(PVC) Encyclopedia of Chemical Technology-White Paper
(PVC) Encyclopedia of Chemical Technology-White Paper
(PVC) Encyclopedia of Chemical Technology-White Paper
of
CHEMICAL
TECHNOLOGY
Fourth Edition
POLY(VINYL CHLORIDE)
James W. Summers
TABLE OF CONTENTS
page
INTRODUCTION 4
DISCUSSION 7
PHYSICAL PROPERTIES 7
Morphology as polymerized 7
Hierarchical structure of PVC 12
Morphology during processing 15
PVC fusion (gelation) 17
Plasticized PVC Morphology 20
PVC physical parameters 21
CHEMICAL PROPERTIES 22
Molecular structure - Monomer addition orientation 22
End groups and branching 23
Stereoregularity 24
Polymerization kinetics of mass and suspension PVC 25
PVC RESIN MANUFACTURING PROCESSES 30
Mass Polymerization 30
Suspension Polymerization 31
Emulsion Polymerization 31
Micro-Suspension Polymerization 33
Solution Polymerization 33
Copolymerization 34
COMPOUNDING 36
Stabilizers 36
Impact modifiers 38
Processing aids 40
Lubricants 40
Plasticizers 43
Fillers 47
Pigments 47
Ultraviolet light stabilizers 47
Biocides 48
Flame retardants 48
Foaming or blowing agents 49
PRODUCTION VOLUME AND ECONOMICS 50
Compound manufacture 50
PVC resin manufacture 52
World demand 54
PVC resin price 55
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POLY(VINYL CHLORIDE)
James W. Summers
INTRODUCTION
in North America in 1995 of 6.2 billion kilograms (13.7 billion pounds) (1). See
table 1 for volumes of several thermoplastics. This large volume of sales can be
50% chlorine. Not only does the chlorine provide no fuel, it acts to inhibit
combustion in the gas phase, providing the vinyl with a very high level of
notched Izod impact greater than 0.5 J/mm at -40°C, materials that are
weatherable with good property retention for over 30 years, compounds that
have stiff melts and little elastic recovery for outstanding dimensional control in
profile extrusion, or low viscosity melts for thin walled injection molding.
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POLY(VINYL CHLORIDE)
James W. Summers
[-CH2-CHCl-]n
The first discovery of PVC was in 1872 when E. Baumann found that
exposure of vinyl chloride to sunlight produced a white solid that resisted attack
(2, 3). From 1912 to 1926, German workers at Chemische Fabrik Griesheim-
Electron tried but failed to build machinery that could process PVC and
overcome its instability; finally they gave up their patents (3). In 1926, Waldo
Semon at BFGoodrich, while looking for an adhesive to bond rubber to metal for
tank liners, found that boiling PVC in tricresyl phosphate or dibutyl phthalate,
made it highly elastic (3), thus he invented the first thermoplastic elastomer.
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POLY(VINYL CHLORIDE)
James W. Summers
DISCUSSION
PHYSICAL PROPERTIES
Morphology as polymerized
polyvinyl chloride and polyvinyl alcohol (4, 5). Early in the polymerization,
particles of PVC deposit onto the membrane from both the monomer and the
water sides forming a skin 0.5 - 5 µm thick that can be observed on grains
onto the membrane from the monomer side and water phase polymer, 0.1 µm
diameter, deposits onto the skin from the water side of the membrane (4). These
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POLY(VINYL CHLORIDE)
James W. Summers
domain sized water phase particles may be one source of the observed domain
structure (7).
Figure 1. A grain of suspension PVC and its cross-section showing the skin and
primary particles.
Grain
~ 150 µm dia.
Skin
~ 2-5 µm thick
Primary particles
~ 1 µm dia.
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POLY(VINYL CHLORIDE)
James W. Summers
polymerized PVC skin, compared in figure 3, however, mass PVC would not
mass suspension
150 µm diameter, agglomerate to form grains at 100 - 200 µm diameter (8). With
one droplet per grain, the shape is quite spherical. With several droplets making
up the grain, the shape can be quite irregular and knobby (9). The grain shape
powder (9).
For both suspension and mass polymerizations at less than two percent
slightly below 1 µm diameter (4, 10 - 12). These primary particles are stabilized
by a negative chloride charge (4, 13). Above two percent conversion, these
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POLY(VINYL CHLORIDE)
James W. Summers
or mass resins readily shows the skins, primary particles at 1 µm diameter, and
microscopy reveals a domain structure at about 0.1 µm diameter (8, 15, 16). The
earlier, PVC polymerized in the water phase and deposited on the skin, may be
the source of some of the domain sized structures. Also domain sized flow units
work at 140 - 150°C.(17), that break down the primary particles further.
swelling reaches a limit where the PVC will no longer absorb more plasticizer or
acetone (21). This data suggests a structure where the crystallites of about 0.01
or acetone only swells the amorphous regions without dissolving the crystallites.
Figure 4. Small angle X-ray scattering pattern from PVC plasticized with 20 parts
per hundred resin of dioctyl phthalate (18).
70
60
X-ray Intensity
50
40
30
20
10
0
0 0.5 1 1.5
Scattering Angle, 2 Θ
structure which is built upon even more structure. These many layers of
fillers, and pigments are added to the powder blend for distributive mixing. For
both suspension and mass PVC resins, intensive mixing above the glass
with higher mixing temperatures (23). This increase in apparent bulk density is
due to the smoothing and rounding of the irregular surface. However the grains
of PVC are largely unchanged and are not grossly deformed nor are they broken
In plasticized PVC, liquid plasticizers first fill the voids or pores in the
PVC grains fairly rapidly during powder mixing. If a large amount of plasticizer is
added, the excess plasticizer beyond the capacity of the pores, initially remains
on the surface of the grains making the powder somewhat wet and sticky.
