Lubricating systems for rigid PVC

Joseph B. Williams, Julia A. Falter and Kenneth S. Geick

INTRODUCTION TO RIGID PVC

Overview
More than 30 billion pounds of polyvinyl chloride (PVC) were sold world-
wide in 1995. Almost 60% of PVC is chlorine, which basically comes from
sodium chloride (table salt). This results in a polymer that is inherently
low cost, and one that is affected much less than most plastics by the
cost of petroleum. However, the density of rigid PVC ranges from 1.30
to 1.58 g/ cc, which is relatively high for a polymer. Because most plastic
applications are volume dependent, PVC's high density can result in
more expensive finished items than those made with a lower density
polymer.
PVC polymer has the unusual property that its thermal decomposition
temperature is lower than its melting point. Therefore, to process it one
must add additives to retard the thermal decomposition mechanism
and to lower its melting point. Those that retard thermal decomposition
are known as heat stabilizers.
Those additives that lower the melting point and Tg are plasticizers.
PVC formulations containing plasticizers are known as flexible or semi-
flexible (depending upon the amount of plasticizer) PVc. However,
well over half of PVC usage is in rigid PVC, rPVC, applications. These
are made from formulations that do not contain plasticizers. For rPVC,
the additives that make processing possible are lubricants.
Rigid PVC has good chemical resistance, and may be either opaque or
transparent depending upon the formulation.

G. Pritchard (ed.), Plastics Additives

© Springer Science+Business Media Dordrecht 1998
 Function and classification of lubricants 451
Formulations
Large volume opaque rPVC applications include pipe, siding, lineals and
pipe fittings. In general the cost of the formulation increases in that order.
The first three are extruded applications, while pipe fittings are injection
molded. A typical siding formulation consists of:
• PVC suspension resin (100 parts);
• heat stabilizer system (0.75 to 1.50 parts);
• calcium stearate (0.75 to 1.50 parts);
• acrylic processing aids (1.0 to 1.5 parts);
• lubricant system (1.0 to 1.5 parts);
• acrylic or chlorinated polyethylene impact modifier (4.0 to 6.0 parts);
• calcium carbonate filler (3.0 to B.O parts);
• titanium dioxide (7.0 to 12.0 parts);
• color pigments (0.1 to 2.0 parts).
Large volume clear rPVC applications include thin calendered sheet and
blown bottles. A typical blown bottle formulation consists of:
• PVC suspension resin (100 parts);
• heat stabilizer system (1.5 to 2.0 parts);
• acrylic processing aids (1.5 to 2.5 parts);
• lubricant system (1.0 to 1.5 parts);
• MBS impact modifier (10 parts);
• blue toner «0.001 parts).

Manufacture
The first step in the manufacture of rPVC products consists of mixing PVC
polymer powder with all the appropriate additives in a high intensity
solids mixer. The mixer must be such that the ingredients are heated
through shear during the mixing. Normally the mixer is loaded with
the PVC resin, and the other additives are added at specific temperatures.
After all the ingredients are added, the hot (about 120°C) mixture is
dropped to a cooling, low shear mixer.
The powder mixture is then used directly in an extruder to produce
finished products (siding, pipe etc.) or pellets that are used in other plastic
processing equipment.

FUNCTION AND CLASSIFICATION OF LUBRICANTS

Purpose of lubricants
Like all polymers, PVC is made up of long chain molecules. These are
highly viscous in the melt phase, and tend to stick to the metal components
452 Lubricating systems for rigid PVC
of processing equipment. These properties can be overcome by lubricants.
The major function of lubricants in rPVC (and other polymers) is to
decrease internal and external friction. This results in:

• reduced shear, which results in lower temperature and reduced

tendency for polymer degradation;
• reduced equipment wear;
• increased production rates;
• reduced energy consumption.

