Course: Chemical Technology (Organic) Module VIII

Lecture 3
Polyvinyl Chloride,
Polycarbonate, Thermoset
Resin: Phenol Formaldehyde,
Urea Formaldehyde And
Melamine Formaldehyde

409

LECTURE 3
POLYVINYL CHLORIDE, POLYCARBONATE,
THERMOSET RESIN: PHENOL
FORMALDEHYDE, UREA FORMALDEHYDE
AND MELAMINEFORMALDEHYDE

POLYVINYL CHLORIDE
Polyvinyl chloride is second largest (after polyethylene) and most versatile of all thermoplastics.
Despite various environmental issues raised time to time PVC has enjoyed onstant growth in
demand because of its unique properties which include durability, ease of processing and cost
effectiveness [Chemistry & industry, June, 430, 1996]. PVC has been facing innumerable
challenges to its usage and growth. With use of suitable additives like stabilizer and plasticisers
can be made rigid or flexible for a variety of end uses and can be processed by all types of
processing methods [Venkatraghavan,1998].
It contains about 56.8percent chlorine and balance being hydrocarbon. A major portion of the
chlorine produced in the world is used in the manufacture of PVC. The potential for growth in
PVC consumption is enormous. With the addition of plasticizers, fillers, reinforcements,
lubricants and stabilizer, PVC may be formulated into flexible, rigid, elastomer or foamed
compound
Global production and consumption of Polyvinyl Chloride PVC in 2010 was approx. 34 million
metric tons. Global capacity utilization was 72percent in 2010 (SRI Consulting). Global per
capita consumption of PVC is shown in Figure M-VIII 3.1. It is one of the most widely used
thermoplastic polymers with a total world consumption of about 30 million tonnes. It contains
about 56.8percent chlorine and balance being hydrocarbon. A major portion of the chlorine
produced in the world is used in the manufacturing of PVC. Some of the Indian industries
manufacture PVC is given in Table M-VIII 3.1. Table M.VIII 3.2 gives the details of PVC
manufacturing technology used in India and the capacities of the industries.

PVC has
insulation
PVC Re
two grou
in pipe
insulation
sector (P
F
Sour
Table M
Compa
Relianc
Industri
Indian
Petroch
Corp. L
(IPCL)
Finolex
NOCIL
s outstandin
n properties,
esin End U
ups: rigid PV
fittings, con
n, sheets, ho
VC pipes) a
Figure M-V
rce: Indian V
M-VIII 3.1
any
ce
ies Ltd.
hemical
Ltd.
x
L
ng combinat
, recyclabilit
Uses: The m
VC applicatio
nduits, film
oses tubes, f
are major con
VIII 3.1: P
Vinyls Indust
1: Industri
Location
Hazira, Su
(Gujarat
Vadodar
Gandha
(Gujarat
Ratnagir
(Maharash
Thane
tion of dur
ty excellent l
major end u
ons and Flex
s, bottles e
footwear and
nsumer of PV
Per Capita
try: status &
ies Manuf
Year
start
urat
t)
199
ra
ar
t)
198
200
ri
htra)
199
196
410
rability, stab
long term w
uses applicati
xible PVC ap
etc. Flexible
d other uses
VC.
a Consump
& Business ou

facture PV
r of
up
Capac
y
(000
tonne
91 300
84
00
55
150
93 130
68 25
bility, flame
weather abilit
ions of PVC
applications.
e PVC find
s. Building,
ption PVC
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VC in Indi
cit
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Produ
n
(00
tonne
274.

196.
117.0
24
e retardancy
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C can be bro
Rigid PVC
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mical Weekly
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411

Table M-VIII 3.2: PVC India Technology & Capacities 1998-1999
Company Technology Location 1998
Capacity(MT)
DSCL CaC
2
AcetyleneVCM PVC Kota Rajasthan 36,000
Chemplast Molasses Alcohol C
2
H
4
EDC
VCM PVC Imp
EDCVCMPVC
Mettur, Tamil Nadu 40,000
DCW Imported VCMPVC Tuticorin, Tamil
Nadu
60,000
NOCIL Naptha C
2
H
4
EDC VCMPVC Bombay
Maharashtra
30,000
IPCL (Baroda) Cl
2
} Naptha C
2
H
4
EDC
HCl} VCM PVC
Baroda
Gujarat
55,000
IPCL
(Gandhar)
Imp.C
2
H
4
EDC VCM PVC
Captive Chlorine
Gandhar
Gujarat
150,000
Reliance Imp.C
2
H
4
EDC VCM PVC
Imp.EDC
Hazira
Gujarat
30,000
Finolex Imp.C
2
H
4
EDC VCM PVC
Imp.EDC
Ratnagiri
Maharashtra
150,000
Sources: Subramanian, S. Chlorine and PVC markets- what lies ahead Chemical industry news,
January, 1999. p.39

