UNIT III: Industrial polymer

Important industrial polymers – Synthesis and applications of poly tetra fluoro ethylene
(TEFLON), ion exchange resins. Synthetic route, structure and applications of engineering
plastics - Acrylonitrile butadiene styrene (ABS), Poly amides (PA), Poly ethylene terephthalate
(PET), Polyphenylene Oxide (PPO), Poly sulphone (PSU), Poly ether ether ketone (PEEK), Poly
phenylene sulphide (PPS).
Synthesis and applications of poly tetra fluoro ethylene (TEFLON)

Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene

(Teflon). PTFE is a fluorocarbon solid, as it is a high molecular weight compound consisting of
carbon and fluorine.

PTFE is used as a non-stick coating for pans and other cookware. It is non-reactive,
partly because of the strength of carbon-fluorine bonds and so it is often used in containers and
pipe work for reactive and corrosive chemicals.

Production

PTFE is produced by free-radical polymerization of tetrafluoroethylene. The net equation

is, nF2C=CF2 → −(F2C−CF2)n−

Because tetrafluoroethylene can explosively decompose to tetrafluoromethane and carbon

and special apparatus is required for this reaction. The process is typically initiated with
persulfate, which homolyzes to generate sulfate radicals,

[O3SO−OSO3]2− ⇌ 2 SO4•−

The resulting polymer is terminated with sulfate ester groups, which can be hydrolyzed to
give OH end-groups. Because PTFE is poorly soluble in almost all solvents, the polymerization
is conducted as an emulsion in water. Alternatively, the polymerization is conducted using a
surfactant such as Perfluorooctanesulfonic acid.

Properties of Teflon

 Teflon is a white opaque solid with a waxy appearance and feel.

 Teflon has outstanding electrical insulating properties.
  Teflon has a high crystallinity, and a chemical resistance to everything except molten
alkali metals and fluorine.
 It is insoluble in everything except fluorocarbon oils at very high temperatures
(temperature must be as high as the crystalline melting point temperature.)
 It has good thermal stability and good weather resistance.
 Teflon is self lubricating and its nonstick properties correspond to its very low coefficient
of friction.
 Teflon has a low glass transition temperature.

Applications and uses

1. The major application of PTFE is production of aerospace and computer applications.

2. PTFE has excellent dielectric properties, especially at high radio frequencies, making it
suitable for use as an excellent insulator in connector assemblies and cables, and in
printed circuit boards used at microwave frequencies.
3. Due to its low friction, PTFE is used for plain bearings, gears, slide plates, seals, gaskets,
bushings and more applications with sliding action of parts.
4. It’s extremely high bulk resistivity makes it an ideal material for fabricating long-life
electrets, the electrostatic analogues of permanent magnets.
5. PTFE film is also widely used in the production of carbon fiber composites as well as
fiberglass composites, notably in the aerospace industry.
6. Because of its extreme non-reactivity and high temperature rating, PTFE is used as the
expansion joints and in industrial pipe lines, particularly in applications using acids,
alkalis, or other chemicals.
7. PTFE is often found in musical instrument lubrication product; most commonly, valve
oil.
8. PTFE is used in some aerosol lubricant sprays.
9. PTFE (Teflon) is best known for its use in coating non-stick frying pans and other
cookware.

Other applications

1. It is often found in ski bindings as a non-mechanical AFD (anti-friction device).

 2. It is used widely as a fabric protector.
3. It is used as a film interface patch for sports and medical applications.
4. Expanded PTFE membranes have been used in trials to assist trabeculectomy surgery to
treat glaucoma.
5. Powdered PTFE is used in pyrotechnic compositions as an oxidizer with powdered
metals such as aluminium and magnesium.
6. Aluminium and PTFE is also used in some thermobaric fuel compositions.
7. Certain types of bullets are coated with PTFE to reduce wear on the rifling of firearms.
8. Its high corrosion resistance makes PTFE useful in laboratory environments.
9. It is used in containers for storing fluoroantimonic acid and superacid.
10. PTFE tubes are used in gas-gas heat exchangers in gas cleaning of waste incinerators.
11. PTFE membrane filters are the most efficient industrial air filters.
12. PTFE-coated filters are often used in dust collection systems.
13. Many bicycle lubricants and greases contain PTFE and are used on chains and other
moving parts subjected to frictional forces.
14. PTFE can also be used for dental fillings.
15. PTFE sheets are used in the production of butane hash oil due to its non-stick properties
and resistance to non-polar solvents.
16. PTFE is widely used as a non-stick coating for food processing equipment.

