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High performance Keltan ACE EPDM polymers

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 APRIL 2014
years

125
The Technical Service Magazine For The Rubber Industry Volume 250, No. 1

High performance Keltan

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P T
ACE EPDM polymers

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High performance Keltan ACE EPDM polymers
by Montse Alvarez Grima, Michel van Boggelen, Michiel oped by Nova Chemicals for polyethylene, Lanxess further
Dees, Gerard van Doremaele, Martin van Duin and Petra developed and introduced Keltan ACE, a new class of cata-
Henricks-Knape, Lanxess Elastomers B.V. lysts which are extremely productive (refs. 6-8). The new
catalyst system has a substantially improved heat stability, al-
In the polyolefin industry, in particular for polyethylene and lowing higher reactor temperatures and, as a result, less deep-
polypropylene, the currently used titanium-based Ziegler cooling of the monomer feed is required. Very high catalyst
Natta (ZN) catalysts have already been in place for decades. productivity enables the elimination of the catalyst removal
These catalysts are very productive and do not require any step. The ACE catalyst system allows for the production of a
catalyst removal step. The major driver for developing and complete EPDM grade portfolio with products that perform
introducing (post-)metallocene catalysts in the polyolefin in- identical to EPDM grades, produced by ZN catalysts, but with

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dustry has been product differentiation, resulting in, among a reduced environmental impact. This EPDM portfolio covers
others, syndiotactic polypropylene, homogeneous linear, low the widest range of monomer composition and molecular
density polyethylene and copolymers of ethylene with higher weight. It includes very high ENB grades and (oil-extended)

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α-olefins (plastomers). very high molecular weight grades. The Keltan ACE portfolio
Polymers of ethylene, propylene and a non-conjugated continues to take full advantage of the Lanxess proprietary
diene (EPDM) represent an important class of elastomers controlled long chain branching technology (ref. 9). In addi-

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(refs. 1-3). The fully saturated polymer backbone provides tion, the Keltan ACE catalyst technology creates opportunities
excellent resistance against oxygen, ozone and heat. EPDM to develop products that are not attainable with classical
rubber is commercially produced using homogeneous cata- Ziegler-Natta or state-of-the-art metallocene catalyst technolo-

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lysts, viz., vanadium-based ZN catalysts or, more recently, gies, like high molecular weight high-5-vinyl-2-norbornene-
well-defined, highly active, homogeneous catalysts, such as EPDMs (refs.10-14).
classical metallocenes and other advanced post-metallocene In this study, several EPDM polymer samples, which have

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catalysts (refs. 4 and 5). been produced on a pilot plant scale with the Keltan ACE
The vanadium-based ZN catalysts for EPDM have a rela- catalyst, are compared with their Keltan ZN counter grades

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tively low productivity, and thus, high catalyst levels have to regarding polymer characteristics, processing and vulcanizate
be used and catalyst removal is usually required. Nevertheless, properties. Three very different EPDM grades will be consid-
they are commercially applied, because the resulting EPDM ered, which have been evaluated in the same compound for-
products combine high total compound loading with easy mulation. It will be shown that true perform-alikes can be ob-
compound processing and excellent vulcanizate properties. tained by fine tuning the ethylene content towards identical

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This is the direct result of the optimal and well-defined intra- crystallinity and, thus, low temperature properties, and by
and intermolecular microstructure of the EPDM polymer controlling the LCB level. Our findings have been reinforced
chains, viz., a very homogenous incorporation of the mono- by the positive customer feedback.