Continued heating increases the diffusion rate of plasticizer into the PVC mass
where the excess liquid is eventually absorbed and the powder dries.
PVC powder compounds are heated, sheared, and deformed during melt
processing. During this process, the grains of PVC are broken down. First the
skin is torn, exposing the PVC grain’s internal structures (24). Then the grains
as the melt flow units. The primary particles seem to be persistent and fairly
stable structures in the melt (25 - 32). This processing window of stable primary
particles exists even with continued melt processing. The primary particle is
The PVC crystallites are small (average 0.7 nm = 3 monomer units) in the
PVC chain direction, and are packed laterally to a somewhat greater extent (4.1
nm) (21, 33). A model of the crystallite is drawn in figure 6. The crystalline
structures, two monomer units per unit cell, and 1.44 - 1.53 specific gravity (34 -
37).
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POLY(VINYL CHLORIDE)
James W. Summers
0.7 nm
4.1 nm
4.1 nm
The PVC primary particle flow units (billion molecule bundles) can
partially melt, free some molecules of PVC, which can entangle at the flow unit
secondary crystallites, and tie the flow units together into a large three
previous processing temperature and the molecular weight of the PVC (38 - 44).
and reformed as secondary crystallinity (54, 55). X-ray defraction has been used
fusion (44, 56 - 59). Sometimes the acetone swollen specimens are sheared
between glass slides to further establish the strength of the three dimensional
structure (59). Fusion has also been assessed based on scanning electron
microscopy of fractured surfaces (29, 30, 46). And inverse gas chromatographic
measurements have also been useful in accessing the degree of fusion of PVC
(60).
The strength of this large three dimensional fused (gelled) structure has
been shown to be critical in determining Izod impact, creep rupture strength, and
even flow in rigid injection molding. In these cases both the melt temperature
during processing and the PVC molecular weight play a large role in the Izod
and creep rupture (38 - 41). In plasticized PVC, this large three dimensional
temperature) determines tensile strength, creep, and cut resistance. A model for
Figure 7. Model for PVC fusion, accounting for molecular weight effects and
properties with higher melt temperatures (42, 56). This has been shown to be
caused by melt fracture, when PVC fuses and flows as large melt flow units of
multiple primary particles (61). These flow units of fused multiple primary
particles can lead to surface roughness during extrusion, in both rigid and
plasticized PVC (44, 56, 62); they can also be responsible for roughness when
While most of the discussion has been on rigid PVC, plasticized PVC has
the same structures as rigid PVC, except that plasticizer enters the amorphous
phase of PVC making the tie molecules elastomeric. The grains break down to 1
µm primary particles which become the melt flow units (44). The crystallites are
not destroyed by plasticizer (21). Partial melting allows entanglement at the flow
CHEMICAL PROPERTIES
carbon atom,
(-CH2-CHCl-CH2-CHCl-CH2-CHCl-CH2-CHCl-)n
carbon atoms.
(-CH2-CHCl-CHCl-CH2-CH2-CHCl-CHCl-CH2-)n
positions, then 13.5% of the chlorine should remain at the end of reaction. Dilute
solutions of PVC treated with zinc, removes 87% of the chlorine, proving the
60% of the chains have unsaturated chain ends (72) and the percentage of
chain ends containing initiator fragments is low (73). Chain transfer to polymer
PVC, removing chlorine with lithium aluminum hydride. The ratio of methyl to
and 1350, or 1370 and 1386 cm-1. Conventional PVC resins, made by mass or
Stereoregularity
The addition of monomer fixes the tacticity of the previous monomer unit.
Syndiotactic structure has the adjacent chlorine atoms oriented to opposite sides
energy for syndiotactic conformation is 4.2 - 8.4 kJ/mol (1-2 kcal/mol) lower than
for isotactic conformation (74, 75). Then the ratio of propagation rates for
(76, 77).
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POLY(VINYL CHLORIDE)
James W. Summers
80
Percent Syndiotactic Diads
70
60
50
40
30
-50 -25 0 25 50 75 100
Polymerization Temperature, C.
polymerization, the polymer precipitates from the monomer when the chain size
monomer, but has a reduced radical termination rate. This leads to a higher
ki
initiation M -→ M .
kp
propagation R . + M -→ R(M) .
kt
termination R . + R . -→ P
molecule in the polymer gel phase, P = polymer in monomer, (P) = polymer gel,
and ki,, kp,, and kt are reaction rate coefficients for initiation, propagation and
termination. Values for kp,, and kt at 60°C are 1.23 X 105 and 2.3 X 1010 L/(mol
Polymerization in two phases, the liquid monomer phase and the swollen
polymer gel phase, form the basis for kinetic descriptions of PVC polymerization
(79 - 81). The polymerization rate is slower in the liquid monomer phase than in
the swollen polymer gel phase due to the greater mobility in liquid monomer
which allows for greater termination efficiency. The lack of mobility in the
radicals, and thus creating a higher polymerization rate. Thus the polymerization
monomer, Cm, is the ratio of the rate coefficient for transfer to monomer to that of
chain propagation. Cm = 6.25 X 10-4 at 30°C and 2.38 X 10-3 at 70°C and a
happens once in every 1600 monomer propagation reactions and at 70°C, chain
transfer happens once every 420 monomer additions (80, 82 - 84). Thus
in figure 9.
