Polymer Science & Engineering Course

Poly(vinyl chloride)

1. Introduction
Poly(vinyl chloride) (PVC) has a chemistry and a physical structure that makes it
broadly unique in the polymer world. PVC (often referred to vinyls or vinyl resins) is
made commercially at several molecular weights, depending on the intended
applications: from Mw = 39000 g/mol, to Mw = 168000 g/mol. PVC chemistry follows:

(I)

where n, i.e. degree of polymerization, ranges commercially from 625 to 2700.

PVC has grown to be one of the major plastics of the world. It was the largest group of
thermoplastic materials; however, the vinyl resins have been suppressed in volume by the
olefin polymers. PVC is second in volume to polypropylene among plastic materials,
Figure 1. The volume of each individual categories of polyethylene is smaller than
PVC’s.

1.1 Raw material

The chemical process for making PVC involves three steps: first, production of the
monomer, vinyl chloride; then the linking of these monomer units in a polymerization
process; and finally the blending of the polymer with additives, Figure 2. In this section,
the production of raw materials will be considered.
Ethylene comes from oil or natural gas which is refined and 'cracked' by heating
ethane, propane or butane or naptha from oil. Ethylene reacts with chlorine to form
ethylene dichloride (EDC), which is finally cracked to the monomer. Chlorine is
produced from electrolysis of salt (NaCl). In this process, the dissolved salt is chemically
decomposed by passing an electric current through it. This produces chlorine and sodium.
Sodium reacts with water to form caustic soda (sodium hydroxide) and hydrogen gas.
The manufacture of PVC accounts for 35% of the chlorine produced industrially and
0.3% of the worlds supply of gas and oil, Figure 3. Most other polymers are largely

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hydrocarbons and thus are highly dependent on supplies of oil and gas; whereas PVC is
much less dependent on the supply of oil and gas.

Figure 1. Annual worldwide use of plastics (year 2000).

Figure 2. PVC production.

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Figure 3. the raw materials for PVC.

2.2 Chlorine content

Vinyl compounds often contain nearly 50% chlorine. Because of this, in a fire, vinyl
provides only about half the fuel compared to other polymers. Halogens in flame-
retardants, including chlorine in PVC, additionally provide condensed phase and gas
phase combustion resistance by a radical- trapping, flame-poisoning mechanism. This is a
reaction of the neutral halogen with hydrogen on the fuel to remove hydrogen as a fuel
element and to form hydrogen halide. Thus, vinyl is unique in its resistance to
combustion because it has lower intrinsic fuel content than other polymers, it can form
hydrogen chloride in the condensed phase to reduce available fuel, and it can inactivate
hydrogen from fuel in the gas phase. This chemistry is as follows:

R−X + H ~~~~~~~~ → R • + H − Cl + • ~~~~~~~~ (1)

Flame Hydrogen Flame Fuel, less
retardant on fuel retardant hydrogen
fragment

Additionally, the hazards in a fire are mainly carbon monoxide and heat; these are
especially a problem with materials other than vinyl that readily burn. When forced to
burn, vinyl produces carbon monoxide, carbon dioxide, and hydrogen chloride. Of these,
the most hazardous is carbon monoxide. Hydrogen chloride is an irritant gas that can be
lethal at extremely high levels, which are never reached or even approached in real fires.

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3. Polymerization
Vinyl chloride monomer (VCM) is a clear, colorless liquid that boils at -13 ºC. VCM is
polymerized via free-radical methods, Scheme 1. VCM has a liquid density at normal
polymerization temperature between 0.85-0.9 g/cm3. The polymer has a density of 1.4
g/cm3 which is a sign of the large shrinkage during polymerization.

Scheme 1. VCM polymerization.

3.1 VCM vs. oxygen

Oxygen is an effective but undesirable shortstop for the polymerization reaction. An
alternating copolymer of oxygen (peroxide, R-O-O-R') and VCM (called poly(vinyl
chloride peroxide)) will form until oxygen is consumed and the polymerization reaction
starts. Thus, oxygen must be excluded from the polymerization.

