POLY VINYL CHLORIDE

POLYAMIDE
Nylon 66
INTERMEDIATES
1. Adipic Acid
2. Hexamethylenediamine
MANUFACTURING

The nylon 66 salt is prepared by reacting the hexamethylenediamine and adipic acid in boiling methanol, the
comparatively insoluble salt (melting point 190-191°C) precipitating out.

A 60% aqueous solution of the salt is then run into a stainless steel autoclave together with a trace of acetic acid
to limit the molecular weight (9000-15000). The vessel is sealed and purged with oxygen-free nitrogen. The
temperature and pressure are then controlled as below.
Reaction Conditions at Autoclave Reactor(Stage by Stage)
Stage 1: Temperature raised to about 220°C, pressure of 250 psi (1.7MPa) for 1-2 hours.
Stage 2: Temperature is raised to 270-280°C and steam bled off to maintain the pressure at 250 psi
Stage 3: Pressure is then reduced to atmospheric for one hour
The polymer is extruded by oxygen-free nitrogen on to a water-cooled casting wheel to form a ribbon which is
subsequently disintegrated.
Nylon 6
INTERMEDIATES
Caprolactam
Caprolactam is preferred to ω-aminocaproic acid for the manufacture of nylon 6 because it is easier to make and to
purify.
MANUFACTURING
Batch Process
Caprolactam, + water (catalyst) + acetic acid (molecular weight regulator) charged into the vessel and reacted under
a nitrogen atmosphere at 250°C for about 12 hours. The product consists of about 90% high polymer and 10% low
molecular weight material such as the monomer which may be removed by leaching and/or vacuum distillation.

The main characteristics of Nylon are:

¾ It has good sliding properties
¾ Is very abrasion resistant
¾ Resistant to many oils, greases, diesel, petrol, cleaning fluids
¾ Strong, tough and rigid
¾ Electrically insulating
¾ Easily machined
¾ Easily welded and bonded very good physical properties
¾ moisture has significant effect on properties
¾ very good heat resistance
 ¾ excellent chemical resistance
¾ excellent wear resistance
¾ moderate to high price

Applications
• Fiber applications
– 50% into tire cords (nylon 6 and nylon 6,6)
– rope, thread, cord, conveyor belts, and filter cloths.
– Monofilaments- brushes, sports equipment, and bristles (nylon 6,10)
• Plastics applications
– bearings, gears, cams
– rollers, slides, door latches, thread guides
– clothing, light tents, shower curtains, umbrellas
– electrical wire jackets (nylon 11)
• Adhesive applications
– hot melt or solution type
– thermoset reacting with epoxy or phenolic resins
– flexible adhesives for bread wrappers, dried soup packets, book bindings

ACRYLICS

POLYMERISATION
BULK POLYMERISATION
Bulk polymerisation is extensively used in the manufacture of the sheet and to a lesser extent rod and
tube. Methyl methacrylate will polymerise readily and the effect may be observed with non-inhibited
samples of monomers during storage. In commercial practice the monomer is supplied with up to 0.10%
of an inhibitor such as hydroquinone, which is removed before polymerisation, either by distillation under
reduced pressure or, in some cases, by washing with an alkaline solution.
Free-radical polymerisation techniques involving peroxides or azo-di-isobutyronitrile (AIBN) at
temperatures up to about 100°C are employed commercially.

SUSPENSION POLYMERISATION
The reaction temperature was 80°C initially but this rose to 120°C because of the exothermic reaction.
Polymerisation was complete in about an hour.

Properties
 1. Commercial poly(methyl methacrylate) is a hard, rigid, transparent material,
2. Extremely good weathering resistance compared with other thermoplastics
3. Tougher than polystyrene, but is less tough than cellulose acetate or the ABS polymers.
4. Light transmission of normal incident light through a parallel sheet of acrylic material free from
blemishes is about 92%.
5. Good electrical insulator for low-frequency work, but is inferior to such polymers as polyethylene
and polystyrene, particularly at high frequencies.

Applications
a) Display signs, illuminated and non-illuminated, and for both internal and external use.
b) Lighting fittings
c) Glazing material
d) Roof lights, motor cycle windscreens
e) Transparent guards for foodstuffs, machines and even baby incubators may be fabricated simply
from acrylic sheet.
Acrylic sheet is also employed for many other diverse applications, including baths and wash-basins, in a
wide range of colours, and are cheaper and much lighter than similar products from other materials.