Ion-exchange resin

An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a

medium for ion exchange. It is an insoluble matrix normally in the form of small (0.25 - 0.5 mm
radius) microbeads, usually white or yellowish fabricated from an organic polymer substrate.

The beads are typically porous, providing a large surface area on and inside them. The
trapping of ions occurs along with the accompanying release of other ions and thus the process is
called ion exchange. There are multiple types of ion-exchange resin. Most commercial resins are
made of polystyrene sulfonate.
 Ion-exchange resins are widely used in different separation, purification, and
decontamination processes. The most common examples are water softening and water
purification. Also, ion-exchange resins are highly effective in the biodiesel filtration process.

Types of resins

Most typical ion-exchange resins are cross-linked polystyrene. In the case of polystyrene,
cross-linking is introduced by co-polymerization of styrene and divinylbenzene. Crosslinking
decreases ion-exchange capacity of the resin and increases the time to complete the ion-exchange
processes, but improves the toughness of the resin. Particle size also influences the resin
parameters; smaller particles have larger outer surface, but cause larger head loss in the column
processes.

Four main types of ion-exchange resins differ in their functional groups,

 Strongly acidic, typically featuring sulfonic acid groups, e.g. sodium polystyrene
sulfonate or polyAMPS.
 Strongly basic, typically featuring quaternary amino groups, for example,
trimethylammonium groups, e.g. polyAPTAC).
 Weakly acidic, typically featuring carboxylic acid groups.
 Weakly basic, typically featuring primary, secondary and/or tertiary amino groups, e.g.
polyethylene amine.

Specialized ion-exchange resins are also known such as chelating resins (iminodiacetic
acid, thiourea-based resins, and many others). Anion resins and cation resins are the two most
common resins used in the ion-exchange process. While anion resins attract negatively charged
ions, cation resins attract positively charged ions.

Anion resins

Anion resins may be either strongly or weakly basic. Strongly basic anion resins maintain
their positive charge across a wide pH range, whereas weakly basic anion resins are neutralized
at higher pH levels. Weakly basic resins do not maintain their charge at a high pH because they
undergo deprotonation.
Cation-exchange resin

Cation exchange method removes the hardness of water but induces acidity, which is
further removed in next stage of treatment of water by passing this acidic water through anion
exchange process Formula: R−H acidic

Reaction: R−H + M+ = R-M+ + H+

Anion-exchange resin

Formula: NR4 + OH−

Often these are styrene-divinylbenzene copolymer resins that have quaternary ammonium cation
as an integral part of the resin matrix.

Reaction: NR4 + OH− + HCl = NR4 + Cl− + H2O

Anion-exchange chromatography makes use to extract and purify materials from mixtures or
solutions.

Uses

a) Water softening

Ion-exchange resins are used to replace the magnesium and calcium ions found in hard
water with sodium ions. When the resin is fresh, it contains sodium ions at its active sites. When
in contact with a solution containing magnesium and calcium ions (but a low concentration of
sodium ions), the magnesium and calcium ions preferentially migrate out of solution to the active
sites on the resin, being replaced in solution by sodium ions. This process reaches equilibrium
with a much lower concentration of magnesium and calcium ions in solution than was started
with.