3.2 VCM vs. nitrogen

Nitrogen is quite soluble in VCM, so it is not good practice to use nitrogen pressure to
move the monomer about the plant or the laboratory. Different alternatives are available:

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o Pumps
o Slight heating of the storage tank to generate enough pressure for monomer transfer
o Gravity transfer

Nitrogen does not interfere with the polymerization; however, because nitrogen is
soluble in the monomer and not soluble in the polymer, significant pressure can build up
in the polymerization vessel during polymerizations containing nitrogen, especially if
there is not a lot of headspace in the vessel.

3.3 Polymerization
Because of the low boiling point of the monomer and the limited stability of the
polymer, polymerization of vinyl chloride must be carried out under conditions giving
rapid reactions at low temperatures (polymerization temperature is 50 ºC). Bulk
polymerization cannot be carried to high conversions because of local overheating
leading to deterioration of the polymer. Solvents are often used to prevent this effect.
PVC is mostly produced by suspension polymerization since the reaction can be
controlled better.

PVC solubility in its monomer

PVC is highly insoluble in its own liquid monomer. PVC precipitates as tiny particles
during polymerization and the agglomeration of these particles produces a porous
internal structure in the resin particles.
VCM, however, is fairly soluble in PVC, and thus the particles of PVC precipitated
during the polymerization are highly softened by the monomer. The rate of
polymerization of the VCM inside the swollen particle is substantially faster than the rate
of polymerization inside the liquid phase, because the gel prevents mobility of the
growing polymer radicals and therefore results in a substantial lowering of the radical
termination rate in the gel; notice that polymerization termination takes place by either
combination or disproportionation. Thus, PVC polymerizations are auto-accelerating. As
the conversion increases, more of the fast polymerizing (swollen) phase present. With a
long half-life initiator, this results in a reaction rate that is proportional to the conversion.
Long-life initiators are generally not used, so the acceleration tends to drop off as the
active initiator is consumed.

Polymerization kinetics
A typical reaction rate curve of heat versus conversion is shown in Figure 4. This curve
is generated by a computer model simulation, but similar curves result from real

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measurements of the heat release from actual polymerization reactions. The solid line is
the predicted reaction curve and the dotted line is the actual heat that must be removed
from polymerization reactor. Note that the dotted line is slightly lower than the solid line,
because of the effect of water injection. Starting at about 60% conversion, a rate peak is
observed. The rate peak starts when all of the liquid monomer has been consumed and
pressure-drop starts. Further polymerization produces a change in the composition of the
remaining swollen polymer phase. As the composition changes, the local mobility of the
growing polymer chain is reduced relative to the mobility of the low molecular weight
monomer. The radicals are not able to find each other easily. The termination rate is
therefore reduced, causing the concentration of free radicals to rise and the rate of
polymerization rises accordingly. At approx. 75% conversion, the composition has
changed enough that now the monomer has reduced mobility and concentration and the
polymerization rate starts to fall owing to a reduced propagation rate. At just over 90%
conversion, the rate essentially approaches zero, because the polymer VCM phase passes
through the glass transition temperature and essentially all mobility stops. Commercially,
reacting beyond approximately 80-85% conversion is not very efficient. In order to keep
this reaction under control during the rate peak, the polymerization reactor used for this
reaction would need to be able to remove 2250 kilowatts of energy, allowing a slightly
excess heat removal capability for margin of error. Note that the polymerization depicted
in Figure 4 has a built-in safety feature. The reaction rate accelerates at 60% conversion
as the pressure is dropping. A run away reaction at this conversion is not likely to
produce a reactor over-pressurization situation.

Figure 4. Plot of heat load versus conversion predicted by a computer model for an
isothermal polymerization.

