CHAPTER 1

Introduction
W. V. TITOW

1.1 PVC: GENERAL TERMINOLOGY AND RELEVANT

DEFINITIONS

The letters 'PVC' stand for 'polyvinyl chloride'. Thus the abbreviation,
like the full name, should-strictly speaking-specifically denote a
homopolymer of vinyl chloride. However, both terms-and in
particular the abbreviation-have acquired a different, wider meaning
in common usage: to the processor and user, as well as the
technologist, 'PVC' is any material or product made of a PVC
composition, i.e. of an intimate mixture of a vinyl chloride polymer or
copolymer with various additives, some of which (e.g. plasticisers in a
flexible PVC composition) may be present in very substantial,
occasionally predominant, proportion. It is usual to refer to the
polymer constituent of such compositions as PVC resin or PVC
polymer. The terms 'compound' and 'formulation' are also sometimes
used as if they were synonymous with 'composition', although the
purist may claim, with some justification, that 'formulation' is the
make-up of a composition (e.g. as recorded on paper), and that the
word 'compound' should be reserved for those PVC compositions
which are produced by melt compounding (in contradistinction to, say,
dry blends or plastisols-see Chapters 13 and 21, respectively).
Some of the additives which the formulator includes in a PVC
composition are heat stabilisers, necessary in all cases to counteract the
inherent thermal instability of PVC resins (especially at the high
processing temperatures); others also function as aids in processing
(e.g. certain polymeric modifiers, lubricants), whilst still others (e.g.
1

W. V. Titow, PVC Technology

© Elsevier Applied Science Publishers Ltd 1984
2 W. V. Titow

plasticisers, fillers) modify the material properties to provide the wide

applicational versatility that makes PVC so important among the major
thermoplastics. In terms of the extent of their effect on the material
properties of PVC, plasticisers are the most important group of
additives. PVC compositions incorporating plasticisers (and the
materials and products made from such compositions) are known as
plasticised PVC (sometimes abbreviated to pPVC*); flexible PVC and
soft pvc contain plasticisers in quantities high enough to impart these
properties to the material. PVC compositions and products which do
not incorporate plasticisers are commonly called unplasticised PVC
(uPVC*) or sometimes rigid PVC, although the latter term properly
extends also to PVC materials which may contain some plasticisers but
in a proportion not sufficient to lower the modulus appreciably.
Plasticised materials whose plasticiser contents-whilst generally
low-do reduce the modulus (and usually the strength and hardness) in
comparison with uPVC (but only to values still higher than those
normal for flexible or soft PVC) are sometimes referred to as
semi-rigid PVc.
The term 'vinyl' is also used, as an adjective or noun, in the place of
'PVC' (e.g. in such expressions as 'processing of vinyls', 'vinyl
composition', 'vinyl material', 'vinyl upholstery', 'vinyl foam'), espe-
cially-and most commonly-where the material concerned is a
flexible or soft PVC. This terminology is quite common, and thus
sanctioned by usage, but it is worth bearing in mind that it tallies
neither with standard definitions in the PVC field nor with systematic
chemical nomenclature. Thus the current international standard
definition of vinyl resin (ISO 472-1979(E» is a resin made by
polymerisation of monomers containing the vinyl group, and hence
includes, for example, polystyrene (which is polyvinylbenzene),
polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride and polyvinyl
pyrrolidone, along with polyvinyl chloride and all the other polymers
of compounds whose main structural component is the vinyl grouping
CH z = CH-. Whilst the definition is sound and properly based on the
relevant chemical structure, no polymer technologist would refer to,
say, expanded polystyrene as 'vinyl foam': in the common parlance of
* These designations (with a space after the first, lower case letter) are
prescribed by two international standards: ISO 2898/1 and ISO 1163/1 (but
current revision proposals include changes from u PVC and p PVC to PVC-U
and PVC-P). The letters iPVC are sometimes used to designate a high-impact
compound.
 i introduction 3

the plastics industry the term 'vinyl' is firmly associated with PVC, in
the way just mentioned.
A few other relevant standard definitions may be noted in passing.

Vinyl chloride plastic: 'A plastic based on polymers of vinyl chloride

or copolymers of vinyl chloride with other monomers, the vinyl chloride
being in the greatest amount by mass'. (ISO 472-1979).

Rigid PVC compounds: 'Rigid plastic compounds composed of

poly(vinyl chloride), chlorinated poly(vinyl chloride), or vinyl chloride
copolymers, and the necessary compounding ingredients. The resin
portion of copolymer compounds shall contain at least 80 percent vinyl
chloride. The compounding ingredients may consist of lubricants,
stabilizers, non-poly(vinyl chloride) resin modifiers, and pigments,
essential for processing, property control and colouring.' (ASTM
D 1784-81).

Unplasticised compounds of polymers of vinyl chloride: 'Compounds

based on homopolymers of vinyl chloride, or copolymers with at least
50% of vinyl chloride, or chlorinated poly(vinyl chloride), or mixtures
of such polymers with each other or with other polymers, the principal
ingredient being a polymer of vinyl chloride. These compounds may
also contain fillers, colorants, and such small quantities of other
ingredients as are necessary to facilitate fabrication, such as stabilizers
and lubricants.' (ISO 1163/1-1980(E)).

Non-rigid vinyl chloride polymer and copolymer moulding and

extrusion compounds: Compounds based on '... nonrigid vinyl
chloride polymer and copolymer classes in which the resin portion of
the composition contains at least 90% vinyl chloride. The remaining
10% may include one or more monomers copolymerized with vinyl
chloride or consist of other resins mechanically blended with polyvinyl
chloride or copolymers thereof. These nonrigid vinyl compounds are
defined by a hardness range and include the necessary stabilizers,
plasticizers, fillers, dyes, and pigments to meet the designated
requirements'. (ASTM D 2287-81).

Flexible PVC compounds: 'Compounds ... manufactured from poly-

vinyl chloride or from a copolymer of vinyl chloride of which the major
constituent is vinyl chloride, or from both. Such materials shall be
4 W. V. Titow

suitably compounded with plasticisers and other ingredients.' (BS

2571: 1963).

Plasticised compounds of polymers of vinyl chloride* (pPVC):

'Compounds based on homopolymers of vinyl chloride or copolymers
with at least 50% of vinyl chloride, or chlorinated poly(vinyl chloride),
or mixtures of such polymers with each other or with other polymers,
the principal ingredient of the mixtures being a polymer of vinyl
chloride. These compounds contain plasticizers and may also contain
fillers, colorants, and small quantities of other ingredients such as
stabilizers and lubricants'. (ISO 2898/1-1980(E)).

For the sake of convenience, abbreviations (letter symbols) are used

for some polymers and copolymers in many places in this book. Such
abbreviations are generally in line with the recommendations of the
relevant international standard (ISO 1043-1978). However, in a few
cases where those recommendations are at variance with common
general usage, or in order to avoid inconsistency, the ISO standard has
not been followed. Two notable examples are the author's preference
for EVA (over 'EN AC' recommended by the ISO standard) as an
abbreviation for ethylene/vinyl acetate copolymer, and VCNA for
vinyl chloride/vinyl acetate copolymer. The EVA symbol is very widely
used (and indeed also recommended by another English-language
standard-ASTM D 1600-83), whilst-given its use-IVA' for vinyl
acetate is then more consistent than 'VAC' (the abbreviation favoured
by all standards), and should be acceptable especially in contexts
where there is no chance of confusion with vinyl alcohol (which is in
any case usually designated by 'VAL'). It may also be noted that 'A'
for acetate is recognised, though not preferred, by ISO 1043-1978.

