Course: Chemical Technology (Organic) Module VIII

Lecture 1
Introduction to Polymer,
Elastomer and Synthetic
Fibre, Polymerisation



380

LECTURE 1

INTRODUCTION TO POLYMER, ELASTOMER
AND SYNTHETIC FIBRE, POLYMERISATION
Polymers were accidentally synthesized, however as more and more applications were
later discovered. Polymers have penetrated into all fields of application and in volume of around
205 million tonnes per annum including standard polymers, engineering resins, elastomers,
duromers, fibers and textiles, dispersions. Polyolefins (LDPE, LLDPE, HDPE and
polypropylene) are by far the largest group of thermoplastic polymers [CMAI 2003].
Polypropylene resins along with polyester resins (PET), are one of the fastest-growing categories
of commodity thermoplastic resins in the world. The United States and China now represent
more than 15% and 22%, respectively, of world polypropylene consumption. Polymers have
penetrated into all fields of application and in volume of around 205 million tonnes per annum
including standard polymers, engineering resins, elastomers, duromers, fibers and textiles,
dispersions. Amongst the plastics, thermoplastic market represents approximately 10 percent of
global chemical industry. World polymer demand in 2010 was 280 million tones. Type of
polymer and there global demand is shown in Figure M-VIII 1.1. Typical consumption of plastic
by industry and as polymer is shown in Figure M-VIII 1.2.
Polyolefins are by far the largest group of thermoplastic polymers. As per CMAI 2003,
polyolefins (LDPE, LLDPE, HDPE and polypropylene) represent the largest segment of the
global thermoplastics business at approximately 88 million tonnes (about 62percent of the total
market in 2002). Major success factors for polyolefins are: easy accessible, reasonable raw
materials (oil & natural gas based), low production cost by modern energy saving and non
polluting processes, resources saving products, environmentally harmless products, energetically
exploitable products after usage, broad product portfolio, and tailor made products. Various type
of polymer and their use is illustrated in Figure M-VIII 1.3.
Polyvinyl Chloride (PVC) is the second largest commodity thermoplastic in the world, after the
polyethylenes. According to global production and consumption of polyvinyl chloride (PVC) in
2010 was approx. 34 million metric tons. Global consumption of polyethylene in 2009 was
approximately 64 million metric tons. Global capacity utilization was 80% in 2009, down from
381

82% in 2008. Average global utilization of polyethylene rates are expected remain under 80%
during the next five years, gradually increasing to the high-80s by 2019. World polyethylene per
capita consumption is targeted to grow from 9.0 kg - 11.0 kg from 2001-06. High density PE
(HDPE) accounted for around 45% of global polyethylene consumption in 2009, followed by
linear low density PE (LLDPE) and low density PE (LDPE). Figure M-VIII 1.4 show the use of
plastic in different fields.


Figure M-VIII 1.1: World Total Polymer Demand in 2010 approx: 280 million
tones
Courtesy: CAMI Consulting, 2010
ABS, 2%
EPS, 1%
Other, 10%
HDPE, 13
%
PP, 19%
PVC, 19%
LDPE, 24
%
PS, 6%
PET, 6%
Agriculture,
7%
Transport,
8%
Houseware,
8%
Eectrical
sector, 8%
Building
and
constructio
n, 23%
Packaging,
37%

Figure M-VIII 1.2: Plastic Consumption, according to Industry and Polymer
Source: Ways to get rid of the plastic, Chemical News, October 2011, Page No 21
382

Figure M-VIII 1.3: Various Types of Polymer and their Application
Source: Mall, 2007
383

Others, 3%
Agriculture, 7%
Transport, 8%
Furniture/House
wares, 8%
Electrical and
Electronics, 8%
Building and
Construction, 23
%
Packaging, 35%
Footware, 1%
Medical, 2%
Mechanical
Engineering, 2%
Toys /Sports, 3%