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3.4 Molecular weight

The molecular weight of PVC is controlled by altering the polymerization temperature,
chain transfer to monomer controls the molecular weight. A typical radical will chain
transfer about ten times before it ultimately terminates. The higher the polymerization
temperature, the lower the molecular weight. As the temperature increases, the rate of
chain transfer to monomer increases faster than the chain propagation rate. The reaction
temperature can be isothermal for narrow molecular weight distribution or temperature
ramped to give wider distribution.
Normal commercial polymerization temperatures range from 50°C to approximately
70°C. Below 50 °C, the reactions become too slow and the molecular weight is generally
too high for most processing needs. Above 70°C, the reactor pressure becomes too high.
If extremely fast polymerizations are run, however, e.g., with a total polymerization time
faster than approximately three hours, the concentration of free radicals can get high
enough that the termination reaction can start to play a role in molecular weight control.
Normal polymerization times run from 3 to 6 hours, but reactor design can greatly affect
this.
It should be pointed out that for PVC, the term chain transfer to monomer takes on a
special meaning. Mechanistically, it is not a classical chain transfer mechanism. The
chain transfer process in PVC actually starts with a monomer unit adding in a head-to-
head fashion. The resulting growing radical structure does not continue to polymerize fast
enough and generally, before another monomer can add, the structure rearranges, inserts
a double bond at the end of the chain, and another new radical is formed, which in turn
initiates a new growing chain. The process looks like chain transfer to monomer, but this
mechanism is somewhat unique to PVC.

3.4.1 Molecular weight extension

There are occasions, when a molecular weight is desired higher or lower than that
produced at polymerization temperatures between 50 and 70°C. Polymerization
temperatures lower that 50°C can be used without over-pressurization risk, but as the
temperature is lowered, the reaction temperature approaches the temperature of the
cooling water and the ability to remove heat is reduced or lost entirely. Higher molecular
weight products can be made at normal polymerization temperatures with the addition of
a multifunctional monomer such as di-allyl phthalate. This produces a branched polymer
of higher molecular weight but not higher crystallinity. The amounts of multifunctional
ingredients that can be used are limited, however, because eventually a cross-linked

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product results. It is often good practice to meter the multifunctional monomer to keep its
concentration low.
Making lower molecular weight polymers is a bit more challenging. Going up in
polymerization temperature is easy from a heat transfer perspective but usually the
polymerization vessel cannot withstand the VCM vapor pressure. In order to make lower
molecular weight PVC it is often necessary to employ chain transfer agents. Unlike
polyolefins, however, there are no effective chain transfer agents yet. All of them have
some problem. Some produce PVC with poor heat stability. Some retard the
polymerization rate too much. Some require such a high level that they must be recovered
with the VCM (with the resulting contamination of the recovered monomer). The most
popular chain transfer agent in use today is 2-mercapto-ethanol (2-ME), which is not a
real chain transfer agent, but rather it is a chain terminator. Additional initiator is needed
to overcome the rate reduction. Another problem associated with making low molecular
weight polymer is that high temperature and low molecular weight produces particularly
soft and sticky primary particles and porosity is lost. Often, one's ability to make a very
low molecular weight PVC is related to having a secondary dispersant that can produce
enough porosity to allow effective VCM recovery.

3.5 Structure
PVC has a linear structure formed by either head to tail (most common) or head to hear
addition of monomer molecules to the growing polymer chain, Figure 5. Thus, the
molecular structure is primarily –CH2- units alternating with –CHCl- units.

(A) (B)

Figure 5. Head-to-tail (A) and head-to head (B) addition of VCM to the growing PVC chain,
X ≡ Cl.

PVC shows a tendency to add via syndiotactic placement; it is found that PVC is
approximately 56 % syndiotactic at 50 ºC polymerization temperature. This irregularity
of structure accounts for its low crystallinity. However, PVC achieves strength because of
the bulky polymer chains as a consequence of the large Cl groups on every other carbon.

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3.6 Stability
PVC is almost certainly the least naturally stable polymer in commercial use. During
processing, storage and utilization, PVC degrades as it is exposed to high temperatures,
high mechanical stresses or ultraviolet light, all in the presence of oxygen. Degradation of
the polymer occurs by successive elimination of hydrogen chloride (HCl), which is called
dehydrochlorination, yielding long polyenes, Scheme 2, which are consequently causing
discoloration, deterioration of the mechanical properties and a lowering of the chemical
resistance.