1.2 EARLY HISTORY AND DEVELOPMENT OF PVC

Although Regnault l - 3 prepared some vinyl and/or vinylidene monom-

ers in 1838, and observed the conversion of the latter to a white
powder when exposed to sunlight in sealed tubes,2 it is Baumann's
polymerisation of vinyl chloride (as well as bromide) in 18724 that is
often regarded as the earliest documented preparation of PVC
homopolymer: this was certainly among the 'white, solid masses
* NB called simply 'plasticised vinyl compounds' in an earlier version of this
definition (ISO/DIS 2898, International Draft Standard, 1972).
 I Introduction 5

unaffected by solvents and acids' obtained in that work. The polymer

was found to be stable on heating up to Boac, but to decompose
rapidly with evolution of acid vapour at higher temperatures. 5 Early
manifestations, or at least precursors, of budding practical interest in
PVC came in 1912, in the form of British and German patents6 to
Ostromislensky (for the production of 'rubber-like masses' from vinyl
halides), and in the work in Germany by F. Klatte considered by some
to have laid the foundation for the technical production of PVC: 3
Klatte took out a German patent for the production of PVC fibres,3
and Ostromislensky went on to obtain patent cover for 'polyvinyl
halides' (in the USA in 1929). 2 In the meantime (c. 1928) patents were
also being granted for vinyl chloride/acetate copolymers; in the USA to
Du Pont and the Carbide and Carbon Chemicals Corporation, and in
Germany to I. G. Farbenindustrie (now BASF).3,7 The first production
of the copolymers in America (by the Carbide and Carbon Chemicals
Corp.) falls in the period 1928-1930: soon after (1931) B. F. Goodrich
introduced their own 'non-rigid vinyl chloride plastics'. 2 In Germany,
1931 saw the first technical-scale production of vinyl chloride polymer
and copolymers, and the first preparation (by Hubert and Schonburg)
of chlorinated PVC fibres (followed by the first technical production of
both the CPVC polymer and the 'Pe-Ce' fibres from it in 19343).
Industrial development (with emphasis eventually shifting from the
vinyl chloride/acetate copolymer to the homopolymer) thereafter
proceeded in both countries, with full commercial production achieved in
the late 1930s. Whilst some development work was taking place in the
UK in the same period, PVC was first produced there on a commercial
scale in 1942-1943 (by ICI and the Distillers Company).
It is thus comparatively recently that PVC became a commercial
plastics material. The early interest in copolymers (in particular
polyvinyl chloride/acetate) was associated with their use as the first
practical solution to the problem of thermal decomposition in
processing: whilst the general thermal stability of the copolymers is
somewhat poorer than that of the homopolymers they can be
processed at significantly lower temperatures, at which they are
reasonably stable. The effects in this respect of the co-monomer units
in the polymer molecules-sometimes referred to as 'internal plasti-
cisation'-are now well understood.
Effective 'external' plasticisation of PVC homopolymer by the
incorporation of plasticisers first came around 1930, with the finding by
several workers5 ,8 that compounding with dibutyl phthalate (DBP) and
certain other esters would convert the intractable polymer to a material
6 W. V. Titow

of lower softening point; this could be processed satisfactorily at lower

melt temperatures and was-in the solid state at room temperature-
relatively soft and similar to rubber in some respects. Thus,
chronologically, external plasticisation came after 'internal' plasticisa-
tion by copolymerisation, although it is now the main route to the
formulation of flexible and most semi-rigid PVC materials. Among
early suggestions of substances for use as plasticisers, now of only
historical interest, were tung oil9 and alkyd resins. 1o It was also realised
at about the same time (the early 19305) that certain additives, e.g.
alkaline-earth metal soaps,11 would act as heat stabilisers. The main
present-day applications in which vinyl chloride/acetate copolymers are
more suitable than plasticised homopolymer compositions are gra-
mophone records and floor coverings. It is interesting to note that the
first of these applications was originally disclosed in the early 1930s,8,12
i.e. around the time when other less practicable and now long defunct
proposals were also current, e.g. moulded PVC dentures,13 and an
adhesive, consisting of a mixture of PVC with rubber and a cellulose
derivative, for sticking patches on worn places in clothing!14
It was World War II that first brought PVC into its own. It was soon
realised that plasticised PVC was an effective replacement for rubber
in some important applications, notably cable insulation and sheathing.
Thus PVC helped to relieve the acute rubber shortage, and at the same
time established itself as a material in its own right. From then on it
continued growing rapidly in importance, to attain the dominant
position which its properties and versatility secure for it today in so
many applications.
The early processing of PVC, in the pre-war period and to some
extent during the war, was largely carried out by methods and on
machinery originally developed for rubber or celluloid. The processes
involved were mixing, calendering, compression moulding, and
extrusion (including wire coating).
The paddle-type (Gardner) pre-mixers were in use at an early
period, but between about 1942 and 1945 open-mill mixing was widely
practised. The use of internal mixers was also adopted when it was
found that PVC compounds could be readily mixed in them. The open
mills and other machines had to be run at temperatures higher than
those appropriate for rubber: as they were normally steam-heated
steam pressures had to be increased at the risk of grease melting
extensively and draining away from bearings. Electrical heating,
particularly for extruders, was a logical development, but one which
proposals were also current, e.g. moulded PVC dentures,13 and an
adhesive, consisting of a mixture of PVC with rubber and a cellulose
 1 Introduction 7

was fully utilised only slowly. The need to modify the rubber extruders
employed for the early production work soon became plain, and
modifications were made, e.g. to enable the material to be fed-in in
granular form, and to provide higher processing temperatures (by
electrical heating). A special ram extruder was employed in Germany
for a time to produce rigid pipe from a PVC billet. 15
Thanks to the work of Kaufman the early history of PVC polymers,
compounds, and processing is well recorded and documented. 15 ,16 The
development of modern PVC-processing equipment and of the many
specialised processes which form such an important part of present-day
PVC technology has paralleled the remarkable expansion of the
production of PVC and the scope and number of its applications.
The 1970s brought two unforeseen events of major significance both
in their initial impact and their lasting effects upon the PVC
industry-the oil crisis of 1973/74 (with its aftermath of continuing oil
price rises), and the finding that vinyl chloride monomer (VCM) is a
carcinogen.
The oil crisis-after first causing a serious temporary shortage of the
oil-derived principal feedstocks for VCM production (ethylene and
acetylene-see also Chapter 2), and hence of PVC polymers (ct. the
drop, c. 1974, of the curves of Fig. 1.1)-resulted in large, and
continuing, increases in polymer prices. These are the outcome of
higher costs of both the feedstocks and the energy (also largely
oil-supplied) used to process them into monomers and thence into
polymers. It may be noted that one of the developments prompted by
this situation has been a refocusing of interest on coal-based raw
materials and processes, with special reference to the acetylene route
to the production of VCM:

HC:=CH + HCI ~ CHr-CHCl (1)

Albeit normally more energy-intensive than the ethylene route

(generally favoured with oil feedstocks also because of the higher cost
of acetylene from that source) it can be made completely independent
of petrochemicals by producing the acetylene from coke and quicklime
via calcium carbide:
3C + CaO~ Ca~ + CO (2)
(coke)

Ca~ + 2H20~ HC:=CH + Ca(OH)2 (3)

 00
5

"",. /.~
/"
/'
/'
/'
/'
./
4 ./
/"
,/
./
W~st~rn /'
/"
Europ~ /' /'/'
/'
CIl /'/'
tI /'
C ,...
g3 ,/
"
+' /',/
u ,,'/
"t:
"c;l ~
E :0:::::
c
o
=: 2 __ x ~
~
i

x--~/x--'-~ x Japan -- -- -- ---

. ----- ~,.------
/
01 I ¥,-----
1964 1968
I 1972
I 1976I 1980I 1984 I

Fig. 1.1 Consumption of PVC polymers in the principal consuming areas.

 1 Introduction 9

The chlorine and hydrogen needed for the HCI used in reaction (1) can
be produced by electrolysis of brine (with caustic soda as a saleable
by-product). Some industrial plants manufacturing VCM and PVC
polymer by this process have been in operation for many years (e.g.
the AECI 'Coalplex' plant at Sasolburg, RSA).
The discovery, in the early 1970s, that exposure to VCM could cause
certain forms of cancer, coupled with the realisation that VCM
concentrations in factory atmospheres and its residual contents in PVC
polymers were comparatively high, had repercussions on PVC polymer
production in several countries. It also caused a serious decline
(especially in the USA and Japan) in the use of uPVC films for food
packaging, and blow-moulded bottles for beverages and oils. The legal
action for 285 million dollars brought in the USA against Borden
Chemical and Goodyear Tire and Rubber Co. (two PVC polymer
producers) by some supermarkets, in respect of 'damage to health' by
PVC film used to wrap meat,17 is an example of the extremes of feeling
in some quarters. Soft PVC was comparatively less affected, as the
dilution effect of large amounts of plasticiser and greater loss in
processing reduced the VCM concentration in the compounds to
relatively low proportions. The considerable effort expended on
investigating and remedying the situation, together with relevant
regulations brought out in the major industrial countries, led to a vast
reduction of VCM contents in both the factory air and PVC polymers
produced by virtually all main manufacturers. The 'clean-up' brought
the content levels down to values now regarded as acceptable on the
basis of data obtained in extensive studies. The subject is discussed in
more detail in Chapter 12 (Section 12.9.1), and also mentioned in
Chapters 2 and 7.
A third topic-albeit of comparatively lesser importance in the PVC
context than the oil crisis and the VCM problem-which has been
receiving increasing attention in recent times is the disposal of plastics
waste and re-usable material. Concern with preservation of resources
and conservation of the environment provides the main incentive in
these two related areas. Dealing with PVC waste involves special
considerations. Selective reclamation, i.e. separation from waste
mixtures with other plastics (which operation is not a straightforward
proposition in itself), and subsequent re-processing are complicated by
the wide variety of PVC formulations, and the increased susceptibility
to heat degradation in re-processing: the main factors in the latter are
the 'heat history' already acquired and the possible presence of
10 W. V. Titow