Process Technology for PVC
The basic monomer for manufacture of PVC is vinyl chloride which is made from either
acetylene or ethylene. However, ethylene is the chief source of vinyl chloride throughout world.
Various sources of ethylene are naphtha gas cracking, acetylene route and alcohol route. Figure
M-VIII 3.2 illustrates the process flow diagram of PVC manufacturing. Using a free radical
initiator, PVC can be made with any of four general methods of polymerisation suspension,
(Maharashtra)
Chemiplast Mettur
(Tamilnadu)
1967 60 58.0 Alcohol
DCW Tuticoran
(Tamil Nadu)
1972 60 45.0 Acetylene
DCM Shriram Kota
(Rajasthan)
1964 33 24.7 Acetylene
Total 813.00
412

emulsion, bulk and solution polymerises vinyl chloride monomer. However, bulk of PVC is
made by suspension polymerisation. Most resins produced by the suspension polymerisation are
in the range of 125 - 165 microns in diameter while those produced by bulk polymerisation
process are in the range of 1 micron diameter [http://www.geomembrane.com/
TechPapers/WhatISPVC.htm]. Suspension polymerization of PVC has significant advantages
such as low investment, large reactor technology, clean reactor wall technology, low personal
requirement, environmentally safe [Mehta, 1991]
Vinyl chloride is copolymerized with other monomers to improve quality of the resin. When
vinyl acetate is used as copolymer, polymer is more stable to light and heat than the
homopolymer of vinyl chloride. With vinylidene chloride has a higher melting point than
homopolymer and may be spun into a fibre [Hatch & Mater,1970]

POLYVINYL CHLORIDE

Figure M-VIII 3.2: Flow Diagram for Manufacturing of PVC

Suspension Polymerisation Process
Suspension polymerization of PVC manufacture involves dispersion of vinyl chloride monomer
in water along with a suspending agent polyvinyl chloride. Polymeristion is initiated by
activators at temperature around 40-70
o
C heat produced is continuously removed using heat
transfer medium. After the polymerization is completed the suspension is transferred to
413

degassing unit where unreacted monomer is removed, purified, condensed and recycled. Polymer
is from suspension is separated by centrifuging and dried by hot air.

POLYCARBONATES
Polycarbonates are thermoplastics and are the one of the fastest growing engineering plastics.
Global demand for polycarbonates exceeds 1.50 million tonnes. Global demand for
polycarbonate is expected to grow at an average annual rate of around 5.8percent over the next
five year, reaching around 4.4 million metric tons by the end of 2015. The history of
polycarbonate dates back to eighteenth century when Einhorn, a German chemist observed the
formation of an insoluble, infusible solid while endeavoring to prepare cyclic carbonates by
reacting hydroquinone with phosgene. In 1902, Bishoff and Hedenstrom obtained similar cross
linked, high molecular polycarbonate. In 1953, Bayer Laboratories produced linear thermoplastic
polycarbonate of high molecular weight. In 1957, Bayer and General Electrics announced
independent development of polycarbonate and in 1960 commercial production started
[http://www.bpf.co.uk/bpfindustry/plastic_materials_Polycarbonate_PC.cfm]. Polycarbonate are
transparent and are break resistance Polycarbonates are thermoplastics used in several
applications and have exceptional optical clarity, impact strength, flame resistance, low wrap
page, excellent electrical properties and dimensional stability, high heat distortion temperature,
lightness, durability.
Polycarbonate is produced by condensation polymerization of sodium salt of bisphenol and
phosgene in presence of organic solvent. The sodium chlorideformed during the process
isprecipitated and the solvent is recovered by distillation or evaporation.





THERMOSET RESINS
Thermoset resins are characterized by a high degree of cross-linking, resist deformation and
solution once their morphology is achieved and are usually prepared in molds that yield the
C
CH
3
CH
3
OH HO n. + n.COCl
2
C
CH
3
CH
3
HO OCO-
n
NaOH
Bisphenol-A Polycarbonate
414

desired shape. These polymers once formed cannot be reshaped by heat. Some of the important
thermoset resins are phenol formaldehyde, urea formaldehyde, melamine formaldehyde, epoxy
resin, poly urethane etc.

Phenol Formaldehyde Resins
Phenolic resin a production of condensation polymerization of phenols and formaldehyde is the
oldest condensation reaction and the product is the most important of the thermosets. Depending
upon the ratio of reactants (formaldehyde and phenol molar ratio) and catalyst type (acidic or
basic), polymer with different properties are formed. Two types of products are produced during
reaction of phenol and formaldehyde-Novalik Phenol formaldehyde and Resole Phenol
formaldehyde. Novalik resins are acid catalyzed polymer while Resole are base catalysed
polymers.
In Novalak process molten phenol and formaldehyde is polymerized in presence of acid catalyst
acid catalyst. A formaldehyde to phenol molar ratio of 0.75:1 to .85:1 is maintained. The
polymerization is completed in about 6-8 hr at 95
o
C. The volatiles and phenol are removed and
the polymer isrecovered and converted to desired form.