The resin can be recharged by washing it with a solution containing a high concentration
of sodium ions (e.g. it has large amounts of common salt (NaCl) dissolved in it). The calcium
and magnesium ions migrate from the resin, being replaced by sodium ions from the solution
until a new equilibrium is reached. The salt is used to recharge an ion-exchange resin, which
itself is used to soften the water.
 b) Water purification

Ion-exchange resins are used to remove poisonous (e.g. copper) and heavy-metal (e.g.
lead or cadmium) ions from solution, replacing them with more harmless ions, such as sodium
and potassium.

Few ion-exchange resins remove chlorine or organic contaminants from water this is
usually done by using an activated charcoal filter mixed with the resin. There are some ion-
exchange resins are remove organic ions such as magnetic ion-exchange resins.

c) Catalysis

Ion exchange resins are used in organic synthesis, e.g. for esterification and hydrolysis.
Being high surface area and insoluble, they are suitable for vapor-phase and liquid-phase
reactions. Example, basic (OH− form) of ion exchange resins are used to neutralize of ammonium
salts and convert quaternary ammonium halides to hydroxides. Acidic (H+ form) ion exchange
resins have been used as solid acid catalysts for ether protecting groups and for rearrangement
reactions.

d) Juice purification

Ion-exchange resins are used in the manufacture of fruit juices such as orange and
cranberry juice, where they are used to remove bitter-tasting components and so improve the
flavor.

e) Sugar manufacturing

Ion-exchange resins are used in the manufacturing of sugar from various sources. They
are used to help convert one type of sugar into another type of sugar and to decolorize and purify
sugar syrups.

f) Pharmaceuticals

Ion-exchange resins are used in the manufacturing of pharmaceuticals, not only for
catalyzing certain reactions, but also for isolating and purifying pharmaceutical active
ingredients. Three ion-exchange resins, sodium polystyrene sulfonate, colestipol and
cholestyramine are used as active ingredients.

Sodium polystyrene sulfonate is a strongly acidic ion-exchange resin and is used to treat
hyperkalemia. Colestipol is weakly basic ion-exchange resin and is used to treat
hypercholesterolemia. Cholestyramine is a strongly basic ion-exchange resin and is also used to
treat hypercholesterolemia.

g) Ion exchange in metal separation

Ion-exchange processes are used to separate and purify metals, including separating
uranium from plutonium and other actinides, including thorium; and lanthanum, neodymium,
ytterbium, samarium, lutetium, from each other and the other lanthanides. Ion exchange was for
many years the only practical way to separate the rare earths in large quantities.

Ion-exchange beads are also an essential component in in-situ leach uranium mining. In-
situ recovery involves the extraction of uranium-bearing water (grading as low as 0.05% U3O8)
through boreholes. The extracted uranium solution is then filtered through the resin beads.
Through an ion-exchange process, the resin beads attract uranium from the solution. Uranium-
loaded resins are then transported to a processing plant, where U3O8 is separated from the resin
beads, and yellowcake is produced. The resin beads can then be returned to the ion-exchange
facility, where they are reused.

The ion-exchange process is also used to separate other sets of very similar chemical
elements, such as zirconium and hafnium, which incidentally is also very important for the
nuclear industry.

Acrylonitrile butadiene styrene (ABS)

Acrylonitrile butadiene styrene (ABS) is a common thermoplastic polymer. ABS is a

terpolymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The
result is a long chain of polybutadiene criss-crossed with shorter chains of poly(styrene-co-
acrylonitrile). The nitrile groups from neighboring chains, being polar, attract each other and
bind the chains together, making ABS stronger than pure polystyrene.

Molecular Structure of Acrylonitrile Butadiene Styrene

Production

ABS is derived from acrylonitrile, butadiene and styrene. Acrylonitrile-butadiene Styrene

(ABS) has processed on,

1. Injection Molding
 Pre-Drying: 4 hours at 80°C.
 Melt temperature: 210-270°C.
 Mold temperature: of 40-70°C.
 Material Injection Pressure: 50 - 100 MPa.
 Injection Speed: Moderate - High
 2. Extrusion
 Pre-Drying: 3 hours at 70-80°C.
 Extrusion temperature: 210 to 240°C.
 Screw Design: L/D ratio of 25-30.