Lubricant characteristics
Lubricants are normally classified as external or internal. Although
both types of lubricants are mixed with the PVC polymer as
described above, they function differently. External lubricants are
largely insoluble in PVc. They work 'externally' by migrating to the
surface of the polymer melt during processing and lubricating the
melt from the metal of the processing equipment. Internal lubricants
are mostly soluble in PVc. They work 'internally' by 'lubricating'
the movement of PVC molecular chains past one another during
processing.
However, most lubricants have some combination of both external
and internal characteristics. The lubricant's solubility is determined
by molecular structure and its polarity in relation to the polymer.
Total solubility, which indicates high bond strength between lubricant
and polymer is undesirable and can actually embrittle the polymer.
The desirable effect for an 'internal' lubricant is for a slightly weaker
attraction between lubricant and polymer in which the molecules
arrange themselves in the direction of flow and slide by each other
creating a ball bearing effect. This reduces shear stress between
polymer molecules, thus lowering melt viscosity and temperature
buildup.
Lubricants which are less soluble or incompatible with the base poly-
mer provide external lubrication in the molten phase. In this case the
bond strength between polymer and lubricant is weak and under high
shear the lubricant is, in effect, squeezed out of the compound. Thus,
the lubricant provides external lubrication by covering the surfaces of
the processing equipment, reducing friction at the interface of the poly-
mer and the metal surfaces of the machinery.
The fact that essentially all lubricants have both external and internal
characteristics make it impractical to describe lubricants by external
versus internal classification. Instead, PVC lubricants will be grouped
by chemical class, and the effect of each class on rPVC properties will
be covered.
 Chemical classes of lubricants 453
CHEMICAL CLASSES OF LUBRICANTS
Although there is a fairly wide range of chemical classes of lubricants for
rPVC, most are thought of as waxes or soaps. The five major chemical
classes to be covered are:
• amides;
• hydrocarbon waxes;
• fatty acid esters;
• fatty acids;
• metallic soaps.

Amides
Although the term 'amides' is commonly used as a class of lubricants for
rPVe, in fact only one amide, ethylenebisstearamide (EBS), is normally
used. EBS is often referred to as 'amide wax'. It is made from largely
renewable sources, being the reaction product of about 90% stearic acid
from animal or vegetable fats or oils and about 10% ethylene diamine
as shown in the following reaction.
o H H 0 0
II I I II II
2C 17 H 3S COH + HNCH2CH2NH ---> C17H3SCNCH2CH2NCC17H3S + 2H20
I I
H H
EBS has a good balance of internal and external lubricating properties.
It was the first major lubricant used in rPVe. It has a broad processing
latitude and is quite forgiving of formulation errors. Until the late
1980s, EBS was the lubricant of choice for siding and pipe in the United
States. Since then the switch from single screw to twin screw extruders
has required more external lubrication, and most producers now use a
paraffin/ oxidized polyolefin lubrication system.

Hydrocarbons
This class of lubricants is composed of several subclasses, which are often
referred to as separate classes. The various subclasses include paraffin
waxes, microcrystalline waxes, polyethylene waxes, and oxidized poly-
ethylene waxes. All are based on -fCH21n species where n varies from
about 20 to over 80.
The paraffin and microcrystalline waxes are mixtures of solid,
saturated hydrocarbons that are produced by distillation and solvent
refining from crude oil. The paraffin waxes are mostly linear alkanes
with chain lengths varying from about 20 to about 50 carbons. The micro-
crystalline waxes contain many more branched chains and/or cyclic
454 Lubricating systems for rigid PVC
chain molecules. The number of carbon atoms in a microcrystalline wax
can vary from about 30 to over 80. Consequently their average molecular
weight is much higher than that of paraffin waxes.
The polyethylenes are produced by directly polymerizing ethylene at
relatively low pressures and temperatures. The molecular weights
range from about 500 to 1000, which corresponds to 35 to 70 carbon
atoms. The molecular chains can be either linear or branched depending
upon the catalyst and conditions used to make the product. They differ
from the paraffin and microcrystalline waxes in end groups and catalyst
residues.
Oxidized polyethylene waxes are produced by melting polyethylene
waxes in a column, and forcing air up through the column. This
oxidizes the homopolymer at branch points, breaking the molecular
chains and forming acid groups. Other oxidized species such as esters,
aldehydes, ketones, hydroxides and peroxides are also formed. This
results in products with a broad molecular weight distribution with an
average molecular weight of about half that of the starting polyethylene
wax.
All of the hydrocarbon waxes are very external in rPVe. One would
expect the oxidized polyethylene waxes, because of their polarity, to
have more internal characteristics than the other hydrocarbon waxes.
However, they seem to be the most external in processing equipment,
probably because of their excellent metal release characteristics. The
lower molecular weight paraffin waxes do have some internal character,
but, in general, rPVC lubricated with any of the hydrocarbon waxes
requires additional internallubricant(s).

Esters
There are many types of ester lubricants that are used in various rPVC
formulations:
• simple esters;
• glycerol esters;
• polyglycerol esters;
• montan esters;
• partial esters of polyfunctional alcohols;
• fully esterified esters of polyfunctional alcohols.
Except for the montan esters, these esters are made from various alcohols
and from fatty acids; these lubricants are often referred to as fatty acid
esters. Esters, in general, are extremely versatile and can range from
internal to external lubricants with increasing carbon chain length and
degree of esterification. Therefore, an ester's lubrication characteristics
can be tailored for specific applications.
 Chemical classes of lubricants 455
The monoesters of the higher saturated fatty acids are colorless, odor-
less, crystalline solids. These are the most internal functioning of the
esters. The most common is glycerol monostearate (GMS). GMS is a
mostly internal lubricant with some external properties. Increasing the
degree of esterification increases the external lubrication characteristics.
Polyglyceryl esters are made from polyglycerol and fatty acids. They
are more external than GMS, and their external character increases as
the degree of polymerization and esterification increases. An increas-
ingly important characteristic of both GMS and polyglyceryl esters is
their low toxicity. Most are actually approved in the USA as food
additives.
Montan wax is naturally occurring fossil vegetable wax. It is found in
almost all lignite deposits in the world. It consists of esters of montanic
acid with long chain aliphatic alcohols. The chain length of both the
montanic acid and the alcohols is about 28 to 32 carbons. Montan
waxes have a broad range of lubricant functionality with both internal
and external properties. The use of montan waxes in rPVC formulations
is limited due largely to the cost associated with purifying and upgrad-
ing crude montan wax to plastics additive quality. However, montan
waxes are utilized in rPVC formulations for the blow molding of
water bottles, where good internal lubrication and high melt strength
are required.

Fatty acids
Although a large number of fatty acids are commercially available, the
only one that is used to any extent as a lubricant for rPVC is stearic
acid. The most common stearic acid used is the so-called 'triple pressed'
grade, which is a blend of palmitic (carbon chain length of 16) and
stearic (chain length of 18) acids. It is a good external lubricant with a
balance of some internal lubricating properties. Its major drawback is
its volatility.

Metallic soaps
The largest volume class of lubricants for plastics, in general, is metallic
soaps. The largest volume metallic soap is calcium stearate. More
pounds of calcium stearate are used in rPVC than any of the other
materials covered in this section, but its classification as a lubricant in
rPVC is not straightforward. For example, calcium stearate in rPVC
• improves flow (internal lubrication),
• increases internal shear (opposite of most internal lubricants), which
leads to improved physical properties of finished parts,
456 Lubricating systems for rigid PVC
• acts as an acid scavenger,
• increases mold release (external lubrication).
Calcium stearate is more of a colubricant, both internal and external,
than an independent lubricant. However, because of its capacity for co-
stabilizing, co-lubricating, and physical property improvement, it is
used in essentially every pound of opaque rPVC produced in the
world. Its weaknesses are that it cannot be used in clear formulations
due to haze formation, and it tends to react with external lubricants to
increase die buildup and plateout.
Other smaller volume metallic stearates used as lubricants include
those based on aluminum, lead, sodium, tin and zinc.

Mixed
As rPVC processing becomes more sophisticated, rates increase, and
parts become more complicated, it becomes more critical to have well-
balanced lubrication systems with good internal and external charac-
teristics. This usually requires two or more lubricants - a mixture of
those with mostly internal characteristics and those with mostly external
characteristics.
Examples include paraffin/oxidized polyethylene/calcium stearate,
oxidized polyethylene/fatty acid ester, mixtures of fatty acid esters,
paraffin/ amide etc. (A conceptual graph of the external! internal
characteristics of the major rPVC lubricants is shown in Figure 1.)

ext.rnal Internal

EBS

P....tnnWax

pofyettly\ene Wax

OxIdIDd PE Wu.

Glycerol & PG Estars

StNrtcAdcI

Calcium 8tH...... L________~~~~~~~~~___J

Figure 1 rPve lubricant balance (conceptual).
 Testing of lubricants 457
TESTING OF LUBRICANTS

Lubricating effects
As previously stated, internal lubricants are soluble in the resin system
and act by reducing friction between polymer molecules, leading to
lower melt viscosity and lower energy requirements needed for proces-
sing. External lubricants are generally incompatible with the polymer
and act to reduce the friction at the interface between the polymer and
the surface of the processing equipment.
As it is very costly to run commercial scale equipment, initially the
effects of a newly developed lubricant system on the properties of a
rPVC compound are measured using laboratory scale equipment such
as rheometers, dynamic two-roll mills and small scale molders and
extruders. An example of the effect of various lubricants on output in a
laboratory extruder is shown in Figure 2.
Determining whether a material is an internal or external lubricant can
be defined by its effects on the fusion and mill stick times and melt viscosity
of the rPVC compound. Internal lubricants will not significantly affect
fusion or mill stick times of the compound but will lower melt viscosity.
External lubricants will increase both the fusion and mill stick times but
will not significantly lower the compound melt viscosity. These properties
can be measured on a torque rheometer and a dynamic two-roll mill.

Processing properties
The effect of lubricant systems on processing can be measured on labora-
tory sized extruders and injection molders; however, reformulation or

12
output (gl10_
,...--~-
min)
_ _ _ _...,-_ _ _ _ _ _ _ _-, montan wax (Ca soap)

10 --------------------- oxidized PE wax

8 ---------------------

6 --------------------- PEwax
fatly acid ..tar
4 montan acid ..tar

340 400
Pressure Before Die (bar)
Figure 2 Rheometer flow properties of rPVe.
458 Lubricating systems for rigid PVC
tweaking of the lubricant loading or type may be necessary once the
compound is tested in commercial trials.
Rigid PVC can be processed on a wide variety of equipment such as
extruders (both single and counter-rotating twin screw), calenders and
injection molders. The lubricant system has to be balanced for the process
and end use property requirements.
Single screw extruders require a balance of internal and externallubri-
cation while twin screw extruders, calenders and injection molders
require more external lubrication. Not only does the system need to be
balanced for the processing equipment, the lubricants cannot adversely
affect required end use properties.
A fully optimized formulation provides high outputs, low scrap rates,
high-quality finished products and the required compound physical
properties. Deficient or excessive amounts of lubricant lead to reduced
processing efficiencies or can even shutdown the operation. A balanced
lubricant system (right amounts of both internal and external lubrication)
provides control over the compound fusion and thermal stability times,
output rate, blooming, compound clarity and physical properties.

BIBLIOGRAPHY
Nass, L.I. and Heiberger, CA. (eds) (1988) Encyclopedia of PVC, Vol. 2, 2nd edn,
Marcel Dekker, Inc, New York and Basle, pp. 31-43, 263-390.
Riedel, T. (1990) Lubricants and Related Additives in Plastics Additives, 3rd edn
(eds R. Giichter and H. Miiller), Hanser Publishers, Munich, Vienna, New
York, pp. 423-470.
Edenbaum, J. (ed.) (1992) Plastics Additives and Modifiers Handbook, Van Nostrand
v Reinhold, New York, pp. 41-55, 773-842, 858-867.
Sh~pek, J. and Daoust, H. (1983) Additives for Plastics, Springer-Verlag, New York,
Heidelberg, Berlin, pp. 34-42.

Keywords: lubricants, solubility, compatibility, amides, waxes, fatty

acids, esters, metallic soaps, melt viscosity, extruders, rheometer.

See also: Release agents.