polymer already partly degraded in the course of past heat treatments

and/or service. Re-processing PVC-containing plastics waste without
separation will normally entail dealing with mixtures in which large
proportions of polyolefins (mainly polyethylene) are present: in view of
the poor compatability of polyolefins with PVC this is not a particularly
attractive practical proposition either with respect to processing or the
resulting product.
Disposal of PVC waste also has its special problems, since the
polymer is not biodegradable, whilst incineration produces irritant,
corrosive and toxic products (see Chapter 12, Section 12.9.3).
Claims are made from time to time of successful reclamation of PVC
from mixed plastics scrap and waste (e.g. by the 'Mesco' process
developed in Japan by Mitsui 18) but the scale of commercial recovery
is still relatively small, and the practical limitations of all existing
methods are recognised. 18 ,19 The re-use of material from discarded
PVC bottles is sometimes cited as a case where a certain measure of
success has been achieved. In France such bottles have been processed
for some time (on a limited scale) by Societe Dorlyl, to produce
reclaimed PVC compounds said to be suitable for the production of
certain grades of sewage and drainage pipes, and telephone cable
sheathing. * The use of granulated PVC bottles as road-surfacing
material in the USA has also been reportedt (as indeed has that of
ground glass bottles!).
Normal recirculation, in the same process, of the clean PVC scrap
generated (e.g. edge trim in calendering-see Chapter 18) is widely
practised, in particular with pPVC for non-critical applications.
General pPVC scrap, both own and from external sources, is also
converted by some processors into such products as cheap garden hose
or core composition for cables (see Chapter 13, Section 13.4.2(d».

1.3 GENERAL STATISTICS

Today the amount of PVC produced worldwide represents about 30%

of the total production of thermoplastics: this is second only to the
production of all polyolefins (i.e. low and high density polyethylene
and polypropylene together). The consumption of PVC in the principal

* Eur. Plast. News, (February 1979), 6(2), 3.

t J. Burbidge, Chapter 8, p. 130, of the general source given in Ref. 5.
 1 Introduction 11

consuming areas (where most of the production also takes place) is

illustrated in Fig. 1.1. A breakdown, by main use, of PVC
consumption in 1970 and 1976 is given in Table 1.1 for Western
Europe and the USA.
Production and consumption statistics for PVC (as well as other
plastics) are published each year in the January issue of Modern
Plastics International: some relevant information will also be found in
the current issue of the Modern Plastics Encyclopedia. Data,

TABLE 1.1
Consumption of PVC Polymers, by Main Outlet, in Western Europe (Includ-
ing UK) and the USA in 1970 and 1976
Outlet Western Europe USA
(1000 metric tonnes) (1000 metric tonnes)

1970 1976 1970 1976

Film and sheet (rigid and

flexible)
Calendered
Extruded } 430
(21'5%) } 605
(19·1%)
259} 341
82 (24,8%) } 200 305
105 (14,2%)
Flooring
Calendered
Coated } 178
(8'9%) } 195
(6·1%)
113} 147
34 (10'7%) } 75
70
145
(6'8%)
uPVC pipe, conduit and 550 785 215 682
fittings (27'5%) (24'7%) (15'7%) (31'9%)
Wire and cable covering 230 335 186 150
(11·5%) (10'6%) (13-5%) (7'0%)
Records 40 78 64 68
(2,0%) (2'4%) (4'8%) (3·2%)
Blow-moulded bottles 110 235 32 35
(5'5%) (7-4%) (2·3%) (1·6%)
Misc. injection mouldings 20 82 39 104
(1·0%) (2'6%) (2'8%) (4'9%)
Misc. extruded products 235 505 23 177
(including rigid profiles (11'8%) (15·9%) (1·7%) (8'3%)
and cladding, flexible
tubing and profiles)
Misc. coatings (other than 134 265 187 190
flooring) (6'7%) (8'3%) (13'6%) (8'9%)
Others (including plastisol 72 90 138 283
products other than (3-6%) (2'9%) (10,1%) (13-2%)
coatings)

2000 3175 1372 2139

Total
(100·0%) (100,0%) (100'0%) (100,0%)
12 W. V. Titow

predominantly for the UK and Europe, usually appear in the January

issue of European Plastics News.

1.4 OUTLINE OF THE PVC SECTOR OF THE

PLASTICS INDUSTRY

Companies operating in the PVC sector of the plastics industry

generally fall into one of four main categories, which are as follows:
(i) polymer producers;
(ii) compounders;
(iii) processors;
(iv) companies selling finished goods consisting of or containing
PVC.
Polymer importers have not been included in this sequence because
they do not normally engage in technical activities. They are however,
with the producers, members of the more general category of polymer
suppliers.
Some companies fall within more than one of the categories listed:
for example, the polymer producers all produce compounds; some also
produce semi-finished goods. It should be appreciated at this early
stage that the number of polymer producers in any country is very
small when compared with the large numbers of companies in the
other categories. Category (iv) above will contain many companies for
which PVC is but a small part of their interests. Nevertheless, such
companies, e.g. the automobile producers, can use very large
quantities of PVC and are very important to the industry.
The principal processes used to convert the PVC to finished and
semi-finished goods are extrusion, calendering, injection moulding and
spread coating. Although some companies are concerned with more
than one of these processes, most tend to specialise in one process. In
some cases the processed PVC is marketed directly by the processor
(e.g. unplasticised PVC pipes), whilst in other areas the processor
passes on the PVC in semi-finished form to another company which
employs the material in its products, e.g. vinyl automobile upholstery.
In addition to the material producers, converters and users, there
are many companies which specialise in the supply of additives for use
in PVC compounds, e.g. plasticisers, stabilisers, lubricants, fillers, etc.
It is relevant to point out that the value of the total market for some of
these materials exceeds that of many other plastics materials.
 I Introduction 13

Also worthy of mention-since without them there would be no

PVC industry-are the machinery manufacturers. Many companies
have specialised in equipment for PVC processing, and through their
development work on plant and equipment new applications for PVC
have been made possible.

1.5 VINYL CHLORIDE POLYMERS AND COPOLYMERS

1.5.1 PVC Homopolymers

(a) Chemical Structure

The basic repeat unit of the PVC polymer chain is

HI HI ]
-C-C-
[
h tl i

where i is the degree of polymerisation, i.e. the number of repeat units

in the molecular chain. The units are linked virtually exclusively
'head-to-tail', i.e. -CHz-CHCI-CHz-CHCI-.
In commercial PVC polymers the average values of i range between
about 500 and 1500; this corresponds to a theoretical molecular weight
range of about 31000-94000.
Note: In practice a given amount of linear, thermoplastic polymer
(i.e. a test specimen, processing batch, etc.) will consist of
chain molecules made up of the same basic repeat units, but
differing in size (chain length). A single chain (polymer
molecule) consisting of i repeat units is said to have a degree
of polymerisation of i. The molecular weight of such an
individual chain (neglecting any small difference due to end
groups) may be designated M i , and the species may be
referred to as an 'i-mer' or'ith species'. Since, at least in the
ideal case, M i is the sum of the weights of all the repeat units
in the chain, its value will be different for molecular chains
differing in the value of i. The scatter of Mi values (the
molecular weight distribution) in a given amount (i.e. sample,
batch, etc.) of polymer may be wide or narrow but, as the
chains are not all identical, a single molecular weight figure
quoted for the whole amount can only be an average value.
14 W. V. Titow

Depending on the method of determination, this value will in

practice normally be a number-average molecular weight
(M o ) , weight-average molecular weight (Mw ) , or viseosity-
average molecular weight (Mv ).20 For the same batch of
polymer these values are numerically in the sequence
M w > Mv > Mo, with M v usually closer to Mw than to Mo. In
the ideal, theoretical case of all chains being of identical
length (the same value of i) M o = M w •
Solution viscosity measurement is comparatively straight-
forward (especially with polymers soluble in convenient
solvents) and the data it yields can be used to calculate either
M v or-more commonly with PVC in industrial practice-
such related quantities as specific viscosity, * viscosity num-
,*
ber, t logarithmic viscosity number or K value§ (ct. also
Chapter 2, Table 2.1).
The relationships between these various quantities (valid
only when the relevant viscosities are determined under the
same, standard conditions) are as follows:
Specific viscosity (viscosity increment): (Tf - Tfo)/Tfo
Viscosity number (formerly known as 'reduced viscosity'
or'RV'): (Tf - Tfo)ITfoc
Logarithmic viscosity number II (formerly known as
'inherent viscosity' or 'logarithmic reduced viscosity', Le.
'IV' or 'RV'): [In (TfITfo)]le
where Tf is the viscosity of a dilute polymer solution (or its
time of flow in standard conditions); Tfo is the viscosity of the
solvent alone (or its time of flow in standard conditions); c is
the concentration of the polymer, in g per ml of solution; and
TfITfo is the viscosity ratio (formerly known as 'relative
viscosity').