Applications

Several properties like high impact strength, heat performance etc. make ABS suitable for
use in automotive, home appliances, electronics, building & construction, transportation
industries and many more.

1. Automotive Applications
ABS is the preferred engineering plastic when it comes to dealing with automotive
applications. There has been an increasing focus on weight reduction in automotive.
Being a great substitute to metals, ABS has been extensively used in manufacturing
automotive parts.

Acrylonitrile Butadiene Styrene applications in automotive and transportation include,

 Instrument panels.
 Pillar trim.
 Dashboard components.
 Door liners and handles.
 Seat backs, seat belt components, etc
2. Appliances
Used of ABS in appliances include appliance control panels, housings (shavers, vacuum
cleaners, food processors), refrigerator liners, etc. Household and consumer goods are the
major applications of ABS. Keyboard keycaps are commonly made out of ABS.
3. Electrical & Electronics Applications
ABS provides good all-round performance for electronic enclosures, computer keyboards
etc.
 4. Pipes and fittings made from ABS are widely used as they are easier to install and do
not rot, rust or corrode. Under proper handling, they withstand earth loads and shipping
and can also resist mechanical damage, even at low temperatures.

Poly amides (PA)

A polyamide is a macromolecule with repeating units linked by amide bonds. Polyamides

occur both naturally and artificially. Examples of naturally occurring polyamides are proteins,
such as wool and silk. Artificially made polyamides can be made through step-growth
polymerization or solid-phase synthesis yielding materials such as nylons, aramids, and sodium
poly(aspartate).

Synthetic polyamides are commonly used in textiles, automotive applications, carpets and
sportswear due to their high durability and strength.

Classification

Polymers of amino acids are known as polypeptides or proteins. According to the composition of
their main chain, synthetic polyamides are classified as follows,

Polyamide Main chain Examples of polyamides

Aliphatic polyamides Aliphatic Nylon PA 6 and PA 66
Polyphthalamides Semi-aromatic PA 6T = hexamethylenediamine + terephthalic
acid
Aromatic polyamides Aromatic Paraphenylenediamine + terephthalic acid

All polyamides are made by the formation of an amide function to link two molecules of
monomer together.

Preparation of polyamide 6

Both polyamides are manufactured from benzene via cyclohexane. Hydrogen is passed
through liquid benzene in the presence of a nickel catalyst under pressure,
 Cyclohexane is oxidized by passing air through the liquid under pressure in the presence
of a catalyst (often a cobalt salt) to yield two products.

To prepare polyamide 6, pure cyclohexanone is required. When the mixed oil is heated
under pressure with copper(II) and chromium(III) oxides, the cyclohexanol, which is a secondary
alcohol, is dehydrogenated to the corresponding ketone, cyclohexanone.

Cyclohexanone is then converted into caprolactam via the oxime.

The isomerisation of the oxime to caprolactam by sulfuric acid and is transformed into
amide in the presence of acid.
 The caprolactam and ethanoic acid are poured into a vessel and heated under nitrogen at
500 K for about 12 hr to produce the polymer.

Uses of polyamides

1. The properties of the polyamides (nylons), which include high strength, abrasion
resistance and resilience, make them very important in the manufacture of clothing and
carpets.
2. The polyamides (nylons) are also used in engineering plastics, for example, in cars, and
for making films for food packaging. They are used in films for their good balance
between mechanical strength and barrier properties against oxygen, smells and oils.
3. Polyamides 6 and 6,6 are the most widely used polyamides for fibres and for engineering
materials.
4. The remaining commercial polyamides, for example, polyamides 11 and 12, and 6,10, are
most used as engineering plastics.

Poly ethylene terephthalate (PET)

Polyethylene terephthalate commonly abbreviated PET, PETE, or the obsolete PETP or

PET-P, is the most common thermoplastic polymer resin of the polyester family. PET consists of
polymerized units of the monomer ethylene terephthalate, with repeating (C10H8O4) units.

Preparation

Polyethylene terephthalate is prepared from ethylene glycol and dimethyl terephthalate

(DMT) (C6H4(CO2CH3)2) or terephthalic acid.