Scheme 2 Dehydrochlorination

Therefore, PVC requires stabilization for practically any technical application.

Stabilization mainly proceeds by the addition of compounds, such as metal oxides,
carbonates, fatty acid salts as well as HCl acceptors as ethylene oxide compounds. These
additives stabilize PVC by slowing down the dehydroclorination reaction and absorption
of the evolved hydrogen chloride.

3.6.1 The causes for the low thermal stability of PVC

It is known that the quality, or thermal stability, of PVC decreases when monomer
conversion increases. VCM is polymerized in a batchwise process, which means that the
monomer supply gets more and more exhausted with increasing monomer conversion. As
a consequence side-reactions by the macroradicals will increasingly occur, resulting in

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the formation of a lot of different types of structural irregularities. Some of these defects
are shown to have a dramatic influence on the thermal stability. The most occurring
structural defects in PVC are a wide range of branches, which are formed by various
routes. Some of them seem to affect the thermal stability while others are completely
harmless. The frequently occurring branches and the most important types of branches
concerning the thermal stability of PVC are described below.
Besides head-to-head units within the polymer backbone, head-to-head emplacement
of VCM to a growing polymer chain can also result in other types of irregularities within
the chain. Chloromethyl (MB) and 1,2-dichloroethyl branches (EB) result from one or
two successive 1,2-Cl shifts respectively, followed by regular chain growth as is shown
in Scheme 3. The MB and EB structures are expected to have minor, if any, influence on
the initiation of dehydrochlorination of PVC.
This insignificant influence of MB and EB is probably due to the absence of tertiary
chlorine at the branchpoint carbons, as it has been proven that an increase in the amount
of tertiary chlorine in the polymer chain increases the thermal degradation. Other types of
branching do contain tertiary chlorine at the branchpoint carbon such as the 2,4-dichloro-
n-butyl branch and various types of long chain branching.

Scheme 3. Chemical consequences of head-to-head addition during the polymerization of

VCM

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The 2,4-dichloro-n-butyl branch (BB) is formed via a 1,5-backbiting mechanism

(Scheme 4). The growing macroradical abstracts a hydrogen atom from the CH2 group at
the fifth position in the chain leaving a radical at that point, after which propagation
continues from there and a polymer chain bearing a butyl branch is created.
Long chain branching (LCB) results from hydrogen abstraction, from a
chloromethylene or a methylene unit of a polymer chain, by a growing macroradical or
possibly a chlorine atom (Scheme 5). The newly formed macroradical will propagate
further, generating long chain branches. About 66% of all LCB formed do contain
tertiary chlorine at the branchpoint carbon, meaning that hydrogen abstraction from the
chloromethylene unit occurs more often.

Scheme 4. 1.5-backbiting mechanism generating a 2,4-dichloro-n-butyl branch

Scheme 5. Formation of long chain branching after hydrogen abstraction from

chloromethylene and methylene by macroradicals or chlorine atoms

Both BB and LCB are mainly formed when the monomer supply is almost exhausted.
Due to monomer starvation the growing macroradicals start reacting with themselves or
with neighboring polymer chains as described.