* Still sometimes determined by the (now superseded) Method B of ASTM D

1243-58T.
t Method of ISO 174-1974.
:j: Method of ASTM D 1243-66 (reapproved 1972).
§ For PVC normally the Fikentscher K value-ct. DIN 53 726-1983. (see also
Chapter 2, Note in Section 2.2.2, and Table 2.1).
II Not to be confused with the 'limiting viscosity number' (formerly known as
'intrinsic viscosity'): Iimc-+o [(fl- flo)/f/o C] or limc-+o [(In fl/flo)/c).
 1 Introduction 15

The Fikentscher K values corresponding to a range of

viscosity ratios of dilute solutions (0·005 g ml- 1 ) of PVC
polymer in cyclohexanone at 25°C are listed in DIN 53726-
1983.
Most commercial PVC polymers have Fikentscher K values within
the range 50-80, equivalent to about 50000-500 000 M w , and 30000-
90 000 MD. The relationship is illustrated in Fig. 1.2. Polymers of much
higher molecular weight have also been made. Like those of other
thermoplastics, the properties of PVC polymer are influenced by both
the molecular weight and molecular weight distribution: the ratio

100000 5'8

90000

80000

70000

r{ 60000 5-2 ~
I~

'"
o
.J
50

5-0+-100000

40000

30000 4·8

--50000

20000
4·6

Fig. 1.2 Relationship between the molecular weight (weight-average and

number-average) and the K value of PVC polymers (the Fikentscher K value
determined at 25°C on 0·005 g ml- 1 polymer solution in cyclohexanone--d.
Chapter 2, Table 2.1 and Note in Section 2.2.2).
16 w. v. Titow

Mw/M n (known as the 'dispersion of distribution') is a function of the

extent of the latter (i.e. the width of the distribution curve, although it
is not influenced by its shape). The evaluation of the molecular weight
of vinyl chloride homo- and copolymers by gel-permeation chroma-
tography was reviewed recently by Janca and Kolinsky?!
The polymerisation temperature influences the molecular weight,
and hence the dilute-solution viscosity, of PVC polymers (higher
molecular weights obtained at low temperatures). This factor was
examined by Ravey and Waterman 22 for the polymerisation tempera-
ture range 0-70°C. Intensive heating may be necessary to ensure
complete dissolution of PVC polymers produced at sub-zero tempera-
tures, for solution viscosity measurement and determination of M w by
light scattering and gel-permeation chromatography.23
The structure of PVC polymer molecules deviates in practice from
the theoretical ideal of linear chains of -CHz-CHCl- units
terminating in -CHz-CHzCl and -CHCl-CH3 groups. The main
differences are listed below:

CHAIN BRANCHING
The chains of commercial PVC polymers are branched. Estimates of
the extent of branching, based on determinations by various
techniques,24,25 range from 0·5 to 20 branches per 1000 carbon atoms,
and include the suggestion that 5 out of every 1000 carbons are
methyl-branched whilst up to 2 per 1000 carry side-chains of more than
5 carbon atoms. Z6 The two most probable structures for a branch
junction are believed to be Z5

~CH2-CHCI-CH-CHa-CH2-CHCl~
I
R
and

~CH2-CHCI-CH2-TH-CH2-CHCl~

where the side-chain R is -CHz-CHCI~, or -CH3 .

The presence in PVC polymers of branch junctions involving the
 1 Introduction 17

existence of a tertiary chlorine

~CHz-CCl-CHz-eHCI~
I
CHz
I
CHCI
1
has been the subject of much speculation,25 * as their formation (by
appropriate radical transfer to polymer in the course of polymerisa-
tion) is a valid theoretical possibility, whilst-if present-they would
constitute important sites for initiation of thermal or photo degradation
of the polymer (owing to the relative ease with which the tertiary CI
can be split off-see discussion in Chapter 9). However, no direct
evidence of the presence of tertiary CI, or of any functional
relationship between the number of chain branches and thermal
stability, could be found in a number of studies concerned with these
subjects. 25 ,27-30

END-GROUPS
A large variety of end-groups is encountered in commercial PVC
polymers. Some are acquired by reactions, in the course of
polymerisation, with fragments of initiators, emulsifying or suspending
agents, or other 'external' compounds present (to which chain transfer
can occur). Others are formed in terminating reactions (chain transfer
to monomer or polymer, disproportionation, coupling) involving the
monomer and/or any of the species generated during polymerisation.
Examples of the end-groups originating in the former way are
~CH2-0C-C6H5; ~CH2-o-S02-0R; and ~CH20H (where R
is an alkyl radical): those formed in the 'internal' terminating reactions
are ~CHCI-CH=CH2 (an allyl-chloride type of structure in which
the CI atom is activated by the unsaturated linkage at the 3,4-position
relative to it31 ); ~CH CHCI; ~CCl=CH2; ~CH2-CHCI2;
~CHCI-CH2Cl; and ~CHr-CH2Cl.

* cf. also, for example, the discussion by L. I. Nass of the thermal stability of
PVC, in the Encyclopedia of pvc (see General Bibliography section at the end
of this chapter).
18 w. V. Titow

OTHER STRUCTURAL PEATURES

The results of several studies32 ,33 confirm the presence of double
bonds, distributed randomly in the polymer chain: ordinary PVC
polymers may contain up to 15 such bonds per 1000 carbon atoms. 25
Some evidence has also been obtained of the presence of oxygen: 25
apart from oxygen-containing end-groups (see above) some oxygen
could be incorporated in the chain during polymerisation, or acquired
through oxidation of the polymer; however, the resulting chemical
groupings have not been identified.

(b) Morphology
Commercial PVC polymers may be regarded as essentially
amorphous,34 although crystalline material contents of about 2-10%
have been reported on the basis of determinations by X-ray diffraction
methods, thermal analysis (DTA, DSC, TMA) , and density
measurements. 35-37 The crystallinity is associated with the stereoregu-
lar (syndiotactic) polymer fraction. 38-40
The glass transition temperatures (Tg ) of commercial homopolymers
lie in the range 80-84°C (as determined by DTA, DSC and TMA).34,35
Annealing above the Tg increases crystallinity and also the crystalline
melting temperature (as given by the endothermic peak on DTA
curves).35,37 The density of the crystalline fraction has been reported as
1530 kg m-3 (1,530 g cm-3) and that of totally amorphous (quenched)
polymer as 1337kgm- 3 (1·337gcm- 3).35
As would be expected, annealing below the Tg has no effect on
crystallinity: however it can increase the density-this has been
attributed to a reduction of the free volume in the polymer without
ordering of its fine structure. 35 Apparently the kind of short-range
non-crystalline ('domain') order which can develop in some essentially
glassy, but partly crystallisable polymers (bisphenol-A polycarbonate,
polyethylene terephthalate)41-44 on heating below the Tg , does not
arise in PVc.
Relatively highly crystalline PVC polymers (up to about 45%
crystallinity) with high syndiotactic material content, have also been
prepared (by polymerisation at low temperatures or in certain
solvents).24,36,38,45,46 The preparation of fibres and film from such
polymers has been reported47 as well as that of plasticised compounds
(with about 50 phr DOp).38,47 The melting points of the crystalline
polymers can be as high as 265_273°C24 ,46 (cf. commercial PVC
polymer-about 210°C in the absence of decomposition). The
 i introduction 19

above-mentioned plasticised compounds of crystalline PVC had a

higher modulus and hardness, and lower tensile creep at room
temperature than a similar compound of ordinary commercial PVC
polymer (but lower tensile strength and extension at break): below
-25°C the modulus and hardness were lower (i.e. the flexibility greater)
than those of the normal PVC.38
Molecular orientation of the PVC polymer, and the associated
structural anisotropy, can be an important factor in the morphology
(and the properties) of PVC products (especially uPVC). Thus in PVC
mouldings the skin-and-core effects (a well-known, common feature
also of other polymer mouldings) can involve, inter alia, a considerable
degree of orientation in the skin. 48 Biaxial orientation of the polymer
in PVC bottles, films and thermoformed articles increases impact
resistance (ct., for example, Chapter 17) and reduces permeability (ct.
Chapter 12, Section 12.4). The tensile strength and retraction on
heating of extruded products is strongly influenced by longitudinal
molecular orientation imparted by stretching in production (ct., for
example, Chapter 12, Section 12.3), whilst the high degree of
orientation produced in PVC fibres by the drawing process in
manufacture is responsible for their very high tensile strength in
comparison with other PVC products (cf. Appendix 3). The fracture
and yield behaviour of PVC polymers and uPVC compositions is
strongly influenced by the extent and nature of molecular orientation.
Useful investigational work in these areas has been reported by several
authors.49.50--52