1. Dimethyl terephthalate process (DMT)

In dimethyl terephthalate (DMT) process, this compound and excess ethylene glycol are
reacted in the melt at 150 - 200°C with a basic catalyst. Methanol (CH3OH) is removed by
distillation to drive the reaction forward. Excess ethylene glycol is distilled off at higher
temperature with the aid of vacuum. The second transesterification step proceeds at 270 - 280°C,
with continuous distillation of ethylene glycol.
The reactions are idealized as follows:

First step
C6H4(CO2CH3)2 + 2 HOCH2CH2OH → C6H4(CO2CH2CH2OH)2 + 2 CH3OH
Second step
n C6H4(CO2CH2CH2OH)2 → [(CO)C6H4(CO2CH2CH2O)]n + n HOCH2CH2OH

2. Terephthalic acid process

In the terephthalic acid process, esterification of ethylene glycol and terephthalic acid is
reacting directly at moderate pressure and high temperature (220 - 260°C). Water is eliminated in
the reaction and it is also continuously removed by distillation.

n C6H4(CO2H)2 + n HOCH2CH2OH → [(CO)C6H4(CO2CH2CH2O)]n + 2n H2O

Applications of PET

Polyethylene Terephthalate is used in several packaging applications as mentioned below,

1. Because Polyethylene Terephthalate is an excellent water and moisture barrier material,

plastic bottles made from PET are widely used for mineral water and carbonated soft
drinks.
 2. Its high mechanical strength makes Polyethylene Terephthalate films use in tape
applications.
3. PET sheet can be make packaging trays and blisters.
4. Its chemical inertness, together with other physical properties, has made it particularly
suitable for food packaging applications.
5. Other packaging applications include rigid cosmetic jars, microwavable containers,
transparent films, etc.
6. PET has wide applications in textile industry. Polyester fabrics are strong, flexible and
offer additional benefit of less wrinkles and shrinkage over cotton.
7. PET is successfully being used in many applications in the automotive industry.

Polyphenylene Oxide (PPO)

Poly(p-phenylene oxide) or poly(p-phenylene ether) (PPE) is a high-temperature

thermoplastic. It is rarely used in its pure form due to difficulties in processing. It is mainly used
as blend with polystyrene, high impact styrene-butadiene copolymer or polyamide.

Structurally, PPO is made of phenylene rings linked together by ether linkages in the 1,4
or para- positions, with a methyl group attached to carbon atoms in the 2 and 6 positions.

Preparation

PPO is made by what we call oxidative coupling polymerization of the monomer 2,6-
dimethylphenol. Water is a by-product, and so this is a condensation polymerization.
Applications

1. PPO are used for structural parts, electronics, household and automotive items that
depend on high heat resistance, dimensional stability and accuracy.
2. They are also used in medicine for sterilizable instruments made of plastic.
3. This plastic is processed by injection molding or extrusion; depending on the type, the
processing temperature is 260-300°C.
4. This plastic is also used to produce air separation membranes for generating nitrogen.
5. PPO used for preparation of electrical and TV components, washing and dish-washing
machine parts, automobile parts and structural foam.

Poly sulphone (PSU)

Polysulfones are a family of thermoplastic polymers. These polymers are known for their
toughness and stability at high temperatures. They contain the subunit aryl-SO2-aryl group.
Polysulfones are used in specialty applications and often are a superior replacement for
polycarbonates.

Production

Polyethersulfones are prepared by a polycondensation reaction of the sodium salt of an

aromatic diphenol and bis(4-chlorophenyl)sulfone. The sodium salt of the diphenol is formed in
situ by reaction with a stoichiometric amount of sodium hydroxide (NaOH).

The formed reaction water must be removed with an azeotropic solvent (e.g.
methylbenzene or chlorobenzene). The polymerization is carried out at 130 - 160°C under inert
conditions in a polar, aprotic solvent, forming a polyether by elimination of sodium chloride.
 Also bis(4-fluorophenyl)sulfone can be used, it is more reactive than the dichloride.
Through chain terminators (e.g. chloromethane), the chain length can be regulated in a range that
a technical melt processing is possible.