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POLY(VINYL CHLORIDE)
James W. Summers
100000
80000
60000
40000
20000
45 55 65 75 85
Polymerization temperature, C.
PVC molecular weights are usually determined in the USA using inherent
viscosity, K value, number average molecular weight (Mn), and weight average
molecular weight (Mw) for commercial grades of PVC are shown in table 4 (85).
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POLY(VINYL CHLORIDE)
James W. Summers
Inherent Relative
viscosity, viscosity, K value, Number average Weight average
ASTM ASTM (Fikentscher: molecular weight molecular weight
D1234 D1234 DIN 53726) Mn (X 10-3) Mw (X 10-3)
0.42 1.09 45.0 15.0 30.0
0.47 1.10 47.1 18.0 36.0
0.52 1.11 49.3 20.0 40.0
0.57 1.12 51.3 22.5 45.0
0.62 1.13 53.6 25.0 50.0
0.67 1.14 56.1 27.5 55.0
0.73 1.16 58.2 30.5 61.0
0.78 1.17 60.5 33.0 67.0
0.83 1.18 62.9 36.0 72.0
0.88 1.19 64.9 38.5 78.0
0.92 1.20 67.1 41.0 82.5
0.98 1.22 69.2 44.0 89.5
1.03 1.23 71.5 47.0 95.0
1.08 1.24 73.3 50.0 101.0
1.13 1.25 74.9 52.5 107.5
1.21 1.27 77.5 57.0 117.0
1.30 1.30 80.7 62.5 128.5
1.40 1.32 83.8 68.5 141.0
1.60 1.38 90.8 81.0 168.0
1.80 1.43 96.7 93.5 195.0
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POLY(VINYL CHLORIDE)
James W. Summers
Mass Polymerization
weight distribution (86). A two stage process that overcomes these problems
was originally developed by Saint Gobain (France), The first stage of the
process is carried out in a prepolymerizer with flat blade agitator and baffles to
about 7 - 10% conversion. This first stage forms a skeleton seed grain for
monomer and initiator are added. This vessel is equipped with a slow moving
agitator blade running close to the vessel wall. The reaction proceeds through
the liquid stage and at about 25% conversion, becomes a powder. Heat removal
is achieved, 30% by the jacket, 60% by a condenser, and 10% by the cooled
agitator shaft (88). Unreacted monomer is removed by vacuum. While the mass
process saves drying energy, it has remained a minor process when compared
Suspension Polymerization
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POLY(VINYL CHLORIDE)
James W. Summers
properties of the suspension stabilizers are key to resin properties and grain
agglomeration (89).
column to a residual monomer level of about 0.0001 % (10 ppm), excess water is
Emulsion Polymerization
Polymerization takes place when the radical enters the monomer swollen micelle
(91, 92). Additional monomer is supplied by diffusion through the water phase.
interactions. A theory for true emulsion polymerization postulates that the rate is
proportional to the number of particles [N]; N depends on the 0.6 power of the
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POLY(VINYL CHLORIDE)
James W. Summers
soap concentration [S] and the 0.4 power of initiator concentration [I]; the
However, the kinetics of PVC emulsion does not follow the above theory.
The rate shows the same increasing behavior with conversion as mass
polymerization (94, 95). [N] depends on [S], but the relationship varies with the
emulsifier type (96, 97). However the rate is nearly independent of [N] (95). The
average number of radicals per particle is low, 0.0005 to 0.1 (95). The high
solubility of vinyl chloride in water, 0.6 weight %, accounts for a strong deviation
from true emulsion behavior. Also PVC’s insolubility in its own monomer
Emulsions of up to 0.2 µm diameter are sold in liquid form for water based
paints, printing inks, and finishes for paper and fabric. Other versions, 0.3 to 10
resins. Plastisols are dispersions of PVC in plasticizer. Heat allows fast diffusion
crystallites.
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POLY(VINYL CHLORIDE)
James W. Summers
Micro-Suspension Polymerization
make plastisols for flooring, seals, barriers, etc. These plastisols are also
dispersions of PVC in liquid plasticizer and are cured by heating. Heating allows
plasticizer to uniformly diffuse into the PVC particles and at higher temperatures,
Solution Polymerization
obtain very uniform copolymers. Polymerization rates are normally slower than
for suspension or emulsion PVC. For example, vinyl chloride, vinyl acetate, and
sometimes maleic acid are polymerized in a solvent where the resulting polymer
Copolymerization
reduce crystallinity which aids fusion and allows lower processing temperatures.
contains maleic acid or vinyl alcohol (hydrolyzed from the polyvinyl acetate) to
with vinylidene chloride are used as barrier films and coatings. Copolymers of
vinyl chloride with maleates or fumerates are used to raise heat deflection
temperature. Copolymers of vinyl chloride with acrylic esters in latex form are
coatings. Copolymers with olefins improve thermal stability and improve melt
temperature
M2 r1 r2 e Q °C. ref.