Acrylonitrile Butadiene Styrene (ABS)

Production
Today the term ABS usually refers to a product consisting of discrete cross-linked polybutadiene rubber particles
that are grafted with SAN and embedded in a SAN matrix.
To produce ABS polymers, styrene and acrylonitrile are added to polybutadiene latex and the mixture warmed to
about 50°C to allow absorption of the monomers. A water-soluble initiator such as potassium persulphate is then
added to polymerise the styrene and acrylonitrile. The resultant materials will be a mixture of
1. Polybutadiene
2. Polybutadiene grafted with acrylonitrile and styrene
3. Styrene-acrylonitrile copolymer
The presence of graft polymer is essential since straightforward mixtures of polybutadiene and styrene-acrylonitrile
copolymers are weak. In addition to emulsion processes such as those described above, mass and mass/suspension
processes are also of importance.
Properties
9 High toughness
9 High impact resistance,
9 Very good dimensional stability,
9 Good heat distortion Resistance (relative to the major tonnage thermoplastics)
9 Good low-temperature properties
9 Capability of being electroplated without great difficulty.
Applications
9 Automotive Applications - fascia panels, door covers, door handles, radiator grilles, ventilation system
components, heater housings, seat belt fastenings, console panels, loudspeaker housings, interior trim and
other uses. Electroplated ABS continues to be used for nameplates, reflectors and other parts where a bright
reflecting surface is a requirement.
9 Household appliances – Body cover for washing machine, refrigerator, telephones etc
9 Consumer electronic equipment - Body cover for printer, fax, UPS etc.
9 Refrigerator sheeting
9 Toys
9 Recreational equipment,
9 Luggage
 POLYCARBONATES
Production
Phosgenation Process
Today the most important process is that of interfacial polymerisation. In a typical process the disodium
salt of bisphenol A in an alkaline aqueous solution or suspension is reacted with phosgene in the presence
of an inert organic solvent such as methylene chloride, chlorobenzene, tetrahydrofuran or dioxane.
Reaction temperatures are in the range 10-35°C. The polymer is recovered by washing the organic phase
with water, neutralisation of the caustic soda and either precipitation of the polymer by a non-solvent or
evaporation of the solvent by thorough washing.

Ester Exchange Process

In this method the reaction is typically carried out at 180-220°C at 20-30mmHg pressure until 80-90% of
the phenol of condensation has been removed. The temperature is then gradually raised to 290-300°C and
the pressure reduced to 1 mmHg or below. The melt viscosity increases considerably during this period
and the reaction is stopped while the material can still be forced out of the kettle by an inert gas.
The high melt viscosity limits the molecular weights obtainable and although number average molecular
weights of 50000 can be obtained it is difficult to attain values of above 30 000 without special
equipment.

PROPERTIES

¾ Outstanding impact strength—even at low temperatures

¾ Good mechanical properties over a broad temperature range
¾ Excellent dimensional stability, even at elevated temperatures
¾ Outstanding optical properties
¾ Low birefringence [for compact disc (CD) manufacture]
¾ Natural water-clear transparency
¾ Ability to be integrally colored to form transparent, translucent, or opaque parts in virtually any
hue and a wide variety of special effects for parts with high aesthetics
 ¾ Amenability to plating, painting, and in-mold decoration
¾ Product purity and safety for food-contact and medical applications (many BPA-PC grades have
agency compliance around the globe)
¾ Good thermal stability [relative thermal index (RTI) to 125°C]
¾ Good electrical insulating properties (although it can be made electroconductive via additives)
¾ Good ultraviolet (UV) stability and weatherability
¾ Very good flame retardancy, inherent V-2 rating.
¾ Good processability with fast cycle times

APPLICATIONS
Electronic Components
Polycarbonate is mainly used for electronic applications that capitalize on its collective safety features.
Being a good electrical insulator and having heat resistant and flame retardant properties, it is used in
various products associated with electrical and telecommunications hardware. It also serves as dielectric
in high stability capacitors.[3]

Construction materials
The second largest consumer of polycarbonates is the construction industry, e.g. for dome lights, flat or
curved glazing, and sound walls.