Figure M-VIII 1.4: Uses of Plastic
Source: Envis, Volume 5, Issue 2, Apr.-J un. 2007, Page No.15

Global demand for polymers is estimate to increase at 5% per annum to reach 227 MMT by
2015. Polymer demand in India is expected to grow at 13-14% p.a. and will account for 9% of
global polymer demand by 2015. The total polymer demand in India by 2015 is estimated to be
around 22 MMT. Table M-VIII 1.1 gives the detail of India share in global polymer demand

Table M-VIII 1.1: Indias share in The Global Polymer Demand by 2015
2004 2015
India 4% 9%
Rest of world 96% 91%
Source: Dept of Chemicals& petrochemicals, GOI, IMaCS Analysis

PLASTIC INDUSTRY IN INDIA
Consumption 4.8 million tons/annum
Over 96% (4.6 million tons) is accounted for commodity plastics
Per capita consumption, 4.8 Kg as against world average 20 Kg.
Projected demand in 2010-11- 8.5 million tons (Growth rate @ 15%).
Raw material prices are influenced by international demand and supply of crude oil.
384

CLASSIOFIACTION OF POLYMER: Natural and synthetic polymers could be

classified in several other ways, viz., organic and inorganic; on the basis of physical properties as
plastomers (plastics), elastomers (elastic) and fibrous (fiber); on the basis of response to
temperature as thermoplastics and thermosets. Various ways of classification of polymer is given
in Figure M-VIII 1.4 [Mall 2007]: Polymers or resins are generally classified in two broad
categoriesThermoplastic and Thermosetting. Repeated heating and cooling doesn't alter the
chemical nature of thermoplastic while Thermosets are permanent setting resin and once
solidified these materials may not be reshaped or formed by applying heat. Thermoset plastic are
stronger than thermoplastic.[Mall,2007]

THERMOPLASTICS PLASTICS: Thermoplastics are organic chain polymers that

usually become soft when heated and can be molded under pressure. Thermoplastic resin are
linear or branched chain polymers with little or no cross linking [Hatch & Mater 1979]. Major
thermoplastic demand in world is shown in Figure M-VIII 1.5. Various thermoplastic resins are
polyethylene, polypropylene, PVC, polyvinyl acetate, poly methylmethaacrylate, poly
carbonates, polystyrene [Table M-VIII 1.2]

Figure M-VIII 1.5: Breakup- World Major Thermoplastics Demand
Estimates-2007(183 Million MT)
Source:Technical EIA Guidance Manual, Project Sponsored by the Ministry of Environment and Forests

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Table M-VIII 1.2: Major Thermoplastic polymers

Name Abbreviation Family Formula Melting
temp.
Density
Low density polyethylene LDPE Polyolefin

110 (Tm) 0.910
High density
polyethylene
HDPE Polyolefin

120 (Tm) 0.950
Polypropylene PP Polyolefin

175 (Tm) 0.902
Polyvinyl chloride PVC Vinyl

100 (Tg) 1.35
Polyvinyl acetate PVA Vinyl


Polystyrene PS Styrenic

100 (Tg) 1.05
Acrylonitrilebutadiene
styrene
ABS Styrenic
------- ---- ---
Acrylonitrile styrene SAN Styrenic ------- ---- ---
Polymethylmethacrylate Acrylic


Polyhexamethylenediami
de
Nylon 66 Polyamide

265(Tm) 1.14
Polycaprolactum Nylon 6 Polyamide

225(Tm) 1.14
Polyethyleneterephthalate PET Polyester

270(Tm)
Polybutyleneterephthalate PBT Polyester

250(Tm) 1.3
387

Polycarbonates PC Polyester

190 (Tg) 1.2
Polyacetals Polyethers

181(Tm)
Source: Hatch & Matar,1979
THERMOSETTING RESINS: Thermosetting Resins are a network of long chain
molecules that are cross-linked which gives the polymer a three dimensional, infusible structure.
They poloymerise irreversibly, under heat or pressure to form hard, rigid mass. Various
thermoset resins are Phenol-, urea-, melamine- formaldehydes, polyurethane, alkyd resins, epoxy
resins etc. Various Thermo set resins are given in Table M-VIII 1.3.
Table M-VIII 1.3: Various Thermo Set Resins
S.
No
Name Family Formula
1. Polyurethane Ester-
amide
C
O
C
O
NH NH R O O R
`
2. Alkyd resins Polyester