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mers and the possibility to incorporate long chain branches
(LCB) in a controlled manner. Experimental
It is rather challenging to achieve the same, excellent ZN- Polymers
like product performance with new catalysts. Moreover, as The EPDM polymers described in this study have been pro-
evidenced by limited EPDM portfolios based on (post-)metal- duced in the Lanxess Elastomers’ research and development
locene catalysts, until recently it has apparently remained a pilot unit or in the Lanxess Elastomers’ EPT plant (both in
challenge to the industry to cover the entire EPDM grade slate Geleen, The Netherlands), applying a solution polymerization
with (post-)metallocene catalysts. Hardly any EPDM prod- process in combination with, respectively, Keltan ACE or ZN
ucts with high ENB content and/or (oil-extended) high mo- catalyst technology. Polymerization conditions were fine
lecular weight grades based on (post-) metallocene catalysts tuned in such a way that polymers with the same polymer
are commercially available. In addition, introduction of a characteristics within experimental error were obtained with
significant degree of LCB proved to be difficult in commer- both types of catalysis. The chemical composition of the
cial (post-)metallocene-based EPDMs. In order to achieve EPDM polymers with 5-ethylidene-2-norbornene (ENB) as
good processing behavior, EPDM polymer blending strate- third monomer was determined with Fourier transform infra-
gies have been proposed, but polymer blending will always red spectroscopy, the molecular weight data with gel perme-
imply a trade-off between compound processing and vulcani- ation chromatography (GPC; universal calibration) and the
zate performance. thermal characteristics with differential scanning calorimetry
With sustainability as an overall aspiration and key driver, (DSC; first heating to 200ºC, then cooling at -10ºC/min. to
and high product quality as a non-negotiable condition, -70ºC). The so–called Δδ value, which is used as a measure of
Lanxess Elastomers has taken up the challenge to develop a the non-Newtonian, viscoelastic behavior of EPDM polymers
new, very efficient catalyst system that reduces the environ- and, thus, for the degree of LCB, has been measured with dy-
mental impact. Based on licensed catalyst technology devel- namic mechanical spectrometry (DMS; 125°C; 20% strain).

Reprinted with permission from Rubber World

 Physical properties
Table 1 - composition of sulfur-vulcanized Press plates (2 and 6 mm) were compression molded at 40 bar
compounds used for comparison of Ziegler and 180°C. The 2 mm press plates used for tensile measure-
Natta versus Keltan ACE EPDMs ments were obtained after curing for t90 + 10%, whereas the
6 mm press plates, used for hardness and compression set
1ZN/ACE 2ZN/ACE 3ZN/ACE
EPDM, phr 100 115 200 measurements, were cured for t90 + 25%.
ZnO, phr 5 5 5 Evaluation of the vulcanized (and aged) test pieces focused
Stearic acid, phr 1 1 1 on the following properties (abbreviations listed below are
Carbon black N-550, phr 70 70 70 used in table 3):
Carbon black N-772, phr 40 40 40 • Hardness IRHD (HS); normal at standard laboratory tem-
Oil, Sunthene 4240, phr 70 55 0
MBTS-80, phr 1.31 1.31 1.31 perature (SLT) (DIN 53505).
ZBEC-70, phr 0.7 0.7 0.7 • Hardness IRHD after hot air aging 168 hours @ 100°C
ZDBP-50, phr 3.5 3.5 3.5 (ISO 188) (HSag); normal at SLT (DIN 53505).

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Vulkalent E/C, phr 0.5 0.5 0.5 • Tensile properties dumbbell #2 (ISO 037): Modulus at
S-80, phr 1.25 1.25 1.25 100% and 300% elongation (M100% and M300%; MPa),
Total phr 293.26 293.26 323.26
tensile strength (TS; MPa) and elongation at break (EB; %).

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• Tensile properties after hot air aging 168 hours @ 100°C
The Δδ parameter is defined as the difference between the loss (ISO 188), dumbbell #2 (ISO 037): Modulus at 100% and
angle (δ) at frequencies of 10-1 rad/s and 102 rad/s, as derived 300% elongation (M100% ag and M300% ag; MPa), tensile

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from frequency sweep plots obtained in a DMS experiment strength (TS ag; MPa) and elongation at break (EB ag; %).
(ref. 15). • Tear strength Delft at SLT (tear; N).
• Tear strength Delft at SLT after hot air aging 168 hours @

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Compounds 100°C (tear ag; N) (ISO 188).
In this study, the ENB-EPDM polymers were compared in a • Compression set for 22 hours @ -25°C (CS -25°C; %);
typical extrusion formulation, viz., a compound with 70 phr ISO type B.