1.5.2 Vinyl Chloride Copolymers

Some of these are long-established commercial materials. Others,

more recent, have also become of more than academic interest. The
oldest, and still most widely used, are vinyl chloride/vinyl acetate
copolymers (VCNA).
In most of the vinyl chloride copolymers of commercial interest the
co-monomer units are in a minor proportion (and randomly distri-
buted) in the polymer chain, i.e. most are internal, random
copolymers, with the VC units predominating. Copolymers with
vinylidene chloride (VCNDC) are a notable partial exception here, in
that whilst those used in certain PVC compositions (e.g. some
calendering compounds) for ease of heat-processing contain relatively
small amounts of VDC co-monomer, in others (e.g. those for making
20 W. V. Titow

self-supporting, low-permeability films, or barrier layers in composite

films) it is the VC co-monomer which is the minor constituent (usually
10-15%). Another exception is constituted by acrylic and (some)
modacrylic fibres: by definition,53 the former must contain not less
than 85% of acrylonitrile units in the chain (i.e. only up to 15% of a
co-monomer, which may be VC), and the latter between 85% and
35%-although the material of Dynel (Union Carbide), a well-known
modacrylic fibre, was in fact a 60/40 copolymer of vinyl chloride and
acrylonitrile (see also Table 1.2).
Some PVC graft copolymers are also noteworthy, e.g. those with
ethylene/vinyl acetate copolymers (EVA),62,67 polyolefins,62,68 buta-
diene/acrylic ester copolymers,62 and acrylic ester polymers. Graft
copolymers of the first three kinds were the subjects of early patents
by, respectively, Bayer and Dynamit Nobel, Montecatini, and
Pechiney-Saint-Gobain. 47 VClEVA graft copolymers are used (typi-
cally in blends with PVC homopolymer) in uPVC compositions for
outdoor service, notably in window frames, where good weatherability
and impact resistance at low temperature are required;3 VC/acrylate
grafts are also employed for this application (see Chapter 19, Section
19.4.3). Some graft copolymers with sufficiently high polyvinyl chloride
contents (e.g. VC/EVA with 50-70% EVA) can act as plasticisers for
PVC homopolymer, or as processing aids. The graft copolymers are, as
a rule, more expensive than main-chain copolymers.
As has been mentioned in Section 1.2, the chief effects of the
presence of a significant proportion of a co-monomer in the vinyl
chloride polymer chain are normally similar to (but, in general, more
permanent than) those of plasticising a homopolymer with 'external'
plasticisers: the processing temperature is reduced (albeit the heat
stability also decreases) as is the Tg (and hence the softening
temperature and temperature of deflection under load); the hardness
also usually decreases, and the extensibility increases.
Note: A partial exception to the general trend, which is of some
practical significance, may be noted: some copolymers of vinyl
chloride with N-substituted maleinimide derivatives 3,69 have
Tg values and Vicat softening points significantly higher than
those of vinyl chloride homopolymer: ct., e.g., Hostalit LP
HT 5060 (Hoechst)-a copolymer containing 5% of N-
cyclohexylmaleinimide. 69
Copolymers are normally more readily soluble than homopolymers
(see Chapter 12, Section 12.8, and Chapter 24): when used as surface
 1 Introduction 21

coatings they adhere better to many substrates (the adhesion may be

further improved by the incorporation of a suitable third co-monomer
in the chain-see Chapter 24).
Broadly speaking, the morphology of most copolymers is similar to
that of PVC homopolymer, except that the reduced regularity of the
chain is an extra hindrance to crystallisation. This occurs also in
VDCNC copolymers where VC is the minor component: the chain
structure of PVDC is favourable to crystallisation and the crystallinity
of the homopolymer is normally high;4o.56 the structural regularity and
hence ease of crystallisation is progressively reduced as the VC unit
content of the polymer chain is increased, until at VC contents;?; 30%
the copolymer becomes non-crystalline. It is for this reason that
VDCNC copolymer films for barrier applications contain only about
10-15% VC. This content level represents a reasonable combination of
easement of processing (the highly crystalline PVDC homopolymer
requires high temperatures) and retention of much of the excellent
barrier effect of the homopolymer associated with its crystallinity
(crystalline regions in polymers are normally impenetrable to diffusant
molecules).

1.5.3 'External' Modification of PVC by Other Polymers

PVC polymers can be modified 'externally' by blending with other
polymers or copolymers (including vinyl chloride copolymers-see
Section 1.5.2 above). On the industrial scale this is widely practised in
uPVC compositions, to improve the melt processability, and/or the
toughness (impact resistance at normal and low temperatures) as well
as-in some cases-the resistance to heat distortion, of the finished
product. The polymeric additives incorporated for these purposes are
known as processing aids and impact modifiers: they are discussed in
Chapter 11.
Those of the polymeric additives which are chlorinated (but not vinyl
chloride) polymers-e.g. chlorinated polyethylene (see Chapter 11)-
as well as copolymers of vinyl chloride (e.g. VCNA, VCNDC, or the
VC graft copolymers mentioned in Section 1.5.2 above) can have
particularly high compatibility with PVC resins: they can sometimes be
blended in such large proportions that the composition becomes a
plasticised PVC (with high permanence of properties, because the
plasticiser is a high polymer-see Chapter 11, Section 11.2). This can
also be done with some chlorine-free polymeric additives, e.g. nitrile
rubbers (see Chapter 11).
 ~
TABLE 1.2
Vinyl Chloride Copolymers
Copolymer Main applications (with indication of the usual Relevant chapters/Remarks Literature/References
method ofproduction of copolymer for use in
the applicationa)
Vinyl chloride/vinyl 1. Unplasticised mouldinss (including gramophone 1. Chapters 2, 3 and 26 Literature on this copolymer is ex-
acetate (VCNA) records) and sheeting (including sheets for ther- tensive-see, e.g., relevant titles
moforming and PVC ftooring)-S in the General Bibliography sec-
tion at the end of this chapter
2. Coatings (solution applications)-SL 2. Chapters 24 and 26. The copo-
lymers used for these applica-
tions sometimes contain a
third co-monomer
3. Adhesives, finishing agents (paper and 3. Chapters 23 and 26
textiles)-E
4. Fibres, e.g. Vinyon H H (American Viscose 4. Mentioned, inter alia, in Refs
Corp.) 53 and 54 ~
Vinyl chloride/vinyl- 1. U nplasticised calendered sheets; mouldings-S 1. Chapters 2, 3, and 18 Refs 40 and 47-general nature and :00:::
idene chloride preparation of the copolymers;
(VClVDC) Ref. 55-packal;\ing films; Ref. ::;j
56-general revIew (with 92 o
references) <t
2. Extruded films (packaging)-S 2. Chapters 19 and 26
3. Viscosity-reducing porymer in pastes-S 3. Chapters 21 and 22
4. Solution applications (esp. barrier 4. Chapters 12, 24 and 26
coatingsr-SL
5. Latex applications (esp. paper and textile 5. Chapter23
finishing)-E
6. Fibres, e.g. Saran" (National Plastics Products 6. Chapter 26
Co.)
Vinyl chloride/acrylo- Fibres (vinyl chloride is the comonomer in some Chapter 26 Refs 40 and 53
rutrile (VClAN) acrylic or modacrylic fibres, e.g. DyneF (Union
Carbide Chemicals Co.)
Vinyl chloride/prop- Extruded films (packaging); injection Commercially available from Air Refs 57 and 58--polymer produc-
ylene (VC/P) mouldings-S Products and Chemicals Ltd, tion, structure and properties;
USA (Airco 400 series) Ref. 59-polymer composition
and density; Ref. ~ackaging
film
Vinyl chloride/ethylene Similar to vinyl chloride/propylene copolymers-S Developed by Union Carbide Ref. 61
Chemicals Co.
Vinyl chloride/EVA I. Extrusion (profiles, esp. window frames), 1. Graft copolymers Refs 3, 47 and 62-polymer prepa-
injection moulding-S ration, structure and propertIes;
Refs 3 and 63-applications
2. Surface coatings; finishing agents (for paper and 2. Polr.mers and/or compounds
textiles)-E avaIlable from various sources
in the USA and Europe (e.g.
Pantasote Inc., USA-Pan-
taprene L; Hiils, West Ger-
many-Vestolit HIS 587;
Wacker-Chemie, West Ger-
many--VinnoIVl\;BIP,
UK-Beetle PVC).
Vinyl Mainly surface coatings-E Heat after-treatment required for Ref. 64
chloride/triftuoro- good adhesion. In melt pro-
chloroethylene cessing processability and
thermal stability (of both melt
and products) increase with
increasing TFCE content
Vinyl chloride/vinyl Calendered sheet-S Available from the Allied Allied Chemical Trade literature '-
cetyl ether Chemical Co., USA, and
some Japanese sources ;;-
Vinyl chloride/vinyl Surface coatings-E; SL Developed by BASF, West Ger- BASF technical literature
isobutyl ether many ~
Vinyl chloride/acrylic 1. Window-frame compositions-8 1. e.g. Vinnoll\ (Wacker Refs 47,65,66 f2-
ester Chemie)-Chapter 19 ~.
2. Film and bottles (uPVC) with good transparen- ;:s
cy, heat weldabihty and impact strength-S
3. Adhesives, finishing agents, coatings-E 3. Chapter 23