Data storage
A major application of polycarbonate is the production of Compact Discs, DVDs, and Blu-ray Discs.
These discs are produced by injection molding polycarbonate into a mold cavity that has on one side a
metal stamper containing a negative image of the disc data, while the other mold side is a mirrored
surface. Typical products of sheet/film production include applications in advertisement (signs, displays,
poster protection).[3]

Automotive, aircraft, and security components

In the automotive industry, injection-molded polycarbonate can produce very smooth surfaces that make
it well-suited for direct (without the need for a basecoat) metalised parts such as decorative bezels and
optical reflectors. Its uniform mold shrinkage results in parts with greater accuracy than those made of
polypropylene. However, due to its susceptibility to environmental stress cracking, its use is limited to
low-stress applications. It can be laminated to make bullet-proof "glass", although "bullet-resistant" is
more accurate for the thinner windows, such as are used in bullet-resistant windows in automobiles. The
thicker barriers of transparent plastic used in teller's windows and barriers in banks are also
polycarbonate.

So-called "theft-proof" large plastic packaging for smaller items, which cannot be opened by hand, is
uniformly made from polycarbonate.

The cockpit canopy of the F-22 Raptor jet fighter is made from a piece of high optical quality
polycarbonate, and is the largest piece of its type formed in the world.

Niche applications
Polycarbonate, being a versatile material with attractive processing and physical properties, has attracted
myriad smaller applications. The use of injection molded drinking bottles and glasses and food containers
has stirred serious controversy
Many kinds of lenses are manufactured from polycarbonate, automotive headlamp lenses, lighting lenses,
sunglass/eyeglass, lenses, and safety glasses. Other miscellaneous items: including durable, lightweight
luggage, MP3/digital audio player cases, ocarinas, computer cases, riot shields, visors, instrument panels,
and blender jars. Many toys and hobby items are made from polycarbonate parts, e.g. fins, gyro mounts,
and flybar locks for use with radio-controlled helicopters.[6]

Polycarbonate is also used as a printing substrate for nameplate and other forms of industrial grade under
printed products. The polycarbonate provides a barrier to wear, the elements, and fading.

Medical applications
Some polycarbonate grades are used in medical applications and comply with both ISO 10993-1 and USP
Class VI standards (occasionally referred to as PC-ISO). Class VI is the most stringent of the six USP
ratings. These grades can be sterilized using steam at 120 °C, gamma radiation, or by the ethylene oxide
(EtO) method.[7] However, scientific research indicates possible problems with biocompatibility. Dow
Chemical strictly limits all its plastics with regard to medical applications

PHENOL FORMALDEHYDE RESIN

NOVOLAKS
The novolaks are prepared by reacting phenol with formaldehyde in a molar ratio of approximately 1 : 0.8
under acidic conditions. Under these conditions there is a slow reaction of the two reactants to form the o-
and p-hydroxymethylphenols

These then condensate rapidly to form products of the bis(hydroxyphenyl)-methane (HPM) type.

There are three possible isomers and the proportions in which they are formed will depend on the pH of
the reaction medium. Under the acid conditions normally employed in novolak manufacture the 2,4’- and
4,4’-HPM compounds are the main products

These materials will then slowly react with further formaldehyde to form their own methylol derivatives
which in turn rapidly react with further phenol to produce higher polynuclear phenols. Because of the
excess of phenol there is a limit to the molecular weight of the product produced, but on average there are
5-6 benzene rings per molecule. A typical example of the many possible structures is shown in.

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked
structures on heating.

RESOLS

A resol is produced by reacting a phenol with an excess of aldehyde under basic conditions. In this case
the formation of phenol-alcohols is rapid but their subsequent condensation is slow. Thus there is a
tendency for polyalcohols, as well as monoalcohols, to be formed. The resulting polynuclear polyalcohols
are of low molecular weight. Liquid resols have an average of less than two benzene rings per molecule,
while a solid resol may have only three to four. A typical resol would have the structure shown in Figure

Heating of these resins will result in cross-linking via the uncondensed methylol groups or by more
complex mechanisms. The resols are sometimes referred to as one-stage resins since cross-linked
products may be made from the initial reaction mixture solely by adjusting the pH. On the other hand the
novolaks are sometimes referred to as two-stage resins as here it is necessary to add some agent which
will enable additional methylene bridges to be formed.