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Diethyl branches (DEB) seem also to be present in PVC fractions produced at very high
VCM conversions and therefore when monomer supply is almost exhausted. This type of
branching is believed to contribute significantly to the thermal degradation of the
polymer, due to the presence of two tertiary chlorines at the branchpoint carbons, Scheme
6.
Internal unsaturation, especially internal allylic chlorines, IA in Scheme 5, proved to
be one of the main structural defects influencing the thermal stability. Just like the
tertiary chlorines the amount of internal allylic chlorines increases dramatically when
monomer supply becomes exhausted. When the amount of allylic and tertiary chlorines in
commercial PVC as well as their reactivity towards thermal degradation is taken into
account, it seems that tertiary chlorine has a somewhat higher reactivity towards
dehydrochlorination.
The effect of head-to-head units, Scheme 3, in PVC on the thermal stability is still not
conclusively proven, but it is known that the amount of these units is very small,
presumably 0-0.2 per 1000 monomeric units. So if these structures have any influence on
the thermal stability, it will be minor compared to other structural irregularities.
Note that chloride groups in any of the defect structures are not stable and hence are
“labile”. The order of chloride lability is: internal allylic chlorides ≈ tertiary chlorides >
terminal allylic chlorides > ordinary secondary chlorides.
Labile chlorides account for less than 0.5 % of all chlorides in PVC, but their effect on
heat stability is dramatic. Because of their presence, PVC begins to noticeably degrade at
temperatures as low as 100 ºC and degrades rapidly in its processing range of 170-220
ºC.

Scheme 6. Diethyl branches

3.7 Plasticization
PVC is a very tough and rigid material with extensive applications. Its range of
utilization is significantly expanded by plasticization, which converts rigid PVC, to
flexible PVC. Plasticization involves blending PVC with plasticizers (e.g., diisooctyl

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phthalate, tritolyl phosphate, epoxidized oils). The plasticizer imparts flexibility by acting
effectively as an ‘‘internal lubricant’’ between PVC chains.

3.7.1 Mechanisms of plasticization

For a plasticizer to be effective, it must be thoroughly mixed and incorporated into the
PVC polymer matrix. This is typically obtained by heating and mixing until either the
resin dissolves in the plasticizer or the plasticizer dissolves in the resin. The plasticized
material is then molded or shaped into the useful product and cooled. Different
plasticizers will exhibit different characteristics in both the ease with which they form the
plasticized material and in the resulting mechanical and physical properties of the flexible
product.
Several theories have been developed to account for the observed characteristics of the
plasticization process. Two of these theories will be described in this course.
According to the Lubricating Theory of plasticization, as the system is heated, the
plasticizer molecules diffuse into the polymer and weaken the polymer-polymer
interactions (van der Waals' forces). Here, the plasticizer molecules act as shields to
reduce polymer-polymer interactive forces and prevent the formation of a rigid network.
This lowers the PVC Tg and allows the polymer chains to move rapidly, resulting in
increased flexibility, softness, and elongation.
The Gel Theory considers the plasticized polymer to be neither solid nor liquid but an
intermediate state, loosely held together by a three-dimensional network of weak
secondary bonding forces. These bonding forces acting between plasticizer and polymer
are easily overcome by applied external stresses allowing the plasticized polymer to flex,
elongate, or compress.

3.8 Copolymers
VCM does not co-polymerize well. It has an unfavorable reactivity ratio with just
about every other monomer except vinyl acetate (VAC), 5-40 % vinyl acetate, Structure
II. Because of the unfavorable reactivity ratios, making other copolymers usually
involves long reactions with slow metering of one of the monomers (the one that reacts
fastest). This is required to produce what is known as a uniform co-polymer, where the
composition at the beginning of the polymerization is similar to that made at high
conversion. There is another general problem associated with copolymers. PVC is
insoluble in the monomer and this produces the porous internal structure that facilitates
monomer recovery. One of the reasons for this insolubility is that the polymer has a
certain level of crystallinity. Random copolymerization tends to break up the
crystallinity. Also, the fact that a second monomer is present changes polymer solubilities

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and makes the polymer become monomer soluble. This produces a non-porous particle
and alters the reaction kinetics dramatically. Today, most copolymers are made using
microsuspension or emulsion methods, because these processes produce small particles
that can be stripped of residual monomer. Copolymers entangle and fuse at lower
temperatures and flow more easily at lower melt temperatures, because they have low or
no crystallinity. Note that this copolymer has a Tg of 28 ºC.
Polymers containing around 10 % vinylidene chloride, Structure III, have better tensile
properties than PVC.
Acrylic esters have also been used to improve copolymer solubility and workability.

(II)

(III)

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