Vinyl ChlOride/fumariC} 1. Extruded products; injection mouldings-8

ester
Vinyl chloride/maleic 2. Low-temperature fusion pastes 2. e.g. PliovicAO (Goodyear. } Refs 40, 47, 61
ester USA)
Vinyl chloride/itaconic
ester
a Key: S = suspension polymerisation; E = emulsion polymerisation; SL = solution polymerisation,
b Also the generic name for vinylidene chloride copolymer fibres containing at least 80% by weight of vinylidene chloride.
C Production suspended in 1975.

N
v.>
24 w. V. Titow

Blends have also been prepared of PVC polymer with a copolymer

of vinyl chloride and an unsaturated dimethacrylate compound
(DMA), in which the latter component could be cross-linked (via the
double bonds in the DMA) to provide a PVC material of improved
strength and stability, and better processability when vacuum-formed
as a sheet. 7o A further refinement of this concept (and a PVC alloy
with an unusual structure) is represented by a blend of PVC polymer
with a butadiene/acrylonitrile copolymer in which both components are
cross-linked to form two separate but intimately interpenetrating net-
works. Depending on the cross-link density the properties of the
material can range from those of a tough elastomer to those of a soft
plastic. 71
Improved ease of processing and higher temperatures of deflection
under load are claimed for blends of PVC with styrene/maleic
anhydride copolymers (d. for example, Bourland and Wambach in
Plastics Engineering, 1983, 39(5), 23-7). Some versions of the blends
are available as commercial injection-moulding compounds (e.g. from
the Arco Chemical Co., USA).

1.5.4 Properties of PVC Compositions

To make their processing possible, and to achieve the required
performance in service, PVC polymers are compounded with various
additives to make up the compositions which are the substance of the
PVC materials and products of industry and commerce. The properties
of these compositions form one of the major topics dealt with in this
book: almost every chapter features one or more of their aspects,
including their durability, their individual and relative importance in
particular contexts and applications, their measurement, the ways in
which they are influenced by formulation and processing, and others.
Many numerical values of properties characteristic of various composi-
tions and products are quoted in Appendix 3, as well as throughout the
text.

1.6 CHLORINATED POLYVINYL CHLORIDE (CPVC)

This is an old-established material, first produced commercially in the

mid-1930s in Germany by chlorination of PVC polymer in solution (in
a chlorinated hydrocarbon solvent-typically tetrachloroethane or
 1 Introduction 25

chloroform) at elevated temperatures (50 to about 100°C). CPVC

made by this process is more soluble in solvents than the parent PVc.
The early commercial materials-e.g. Igelit PC (I. G. Farbenindustrie)
and Rhenoflex (Dynamit Nobel)-were used in solution-applied
surface coatings and adhesives. CPVC fibres were also spun from
solvent solutions. These applications still continue to some extent.
Around 1960 the dispersion chlorination process came into use. In
the originally patented version of this4o ,47 PVC polymer in aqueous
dispersion is treated with a large excess of chlorine at relatively low
temperatures (up to 60°C) in the presence of a swelling agent (a
chlorinated hydrocarbon, e.g. chloroform) under UV light. The early
commercial polymers produced in this way are exemplified by Trovidur
HT (Dynamit Nobel) and Geon HT (Goodrich). Dispersion-
chlorinated CPVC polymers are less soluble than those produced by
the solution process and their thermal stability is better.
In both processes chlorination takes place mainly at the -CHz-
groups of the PVC polymer chain (Le. the 1: 2 chlorinated configura-
tion, -CHCI-CHCI-, is preferentially formed) so that the resulting
chain structure becomes virtually that of a copolymer of vinyl chloride
with 1: 2 dichloroethylene* «a) in Fig. 1.3), rather than that of a vinyl
chloride/vinylidene chloride copolymer «b) in Fig. 1.3) which would
be given by preferential 1: 1 chlorination. t The large preponderance of
the 1: 2 chlorination is shown by the IR spectra of CPVC. It is also
evidenced by the products of thermal decomposition: those generated

-CHCl-CHCl-CHz-CHCl-CHCl-CHCl-CHCl-CHCl-
(a) Vinyl chloride/1:2 dichloroethylene copolymer or a chlorinated PVC
-CHz-CClz-CHz-CHCl-CHz-CClz-CHz-CClz-
(b) Vinyl chloride/vinylidene chloride copolymer
-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl-
(c) Homopolymer of 1: 2 dichloroethylene

Fig. 1.3 Simplified representation of polymer segment structures.

* Production by direct polymerisation of the monomers impracticable,

although some brittle, low molecular weight products have been obtained in
attempts to prepare the homopolymer. 40
t In the dispersion process tendency to 1: 1 chlorination can be increased at
high temperatures if the chlorine concentration is allowed to fall. 4o
26 W. V. Titow

by CPVC contain virtually none of the aromatic hydrocarbons

produced by the pyrolysis of both PVC homopolymer (see Chapter 12,
Section 12.9.3) and VCIVDC copolymers. 4o Complete chlorination
would give a polymer very similar to the symmetrical polydichloro-
ethylene* «c) in Fig. 1.3); however, the degree of chlorination of
commercial CPVC polymers is considerably lower than this (see Table
1.3). The density and Tg (and hence the Vicat softening point) increase
with the chlorine content.

TABLE 1.3
Some Properties of Commercial CPVC and PVC Polymers, and FuUy Chlorin-
ated PVC
CPVC PVC Fully chlorinated
polymer homopolymer PVC polymer

Chlorine content (weight %) 65·67 56·8 73·2"

Density (gcm- 3) 1·52-1·59b 1·40 1·70
Tgeq 99-123 80-84 175
Maximum service temperature
(for commercial compounds) eq
Continuous exposurec 90 65
Intermittent exposure c 110 80

"Theoretical figure for polymer of 1 :2 dichloroethylene.

b Density of commercial compounds: 1·47-1·62. This coincides almost exactly with the
range specified for CPVC pipes and fittings in ISO 3514-1976.
C In non-aggressive environments.

Since the same kind of site (the -CH2- group) is preferentially

chlorinated in the chains of CPVC polymers prepared by either
process, and the total chlorine content ranges are essentially the same,
other structural factors must be responsible for the differences in
solubility and thermal stability between the products of the two
processes. The balance of evidence from investigations carried out
since early times47 indicates that these differences are associated with
the way in which the chlorine atoms substituted into the -CH2-
groups are distributed within the polymer chain: the distribution does
vary according to the method of preparation in a manner suggesting