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N550 carbon black, 40 phr N772 carbon black and 70 phr • Compression set for 168 hours @ 100°C (CS 100°C; %);
Sunthene 4240 oil. This is a relatively polymer-rich compound ISO type B.

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with only 293 total phr and, thus, rather sensitive for small
variations in polymer structure. In case the starting EPDM Results and discussion
polymers already contained oil, the extra oil added to the com- Polymers
pound was corrected; for the polymers with 100 phr oil, this The objective for this polymer compound study is to demon-
was not fully possible and, therefore, the total phr was in- strate that the Keltan ACE technology is capable of producing

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creased to 323 phr. The EPDM compounds were mixed, vul- a complete range of EPDM polymers with similar properties
canized and evaluated at the Lanxess Elastomers’ rubber labo- to their Keltan ZN counter types. In this study, the characteris-
ratory in Geleen, The Netherlands. EPDM masterbatches tics and performance of three sets of two EPDM polymers

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without any sulfur curative (for compositions, see table 1) each (ZN and ACE) will be discussed. Three polymers, Keltan
were prepared on a Shaw K-1 batch mixer at a loading of 54% 8550A (1ZN), Keltan 6951 (2ZN) and Keltan 5569A (3ZN)
(water volume of mixer: 5.3 liters). The mixing time for all are commercially available Keltan EPDM products and have
compounds was kept constant at 3 minutes (including 1.0-1.5 been polymerized with a generic ZN catalyst system based on
minutes for polymer crumbling), resulting in a final batch vanadium oxytrichloride and sesquiethylaluminum chloride.
temperature of around 105°C. The masterbatches
were subsequently dumped on a Troester WNU-5
two-roll mill for cooling. The sulfur curatives (all Table 2 - comparison of Ziegler Natta versus
on solid carriers; for details, see table 1) were Keltan ACE technology, showing compositions and
added to the masterbatches on the two-roll mill at characteristics of EPDM polymers
a batch temperature of approximately 60°C. The
EPDM 1ZN 1ACE 2ZN 2ACE 3ZN 3ACE
compound Mooney viscosity (CML 1+4) was catalyst Zeigler- Keltan Zeigler- Keltan Zeigler- Keltan
measured at 100°C. The Mooney scorch time (t5) Natta ACE Natta ACE Natta ACE
was measured at 125°C. The vulcanization char- ML (1+4) 125°C 80 80 63 63 52 52
acteristics of the compounds, such as the scorch Ethylene, wt. % 55 48 48 44 63 58
time (ts2), the vulcanization time (t90), the maxi- ENB, wt. % 5.5 5.5 9 9 4.5 4.5
Oil, wt. % 0 0 13 13 50 50
mum rheometer torque difference (MH-ML) as a Mn, kg/mol 95 100 120 125 200 150
measure for crosslink density and the cure rate MW, kg/mol 290 330 380 430 590 460
(CR) defined as (MH-ML)/(t90-ts2), were deter- MW/Mn 3.2 3.3 3.1 3.4 3.0 3.1
mined with a Monsanto MDR 2000 rheometer ∆δ,° 16 14 18 18 31 28
according to ISO 6502 at a temperature of 180°C Cryst. temp., °C -34 -38 -48 -41 -22 -25
∆Hc, J/g 4 2 7 5 33 20
for 20 minutes.

Reprinted with permission from Rubber World

 Figure 1 - molecular weight distributions as Figure 2 - crystallization behavior as
determined with gel permeation determined with differential scanning
chromatography for Keltan ACE versus calorimetry (-10°C/min.) for Keltan ACE
Ziegler Natta EPDMs versus Ziegler Natta EPDMs

1 0
1ZN -0.1
0.8 1ACE -0.2

dH (J/g)
-0.3
-0.4
0.6 -0.5
1ZN
I (a.u.)