acrylic acid 0.107 6.8 0.77 1.15 60 101
acrylonitrile 0.04 2.7 1.20 0.60 60 102
butadiene 0.035 8.8 -1.05 2.39 50 103
butene 3.4 0.21 104
n-butyl acrylate 0.07 4.4 1.06 0.50 45 101
105
diethyl fumarate 0.12 0.47 1.25 0.61 60 106
dimethyl itaconate 0.053 5.0 1.34 1.03 50 107
diethyl maleate 0.77 0.009 104
ethylene 3.21 0.21 -0.20 0.015 50 108
ethylhexyl acrylate 0.16 4.15 104
isobutylene 2.05 0.08 -0.96 0.033 60 109,
110
isoprene -1.22 3.33
maleic anhydride 0.296 0.008 2.25 0.23 75 111
methacrylic acid 0.034 23.8 0.65 2.34 60 101
methacrylonitrile 0.68 0.86 60 112
methyl acrylate 0.12 4.4 0.60 0.42 50 113
methyl methacrylate 0.1 10 0.4 0.74 68 114
octyl acrylate 0.12 4.8 1.07 0.35 45 105
propylene 2.27 0.3 -0.78 0.002 115,
110
styrene 0.02 17 -0.80 1.0 60 116
vinyl acetate 1.68 0.23 -0.22 0.026 60 117
N-vinylcarbazole 0.17 4.8 -1.40 0.41 50 118
vinyl chloride 0.20 0.044
vinyl laurate 7.4 0.2 104
vinylidene chloride 0.3 3.3 0.36 0.22 60 119
vinyl isobutyl ether 2.0 0.02 50 120
N-vinylpyrrolidone 0.53 0.38 -1.14 0.14 50 121
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POLY(VINYL CHLORIDE)
James W. Summers
COMPOUNDING
The additives found in PVC help make it one of the most versatile,
commonly used PVC products would not exist. Many materials are useless until
they undergo a similar modification process. Steel, for instance, contains among
other things, chromium, nickel and molybdenum. PVC’s are tailored to the
Stabilizers
Organotin stabilizers are commonly used for rigid PVC, including for pipe,
fittings, windows, siding profiles, packaging and injection molded parts.. These
repair unstable sites on PVC removing unstable chlorine and replacing it with a
ligand from the tin stabilizer molecule(123 - 125). This produces stability at least
isooctlythioglycolate. Certain grades of methyl tins and octyl tins are used in
stabilizers(122).
Calcium-zinc stabilizers are used in both plasticized PVC and rigid PVC
for food contact where it is desired to minimize taste and odor characteristics.
quite useful with barium-zinc and calcium-zinc stabilizers. They are beta
Impact modifiers
brittle. This gave plastics a cheap reputation. It was therefore quite desirable to
develop technology to produce tough plastics. In the early 1950s, The Geon
(127). This can result in cavitation and/or cold drawing, thus allowing the PVC to
absorb large amounts of energy. Impact modifier choices are listed in table 6.
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POLY(VINYL CHLORIDE)
James W. Summers
siding X X X X
windows X X X X
gutters X X X X
pipe & X X X X X X X
conduit
irrigation X X X X
pipe
fittings X X X X X X X
interior X X X X X X X
trim
foam X
interior X X X X X X X
profiles
clear film X X X
clear X X X
bottles
credit X X X X X X X
cards
furniture X X X X
appliances X X X
housings X X X
acr = all acrylic
m-acr = modified acrylic
ABS = acrylonitrile/butadiene/styrene
CPE = chlorinated polyethylene
EVA = ethylene/vinyl acetate
MBS = methyl methacrylate/butadiene/styrene
MABS = methacrylate/acrylonitrile/butadiene/styrene
page 40
POLY(VINYL CHLORIDE)
James W. Summers
Processing aids
glue these particles together before the PVC melts, thus acting as a fusion
promoter. Processing aids also modify melt rheology by increasing melt elasticity
and die swell, or, some reduce melt viscosity, and they reduce melt fracture.
Some processing aids lubricate to reduce PVC sticking to metal. And processing
aids affect dispersion of fillers, impact modifiers, and pigments (129). The most
common processing aids are high molecular weight acrylics based primarily on
polymethylmethacrylate copolymers.
Lubricants
little effect on fusion, or they reduce melt viscosity; external lubricants were
various lubricants (135, 136), but did not explain the nature of that synergy. A
model for the lubrication mechanism has been developed which explains
synergy between certain lubricants (62). This model treats lubricants as surface
active agents. Some lubricants have polar ends which are attracted to other
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POLY(VINYL CHLORIDE)
James W. Summers
polar ends and to polar PVC flow units and to polar metal surfaces. These also
have non-polar ends which are repelled by the polar groups. Synergy happens
when non-polar lubricants are added, which are attracted to the non-polar ends
Figure 10. A model of PVC lubrication mechanism (not to scale) showing a) PVC
adhesion to metal without lubricant, b) surface activity of calcium stearate, c)
non-metal releasing character of just paraffin, and d) synergy between calcium
stearate and paraffin (62).