* Production by direct polymerisation of the monomer impracticable,

although some brittle, low molecular weight products have been obtained in
attempts to prepare the homopolymer. 40
 1 Introduction 27

that the variation is due to different accessibility of the polymer chains

to the chlorine in the two processes. Solution chlorination has been
reported47 to result in a uniform, random, 'statistical' distribution of
the chlorine among the -CHz- groups of the molecular chain, such
as would be expected if all the chains (and all segments within an
individual chain) were equally accessible to the reagent. The
chlorination produced by the dispersior process is believed47 to be
hetrogeneous, in two senses: the chlorine contents of different
molecular chains are not the same, and each individual chain contains
irregularly alternating blocks of polyvinyl chloride and 1: 2 dichloro-
ethylene polymer structures. It has also been found 47 that CPVC
produced by the dispersion process from PVC polymer of high
steroregularity (high syndiotactic material content) has a higher Vicat
softening point than one similarly produced from polymer of low
stereoregularity, whilst there is no corresponding difference between
analogous solution-chlorinated materials.
Chlorination of PVC polymers reduces the forces of attraction
between the molecular chains, as evidenced, for example, by the
comparatively greater ease and extent of stretching of CPVC films
above the Tg . 72 The essentially amorphous morphology of CPVC
polymers is probably a factor in this effect, as even the small amount of
crystalline material present in commercial PVC polymers would have a
constraining effect (with the crystallites acting as quasi cross-links) at
temperatures up to the crystalline melting point. In comparison with
uPVC, the effect of stretching (especially biaxial stretching) of CPVC
sheet upon some of its properties (increases in Young's modulus and
yield stress) is greater, although the permeability to COz of CPVC
sheet was found to increase with biaxial orientation, in contrast with
the reverse effect observed with uPVC: 72 as pointed out by the
investigators, the increase in permeability on biaxial stretching is
characteristic of essentially amorphous polymers which do not
crystallise under tension. 72 ,73 However, the increase in the impact
strength of the CPVC sheet, which was also achieved by biaxial
stretching in the above investigation, was claimed to be greater than
that attainable-in the absence of molecular orientation-through
incorporation of impact modifiers.
Commercial CPVC compounds are formulated on the same general
lines as uPVC compounds (see Chapter 4). However their processing is
influenced by the fact that the melt viscosity of the polymer increases
sharply with the chlorine content. 74 The compounds are used mainly
28 W. V. Titow

for the production of pipes and pipe fittings for hot-water installations
(including, increasingly, domestic central heating systems), where the
general similarity of properties to uPVC (including, inter alia,
suitability for jointing by solvent welding) combined with the greatly
increased temperature resistance in service, are particularly advan-
tageous. Other applications include pipes and fittings for potable water
(CPVC is approved for this purpose by several professional and
regulatory bodies 75), pipework and associated products (fittings,
valves, tanks) for chemical plant (the general chemical resistance of
CPVC is comparable with that of uPVC) , extruded profiles, sheets
(including co-extruded CPVClpPVC sheets), some electrical ap-
pliances, and constructional applications.
Some examples of commercial CPVC compounds are: the Lucalor
range (Rhone-Poulenc, France), which includes Lucalor RB 1266
specially developed, and recently evaluated, for central heating
systems; the Dekadur compounds (Deutsche Kapillar Plastik, West
Germany) and the CPVC compounds in the Geon range (B. F.
Goodrich, USA). Some of the properties of three Geon compounds
are listed, by way of example, in Table 1.4.

TABLE 1.4
Some Properties of 'Geon' CPVC Compounds
(Based on manufacturer's published data)
Property Geon 88933 Geon 88934 Geon 88935
(high temperature (extrusion of (profile co-extrusion
extrusion and pipes and with pPVC-high
injection moulding) profiles) ductility compound)

Tensile strength (lbf in- 2 ) 8200 8400 7300

(ASTMD 1708)
Flexural strength (lbf in- 2) 14500 15600 13600
(ASTMD790)
Flexural modulus (lbf in- 2) 387000 395000 396000
(ASTMD790)
Izod (notched) impact
strength (ft lbf in -1) 2·3 2·0 3·2
Deflection temperature
under load eC): at 100 102 82
264lbf in- 2
(ASTMD648)
Specific gravity 1·52 1·57 1·47
(ASTMD792)
 1 Introduction 29

It may be noted in passing that its higher chlorine content reduces

the flammability of CPVC in comparison with uPVC.

1.7 MATERIAL AND TEST STANDARDS

The properties of PVC materials and products, as well as methods of

their characterisation and testing, are the collective subject of a very
large number of standard specifications. Whilst some companies
(particularly polymer manufacturers) and big user organisations (e.g.
government and military procurement departments, motor car manu-
facturers) operate their own in some cases, the standards of by far the
greatest importance to the PVC technologist and user in the Western
World are those of the following four groups:
(i) Standards developed by the appropriate technical committees
of the International Organisation for Standardization and
published by that organisation (ISO standards). The ISO
committees dealing with plastics are TC 61: Plastics and TC 138:
Plastic Pipes, Fittings and Valves for the Transport of Fluids.
(ii) Standards of the British Standards Institution (BS standards).
(iii) Standards of the American Society for Testing and Materials
(ASTM standards)
(iv) Standards of the German Institute for Standards (DIN
Deutsches Institut fUr Normung: DIN standards).
Most other countries also issue their own national standard specifica-
tions.
Those standards from the four main sources which relate directly to
PVC are listed (by number and title) in Appendix 1. The list is divided
into sections, grouping the standards by subject and also largely
according to their relevance to the chapters dealing with particular
topics in this book. * In addition, many 'plastics' standards not
specifically or primarily directed to PVC, but nevertheless relevant to
particular aspects of PVC materials, products or technology, are
mentioned in the introduction to Appendix 1, in Appendix 3, and in
various appropriate places in the book.
The numerous references to standard specifications throughout this

* For example, Section 4 of Appendix 1 lists standards dealing with various

aspects of plasticisers, and is thus directly relevant to Chapters 5-7.
30 W. V. Titow

book, and the listings in Appendices 1 and 3, contain in almost every

individual case not just the specification number, but also a year of
issue, since this can serve as a useful point of reference. Most of the
years of issue so quoted should be current at the time of going to press,
but it will be appreciated that international and national standards are
being periodically amended and revised, with consecutive issues
appearing under newer dates. Entirely new standards are also being
brought out. The introduction to Appendix 1 provides guidance on
keeping up to date with proposed, new, and revised standards.
The excellent book by Ives et ai. 76 served for a long time as a
valuable source of information on standard tests for plastics (including
PVC). An updated version, produced by an editorial team, is now
available in a new edition. 77

REFERENCES
1. Regnault, V. (1838). Ann. Chim. Phys., 2,69, 151.
2. Drukker, H. L. (1944). Proc. of Symposium on Plastics, Am. Soc. for
Testing Materials, Philadelphia, Pa, USA, pp. 165-77.
3. Domininghaus, H. (1976). Die Kunststoffe und Ihre Eigenschaften,
VDI-Verlag GmbH, Diisseldorf, p. 566.
4. Baumann, E. (1872). Ann. Chim. Phys., 163, 308-12.
5. Tester, D. A. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Chapter 1.
6. Ostromislensky, 1. (1912). British Patent No. 6299; German Patent
No. 264123.
7. Brydson, J. A. (1975). Plastics Materials, Newnes-Butterworths, Lon-
don, pp. 248-9.
8. British Patent No. 408969, Carbide and Carbon Chemicals Corp., (1934).
9. US Patent No.1 938662, Du Pont, (1933).
10. British Patent No. 387928, British Thomson-Houston, (1932).
11. Canadian Patent No. 346164 (1934).
12. British Patent No. 388309 (1933); US Patent No. 1932889 (1933).
13. British Patent No. 412442 (1934).
14. German Patent No. 470 149 (1927).
15. Kaufman, M. (1969). Plast. Polym., 37(129),243-51.
16. Kaufman, M. (1969). The History of PVC, Elsevier, London.
17. Anon. (1974). Chern. Engng. News, 52(35),8.
18. Trevitt, E. W. (1976). Polym. Paint Col. J., 166(3918), 193-4.
19. Anon. (1979). Eur. Plast. News, 6(6), 8.
20. Billingham, N. C. and Jenkins, A. D. (1972). In Polymer Science, Vol. 1,
(Ed. A. D. Jenkins), North-Holland Publishing Co., Amsterdam-
London, Chapter 2.
 i introduction 31