3. Unsaturated
polyesters
Polyester
C
O
C
O
CH CH O OCH
2
CH
2
OCH
2
CH
2
4. Epoxy resins Polyether
CH
OH
CH
2
CH
2
O O R



5. Phenol
formaldehyde
Phenolic

6. Urea
formaldehyde
Urea

388

7. Melamine
formaldehyde
Melamine

Source: Hatch & Matar, 1980

ELASTOMER
Rubber can be broadly classified as natural rubber and synthetic rubber. Natural rubber is a
product of the tree Heveabrasiliensis while synthetic rubber is elastomer derived from
petrochemical feedstock product. Table M-VIII 1.4 shows the general and special purpose of
rubber.
Table M-VIII 1.4: General Purpose and Special Purpose Rubber
General Purpose Rubber Special Purpose
Styrene butadiene rubber (SBR)
Styrene butadiene Emulsion/Solution
Polybutadiene (BR)
Polyisoprene (PS)
Ethylene propylene (EP) and
Ethylene propylene diene (EPDM)
Butyl rubber (BR)
Ethylene vinyl acetate (EVA)
Polychloroprene(CR)
Styrene isoprene rubber(SIR)
Acrylonitrile Butadiene(NBR)
Silicone rubbers
Acrylic rubber
Polyester urethanes
Polyether urethane elastomer Epichlorohydrin
Poly isobutylene
Polydialkyl siloxane (Silicon Rubber)
Vinyl Pyridine butadiene rubber (PBR)
Hypalon
Polysulphide rubber
Fluorocarbon rubber
389

SYNTHETIC FIBRE
First manmade fiber natural occurring polymers from cellulose and protein Viscose
rayon first manufactured in 1986 in England
First true synthetic in 1935 Nylon by DuPont
Nylon was followed by acrylic and mod acrylic fiber based on Acrylonitrile in 1950.
Polyester Fiber in 1953 in India
Viscose rayon in India started in 1950
Acetate rayon in 1954 in India
World consumption of non-woven man-made fibre is mention in Table M-VIII 1.5.
Rayon Grade Pulp : Harihar Polyfibre, Gwalior Rayon, Travancore Rayon, Baroda Rayon,
Andhra Rayon, Shri Ram Rayon, Kesoram Rayon, South India Viscose Rayon
Caprolactam: Gujarat state fertilizer and chemicals vadodara, Fertilizer and chemicals travancore
DMT /PTA: Bombay Dying, BRPL, Reliance (Patal Ganga, Hazira, Vadodara), IOC Panipat
p-Xylene: BRPCL, Reliance (Patal Ganga, Hazira, Vadodara, J amnagar), Indian oil Corporation
Projected Consumption of Fiber in India
Table M-VIII 1.5: World Consumption of Non woven Man-made Fibers (% of
total)
Man-made Fibers 1998 2000 2005 2007
Polyester 24 22.5 23.0 23
Polyamides 1.5 1.5 1.5 1.5
Acrylic fibers 1.5 2.0 3.0 3.0
Polypropylene fibers 62.0 63.0 62.7 62.7
Viscose rayon 8.0 8.0 7.0 7.0
Other synthetic fibers 3.0 3.0 2.8 2.8
Total consumption, million
tonnes
2.4 3.3 2.5 4.0

