Poly Acrylonitrile Fiber

POLY-ACRYLONITRILE FIBER
ACRYLIC Fibers
INTRODUTION
 Acrylic fibers had replaced wool in many major applications.

 Majority of knitting yarns now available in market are made of
Acrylic fibers.
 Pullovers, sweaters, socks, blankets and carpets all are made of
Acrylic fibers because of their high elasticity, colour brilliancy,
voluminosity, ease of washing, resistance to pilling, good light and
colour fastness.
 Acrylonitrile (vinyl cyanide) is the major vinyl monomer used for
synthetic fiber production, as other vinyl monomers lacks cohesive
forces between the molecular chains of their
polymers and therefore cannot compete with
acrylonitrile for fiberous applications.
The term “Acrylic fibers” refers to fiber containing atleast 85% of

acrylonitrile monomer, while in moda-acrylics the percentage of
acrylonitrile must be <85% and >35%.
• Homopolymers of polyacrylonitrile have been used as fibers in hot
gas filtration systems, outdoor awnings, sails for yachts, and fiber-
reinforced concrete.
• Copolymers containing polyacrylonitrile are often used as fibers to
make knitted clothing like socks and sweaters, as well as outdoor
products like tents and similar items.
• If the label of a piece of clothing says "acrylic", then it is made out
of some copolymer of polyacrylonitrile.
• It was made into spun fiber at DuPont in 1941 and marketed under
the name of Orlon.
POLYMER MANUFACTURING
All acrylic fibers are made from 90%-94% ACRYLONITRILE combined with
atleast one or two comonomers.
 Polyacrylonitrile (PAN):-Polyacrylonitrile (PAN) is a synthetic, semi-

crystalline organic polymer resin, with the linear formula (C3H3N)n. Though
it is thermoplastic, it does not melt under normal conditions. It degrades
before melting. For this co-monomers are added.
 For fiber manufacturing, polymer with specific composition, controlled
molecular weight and some dye sites is needed. For this some co-
monomers are added.
 Acrylic fibers are spun from acrylonitrile polymers containing 5-10% of co-
monomer. AN copolymer are much more soluble in common organic
solvents in comparison with Pure-PAN and make the preparation and
storage of the spinning dope much easier.
Comonomers Used
Are of 2 categories
Neutral Co-monomers Ionic Co-monomers
They enhances the solubility of They provides additional sulphonate

polymer in spinning solvents, and sulphate dye sites and
modify fiber morphology and differential water sensitivity
improves dye diffusion rate inside between the elements in bi-
the fiber. component fibers.
Methyl Acrylate (MA) Sodium styrene sulphonate (SSS)

Methyl Methacrylate (MMA) Sodium methallyl sulphonate (SMS)
Vinyl acetate (VA) Sodium allyl sulphonate
METHODS OF POLYMERIZATION
1. Solution Polymerization
Commercially Used
2. Suspension polymerization
3. Emulsion polymerization
1. Solution Polymerization
SOLVENT Used
• Di-methyl formamide (DMF) Very high chain transfer

constant
• Di-methyl acetamide (DMAc)
• Di-methyl sulphoxide (DMSO) Low chain transfer

constant
• Zinc Chloride (ZNCl)
• Sodium thiocyanate (NaSCN)
Co-monomers Used
Methyl Acrylate (MA) Least Active chain transfer

Vinyl Acetate (VA) Active chain transfer
Polymerization solution
• DMF 70.5 parts

• Acetone 20 parts
• Acrylonitrile 24 parts
• Methyl acrylate 1.6 parts
• AIBN 0.5 parts (Thermally active initiators)
Above mixture is heated to 60 ˚C for 20 hrs. The polymer yield is only 20%
Suspension Polymerization
• Most commonly used commercial process :- Free Radical
POLYMERIZATION
Redox initiation is normally used in commercial production of polymers for

acrylic fibers. This type of initiator can generate free radicals in an aqueous
medium efficiently at relatively low temperatures.
For generation of radical, redox system consisting of ammonium/potassium

