Chemical Engineering Department

Mehran University Of Engineering & Technology, Jamshoro

 1. ACRYLONITRILE AND ACRYLIC FIBRE

Introduction
Acrylonitrile is an organic compound with the formula CH2CHCN. It is a colorless volatile
liquid, although commercial samples can be yellow due to impurities. In terms of
itsmolecular structure, it consists of a vinyl group linked to a nitrile. It is an
important monomerfor the manufacture of useful plastics such as polyacrylonitrile. It
is reactive and toxic at low doses.
Acrylic fibres are third largest class of synthetic fibre after polyester and nylons.
Commercial acrylic fibre was developed by Dupont in US as Orlon while modified acrylic
fibre was developed by Union carbide as Dynel. In acrylic fibre monomer is acrylonitrile
while in case of modified acrylic fibre acrylonitrile is co polymerised with Vinylidiene
chloride vinyl chloride. The halogenated monomers impart flame resistance and are suitable
for home furnishing, protective coatings, sleepwear, and hospital blankets.
Acrylic fibres are soft, light weight, durable strong, high crease recovery, color fastness to
both washing & sunlight, easy care- easy laundry & low maintenance cost, high abrasion
resistance, good aesthetics-high lustre, good wicking action- helps in quick transfer of
moisture & sweat resulting in quick drying, no allergic and non toxic, resistance to mild &
insects, oils, chemicals. It is very resistant to deterioration from sunlight exposure.

ACRYLONITRILE (CH2=CH-CN)
Acrylic nitrile is one of the important monomer for manufacture of acrylic fibres, however,
earlier routes of acrylonitrile manufacture by acetylene, ethylene oxide or acetaldehyde route
has being replaced by propylene route due to availability of cheaper propylene from steam
cracker plant. This involves ammono-oxidation of propylene. Other uses of acrylonitrile are
in the manufacture of nitrile rubber, ABS and SAN plastics, adiponitrile and acrylamide. In
addition it is also used in the manufacture of acrylates, intermediates for flocculants,
pharmaceuticals, antioxidants, dyes and surface active agents.
Various route of acrylonitrile manufacturing shown in below
Reactions;

Figure: Various Routes for the Manufacture of Acrylonitrile

Major Synthetic Fibers and Their Characteristics

Figure: Process Technology of Acrylonitrile Manufacture

Acrylic Fibre Manufacture
Acrylic fibres are third largest class of synthetic fibre after polyester and nylons. Commercial
acrylic fibre was developed by Dupont in US as Orlon while modified acrylic fibre was
developed by Union carbide as Dynel.

Process Technology
Manufacturing process shown in below figure. The manufacturing process can be broadly
divided into two parts:

Polymerisation:
Polymerisation includes copolymer composition, catalyst system, polymerisation reaction and
monomer recovery. Major polymerisation processes are bulk polymerisation, suspension
polymerisation, emulsion polymerisation and solution polymerisation. Most of the acrylic
polymers manufactured for fiber grade are made through suspension polymerisation that
gives high percentage of conversion, better product whiteness, shorter residence time and
easy control of polymerisation. Emulsion polymerization is used incase of modified acrylic
fibre. Inorganic compounds such as persulphate, chlorates or hydrogen peroxide are used as
radical generators. Redox initiation is normaaly used in production of acrylic fibre. The most
common redox system consist of ammonium or potassium persulphate (oxidizer), sodium
bisulphate (reducing agent) and ferric or ferrous ion (catalyst)

Spinning: Spinning includes solution/dope preparation, spinning techniques and finishing

operation including after treatment, cutting and bailing.

Dry Spinning:
In dry spinning of acrylic fibre dimethyl formamide (DMF) is used. The DMF spin dope
contains the polymer in the DMF, thermal stabilizers, delustrant. It passed through spinnerate
placed at top of the solvent removal tower. The DMF evaporated by circulating inert gas
through tower at about 300-35 oC to remove the solvent

Wet Spinning:
In wet spinning sodium thiocyanate are commonly used as solvent. Wet spinning fiber is
spun into a liquid bath containing a solvent non-solvent mixture called coagulant. Nonsolvent
is usually water. The fibre emerging from pin bath are washed and dried followed by cutting
and bailing.