The diphenol is typically bisphenol-A or 1,4-dihydroxybenzene. Such step

polymerizations require highly pure monomer to ensure high molecular weight products.

Applications

1. Polysulfone has resistance to high temperatures gives it a role of a flame retardant.

2. Polysulfone allows easy manufacturing of membranes. Such membranes can be used in
applications like hemodialysis, waste water recovery, food and beverage processing, and
gas separation.
3. These polymers are also used in the automotive and electronic industries.
4. Polysulfone can be used as filtration media in filter sterilization.
5. Polysulfone can be reinforced with glass fibers.
6. Polysulfone is often used as a copolymer. Recently, sulfonated polyethersulfones (SPES)
have been studied as a promising material candidate among many other aromatic
hydrocarbon-based polymers for highly durable proton-exchange membranes in fuel
cells.

Poly ether ether ketone (PEEK)

Polyether ether ketone (PEEK) is a colorless organic thermoplastic polymer in the

polyaryletherketone (PAEK) family, used in engineering applications.

Synthesis

PEEK polymers are obtained by step-growth polymerization by the dialkylation of

bisphenolate salts. Typical is the reaction of 4,4'-difluorobenzophenone with the disodium salt of
hydroquinone, which is generated in situ by deprotonation with sodium carbonate. The reaction
is conducted around 300°C in polar aprotic solvents - such as diphenyl sulphone.

Applications

1. Because of its robustness, PEEK is used to fabricate items used in demanding

applications, including bearings, piston parts, pumps, High-performance liquid
chromatography columns, compressor plate valves, and electrical cable insulation.
2. It is one of the few plastics compatible with ultra-high vacuum applications. PEEK is
considered an advanced biomaterial used in medical implants, e.g., use with a high-
resolution magnetic resonance imaging (MRI), for creating a partial replacement skull in
neurosurgical applications.
3. PEEK is extensively used in the aerospace, automotive and chemical process industries.
4. PEEK seals and manifolds are commonly used in fluid applications.
5. Because of its low thermal conductivity, it is also used in FFF printing to thermally
separate the hot end from the cold end.

Poly phenylene sulphide (PPS)

Polyphenylene sulfide (PPS) is an organic polymer consisting of aromatic rings linked by

sulfides. Synthetic fiber and textiles derived from this polymer resist chemical and thermal
attack. PPS is used in filter fabric for coal boilers, papermaking felts, electrical insulation, film
capacitors, specialty membranes, gaskets, and packings.

Polyphenylene sulfide is an engineering plastic, commonly used today as a high-

performance thermoplastic. PPS has not been found to dissolve in any solvent at temperatures
below approximately 200°C.
Production

The PPS (polyphenylene sulfide) polymer is formed by reaction of sodium sulfide with p-
dichlorobenzene,

ClC6H4Cl + Na2S → 1/n [C6H4S]n + 2 NaCl

Applications of PPS

1. Automotive Applications/ Automobile Parts

Polyphenylene Sulfide applications in automotive market have seen strong growth mainly
due to its ability to replace metal, thermosets and other types of plastic, in more
demanding applications.
PPS is a lighter weight alternative to metals, resistant to corrosion by salts and all
automotive fluids.
2. Electronic and Electrical Applications
Owing to its high temperature resistance, high toughness, good dimensional stability and
good rigidity, PPS becomes an ideal material of choice in Electronic and Electrical
market.
3. Industrial Applications
PPS has been replacing metal alloys, thermosets and many other thermoplastics in
mechanical engineering applications. The thermal stability and broad chemical resistance
of Polyphenylene Sulfide make it exceptionally well suited to service in very hostile
chemical environments.
4. Medical and Healthcare Applications
PPS compounds are used in medical application such as surgical instruments and device
components & parts that require high dimensional stability, strength and heat resistance.
PPS fibers are also used in medical fibers and membranes.