RAW MATERIALS FOR MANMADE FIBRE
390

[Technical EIA Guidance Manual Project Sponsored by the Ministry of Environment and
Forests]
Synethetic fibre polymer production needs extremely pure raw materials and chemicals.
The most important chemicals are monomers, catalysts, and solvents.
The most common monomers dealing with large volume organic chemicals are as
follows:
Ethylene, propylene, butadiene, isoprene, styrene
Vinyl chloride, vinyl esters, vinyl ethers, chloroprene
Acrylic and methaacrylic esters, vinyl ethers, chloroprene
Adipic acid, hexamethylenediamine, caprolactam
Terephthalic acid, ethylene glycol
Formaldehyde
Aromatics, like phenol, cresol, bisphenol A
Maleic anhydride, etc
Catalysts are chemicals used to speed up or initiate the polymerization reaction. Common
catalysts include Zieger catalysts (titanium chloride and aluminium alkyl compounds),
chromium-containing compounds, and organic peroxides.
Solvents are sometimes used to dissolve or dilute the monomer or reactants. The use of
solvents facilitates polymer transport through the plant, increases heat dissipation in the
reactor, and promotes uniform mixing in the reactor
Details of man made fibre is shown in Figure M-VIII 1.6.
Some terms used in synthetic fibre industry
Denier: denier is the measure of coarseness of a yarn and is defined as the weight in grams of a
length 9000meter of a yarn or filament.
Tex and Millitex: Tex is the defined as the weight in grams of 1000 meter
Tenacity: The tenacity or strength of rayon is expressed as grams per denier. IF a load of 250
gms will just break at a denier yarn, the tenacity is said to be 2.5 gms per denier.
Elongation at break: Elongation is a important properties of a yarn. If a length of 100cm of a
yarn can be stretched 112 cm before breaks, it is said to have elongation at break of 12%
Moisture regain: Regain is of a fibre is the percentage of moisture calculated on oven dry basis.
391

Staple: The choped fibre is called staple .

Filament yarn: Reeled filaments yarn
Elasticity: The elasticity of a fibre is its ability to recover from strain.

Figure M-VIII 1.6: Manmade Fibre and Raw Material
OVERVIEW OF INDIAN MAN-MADE TEXTILE INDUSTRY
Second Largest producer of cellulosic fibre/yarn
Fifth largest producer of synthetic fibres/yarns.
Production of synthetic fibres nearly 10 lakh MT (2009-10)
392

Production of Synthetic yarn about 15 lakh MT (2009-10)

INDIAN: FIBRE DEMAND
Current All fibre demand is arround 80 lakh MT
Cotton 43 lakh MT and polyester around 30 lakh MT
All fibre demand to grow nearly 130 lakh MT by 2020 @ 5% CAGR
PFY has grown at around 10% CAGR in last decade and is likely to sustain similar
growth rates
INDIAN: TEXTILE GROWTH DRIVERS
Figure M-VIII 1.7 shows emerging trends of man made textiles
Higher disposable income and changing life style
Increasing fashion awareness even in tier B, C cities
New emerging segment of non-apparel application
Increasing urban households and working women population
Rapid spread of organised retail sector
Rise in exports to traditional and new markets
Favourable govt policies like TUFS, SITP (textile Parks)
Table M-VIII 1.6 give the details of demands of man-made fibre in India. Brief details of various
synthetic fibre producing units in India is given is Table M-VIII 1.7. Table M-VIII 1.8 gives the
details of rising demand of polyester. Per-capita consumption of cotton and manmade fibre is
mention in Table M-VIII 1.9.



Figure M-VIII 1.7: Emerging Trends in Man-made Textiles
393

Source: Rakesh Mehra, Emerging trends in Man-Made Textiles, the Synthetic & Rayon Textiles Export
Promotion Council (SRTEPC), 5
th
Texcon Asian textile Conference