a) b)
PVC
PVC
PVC PVC PVC
calcium stearate
metal
c) d)
paraffin wax
PVC PVC PVC
PVC
paraffin wax
calcium stearate
page 43
POLY(VINYL CHLORIDE)
James W. Summers
Plasticizers
solutions are flexible, elastic, and exhibit a high degree of chemical inertness
that act as physical crosslinks, but allow the PVC to accept large amounts of
room temperature, thus making it rubbery. Thus PVC was the first thermoplastic
elastomer (TPE). This rubber-like material has stable properties over a wide
example, citrate esters are used in food contact applications, benzoates are
used for stain resistance, and chlorinated hydrocarbons impart flame resistance
and good electrical properties. Aliphatic diesters offer good low temperature
flexibility; linear alcohol based phthalates offer good low temperature flexibility
trimellitates have low volatility, are used for high temperature applications, and
migrate easily but suffer from poor low temperature flexibility. Epoxy plasticizers
page 44
POLY(VINYL CHLORIDE)
James W. Summers
are also good plasticizers with low volatility and they act as costabilizers,
Plasticizer Abbreviation
Aliphatic ester
di(2-ethylhexyl) adipate DOA
di(2-ethylhexyl) azelate
di(2-ethylhexyl) sebacate
Phthalate
di(2-ethylhexyl) DOP or DEHP
diisooctyl DIOP
diisodecyl DIDP
butylbenzyl BBP
butyloctyl BOP
diisononyl DINP
ditridecyl DTDP
diundecyl DUP
linear C7-C11 711 phthalate
di(2-ethylhexyl) terephthalate DOTP
Phosphates
trioctyl TOP
cresyl diphenyl CDP
tricresyl TCP
triphenyl
tri(2-ethylhexyl) TEHP
Trimellitates
tris(2-ethylhexyl) TOTM
triisooctyl TIOTM
Epoxies
epoxidized soybean oil ESO
epoxidized linseed oil
epoxy stearate
2-ethylhexyl epoxytallate
determine their potential impact on human health and the environment. DEHP
blood bags, saline solutions, meat wraps and other highly credible uses,
however, there has been much debate over that impact due to the differing
page 46
POLY(VINYL CHLORIDE)
James W. Summers
rapidly becoming available and the reader may want to update this information in
the years following publication of this article). While the U.S. National Toxicology
Program and the International Agency for Research on Cancer have classified
been criticized for potentially inaccurately ascribing results obtained with rodents
metabolic changes that are specific to that species. Because the evidence
indicates the response is an artifact to that species and not a true indication of
Commission for instance, has concluded that there is no evidence to warrant the
carcinogen by the U.S. Food & Drug Administration, which has long governed
known to actually protect red blood cells from deterioration. Flexible PVC film is
oxygen-permeable and maintains the bright red color needed to make meats
Fillers
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POLY(VINYL CHLORIDE)
James W. Summers
Fillers are used to improve strength and stiffness, to lower cost, and to
control gloss. The most common filler is calcium carbonate. It ranges in size from
0.07 to well over 50 µm. Some forms are treated with a stearic acid coating.
fibers, talc, and mica improve tensile strength and stiffness, but at a loss in
ductility.
Pigments
dioxide and carbon black are strong ultraviolet light absorbers and effective in
protecting the PVC. The carbon black is a stronger absorber than titanium
dioxide and can therefore be used at lower levels in PVC for protection. For
Biocides
Although PVC itself, and rigid PVC compounds are resistant to attack by
sealing boots on roofs, shower curtains, and swimming pools, may need
protection. Many biocides, often containing arsenic compounds, are available for
Flame retardants
Since PVC contains nearly half its weight of chlorine, it is inherently flame
retardant. Not only is chlorine not a fuel, but it acts chemically to inhibit the fast
oxidation in the gas phase in a flame. When PVC is diluted with combustible
plasticized PVC with >30% plasticizer, may require a flame retardant such as
physical blowing agent into the melt, or using a chemical blowing agent which
which decomposes with heat to release nitrogen gas. Typically the closed cell
foams of rigid PVC range down to a density of 0.4 grams/cc. Physical blowing
when used with a copolymer PVC. Because of the damage to the ozone layer in
the stratosphere, not all chlorofluorocarbons are acceptable and newer types of
depletion.
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POLY(VINYL CHLORIDE)
James W. Summers
Compound manufacture
All PVC must be compounded before it is used. For the wide variety of
balanced to meet the range of properties required and to do the best job
figure 11 according to their approximate share (147). The total volume is not
tons (160,000 lbs.), in bulk trucks containing 20 tons (44,000 lbs.), boxes
process. These businesses are not included in the following chart of merchant
manufacturing, barrier & packaging film manufacturing, and wire & cable
manufacturing.
PVC resins are manufactured and sold for a wide variety of applications.
About 14.5 billion pounds of resin are manufactured in North America and 53
billion pounds world wide. These resin manufacturers are broken down in figures
12 and 13. These resins are available in bulk railcars containing 80 tons
(160,000 lbs.), in bulk trucks containing 20 tons (44,000 lbs.), boxes containing
Figure 12. North American PVC resin capacity - 1995 - 6.6 billion Kgrams,
(4.5 billion pounds) (1, 147, 148). Source for both fig 12 & 13: CMAI (148).
SHINTECH
19% Geon 16%
6 Others 5%
FPC 14%
Goodyear 1%
Policyd 2%
Esso 2%
Primex 3%
Westlake 4%
Oxy 10%
Vista 7%
Georgia Gulf Borden 9%
8%
Figure 13. World PVC resin capacity - 1995 - 24 billion Kgrams (1, 147, 148).
N. America
27%
Asia 30%
Africa 2%
Australia 1%
Mid East 3%
S. America 4%
E. Europe 9% W. Europe
24%
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POLY(VINYL CHLORIDE)
James W. Summers
World demand
World demand is 22 billion kilograms (49 billion pounds) in 1995, with the
Figure 14. World demand for PVC. (1, 147, 148). Source: CMAI (148).
25
BILLIONS KILOGRAMS
20
15
10
0
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
YEAR
Per capita demand for PVC is high in Canada, USA, Japan, and Western
Europe, with lots of room for growth in Africa, the Mideast, the Far East, Mexico,
Figure 15. Per capita demand for PVC by region. (1, 147, 148). Source: CMAI
(148).