21. Janca, J. and Kolinsky, M. (1976). Plasty a Kaucuk, 13(5), 138-41.

22. Ravey, M. and Waterman, J. A. (1975). J. Polym. Sci., Polym. Chem.
Ed., 13(6), 1475-8.
23. Tavan, M., Palma, G. and Carenza, M. (1975). J. Appl. Polym. ScL,
19(9),2625-7.
24. Pezzin, G. (1969). Plast. Polym., 37(130), 295-301.
25. Braun, D. (1975). In Degradation and Stabilisation of Polymers, (Ed. G.
Geuskens), Applied Science Publishers, London, Chapter 2.
26. Schwenk, V., Cavagna, F., Lomker, F., Konig, I. and Streitberger, H.
(1979). J. Appl. Polym. Sci., 23, 1589-93.
27. Caraculacu, A. A. (1966). J. Polym. Sci., A-i, 4, 1829, 1839.
28. Caraculacu, A. A., Bezdadea, E. C. and Istrate-Robila, G. (1970). Ibid.,
8, 1239.
29. Braun, D. and Weiss, F. (1970). Angew. Makromol. Chem., 13(55),
67-71.
30. Suzuki, T., Nakamura, M., Yasuda, M. and Tatsumi, J. (1971). J. Polym.
Sci., C, 33, 281.
31. Fieser, L. F. and Fieser, M. (1944). Organic Chemistry, D. C. Heath &
Co., Boston, pp. 152-5.
32. Valko, L. and Tvaroska, I. (1972). Angew. Makromol. Chem., 23, 173.
33. Braun, D. and Quarg, W. (1973). Ibid., 29/30, 163.
34. Haward, R. N. (Ed.) (1973). The Physics of Glassy Polymers, Applied
Science Publishers, London, pp. 201-6.
35. Gray, A. and Gilbert M. (1976). Polymer, 17(1), 44-50.
36. D'Amato, R. J. and Strella, S. (1969). Applied Polymer Symposia, No.8,
275-86.
37. Ohta, S., Kajiyama, T. and Takayanagi, M. (1976), Polym. Engng. Sci.,
16(7), 465-72.
38. Gugelmetto, P., Pezzin, G., Cerri, E. and Zinelli, G. (1971). Plast.
Polym., 39(144), 398-402.
39. Abdel-Alim, A. H. (1975). J. Appl. Polym. Sci., 19(8), 2179-85.
40. Brighton, C. A. (1962). In Advances in PVC Compounding and Processing
(Ed. M. Kaufman), Maclaren & Sons Ltd, London, Chapter 1.
41. Titow, W. V., Braden, M., Currell, B. R. and Loneragan, R. J. (1974). J.
Appl. Polym. Sci., 18,867-86.
42. Frank, W., Goddar, H. and Stuart, H. A. (1967). Polym. Lett., J. Polym.
Sci.. 5,711.
43. Siegmann, A. and Geil, P. H. (1970). 1. Macromol. Sci. (Phys.), 84(2),
239.
44. Kashmiri, M. I. and Sheldon, R. P. (1969). Polym. Lett., J. Polym. Sci.,
B,7,51.
45. Bockman, O. C. (1965). Brit. Plast., 38(6), 364-5.
46. Gouinlock, E. V. (1975). J. Polym. Sci., Polym. Phys. Ed., 13(5),961-70,
and 13(8), 1533-42.
47. Bier, G. (1965). Kunststoffe, 55(9),694-700.
48. Copsey, C. J., Gilbert, M., Marshall, D. E. and Vyvoda, J. C. (1978).
'The dependence of PVC structure and properties on injection moulding
variables', paper presented at the PRI International Conference on PVC
32 w. V. Titow
Processing, Egham Hill, Surrey, England, 6-7 April, 1978.
49. Rider, J. G. and Hargreaves, E. (1969). J. Polym. Sci., A-2, 7,829-44.
50. Miller, L. E., Puttick, K. E. and Rider, J. G. (1971). J. Polym. Sci., C,
33, 13-22.
51. Smith, K., Hall, M. G. and Hay, J. N. (1976). Polym. Lett., J. Polym.
Sci., 14(12), 751-5.
52. Brady, T. E. (1976). Polym. Engng. Sci., 16(9),638-44.
53. Cook, J. G. (1964). Handbook of Textile Fibres, Merrow Publishing Co.,
Watford, England.
54. Dux, J. P. (1970). 'Vinyon and related fibres' in Kirk-Othmer Encyc-
lopedia of Chemical Technology, Vol. 21, 2nd Edn, John Wiley, New
York, pp. 441-51.
55. Oswin, C. R. (1975). Plastic Films and Packaging, Applied Science
Publishers, London.
56. Sauntson, B. J. and Brown, G. (1971). Reports on the Progress of Applied
Chemistry: Plastics, LVI, 66-76 (Society of Chemical Industry).
57. Cantow, M. J. R, Cline, C. W., Heiberger, C. A., Huibers, D. Th. A.
and Phillips, R (1969). Mod. Plast., 46(6), 126-38.
58. Heiberger, C. A., Phillips, Rand Cantow, M. J. R (1969). Polym.
Enging. Sci., 9(6), 445-51.
59. Ravey, M. (1975). J. Polym. Sci., Polym. Chem. Ed., 13(11),2635-7.
60. Briston, J. (1976). Packag. Rev., 96(3), 71-2.
61. Sarvetnik, H. A. (1969). Polyvinyl Chloride, Van Nostrand, New York.
62. Goebel, W., Bartl, H., Hardt, D. and Reischl, A. (1965). Kunststoffe, 55,
329-32.
63. Edser, M. H. and Bulezuik, B. W. (1974). Polym. Paint Col. J., (4th
December), 1051-6.
64. Ulbricht, J. and Rassler, K. (1976). Plaste u. Kaut., 23(7),487-90.
65. Albert, W. (1963). Kunststoffe, 53(2), 86-93.
66. Bohn, L. (1963). Kunststoffe, 53(2), 93-9.
67. Edser, M. H. and Bulezuik, B. W. (1974). Loc. cit., (18th December),
1090-4.
68. Pegoraro, M., Szilagyi, L., Locati, G., Ballabio, A., Severini, F. and
Natta, G. (1968). Chimica e Ind., 50(10), 1075-81.
69. Kiihne, G., Andrascheck, H. J. and Huber, H. (1973). Kunststoffe, 63(3),
139-42.
70. Sasaki, I. and Ide, F. (1975). Polym. Lett., J. Polym. Sci., 13(7), 427-32.
71. Sperling, L. H., Thomas, D. A., Lorenz, J. E. and Nagel, E. J. (1975). J.
Appl. Polym. Sci., 19(8), 2225-33.
72. De Vries, A. J. and Bonnebat, C. (1976). Polym. Engng. Sci., 16(2),
93-100.
73. Hopfenberg, H. B. and Stannett, V. (1973). In The Physics of Glassy
Polymers, (Ed. R N. Haward), Applied Science Publishers, London,
Chapter 9.
74. Arnold, G. H. (1970). Plast. Polym., 38(133),21-6.
75. Anon. (1979). Plast. Technol., 25(9), 31.
76. Ives, G. c., Mead, J. A. and Riley, M. M. (1971). Handbook of Plastics
Test Methods, Iliffe Books, London.
 I Introduction 33

77. Brown, R. P. (Ed.) (1981) Handbook of Plastics Test Methods. 2nd Edn,
George Godwin Ltd. and the PRI, London.

GENERAL BIBLIOGRAPHY ON PVC

SPE Vinyl Professional Activity Group (1964). A Guide to the Literature and
Patents Concerning Polyvinyl Chloride Technology, SPE, Stamford, Conn.,
USA.
Sarvetnik, H. A. (1969). Polyvinyl Chloride, Van Nostrand, New York.
Canton, M. J. R. (1970). 'Vinyl Polymers (Chloride)', in Kirk-Othmer
Encyclopedia of Chemical Technology, Vol. 21, 2nd Edn, John Wiley, New
York, pp. 369-412.
Dux, J. P. (1971). 'Vinyl Chloride Polymers', in Encyclopedia of Polymer
Science and Technology, Vol. 14, (Eds H. F. Mark and N. G. Gaylord),
Wiley-Interscience, New York, pp. 305-483.
Matthews, G. (1971). Vinyl Chloride and Vinyl Acetate Polymers, Plastics
Institute Monograph, IIiffe Books, London.
Sedlacek, B. (Ed.) (1971). Polyvinyl Chloride: Its Formation and Properties,
Proceedings of IUPAC Symposium, Prague 1970. Butterworths, London.
Sarvetnik, H. A. (Ed.) (1972). Plastisols and Organosols. Van Nostrand, New
York.
Brydson, J. A. (1975). Plastics Materials, 3rd Edn, Newnes-Butterworths
London, Chapter 12.
Yescombe, E. R. (1976). Plastics and Rubber: World Sources of Information,
Applied Science Publishers, London, pp. 151, 177-80,359.
Nass, L. I. (Ed.) (1978). Encyclopedia of PVC, Marcel Dekker, New York.
Burgess, R. H. (Ed.) (1981). Manufacture and Processing of PVC, Applied
Science Publishers, London.
Owen, E. D. (Ed.) (1984). Degradation and Stabilisation of PVC, Elsevier
Applied Science Publishers, London.
 w
-""

wave length, lim

·~H ,I",,' I I ! ? I I " I,
" "...I

t.
~ ..,;; 't . illlEtmmnnmuI:H~: I ~I ·nn:, 1·1' I'l~ ',,:;mml,,!T .1: . , I 'I: ;.1 fT:, IHF.!"ill''' I, Ii, liI::~~ I:HiI, r~" .Itla·:. .'1: I
~

~
:<:::
:::;j
c;;:
:to

wave number, em- 1

[A]
Fig. 1.4(A) Infra red spectra of commercial PVC resin (Corvic D60/11-ICI Ltd).
 wave length. lim

~
c·
0
':i
EIt
::
c a
Q..
•.. :::
!:l
- Q'
::

wave number. cm-'

[8]
Fig. 1.4(B) Infra red spectra of plasticised PVC (100 parts Corvic D60111, 60 parts DOP-Bisoflex 81-BP Chemicals
Ltd.).

w
V1