776-00301 TYRIN IM bro - The Dow Chemical Company

Window Profile,
Pipe, and Rigid Sheet
Applications for
TYRIN 6000 CPE and
TYRIN 7000 CPE
Impact Modifiers
TYRIN 6000 CPE and TYRIN 7000 CPE
Impact Modifiers
Performance Plastics – Europe, Middle East and Africa
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TYRIN 6000 CPE and TYRIN 7000 CPE Impact Modifiers
TYRIN Chlorinated Polyethylene (CPE) thermoplastic resins are widely used as impact modifiers in PVC extrusion
and injection molding applications. Especially effective in products such as window profiles, pipe, and siding,
TYRIN 6000 CPE and TYRIN 7000 CPE provide excellent corner weld strength and high surface gloss. These resins
offer high impact efficiency and perform well at low temperatures, giving very good weather resistance for all
climate conditions. The resins can be blended with acrylics resulting in an optimum cost/performance solution.
TYRIN 7000 is available in bulk, supplied by truck and can be stored in silos. TYRIN CPE offers the possibility to
reduce the overall color pigment costs on colored window profile applications. Furthermore, TYRIN CPE resins
work particularly well with calcium-zink stabilization to control gelation levels and melt temperature.
All in, TYRIN resins help fabricators and compounders meet increasingly critical performance requirements and
cost-control needs.
Real Solutions
Dow provides solutions that help meet the
unique processing and performance requirements
of current and next generation impact
modification products, along with technical
support that extends from formulation
through processing and end-use requirements.
The Global R&D Center in the USA, along
with Dow’s local Technical Service &
Development facilities, have the scientists,
equipment, and technologies to provide a
very high level of customer-focused services.
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Product Properties
The typical product properties of TYRIN 6000
and TYRIN 7000 are summarized in Table 1.
They are both free flowing white powders,
produced by the chlorination of low pressure
polyethylene in a water slurry.
Table 1: Typical properties of TYRIN CPE grades for impact modification
Typical Properties Units Test Method TYRIN 6000 TYRIN 7000
Chlorine content
Melt Viscosity
wt % ISO 1158 35 35
(145 s-1 , 190°C) Pa.s ISO 11443 2400 2900
Heat of Fusion J/g EH-TYR-QP-AV 2011

PVC Modification
Polyvinyl-chloride (PVC) is an outstanding
material for the production of rigid extruded
goods, such as pipes or profiles. However
due to its high glass transition temperature,
it has shortcomings in impact strength. It has
therefore to be modified to provide impact
strength at ambient and low temperature.
Impact modifiers provide PVC compounds a
consistently ductile behaviour over a broad
temperature range. They are flexible materials
which are partially compatible with PVC.
They form a discrete phase in the PVC matrix,
which absorbs and dissipates shock energy.
During suspension polymerization of PVC grain
particles with a typical diameter of 65-150
microns are formed. (Figure 1). These consist
of smaller particles ranging from 0.2 to 1.5
microns in size: the primary particles. When
the PVC powder is being processed into a
fabricated product (e.g. by extrusion, calendering)
the grain structure is broken down
mainly by shear and the primary particles are
molten together at their surfaces.
The dominant factor in controlling the
degree of fusion is the melt temperature
and the additive package, consisting of
stablizers, lubricants, fillers, and impact
modifiers can affect the range of processing
conditions required for optimum impact
strength. This process is called fusion or
gelation. The achieved impact strength is
controlled by the degree of fusion of the
PVC matrix. An under fused or over fused
melt lowers the impact strength of the
final product.
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Essentially two classes of impact modifiers
exist, which are physically blended with s-PVC
during extrusion on twin screw extruders.
Acrylic based modifiers are often used,
which are core-shell particles of typically a
butyl-acrylate flexible core with a rigid shell
of poly-methyl-methacrylate. The shell
enables a good flowability of the product
and a good compatibility to PVC to enable a
good dispersion.
TYRIN Chlorinated Polyethylene (CPE) is a
thermoplastic material and its morphology
will develop during the melt processing of
the PVC dry-blend. TYRIN CPE and other low
melting ingredients will coat the PVC particles.
Figure 1: Primary particles structure of s-PVC
65-150 Micron
During subsequent extrusion a phase inversion
occurs and creates discrete CPE particles in a
continuous matrix of PVC.
TYRIN CPE offers an excellent combination of
compatibility, processibility, weatherability,
and impact efficiency in many rigid PVC formulations,
like window profiles, pipes, rigid
and foamed sheet, etc. The use of TYRIN CPE
makes it possible to use higher filler levels
because being thermoplastic in nature, it
flows and encapsulates inorganic filler particles.
This coating provides a mechanism to
control the particle adhesion to the PVC
matrix and thus improves the contribution to
impact resistance, whereas the filler aids
TYRIN dispersion.
Primary
Particles
Skin
Grain
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TYRIN CPE in Window Profiles
The main advantages of TYRIN CPE in
window profiles are:
• Good low temperature impact strength
• High surface gloss
• Excellent corner weld strength
• Good filler acceptance
• Good lubrication properties with calciumzink
stabilizers
• Cost effective system
• Compatible with acrylic modifiers
Window profiles manufactured with TYRIN
impact modifiers can meet all requirements of
the European standards. An overview of the
common standards can be found in Table 2.
Table 2: European Standards
for window profiles
Germany DIN 16830
RAL GZ 716/1
UK BS 7413
France P 24-500
Italy UNI 8648
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Window profiles are very demanding in terms
of properties. TYRIN CPE helps to achieve the
best corner weld strength and can provide
very good gloss.
During the welding process, TYRIN CPE act
efficiently as a flow enhancer and can significantly
improve the corner weld strength of
existing formulations. (Figure 2).
TYRIN CPE will give excellent impact properties
in order to meet the requirements under
a wide processing range and it also reduces
waste generated during finishing operations,
such as sawing, drilling, and cutting, due to
its excellent resistance against shattering
and brittle breaks.
The U-notched Charpy impact strength has
been shown to be most sensitive to melt
temperature variations and has been chosen
to give an indication of the impact efficiency
and the processing window. TYRIN 7000 is
more efficient at lower addition levels
(Shown in Figure 3). The Double-V notched
impact strength shows the same trend, but is
not so sensitive at lower addition levels.
Data have shown that a ductile V-notched
Charpy impact is achievable with 6 phr.
TYRIN 7000.
The processing window indicates the temperature
range which allows the production of
window profiles with the required properties.
Figure 4 gives a comparison between profiles
with different impact modification, extruded
at different temperature settings. The difference
in their respective viscosity results in a
more robust behavior of TYRIN 7000 at higher
temperatures and TYRIN 6000 at lower
temperatures, which makes TYRIN 7000
more suitable for high speed extrusion and
calcium-zink stabilization, where higher melt
temperatures are experienced. Typical formulations
can be found in Tables 3 and 4. Due
to the voluntary vinyl agreement, many new
developments will be based on calcium-zink
stabilization, but lead stabilization is still
widely used as an efficient stabilizer system
for PVC window profiles with a good longterm
track record.
Due to their slight lubrication effect, both
TYRIN CPE grades are in general very suitable
for calcium-zink stabilization to control
the gelation levels and melt temperature.

Figure 2: Corner weld strength of window profiles.
Corner Weld Strength (N)
Figure 3: U-Notched Charpy Impact Strength [kJ/m 2 ] as a function of
modifier addition level.
Notched Impact (kJ/m 2)
Figure 4: U-Notched Charpy Impact Strength [kJ/m 2 ] as a function of
processing temperature.
Notched Impact (kJ/m 2)
1,400
1,200
1,000
800
600
400
200
0
60
50
40
30
20
Incumbent Modifier With 6 phr TYRIN 6000
10
0
TYRIN 7000
TYRIN 6000
3 4 5 6 7 8
60
50
40
30
Modifier Level (phr)
20
TYRIN 6000 /Pb
10
0
TYRIN 7000 /CaZn
TYRIN 7000 /Pb
Cold Normal Hot
Processing Temperature Settings
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Table 3: Typical window profile
formulation, lead stabilized, white
S-PVC K-68 100 phr
TYRIN CPE 5-7
Di-basic lead phosphite 3.5
Lead stearate 0.4
Wax ester 0.2
Calcium stearate 0.3
Paraffin wax 0.1
Processing aid 1
Titanium dioxide 4
Calcium carbonate 5
Table 4: Typical window profile formulation,
calcium-zink stabilized, white
S-PVC K-68 100 phr
TYRIN CPE 5-7
Calcium-Zink One-Pack 4.5
Titanium dioxide 4
Calcium carbonate 5
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Weatherability
In rigid PVC window profiles the use of lead
stabilizers is common practice. In the last
decennium the use of calcium-zink stabilizers
has increased substantially, as their cost/performance
has become very attractive as well.
Natural weatherability tests with TYRIN CPE
have been conducted in Bandol (France), an
area with high levels of sun exposure, combined
with a wide range of humidity levels
with an annual solar energy of around 6
GJ/m2 . Relevant profile characteristics like
brightness, yellowness, and impact strength
were compared before and after exposure,
as shown in Figures 5, 6, and 7.
The stabilizer systems were provided by
major European suppliers and the data are
average numbers of the good systems, which
were all within a narrow bandwidth. After
2 years of exposure, the color stability and
the impact properties remain very good and
the requirements, as set by the different
standards and authorities can be met with
profiles modified with TYRIN CPE, when
properly formulated and processed, both with
lead and with calcium-zink stabilization.
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Figure 5: Color change of profiles modified with TYRIN CPE.
b (yellow-blue)
5
4
3
2
1
0
Figure 6: Tensile Impact after natural weathering of profiles modified
with TYRIN CPE.
Tensile Impact (kJm 2 )
700
650
600
550
500
0.0 0.5 1.0 1.5 2.0
Natural Weathering Time (years)
Pb-Stablized
CaZn-Stablized
0.0 0.5 1.0 1.5 2.0
Natural Weathering Time (years)
Pb-Stablized
CaZn-Stablized
Figure 7: Double-V notched impact after natural weathering of profiles modified
with TYRIN CPE.
Notched Impact (kJm 2 )
70
60
50
40
30
20
10
0
0.0 0.5 1.0 1.5 2.0
Natural Weathering Time (years)
Pb-Stablized
CaZn-Stablized

TYRIN CPE in Pipes
The vast majority of PVC pipes is unmodified
and goes into applications where no particular
impact strength is required, such as
sewage pipes.
There are special applications which are
more demanding where impact modifiers can
be beneficial, such as:
• Pressure pipes for mining
• Gas pipes
• Special drain pipes (corrugated pipes)
• Pipes for wells or mining
• Foam core pipes.
Table 5: Starting point formulation
for HI PVC pipe
S-PVC K-68 100 phr
TYRIN 6000 6-8
3 basic lead sulphate 0.8
2 basic lead stearate 0.8
Ca-stearate 0.1-0.2
Stearic acid 0.2-0.3
CaCO3 5
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Typically, the impact strength requirements
are less demanding than for profiles. TYRIN
is the ideal product for pipe applications,
especially regarding the new or coming
European standards for pressure and nonpressure
pipes, where an impact test at 0°C
or even at -10°C will be required. TYRIN
reduces the transition temperature, giving
the end-users an extra margin of excellence
through low temperature impact performance
and ductility. TYRIN CPE modification also
yields a better surface which is useful to avoid
build-up on the inside of the pipe. This effect
is visible at very low levels and already 3-4
phr TYRIN 6000 are sufficient to give ductile
failure below 0°C.
TYRIN CPE offers excellent hot melt tear
strength, ductility, and welding properties,
essential in the extrusion of thin-wall
corrugated pipes. For foam core pipes, TYRIN
CPE can be used in both the compact and the
foam layer. In the compact layer, it improves
the ductility and in the foam section, it can
substitute to some extent the acrylic processing
aids which are used to improve the cell
structure. It will permit cost saving, improvements
of flammability, and a higher ductility
regarding impact tests at low temperature.
TYRIN CPE provides a consistent improvement
of the ductility of PVC pressure pipes and it
is possible to reduce the design coefficient,
where standardization and requirements
allow it. In practice this will yield a substantial
reduction of wall thickness which will
more than compensate for the slightly higher
cost of the impact modified compound. This
concept is not included in the current European
pipe standards.
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TYRIN CPE in Extruded PVC Sheet
PVCsheet is extensively used in advertising
and decorative panels, as it can be easly
printed and laminated with foils. Due to its
resistance against humidity, weathering, and
chemicals it is often used as wood replacement
in construction applications.
Both rigid and foamed PVC sheet can be
modified with TYRIN CPE to improve its
physical properties.
Main properties of foamed sheets are:
• Low density for ease of handling and cost
• Smooth regular surface (esthetics and
ease of cleaning)
• Ductility (must not shatter during cutting
of fixing with nails or screws).
High melt strength is essential to allow the
material to expand without the tearing of the
cell membranes. If the cell membranes tear
up, the foam structure collapses rapidly and
the foam loses its mechanical strength. The
ideal is a very fine, regular cell structure with
no or only little difference in cell size between
the outer and inner layer of the part.
There are two basic processes: free foam and
the Celluka process. In the free foam process,
the melt can expand freely after leaving the
die. After expansion, the extrudate is cooled
at its surface, which limits the cell growth at
the surface, giving foam with low density at
the core and higher density at the surface.
The surface is smoothened through contact
with cool rolls, but keeps some structure.
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In the Celluka process, the extrudate goes
straight into a cooled calibration and expands
inward. The contact of the melt with the
cooled calibration prevents expansion at the
outside and gives a thick (0.1-1mm) compact
skin with the surface quality of a compact
part. The contact of the melt with rolls (for
sheet) or a cooled calibration (for profiles)
hinders the expansion and gives a compact
skin at the part outside. (See table 6).
Free foam allows only the production of very
simple shapes, whereas the Celluka process
Table 6: Starting point formulations for extruded PVC foams
Ingredient Free, Celluka, Free, Celluka,
Pb-stab Pb-stab Sn-stab Sn-stab
S PVC K60 100 100
S PVC K58 100 100
Modifier 1 8 8 8 8
Bas. Pb-Phosphite 2 2
Butyl-Sn mercaptide 1.2 - 1.5 1.2 - 1.5
Ca stearate 0.3 0.3 0.4 - 0.6 0.3 - 0.5
Lubricants 2 0.8 - 1.2 0.8 - 1.2 0.8 - 1.2 0.8 - 1.2
ADC 0.6 0.1 0.6 0.1
Sodium bicarbonate 1.5- 2 1.7- 2
TiO2 4 4 4 4
1 blends with up to 50% TYRIN CPE
2 blends of ester and hydrocarbon waxes
allows also the production of fairly complex
geometries. Lab studies have shown that up
to 50% of the acrylic processing aid can be
substituted with TYRIN, without negative
impact on melt structure and density, but
with improvements of flammability and
impact strength. Formulations use pure or
modified Azodicarbonamide (ADC) or sodium
bicarbonate as blowing agents. ADC gives
very fine, regular cell structures and expands
quickly. Sodium bicarbonate expands more
slowly and gives a coarser cell structure.
Stabilizer systems are lead or tin based.

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Published June 2006
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