Africa &
Mideast
Average
Far East
Mexico
South
America
Eastern
Europe
World
Western
Europe
Japan
USA
Canada
0 10 20 30 40
Pounds per capita
PVC resin prices tend to be more stable than other plastics’ prices, partly
because only about half the molecule is based on hydrocarbon raw material
page 56
POLY(VINYL CHLORIDE)
James W. Summers
Figure 16. PVC prices compared to other plastics’ prices (147, 148). Source:
CMAI (148).
120
ABS
100
80 HDPE
PP
Cents/lb.
60 PS PS
PVC
ABS
40
HDPE PP PVC
20
0
1Q '94
2Q '94
3Q '94
4Q '94
1Q '95
2Q '95
3Q '95
4Q '95
Quarter
page 57
POLY(VINYL CHLORIDE)
James W. Summers
Figure 17. PVC prices over several years ( 147, 149, Chem Data, Inc. ).
50
45
40
35
Cents/pound
30
25
20
15
10
0
1990
1991
1992
1993
1994
1995
Year
Standard Description
ASTM D1755 PVC resin cell classification
ASTM D1784 PVC rigid compound cell classification
ASTM D1785 PVC pipe, schedule 40, 80, 120
ASTM D2287 PVC non-rigid (plasticized) compound cell classification
ASTM D2464 PVC THR fittings
ASTM D2466 PVC socket fittings, schedule 40
ASTM D2467 PVC socket fittings, schedule 80
ASTM D2665 DWV pipe and fittings
ASTM D2729 PVC Sewer pipe and fittings
ASTM D2740 PVC tubing
ASTM D2846 CPVC hot water distribution system
ASTM D2949 PVC DWV, 3 inch thin wall
ASTM D3033 PVC PSP sewer pipe and fittings
ASTM D3034 PVC PSM sewer pipe and fittings
ASTM D4216 PVC rigid building products compounds
NSF 14 PVC potable water, fittings
UL 62 PVC wire insulation
UL 83 PVC T, TW, THW, THWN, THHN wire insulation
UL 444 PVC telecommunications wire insulation jacket
UL 719 PVC NM jacket
UL 758 PVC AWM wire insulation
UL 1272 PVC TC cable jacket
properties and it is used in a wide variety of markets. Most of the products are
durable goods and have long lifetimes. Its use in short term, one time use,
Metric tons
Construction
Flooring 120,000
Pipe & Conduit 2,070,000
Wire & Cable 180,000
Siding 640,000
Windows & Doors 140,000
Extrusions 240,000
Packaging
Bottles 80,000
Extrusions 160,000
Calendering 390,000
Custom Moldings 50,000
Paste Processes 100,000
Textiles & Coating 70,000
Exports & Resale 850,000
Other 60,000
Total 5,360,000
Pipe and fittings are a major market for PVC. These are a prime example
PVC for long term satisfactory performance. The applications are highly
optimized for efficient production at high rates and minimal costs. Pipe
Products include pressure pipe of various sizes and drain, waste, and vent
applications.
as for hot water piping. Because of its superior creep resistance, CPVC is also
Plastic materials are damaged by the sun, particularly by ultraviolet light. PVC’s
processing (150, 151). For this reason it is important to avoid thermal damage to
PVC during processing. The absorbed light breaks bonds and forms free
radicals. This leads to loss of hydrogen chloride and yellowing, and at the same
proper choice of the type of titanium dioxide to control the rate of the oxidation
and bleaching process, and with a proper choice of other weather stable
page 61
POLY(VINYL CHLORIDE)
James W. Summers
weather.
production at high rates and minimal costs. Siding uses powder compounds, twin
Other products such as windows, may or may not use the powder
much more complex operation than for pipe, and requires large investments to
develop and operate the process. Cubed compound, where the PVC grains are
already broken down, can be run faster and on simpler single screw extruders,
because lower melt temperatures are typical. Because elastic swell is reduced at
lower melt temperatures, die design is simpler. Either vacuum sizing or air
standards. Products include siding, soffits, gutters & down spouts, windows,
including the all-vinyl windows, and vinyl protected wood windows, and door
Profiles
and operate extrusion dies, and cooling and sizing equipment that delivers the
exact dimensions required. Cubed compound, where the PVC grains are already
broken down, can be run faster and on simple single screw extruders, because
low melt temperatures are typical. Because elastic swell is reduced at lower melt
temperatures, die design is simpler and often is the same dimensions as the
The low elastic swell is unique to PVC, and is due to the billion molecule
flow units. Other plastics have higher die swell, which increases at lower melt
temperatures (153). Thus those plastics have much more difficulty in designing
PVC has been used in wire & cable applications since World War II, when
compounds on single screw extruders. Some line speeds are 5000 feet/minute
(60 mph). The compounds are optimized for the requirements, including low
page 63
POLY(VINYL CHLORIDE)
James W. Summers
molded from rigid PVC. These take advantage of PVC’s outstanding Underwriter
Laboratories flammability ratings and easy molding into thin walled parts. PVC
has developed melt flow capabilities to the point where it competes with
essentially any other flame retarded engineering thermoplastic and molds easier
than most.
Pipe fittings require quite high tensile and creep resistance, thus they are
molded from compounds have less melt flow than for thin walled housings.
MSDSs available
The potential health and safety effects of PVC and all PVC additives, as
well as all feedstocks, are fully detailed by each manufacturer in material safety
data sheets (MSDS), which are required by U.S. law. These are available to
anyone who wishes to review them, and must be provided to all plant workers.