UREA AND MELAMINE FORMALDEHYDE RESIN
Urea formaldehyde resin is a non transparent resin and find application in adhesives, molded
objects, decorative laminates, textiles, paper, foundry sand molds. Because of its high reactivity
and good performance it is widely used as an adhesive for particle board and hard wood
plywood.
Urea formaldehyde is made by condensation reaction of urea and formaldehyde. The
condensation reaction of urea and formaldehyde takes place in several steps.
C
NH
2
NH
2
O C
H
H
O 3
C
NH
2
HN
O
CH
2
OH
C
HN
HN
O
CH
2
OH
CH
2
OH
2


415

MELAMINE FORMALDEHYDE RESIN

Melamine: Melamine is produced from Urea. When molten urea is heated to about 360-370oC
in presence of quartz sand, urea decomposes to isocynacic acid and ammonia. Further
isocyanicic acid is converted to melamine in the presence of alumina catalyst. Carbon dioxide
produced as by product.
N
C
N
C
N
C
NH
2
NH
2
H
2
N

Process steps involved are urea decomposition, melamine synthesis, melamine scrubbing,
filtration and drying, of gas treatment and ammonia recovery, ammonium carbonate liquor
treatment , mother liquor treatment, ,ammonia reliquification, bagging of product
Melamine formaldehyde resin is commonly used as kitchen ware, a melamine formaldehyde
resin has low water absorption and better chemical and heat resistance than urea resins. However
major application is as bonding and adhesive components.
Melamine is heterocyclic aromatic condensation of urea. Melamine reacts with urea to form
melamine resin. Melamine reacts with formaldehyde through a nuceophilic addition to give
methylaoamine

C
NH
2
HN
O
CH
2
OH
2n
H
H
N C
O
H
N
H
2
C
H
N C
O
H
N
H
2
C n
n-1 H
2
O

EPOXY RESIN
Epoxies are broad class of reactive monomers and resins containing epoxy functionality. Crude
epoxies have good chemical and corrosion resistance, high adhesion to a variety of substrates
416

and low shrinkage during occurring [Knapczyk and Simon]. Coatings and laminating binders are
the largest users of epoxies.
Epoxy resin are made by the reaction between diphenol and epichlorohydrin. Most commonly
used epoxy resin is made by reaction of bisphenol and epichlorohydrin. Epoxy resin find
extensive application in coatings, adhesives and composite materials. Epoxy resin may be
classified into DGEBA resin (Bis A resins), DGEBF resins (Bis-F resin), Epoxy novolac,
Brominated epoxy resins, linear aliphatic resin, cycloaliphatic resins cycloaliphatic resins,
multifunctional resins [Monterio, 1999]. Amongst the various epoxy resins, most widely epoxies
are those derived from bisphenol and epichlrohydrin [Marathe,M.N. Epoxy resin Chemical
engineering world Vol 24, No4 p.27].
Process Technology
Epichlorohydrin is first fed to the Polymerisation reactor in large excess to facilitate the
formation of DGEB. Then bisphenol-A is added and dissolved followed by addition ofstrong
caustic soda at controlled rate and with heating to start reaction. As the reaction proceeds, a
mixture of water and epichlorohydrin distills and is condensed. The water is removed from the
separator and epichlorohydrin is refluxed back to maintain its excess molar ratio. After the
completion of reaction, the contents are drained out and the salt is removed by filtration. The
filtrate is gain charged to reactor to recover excess epichlorohydrin by vacuum distillation.
Raw material requirement per tone of epoxy resin is
Bisphenol-A0.72
Epichlohydrin0.72
Caustic soda (100%basis) 0.28

REFERENCE
1. Chemistry & industry, June, 430,1996
2. Hatch, L.F., Matar, S., From hydrocarbon to petrochemicals Part 16-thermoplastics,
Hydrocarbon, Processing, Vol.58, Sep 1979, p.175 & 141.
3. http://www.bpf.co.uk/bpfindustry/plastic_materials_Polycarbonate_PC.cfm
417

4. http://www.geomembrane.com/ TechPapers/WhatISPVC.htm
5. Knapczyk, J.K. Simon, R.H.M., Synthetic resins and plastics Chapter 19, Riegels
Handbook of Industrial chemistry.
6. Marathe,M.N. Epoxy resin Chemical engineering world Vol 24, No4 p.27
7. Mehta,P.V. Polyvinyl chloride: manufacture applications & markets Chemical
engineering world, Vol 26, No.12, Dec 1991p. 131
8. Monterio, H. A., Epoxy, polyester and vinyl ester resins- market trends and new
developments, Chemical weekly, May 25,199.p.161
9. Venkatraghavan, S. Implications for the PVC business Chemical weekly, March 23,1998,
p.145