Table M-VIII 1.6: India: Man Made Fibre Demand
KT 2000 2005 2010 2015 2020 CAGR
2010/2000
CAGR
2020/2010
Polyester 1381 1672 2844 4591 5513 7% 7%
Nylon 86 117 111 118 107 3% 0%
Viscose 284 271 309 334 293 1% -1%
Acrylic 111 110 96 121 110 -1% 1%
Polypropylene 42 54 64 80 76 4% 2%
Total MMF 1904 2224 3424 5244 6099 6% 6%
All Fibres 4948 5735 7826 10871 12984 5% 5%
Source: PCI
Table M-VIII 1.7: Various synthetic fibre producing units in India
Sl.No Name and Location of Industrial Unit Product
1 J .K.Synthetics, Rajasthan NFY, PFY, NTC,
PSF, ASF
2 Garware Nylon, Pune NFY, PFY
3 Nirlon Synthetic Fibers and Chemicals NFY, PFY, NTC
4 Modipon, Modi Nagar, Uttar Pradesh NFY, PFY
5 Century Enka, Pune, NFY, PFY
6 Baroda Rayon Corporation NFY, PFY, VFY,
NTC
7 Shree Synthetics, Madhya Pradesh NFY, PFY
8 Stretch Fibers NFY
9 Petrofils Cooperative PFY
10 Chemicals and Fibers, Thane PSF
11 Ahmedabad Manufacturing and Calico Printing Company PSF
12 Swadeshi Polytex , Uttar Pradesh PSF
13 Indian Organic chemicals, Manali, Tamil Nadu PSF
14 Bongaigaon Refinery and Petrochemicals PSF
15 Reliance industries [formally Indian Petrochemicals
Corporation, Koyali, Baroda, Gujarat]
ASF
16 Neomar Ltd., PPSF
17 Shriram Fibers, Manali, Tamil Nadu NTC
18 National rayon Corporation, Kalyan, NTC, VTC, VFY
19 Travancore rayon, Rayanopuram, Kerala VFY
20 Century Rayon, Kalyan, VFY, VTC
21 J .K.Rayon,, Uttar Pradesh VFY
394

22 Kesoram Rayon, Triveni, west VFY

23 South Indian Vescose, Tamil Nadu VFY, VSF, PNSF
24 Indian Rayon Corporation, Veraval VFY
25 Sirsilk Ltd, Kaghaznagar, Andhra Pradesh AFY, ATSF
26 Rayon, Nagda, Madhya Pradesh VSF
27 Rayon, Mavoor, Kerala VSF
28 Shriram Rayon, Rajasthan VTC
29 Harihar Poly Fibers, Harihar, Karnataka PNSF
SOURCE: Technical EIA Guidance Manual Project Sponsored by the Ministry of Environment and
Forests

Table M-VIII 1.8: Rising Demand: Domination of Polyester
Year Kg per Capital Mkt share (%)
Cotton Polyester
1960 3.3 0.0 67
1970 3.3 0.5 55
1980 3.2 1.2 48
1990 3.5 1.6 47
2000 3.3 3.2 37
2010 3.6 5.2 33

Table M-VIII 1.9: Percapita Consumption of Cotton and Manmade Fibre
Year Cotton Kg, per capita Man-made fiber kg, per
capita
2005
2010
2015
2020
1.85
1.65
1.51
1.52
2.4
2.75
3.3
3.6

REFERENCE
1. Hatch, L.F., Matar, S., From hydrocarbon to petrochemicals Part 16-thermoplastics,
Hydrocarbon, Processing, Vol.58, Sep 1979, p.175 & 141.
2. Mall, I.D. Petrochemical Process Technology, First edition, Macmillan, New Delhi, India,
2007
3. CMAI Consulting, 2010
4. CMAI, 2003.
5. Ways to get rid of the plastic Chemical News, October 2011, Page No 21
6. Dept. of Chemicals& Petrochemicals, GOI, IMACS Analysis
395

7. Rakesh Mehra, Emerging trends in Man-Made Textiles, the Synthetic & Rayon Textiles
Export Promotion Council (SRTEPC), 5
th
texcon Asian textile Conference
8. Technical EIA Guidance Manual Project Sponsored by the Ministry of Environment and
Forests