While the processing and use of PVC is not any more hazardous than that of
other plastic materials, this section goes into potential concerns in some detail.
decrease in breathing capacity for workers who smoked and were exposed to
vinyl resin dust. This decrease was about one-seventh of that caused by normal
aging and about equal to that expected with a one-pack-a-day cigarette smoker.
utilization of care when dumping bags, sweeping, mixing or doing other tasks
page 65
POLY(VINYL CHLORIDE)
James W. Summers
which can create dust. The use of an approved dust respirator is recommended
may be irritating to the respiratory tract. This is also true for PVC and its
additives, and this irritation may extend to the skin and eyes of sensitive people.
irritation of the respiratory tract, eyes and skin. Depending upon the severity of
respiratory tract.
warning signal, causing exposed personnel to be driven from the area which
low as 1 - 5 ppm.)
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POLY(VINYL CHLORIDE)
James W. Summers
irritation.
of energy is required to break down the polymer into smaller fragments that will
flame quencher in the vapor phase. Polyvinyl chloride will release less heat than
minimum ignition energy for explosion is much higher than that of natural
materials such as corn starch and flour and also exceeds those of other plastic
page 67
POLY(VINYL CHLORIDE)
James W. Summers
occur. Also insure walkways and floors are cleared of polyvinyl chloride dust to
media. Carbon dioxide may be ineffective on larger fires due to lack of cooling
cleanup immediately after a fire as well as during the attack phase of firefighting
operations.
PVC should not be melt mixed with acetal polymers. These polymers are
evolution.
Toxicology
tumorigenic through oral and implant studies. The International Agency for
(ACGIH) has a threshold limit value (TLV) of 10 mg/m3 for inhalable and 3 mg/m3
for respirable while the Occupational Safety and Health Act (OSHA) permissible
exposure limits (PEL's) are 15 mg/m3 for total dust and 5 mg/m3 for the
respirable fraction.
Regulatory
listed through its monomer, vinyl chloride [CASRN: 75-01-4]. In the United
States polyvinyl chloride is an EPA Hazardous Air Pollutant under the Clean Air
Act Section 112 (40 CFR 61) and is covered under the New Jersey Community
to human life. Free chlorine is produced geothermally within the earth, and
occasionally finds its way to the earth's surface in its elemental state (165). More
Hydrochloric acid reacts quickly with other elements and compounds, forming
magnesium chloride and potassium chloride, all found in large quantities in sea
water.
The chlorides found in common salt water are an essential element in all
body fluids, and in this form, makes up about 0.15 percent of total body weight.
produced chemicals, widely present in nature, and play many essential roles
and griseofulvin, which have revolutionized the treatment of human bacterial and
fungal infections.
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POLY(VINYL CHLORIDE)
James W. Summers
are produced from burning wood and other vegetable matter, and are natural
and have been so since before the existence of man. Both dioxins and furans
have been found in lake sediments dating back to 1860 (172) and samples taken
from ice cores in Greenland dating back to 1869 show definite "spikes" in
chlorine content correlating with volcanic activity (173). Given the fact that
and would deprive the world of hundreds of products critical to society's health
Over 30% of the chlorine produced on a global basis goes to make PVC.
number of unique properties that give this versatile plastic a distinct advantage
retardant. PVC is the world's leading electrical material, with over 500 million
pounds used annually for wire and cable insulation and sheathing, electrical
conduit, boxes and components. PVC is over 50% chlorine and as a result, is
one of the most energy efficient polymers. Chlorine makes PVC far more
Although vinyl is the world's second most widely used plastic, less than
one-half percent by weight is found in the municipal solid waste stream. Most of
that consists of vinyl packaging, bottles, blister packaging and flexible film.
That's because most vinyl applications are long-term uses, such as pipe and
house siding, that are not disposed of quickly. Vinyl wastes are handled by all
waste-to-energy).
1994, about 6.5 million pounds of post-consumer vinyl were recycled in the U.S.
An estimated additional 300 million pounds of vinyl post industrial scrap was
diverted from landfills and recycled into second-generation products. More than
vinyl and use PVC pipe to handle liquid leachate and methane gas, to protect
the environment.
paperboard, paper and selected plastics concluded that vinyl was the material
with the lowest production energy and carbon dioxide emissions, and the lowest
fossil fuel and raw material requirements of the plastics studied (175). Vinyl
saves more than 34 million BTUs per 1,000 pounds manufactured compared to
Engineers (ASME), involving the analysis of over 1,700 test results from 155
relationship between the chlorine content of waste and dioxin emissions from
combustion processes. Instead, the study stated, the scientific literature is clear
that the operating conditions of combustors are the critical factor in dioxin
generation (177). This work includes and confirms a number of other studies,
most notably, the work conducted in 1987 by the New York Energy Research
and Development Authority. Those tests revealed that the presence or absence
page 73
POLY(VINYL CHLORIDE)
James W. Summers
of PVC had no effect on the amount of dioxin produced during the incineration
process (178).
incinerators so that they can neutralize a range of acid gases, including sulfur
dioxide and nitrogen oxide, which are produced by a variety of materials. Since
things as table salt and paper products, scrubbers are necessary whether or not
PVC is present in the waste feed (180). A recent study, conducted by Midwest
Research Institute and published by the ASME, concluded that removing vinyl
from the waste stream would not eliminate the need either for air pollution
control devices and monitoring equipment, nor would it influence the choice of
In fact, power plants burning fossil fuels, which produce sulfur dioxide and
nitrogen oxide, are actually the leading cause of acid rain, along with automotive
exhaust (182, 183). In Europe and Japan, studies show that only about 0.02
Not true. Of course, industrial scrap vinyl has been recycled for years, but
now, post-consumer vinyl recycling is growing, too, with about 6.5 million pounds
Council for Solid Waste Solutions (now, the American Plastics Council)
1,100 municipal recycling programs in place or planned in the United States that
include vinyl.