Crosslinking (Hardening)
For novolac, Hexa is used almost universally as the hardener. Hexamethylene tetramine or simply hexa,
most commonly used as the cross-linking agent, decomposes under heat and using the moisture present to
generate formaldehyde (the curing agent) and ammonia (the curing catalyst).
The resols may be hardened by heating and/or by addition of catalysts. Hardening of the novolaks may be
brought about by addition of hexamethylenetetramine (hexa, hexamine). Because of the exothermic
reaction on hardening (cure) and the accompanying shrinkage, it is necessary to incorporate inert
materials (fillers) to reduce the resin content.

PROPERTIES OF PHENOLIC MOULDINGS

¾ Since the polymer in phenolic mouldings is cross-linked and highly interlocked, phenolic
mouldings are hard,
¾ Heat-resistant insoluble materials.
¾ The chemical resistance of the mouldings depends on the type of filler and resin used. Simple
phenol-formaldehyde materials are readily attacked by aqueous sodium hydroxide solution but
cresol- and xylenol-based resins are more resistant.
¾ The resins are stable up to 200°C.
¾ As the mouldings are polar, the electrical insulation properties are not outstanding
¾ Poor arc tracking resistance under conditions of high humidity.

APPLICATIONS
‐ Domestic plugs and switches
‐ Insulators.
‐ In the car industry phenol-formaldehyde mouldings are used in fuse-box covers, distributor heads
and in other applications where good electrical insulation together with good heat resistance are
required
‐ Heat-resistant grades are finding use in saucepan handles, saucepan lid knobs, lamp housings,
cooker handles, welding tongs and electric iron parts.
‐ Laminates

EPOXY RESIN
The reaction scheme suggests that diglycidyl ether would be prepared by a molar ratio of 2: 1
epichlorohydrin : bis-phenol A, probability considerations indicate that some higher molecular weight
species will be produced. Experimentally, it is in fact found that when a 2: 1 ratio is employed, the yield
of the diglycidyl ether is less than 10%. Therefore, in practice two to three times the stoichiometric
quantity of epichlorhydrin may be employed. In a typical laboratory scale preparation 1 mole of bis-
phenol A is dissolved in 4 moles of epichlorohydrin and the mixture heated to 105-110°C under an
atmosphere of nitrogen. The solution is continuously stirred for 16 hours while 2 moles of sodium
hydroxide in the form of 30% aqueous solution is added dropwise. A rate of addition is maintained such
that reaction mixture remains at a pH which is insufficient to colour phenolpthalein. The resulting organic
layer is separated, dried with sodium sulphate and may then be fractionally distilled under vacuum.
 ‐
The general formulae for glycidyl ether resins may thus be represented by the structure shown

CURING OF GLYCIDYL ETHER RESINS

Amine Hardening Systems

Diethylenetriamine and triethylenetetramine are highly reactive primary aliphatic amines with five and
six active hydrogen atoms available for crosslinking respectively. Both materials will cure glycidyl ether
at room temperature.

With amines,

With diamines,

Acid Hardening Systems

Curing with Hydroxyl Group

The epoxy-hydroxyl reaction may be expressed as

Mercaptan Hardening Systems

Both amines and acid anhydrides are extensively used cross-linking agents. The resins may also be
modified by reacting with other polymers containing hydroxyl or mercaptan groupings, e.g.

Advantages of Epoxy Resins over Polyester Resins

Superior heat resistance, chemicals and alkali resistance, mechanical properties and aging resistance.

Epoxy as Universal Adhesive

9 Excellent adhesion,
9 Very good cohesion,
9 Low creep and
9 Low shrinkage on cure
9 Absence of volatiles
The above properties make epoxy as an excellent adhesive, bonding or cementing material for metal-to-
metal, metal to-ceramics, metal-to-plastics and various other combination of substrates.
APPLICATIONS
¾ High strength adhesives and cementing agents, in the building industry and road surfacing
¾ Surface coatings
¾ Potting and encapsulation of electronic components
¾ Glass fibre reinforced cast objects and laminates
¾ Laminates in flooring
¾ Moulding powders
 UNSATURATED POLYESTER RESINS
The polyester laminating resins are viscous, generally pale yellow coloured materials of a low degree of
polymerisation (~ 8 - 10), i.e. molecular weight of about 2000. They are produced by condensing a glycol
with both an unsaturated and a saturated dicarboxylic acid. The unsaturated acid provides a site for
subsequent cross-linking whilst provision of a saturated acid reduces the number of sites for cross-linking
and hence reduces the cross-link density and brittleness of the end-product. In practice the polyester resin,
which may vary from a very highly viscous liquid to a brittle solid depending on composition, is mixed
with a reactive diluents, such as styrene. This eases working, often reduces the cost and enhances
reactivity of the polyester.