persulphate (Oxidizer), sodium bisulphite (reducing agent) and ferrric/ferrous
ion as catalyst is used.
Initiation persulphate
bisulphite
This redox system works at pH 2.0–3.5 where the bisulfite ion predominates
and the ferric ion is soluble.
The sulfate- and sulfonate ion-radicals react with monomer to initiate rapid
chain growth.
Initiation
Sulfonate ion Sulfate ion Acrylo nitrile
Propagation
The AN monomer keeps on adding to the radical site of the growing chain, and
the radical keeps on shifting to the newly attached monomer. In this way the
polymer molecular weight keeps on increasing.
Termination reaction may occur by the following mechanisms;
(A) By radical re-combination
A* + B* A-B
(B) By chain transfer through reagents
A* + X-Y A-X + Y*
Commercial Process:
Continuous Aqueous Dispersion Process
1) A monomer mixture composed of acrylonitrile and up to 10% of a neutral
comonomer, such as methyl acrylate or vinyl acetate, is fed continuously.
2) Polymerization is initiated by feeding aqueous solutions of potassium

persulfate (oxidizer), sulfur dioxide (reducing agent), ferrous iron
(promoter), and sodium bicarbonate (buffering agent).
3) The aqueous and monomer feed streams are fed at rates that give a
reactor dwell time of 40–120 min and a feed ratio of water to monomer in
the range from 2 to 5.
4) The reactor overflow, an aqueous slurry of polymer particles, is mixed with

EDTA (Ethylene diamine tetra acetic acid) acting as a chain stopper or the pH
is raised to stop the polymerization.
5) The slurry is then fed to the top section of a baffled monomer-separation
column. The separation of unreacted monomer is effected by contacting the
slurry with a countercurrent flow of steam introduced at the bottom of the
column.
6) Monomer plus water is condensed from the overheads stream and the
monomer separated using a decanter, the water phase being returned to the
column.
7) The stripped slurry is taken from the column bottoms stream and the
polymer separated using a continuous vacuum filter.
8) After filtration and washing, the polymer is pelletized, dried, ground, and
then stored for later spinning.
DRY/WET SPINNING PROCESS
• Acrylic fibers cannot be melt spun because the polymer degrades when
heated near to its melting point. Therefore acrylic fibers are produced by
solution(dry/wet) spinning process.
• However with development in polymer science, it is now possible to melt

spun PAN polymer by adding some plasticizers.
Ex: Addition of PEG (Poly ethylene glycol) reduces the Tm of PAN

WET SPINNING PROCESS
SOLVENT Polymer conc. (wt

%)
DRY-SPUN (DMF, DMAc, DMSO) 25-32
WET-SPUN (DMF, DMAc, DMSO) 20-28%
NaSCN (45-55% in water) 10-15
ZnCl2 (55-65%) 8-12
HNO3 (65-75%) 8-12
PAN homopolymer is rarely used for fiber spinning and virtually all
commercial acrylic fibers are spun from acrylonitrile polymers containing 5-
10% of co-monomer. AN copolymer are much more soluble in comparison
with PAN and make the preparation and storage of the spinning dope much
easier.
DRY SPINNING PROCESS
• During dry spinning, PAN dope of 30-32 wt% concentration having
temperature at about 120-125 ˚C is extruded through spinnerette in a
vertical column of about 5-6 m height in which preheated inert gas at 300-
400 ˚C is circulated.
• The filaments are continuously removed from bottom of the column,

washed free of solvent and then processed like wet-spun fibers.
• ORLON is the trademark of DuPont’s dry spun acrylic fibers.

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POLY-ACRYLONITRILE FIBER

 Acrylic fibers had replaced wool in many major applications.

The term “Acrylic fibers” refers to fiber containing atleast 85% of

 Polyacrylonitrile (PAN):-Polyacrylonitrile (PAN) is a synthetic, semi-

Neutral Co-monomers Ionic Co-monomers

They enhances the solubility of They provides additional sulphonate

Methyl Acrylate (MA) Sodium styrene sulphonate (SSS)

• Di-methyl formamide (DMF) Very high chain transfer

• Di-methyl sulphoxide (DMSO) Low chain transfer

• Sodium thiocyanate (NaSCN)

Methyl Acrylate (MA) Least Active chain transfer

• DMF 70.5 parts

Redox initiation is normally used in commercial production of polymers for

For generation of radical, redox system consisting of ammonium/potassium

Sulfonate ion Sulfate ion Acrylo nitrile

(A) By radical re-combination

(B) By chain transfer through reagents

2) Polymerization is initiated by feeding aqueous solutions of potassium

4) The reactor overflow, an aqueous slurry of polymer particles, is mixed with

• However with development in polymer science, it is now possible to melt

Ex: Addition of PEG (Poly ethylene glycol) reduces the Tm of PAN

SOLVENT Polymer conc. (wt

• The filaments are continuously removed from bottom of the column,

• ORLON is the trademark of DuPont’s dry spun acrylic fibers.

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