Figure: Process Flow Diagram of Manufacture of Acrylic Fiber

Health Effects:
Acrylonitrile is highly flammable and toxic at low doses. It undergoes explosive
polymerization. The burning material releases fumes of hydrogen cyanide and oxides of
nitrogen. It is classified as a Class 2B carcinogen (possibly carcinogenic) by the International
Agency for Research on Cancer (IARC), and workers exposed to high levels of airborne
acrylonitrile are diagnosed more frequently with lung cancer than the rest of the population. It
evaporates quickly at room temperature (20 C) to reach dangerous concentrations; skin
irritation, respiratory irritation, and eye irritation are the immediate effects of this exposure.
Acrylonitrile increases cancer in high dose tests in male and female rats and mice.

Uses:
Acrylonitrile is used principally as a monomer to prepare polyacrylonitrile, a homopolymer,
or several important copolymers, such as styrene acrylonitrile (SAN), acrylonitrile butadiene
styrene (ABS), acrylonitrile styrene acrylate (ASA), and other synthetic rubbers such
asacrylonitrile butadiene (NBR). Dimerization of acrylonitrile affords adiponitrile, used in
then synthesis of certain polyamides. Small amounts are also used as a fumigant.
Acrylonitrile and derivatives, such as 2-chloro-acrylonitrile, are dienophiles in Diels-Alder
reactions. Acrylonitrile is also a precursor in the industrial manufacture
of acrylamide and acrylic acid.
 2. NYLON FIBER
INTRODUCTION

Nylon is a generic designation for a family of synthetic polymers, more

specifically aliphatic orsemi-aromatic polyamides. They can be melt-processed into
fibers, films or shapes. The first example of nylon (nylon 6,6) was produced on February 28,
1935, by Wallace Carothers atDuPont's research facility at the DuPont Experimental Station.
Nylon polymers have found significant commercial applications in fibers (apparel, flooring
and rubber reinforcement), in shapes (molded parts for cars, electrical equipment, etc.), and in
films (mostly for food packaging).
Nylon was the first truly synthetic fiber to be commercialized (1939). Nylon was developed
in the 1930s by scientists at Du Pont, headed by an American chemist Wallace Hume
Caruthers (1896-1937). It is a polyamide fiber, derived from a diamine and a dicarboxylic
acid, because a variety of diamines and dicarboxylic acids can be produced, there are a very
large number of polyamide materials available to produce nylon fibers. The two most
common versions are nylon 66 (polyhexamethylene adiamide) and nylon 6 (Polycaprolactam,
a cyclic nylon intermediate). Raw materials for these are variable and sources used
commercially are benzene (from coke production or oil refining), furfural (from oat hulls or
corn cobs) or 1,4-butadiene (from oil refining). The chemical reactions are as follows

Characteristics
The characteristic features of nylon 6,6 include:

Pleats and creases can be heat-set at higher temperatures

More compact molecular structure
Better weathering properties; better sunlight resistance
Softer "Hand"
 High melting point (256 C/492.8 F)
Superior colorfastness
Excellent abrasion resistance
On the other hand, nylon 6 is easy to dye, more readily fades; it has a higher impact
resistance, a more rapid moisture absorption, greater elasticity and elastic recovery.

Variation of luster: nylon has the ability to be very lustrous, semilustrous or dull.
Durability: its high tenacity fibers are used for seatbelts, tire cords, ballistic cloth and
other uses.
High elongation
Excellent abrasion resistance
Highly resilient (nylon fabrics are heat-set)
Paved the way for easy-care garments
High resistance to insects, fungi, animals, as well as molds, mildew, rot and many
chemicals
Used in carpets and nylon stockings
Melts instead of burning
Used in many military applications
Good specific strength
Transparent to infrared light (12 dB)

Fiber:
Fiber or fibre (from the Latin fibra) is a natural or synthetic substance that is significantly
longer than it is wide. Fibers are often used in the manufacture of other materials. The
strongest engineering materials often incorporate fibers, for example carbon fiber and ultra-
high-molecular-weight polyethylene.
Synthetic fibers can often be produced very cheaply and in large amounts compared to
natural fibers, but for clothing natural fibers can give some benefits, such as comfort, over
their synthetic counterparts.
a) Natural fiber:
Natural fibers develop or occur in the fiber shape, and include those produced by plants,
animals, and geological processes.
They can be classified according to their origin:

Vegetable fibers are generally based on arrangements of cellulose, often with lignin:
examples include cotton, hemp, jute, flax, ramie, sisal, bagasse, and banana. Plant fibers
are employed in the manufacture of paper and textile (cloth), and dietary fiber is an
important component of human nutrition.
Wood fiber, distinguished from vegetable fiber, is from tree sources. Forms
include groundwood,lacebark, thermomechanical pulp (TMP), and bleached or
unbleached kraft or sulfite pulps. Kraft and sulfite (also called sulphite) refer to the type
of pulping process used to remove the lignin bonding the original wood structure, thus
freeing the fibers for use in paper and engineered wood products such as fiberboard.
Animal fibers consist largely of particular proteins. Instances are silkworm silk, spider
silk, sinew,catgut, wool, sea silk and hair such as cashmere wool, mohair and angora, fur
such as sheepskin, rabbit, mink, fox, beaver, etc.
 Mineral fibers include the asbestos group. Asbestos is the only naturally occurring
long mineral fiber. Six minerals have been classified as "asbestos" including chrysotile of
the serpentine class and those belonging to
the amphibole class: amosite, crocidolite, tremolite, anthophyllite and actinolite. Short,
fiber-like minerals include wollastonite and palygorskite.
Biological fibers also known as fibrous proteins or protein filaments consist largely of
biologically relevant and biologically very important proteins, mutations or other genetic
defects can lead to severe diseases. Instances are collagen[3] family of
proteins,tendon, muscle proteins like actin, cell proteins like microtubules and many
others, spider silk, sinew and hair etc.

b) Man Mad Fiber:

Man-made fibers or chemical fibers are fibers whose chemical composition, structure, and
properties are significantly modified during the manufacturing process. Man-made fibers
consist of regenerated fibers and synthetic fibers.

c) Semi-Synthetic Fiber:

Semi-synthetic fibers are made from raw materials with naturally long-chain polymer
structure and are only modified and partially degraded by chemical processes, in contrast to
completely synthetic fibers such as nylon (polyamide) or dacron (polyester), which the
chemist synthesizes from low-molecular weight compounds by polymerization (chain-
building) reactions. The earliest semi-synthetic fiber is the cellulose regenerated
fiber, rayon. Most semi-synthetic fibers are cellulose regenerated fibers.
Cellulose Fibber:
Cellulose fibers are a subset of man-made fibers, regenerated from natural cellulose. The
cellulose comes from various sources: rayon from tree wood fiber, Modal from beech
trees, bamboo fiber from bamboo, seacell from seaweed, etc. In the production of these
fibers, the cellulose is reduced to a fairly pure form as a viscous mass and formed into fibers
by extrusion through spinnerets. Therefore, the manufacturing process leaves few
characteristics distinctive of the natural source material in the finished products.
Some examples are:

Rayon
Bamboo fiber
Lyocell, a brand of rayon
Modal, using beech trees as input
Diacetate fiber
Triacetate fiber.

d) Synthetic fiber:

Synthetic come entirely from synthetic materials such as petrochemicals, unlike those man-
made fibers derived from such natural substances as cellulose or protein.
Metallic Fiber: Metallic fibers can be drawn from ductile metals such as copper, gold
or silver and extruded or deposited from more brittle ones, such as nickel, aluminum
or iron. See also Stainless steel fibers.
 Carbon fiber: Carbon fibers are often based on oxydized and via pyrolysis carbonized
polymers like PAN, but the end product is almost pure carbon.
Silicon carbide fiber: Silicon carbide fibers, where the basic polymers are
not hydrocarbons but polymers, where about 50% of the carbon atoms are replaced by
silicon atoms, so-called poly-carbo-silanes. The pyrolysis yields an amorphous silicon
carbide, including mostly other elements like oxygen, titanium, or aluminium, but
with mechanical properties very similar to those of carbon fibers.
Fiberglass: Fiberglass made from specific glass, and optical fiber, made from purified
natural quartz, are also man-made fibers that come from natural raw materials, silica
fiber, made from sodium silicate (water glass) and basalt fiber made from melted
basalt.
Mineral fiber: Mineral fibers can be particularly strong because they are formed with
a low number of surface defects, asbestos is a common one. Polymer fiber: Polymer
fibers are a subset of man-made fibers, which are based on synthetic chemicals (often
from petrochemical sources) rather than arising from natural materials by a purely
physical process.

NYLON FIBER:
Nylon fibers are one of the fibers having the longest history among synthetic fibers. They are
used for a variety of uses from clothing to home furnishings and industrial uses.
Comparing other synthetic fibers, great advantages of nylon fibers are resistant to abrasion
and flexing, and of supple tactile feeling. Accordingly, thin, light and flexible woven or
knitted fabric can be manufactured. Further-more, an advantage of easily dye ability makes
possibility recent year to develop many fabrics for clothing.
Nylon fibers can be produced in a variety of cross-section and fineness. Composite fibers,
having unique appearance and tactile feeling, can also be produced by combining with other
types of fibers. Heat storage or warmth retention fibers consisting of extremely fine filament
yarns in which carbonaceous material converting the light to heat is inserted. Anti-static
nylon fibers inhibiting electro-static charge. Transparent nylon fibers exhibiting more
transparent and beautiful colors. Thus a wide variety of nylon fibers are available giving
much more performances and fabric hand.

Figure: Manufacturing Process of Nylon Fiber

 Almost all nylon fibers are filament yarns ranging from very fine to coarse denier to be used
for clothing such as sport wear, lingerie, pantyhose; home furnishing as carpets; and
industrial uses such as fishing nets, ropes, and tire cords.

Staple fibers are used, in the yarns blended with wool and acrylic fibers, for clothing; home
furnishing such as carpets, upholstery; and other fields of sundries.

Features:
1. One of the very strong fibers. Extremely resistant to abrasion and flexing.
2. The specific gravity is 1.14 Very light, i.e., 80% of that of silk fibers, and 70% of that of
cotton fibers.
3. Since nylon fibers absorb little water even though they are wetted., they dry fast and
simple in laundering.
4. Excellent in elasticity and resistant to wrinkle.
5. If properly set, nylon textiles little shrink/ extend or little deform their shape due to
thermoplasticity.
6. Resistant to chemicals and oil. Non-attackable by sea water.
7. Non-attackable by molds and insects.

End Uses:
For Clothing
Pantyhose, Socks, Ski Wear, Swimsuits, Sports Wear, Casual Wear, Lingerie, Women's
Underwear, Rain Wear, Linings, etc.
For Home Uses
Cloth for Bags, Cover Cloth for Futon (Japanese Bedding), Furoshiki (Square Cloth for
Wrapping Things), Cloth for Umbrella, Sewing Threads, Teeth Brush, Interlinings, etc.
For Home Furnishing
Carpets, Automotive Rugs, Upholstery, Artificial Turves, Rugs, etc.
For Industrial Uses
Tire Cords, Automotive Airbags, Fishing Nets, Fishing line, Computer Ribbon, Hoses,
Industrial Sewing Thread, Footwear, Automotive Furnishings, Substrate for Synthetic
Leather, etc.
 3. NEOPRENE RUBBER
Introduction

Neoprene or polychloroprene is a family of synthetic rubbers that are produced by polymerization

of chloroprene. Neoprene exhibits good chemical stability and maintains flexibility over a wide
temperature range. Neoprene is sold either as solid rubber or in latex form, and is used in a wide
variety of applications, such as laptop sleeves, orthopedic braces (wrist, knee,
etc.), electricalinsulation, liquid and sheet applied elastomeric membranes or flashings,
and automotive fan belts.

History

Neoprene was invented by DuPont scientists on April 17, 1930 after Dr Elmer K. Bolton of DuPont
attended a lecture by Fr Julius Arthur Nieuwland, a professor of chemistry at the University of Notre
Dame. Nieuwland's research was focused on acetylene chemistry and during the course of his work he
produced divinyl acetylene, a jelly that firms into an elastic compound similar to rubber when passed
oversulfur dichloride.

General Characteristics & Advantages

Oil and chemical resistant
High temperature rating
Flame resistant
Durometer Range (Shore A): 20-95
Tensile Range (P.S.I): 500-3000
Elongation (Max %): 600
Compression Set: Good
Resilience /Rebound: Excellent
Adhesion to Metals: Good to Excellent
Temperature Range
Low Temperature Usage: 10 to -50 F | -12 to -46 C
High Temperature Usage: Up to 250 F | Up to 121 C
Resistance
Abrasion Resistance: Excellent
Tear Resistance: Good
Solvent Resistance: Fair
Oil Resistance: Fair
Aging Weather / Sunlight: Good

Applications of Neoprene Rubber:

General
Neoprene resists degradation more than natural or synthetic rubber.
 This relative inertness makes it well suited for demanding applications such as gaskets, hoses,
and corrosion-resistant coatings.
It resists burning better than exclusively hydrocarbon based rubbers.
Because of its tolerance of extreme conditions, neoprene is used to line landfills. Neoprene's burn
point is around 260C (500F).
Neoprene foam is also used in many applications. Neoprene foam can be produced in either closed-
cell or open-cell form. The closed-cell form is waterproof, less compressible and more expensive. The
open-cell form can be breathable.
Civil engineering
Neoprene is used as a load bearing base, usually between two prefabricated reinforced concrete
elements or steel plates as well to evenly guide force from one element to another.[11]
Aquatics
Neoprene is commonly used as a material for fly fishing waders, as it provides excellent insulation
against cold. Neoprene waders are usually about 5 mm thick, and in the medium price range as
compared to cheaper materials such as nylon and rubber. However, neoprene is less expensive than
breathable fabrics. A foamed neoprene containing gas cells is used as an insulation material, most
notably in wetsuits.
Home accessories
Recently, neoprene has become a favorite material for lifestyle and other home accessories
including laptop sleeves, tablet holders,remote controls, mouse pads, and cycling chamois. In this
market, it sometimes competes with LRPu (low-resilience polyurethane), which is a sturdier (more
impact-resistant) but less-used material.
Construction Industry
Neoprene seals can be used in a variety of construction jobs including

Neoprene window seals

Custom window gaskets
Highway and bridge seals
Bridge bearing pads
Neoprene washers
Bridge stay-cable anchor components
Deviator pads
Neoprene O Ring
Elevator astragals

Wire and Cable Industry

Neoprene rubber parts are widely used for protective covering solutions in cable and wire systems.
Neoprene's physical toughness and resistance to cracking make it an optimal material for use in cables
that are commonly bent and twisted repeatedly.
Some specific wire and cable applications that benefit from neoprene rubber products include:
Cable jackets
Jacketing in lead press cured mining cables
Jacketing in heavy-duty cables
Additional Applications
 Conveyer belts
Neoprene industrial hose
Neoprene O rings
Neoprene Diaphragms
Grommets and vibration mounds