Selection of Raw Materials

Diols
1,2-Propylene glycol is probably the most important glycol used in the manufacture of the laminating
resins. It gives resins which are less crystalline and more compatible with styrene than those obtained
using ethylene glycol.

Saturated acids
The prime function of the saturated acid is to space out the double bonds and thus reduce the density of
cross-linking. Phthalic anhydride is the most commonly used for this purpose because it provides an
inflexible link and maintains the rigidity in the cured resin. It has been used in increasing proportions
during the past decade since its low price enables cheaper resins to be made. The most detrimental effect
of this is to reduce the heat resistance of the laminates but this is frequently unimportant.

Un-Saturated acids
Most conventional general purpose resins employ either maleic acid (usually as the anhydride) or its
trans-isomer fumaric acid (which does not form an anhydride) as the unsaturated acid.
Diluents
Because of its low price, compatibility, low viscosity and ease of use, styrene is the preferred reactive
diluent in general purpose resins. Methyl methacrylate is sometimes used, but as it does not copolymerise
alone with most unsaturated polyesters, usually in conjunction with styrene in resins for translucent
sheeting. Vinyl toluene and diallyl phthalate are also occasionally employed.
Production of Resins
Polyester laminating resins are produced by heating the component acids and glycols at 150-200°C for
several hours, e.g. 12 hours. In order to obtain a good colour and to prevent premature gelation, the
reaction is carried out under an inert blanket of carbon dioxide or nitrogen. The reaction mixture is
agitated to facilitate reaction and to prevent local overheating. A typical charge for a general purpose
resin would be:
Propylene glycol 146 parts
Maleic anhydride 114 parts
Phthalic anhydride 86 parts
The molar ratios of these three ingredients in the order above is 1.1 : 0.67 : 0.33. The slight excess of
glycol is primarily to allow for evaporation losses. Xylene is often used used to facilitate the removal of
water of condensation by means of azeotropic distillation. The reaction is followed by measuring the acid
number of small samples periodically removed from the reactor. (The acid number is the number of
milligrams of potassium hydroxide equivalent to the acidity present in one gram of resin.) Where there
are equimolecular proportions of glycol and acid the number average molecular weight is given by
56000/acid number. Since there is some deviation from equimolecular equivalence in practice, care
should be taken in using this reationship. Reaction is usually stopped when the acid number is between 25
and 50, the heaters are switched off and any xylene presents is allowed to boil off into a receiver.
When the resin temperature drops below the boiling point of the reactive diluent (usually styrene) the
resin is pumped into a blending tank containing suitability inhibited diluent.
Curing Systems

The cross-linking reaction is carried out after the resin has been applied to the glass fibre. In practice the
curing is carried out either at elevated temperatures of about 100°C where compression mouldings are
being produced, or at room temperature in the case of large hand lay-up structures.
 1) Benzoyl peroxide is most commonly used for elevated temperature curing. The peroxide
is generally supplied as a paste (~50%) in a liquid such as dimethyl phthalate to reduce
explosion hazards and to facilitate mixing. The curing cycle in pressure moulding
processes is normally less than five minutes.
2) In the presence of certain aromatic tertiary amines such as dimethylaniline, benzoyl
peroxide will bring about the room temperature cure of general purpose polyester resins.
3) More frequently either methyl ethyl ketone peroxide (MEKP) or cyclohexanone peroxide
is used for room temperature curing in conjunction with a cobalt compound such as a
naphthenate, octoate or other organic solvent-soluble soap. The peroxides (strictly
speaking polymerisation initiators) are referred to as ‘catalysts’ and the cobalt compound
as an ‘accelerator’. Other curing systems have been devised but are seldom used.

(1) Structures present in polyester resin ready for (2) Structures present in cured polyester resin.
laminating: