Table 1: Commercial Polysulfones

1.2. Literature review

1.2.1. Properties
In spite of their linear and regular structure the commercial polysulfones are amorphous. This
property might be attributed to the high degree of chain stiffness of polymer molecules which
make crystallization difficult. Because of their high in-chain aromaticity and consequent high
chain stiffness, the polymers have high values of Tg (see Table 1), which means that the
processing temperatures must be above 300C.
Commercial polymers generally resist aqueous acids and alkalis but are attacked by concentrated
sulfuric acid. Being highly polar, the polymer is not dissolved by aliphatic hydrocarbons but
dissolves in dimethyl formamide and dimethyl acetamide. In addition to the high heatdeformation resistance, the polymers also exhibit a high degree of chemical stability. This has
been ascribed to an enhanced bond strength arising from the high degree of resonance in the
structure. The polymers are thus capable of absorbing a high degree of thermal and ionizing
radiation without cross-linking.
The principal features of commercial polysulfones are their rigidity, transparency, selfextinguishing characteristics, exceptional resistance to creep, especially at somewhat elevated
temperatures, and good high-temperature resistance. The use temperatures of the major
engineering thermoplastics are compared in Figure 1. Polysulfones are among the higher-priced
engineering thermoplastics and so are only considered when polycarbonates or other cheaper
polymers are unsuitable. In brief, polysulfones are more heat resistant and have greater resistance
to creep, whereas polycarbonates have a somewhat higher Izod and tensile impact strength
besides being less expensive.

Figure 1: Use temperatures of major engineering thermoplastics.

In many fields of use polysulfones have replaced or are replacing metals, ceramics, and
thermosetting plastics, rather than other thermoplastics. Since commercial polysulfones can be

injection molded into complex shapes, they avoid costly machining and finishing operations.
Polysulfones can also be extruded into film and foil. The latter is of interest for flexible printed
circuitry because of its high temperature performance.
Polysulfones have found widespread use where good dimensional stability at elevated
temperatures is required and fabrication is done by injection molding. Some products made from
polysulfones are electrical components, connectors, coil bobbins, relays, and appliances
operating at high temperatures (e.g., hair driers, fan heaters, microwave ovens, lamp housings
and bases). Polysulfones are transparent (though often slightly yellow), have low flammability
(limiting oxygen index typically 38), and burn with little smoke production. Typical properties of
some of the commercial polysulfones are shown in Table 2.
Table 2: Properties of Polysulfones

Plastic technology handbook by Manas Chanda, Salil K, Roy

1.2. Short process Description

The main routes for polysulfones synthesis are as follows:

Aromatic nucleophilic displacement route

Electrophilic Friedel-crafts synthesis
Ring-opening polymerization

These methods were discovered almost simultaneously on two continents in the early to mid1960s. Today the nucleophilic displacement route is used exclusively for commercial production
of these polymers.
1.2.1. Aromatic nucleophilic displacement route
The first successful application of nucleophilic displacement chemistry to the synthesis of
polysulfones emerged from the pioneering efforts of Drs. R. N. Johnson and A. G. Farnham.

The essence of this polycondensation scheme is the reaction of an aromatic dihydric phenol such
as bisphenol A with an aromatic dihalo compound in which the halogens are activated by an
electron-withdrawing group in the presence of base. The synthesis of polysulfone is
accomplished by a two-step process, the first of which involves the in situ conversion of
bisphenol A to its disodium salt of this bisphenol using sodium hydroxide according the
following equation:

The second step involves the reaction of disodium salt of bisphenol A with 4, 4dichlorodiphenylsulfone (DCDPS) monomer:

1.2.1.1 Advantages and disadvantages

The most important method by far for the synthesis of polysulfones is that known as the aromatic
nucleophilic displacement (or substitution) polycondensation reaction. The emphasis of the first
portion of this section will thus focus on a description of this synthesis scheme, especially as it
relates to the synthesis of PSF, PES, and PPSF. High molecular weight of polymer can be
achieved in this method. The reaction rate for polymerizations of this type can be governed by a
number of factors. By starting with more than one bisphenol during a nucleophilic displacement
synthesis, random copolymers and multipolymers can be readily produced.
The primary disadvantage of this route is the high cost of the chloride-containing monomers. In
addition, production of chloride byproducts which must be properly disposed of is also a
drawback of the method.
The reaction of NaOH with bisphenol A generates water. This water can cause hydrolysis of the
DCDPS. With as little 0.5% hydrolysis of the sulfone monomer, the polymerization
stoichiometric balance is sufficiently upset to prevent high molecular weight polymer from being
achieved.

1.2.2. Electrophilic Friedel-crafts synthesis

The oldest approach known for the preparation of polysulfones is a polycondensation process
involving the electrophilic substitution of a phenyl ether group by an aromatic sulfonylchloride
group. Such polycondensation may be based, either on monomers containing both functional
groups in one molecule (Eq. (1)) or by a combination of a nucleophilic and an electrophilic
monomer (E q. (2)). This type of polycondensation is needed to be catalyzed by strong Lewis
acids such as FeCl3, AlCl3, or BF3.

1.2.1.2 Advantages and disadvantages

This process is feasible for two type of monomers, one in which both functional group are in one
monomer and other in which a combination of a nucleophilic and an electrophilic monomer.
This process is discontinued due to the difficulties in melt fabricating the polymer and the
availability of other polysulfones prepared by nucleophilic polyetherification method. Also this
method require expensive inert reaction medium. This method has the disadvantage of requiring
stoichiometric amounts of the Lewis acid catalyst. Characteristic disadvantages of this approach
are the need of an expensive inert reaction medium and side reactions such as substitution
(including branching) in ortho position of the nucleophilic monomer. Furthermore, this approach
is not versatile and limited to a few monomers.
1.2.3. Ring-Opening Polymerization
All synthetic strategies discussed above have in common to be step growth polymerizations.
Over the past ten years a new strategy was elaborated and explored based on the ring-opening
polymerization of cyclic oligo(ether sulfones), OES.
1.2.2.1 Advantages and disadvantages
This chain growth polymerization has the following advantages and disadvantages when
compared to step growth polymerizations. The main problem is the synthesis of the cyclic
monomers, above all, when large quantities are needed. The advantages are, firstly, a
polymerization process which does neither need solvents, nor produce byproducts. Therefore, the
ROP approach is well suited for the reaction-injection molding (RIM) technology. Secondly, the

ROP of strained cyclic OESs offers the chance to prepare PESs with very high molecular weight
(Mn > 105 Da). Thirdly, sequential co-polymerizations with other cyclic monomers may yield a
variety of block copolymers. Unfortunately, cyclic OESs possess high melting temperatures .
Such
high
temperatures
have
two
disadvantages.
Firstly,
high
fractions
of cycles remain unreacted for thermodynamic reasons, and gel particles are formed due to
partial crosslinking.