Not true. In 1989, the University of Toledo identified nearly 100 uses for
recycled vinyl. Overall, the potential demand for recycled vinyl is estimated to be
over twice the potential supply of all vinyl bottles produced in the US each year
(494 million pounds needed vs. 207 million pounds available via recycling of
resins.
resins are just as much a contamination problem for vinyl. Except for
to efficiently separate one plastic from another. Thanks to the chlorine that is
present in it, vinyl lends itself very well to automated sorting technology.
d) PET and HDPE packaging are listed as 1 and 2 in the SPI recycling coding
Not true. The numbers assigned to each plastic in the SPI coding system
effect on the levels of dioxin produced. Rather, it was found that incinerator
incinerating vinyl waste and decided there was no cause for concern.
page 76
POLY(VINYL CHLORIDE)
James W. Summers
additives.
to replace heavy metals is in progress but some use will continue. Banning vinyl
from incinerators will not eliminate this problem. Rather, regulations should
Not true. There is only one ban on vinyl packaging in Europe, and that is
block the sale of French mineral water in that country. There is a voluntary
to change those restrictions with several notable reversals, including Berlin and
concluded there should be no bias against the use of PVC (186 - 188).
Britain, one of the leading retailers, Marks & Spencer, has chosen vinyl over
Switzerland, retailer Migros has stated that its whole attitude toward vinyl will
reduction and make industry a partner in that process. This involves all
industries, not just the vinyl industry. Overall, Europe remains a larger consumer
h) Vinyl plastics decompose in landfills and give off vinyl chloride monomer.
Not true. Like all plastics, vinyl is an extremely stable landfill material. It
materials and found that vinyl consumed the least amount of energy, used the
lowest level of fossil fuels, consumed the least amount of raw materials and
produced the lowest levels of carbon dioxide of any of the plastics studied. In
fact, the Norwegian environmental group Bellona has concluded that "a
generally reduced use of vinyl plastics will, given today's circumstances, lead to
Not true. The real hazards in a fire are carbon monoxide and heat; these
are especially a problem with other materials that readily burn. Because vinyl
products contain chlorine, they are inherently flame-retardant and resist ignition.
When it does burn however, vinyl produces carbon monoxide, carbon dioxide
page 78
POLY(VINYL CHLORIDE)
James W. Summers
Hydrogen chloride is an irritant gas that can be lethal at extremely high levels.
However, research indicates that those levels are never reached or even
approached in real fires. All organic materials, when burned, release a lengthy
list of chemical by-products. For instance, when wood burns, as many as 175
different fire gases may be produced, including benzene and acrolein (189).
Burning wool will produce hydrogen cyanide. Even the simple act of barbecuing
considered the greatest toxic hazard in fires because of the abundant levels
The U.S. fire death rate is decreasing, dropping from a rate of 76 per
million in the 1940s (when most construction and decorative products were
made of "natural" materials), to 29 per million in the 1980s (by which time, PVC
trend can be attributed in large part to improved building codes and the broader
use of sprinkler systems and smoke detectors. However, the increased use of
more fire-resistant materials, like PVC, deserves part of the credit for this
improvement.
Hydrogen chloride is produced when PVC burns. A series of tests for the
Federal Aviation Administration studied this issue. In those studies, test animals
More recent studies indicate less of a potential for delayed effects on lung
page 79
POLY(VINYL CHLORIDE)
James W. Summers
function than expected (194). In a typical fire, hydrogen chloride levels rarely
exceed 300 ppm, a fact confirmed by the Boston Fire Department and Harvard
neither type of material presented a clear-cut advantage in a fire, and that the
ACKNOWLEDGMENT
I wish to thank The Geon Company for allowing me over the years to build
a knowledge of PVC that makes this review possible. I wish to thank Lu Liu and
Dick Roman for assistance in determining the size of this industry, Thanks to
Mark Hross for his assistance on the section on health and safety, and thanks to
D’Lane Wisner and Fred Krause for helping with the environmental
considerations and recycling. Of course the previous authors of this review, John
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page 87
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ABSTRACT
PVC has a large sales volume, second only to polyethylene. Its high
chlorine content provides it with a very high level of combustion resistance for
building products, electrical enclosures, and wire & cable insulation. PVC has a
such as for siding and windows, compounds that have stiff melts and little elastic
viscosity melts which compete effectively with ABS and PC/ABS in thin walled
polymer precipitates from its monomer and grows into primary particles, which
are later the melt flow units. Fusion into larger structures and product strength
are controlled by break-down of the grains into primary particles, by the choice
result, is one of the most energy efficient polymers, makes PVC inherently flame
containers from other plastics in the waste stream. Vinyl is recycled by at least
170 recyclers in the U.S. and Canada and more than 3,500 communities accept
vinyl products in their recycling programs. The analysis from 155 large-scale,
content of waste nor the addition of PVC, and dioxin emissions from combustion
processes. New requirements from the U.S. EPA make scrubbers mandatory on
all incinerators and are necessary whether or not PVC is present in the waste
feed.