-0.6
0.4 -0.7 1ACE
-0.8

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0.2 -70 -20 30 80 130
Temperature (C)
0 0

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3 4 5 6 7 8
-0.1
Log M -0.2

dH (J/g)
-0.3

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1 -0.4
2ZN -0.5
2ACE -0.6 2ZN
0.8
-0.7 2ACE

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-0.8
0.6
-70 -20 30 80 130
I (a.u.)

0.4 Temperature (C)

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0
0.2 -0.1

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-0.2
dH (J/g)

0 -0.3
3 4 5 6 7 8 -0.4
-0.5
Log M -0.6 3ZN
1.2 -0.7 3ACE
3ZN -0.8

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1 3ACE -70 -20 30 80 130

0.8 Temperature (C)

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I (a.u.)

0.6

0.4 incorporation of LCB in the polymer structure provides an

optimal balance of processing and physical properties. In ad-
0.2 dition, 13 weight % of extender oil facilitates improved mix-
0 ing when compared to polymers of similar molecular weight,
3 4 5 6 7 8 providing the opportunity for more economic, single stage
Log M mixing combined with a high quality surface finish of ex-
truded profiles. This type of polymer finds its use in demand-
ing automotive sponge seal applications. Finally, polymer
Their three (advanced) analogues (1ACE, 2ACE and 3ACE) 3ZN/ACE is an EPDM characterized by an extremely high
have been produced in the Lanxess Elastomers’ pilot unit molecular weight with 100 phr extender oil. The extremely
using the proprietary Keltan ACE technology. EPDM polymer high molecular weight in combination with the ethylene crys-
1ZN/ACE is a typical amorphous, high Mooney viscosity tallinity makes this polymer suitable for the economical pro-
EPDM with a medium ENB content. Its high LCB level en- duction of mechanical goods with high total compound load-
ables fast mixing and high extrusion rates. Such a polymer, a ing.
typical all-around EPDM, is used for the production of, e.g., The polymer characteristics of all six EPDMs are presented
automotive dense profiles, radiator hoses and window gaskets. in table 2. The Mooney viscosities of the ZN and ACE combi-
EPDM polymer 2ZN/ACE is an amorphous, very high- nations are kept at the same level to assure, among others,
Mooney viscosity, high ENB grade. The combination of poly- similar processing behavior. From table 2, it can be concluded
mer characteristics of this recently introduced Keltan grade that the ACE technology is capable of producing polymers
provides excellent physical properties and collapse resistance, with a high (1ACE) as well as an extremely high molecular
while the high ENB level allows ultra-fast vulcanization. The weight (3ACE). In fact, the Keltan ACE technology is capable

Reprinted with permission from Rubber World

of producing an analogue of the highest molecular weight zation. Again, the Keltan ACE technology shows its strength
EPDM that is commercially available in the market today by the capability to incorporate not only low to medium ENB
(3ZN). The molecular weight distributions of the various poly- quantities of 1-5 weight %, but also high ENB amounts of 9
mers are presented in figure 1. It can be concluded that the weight % (table 2: 2ACE). Such high levels of ENB content
molecular weight curves of the 1/2ZN and their ACE ana- are crucial for achieving, e.g., high speed extrusions of sponge
logues are identical, i.e., no significant differences at the low profiles and very low compression sets. The data on ethylene
and high molecular weight ends of the curves. The molecular content show a lower weight percentage for the Keltan ACE
weight curves of the 3ZN and its ACE analogue are slightly versions of the EPDM polymers. This can be explained by the
different. However, the difference at the low molecular weight preference of advanced catalyst systems (and, in this respect,
end can be regarded as small and has no consequences for the Keltan ACE catalyst is no exception) to polymerize longer
processing characteristics and/or physical properties. The mo- ethylene sequences at a similar weight/weight ratio of ethylene
lecular weight distributions (Mw/Mn) of both polymers are and propylene in the polymer when compared to traditional
very similar. It is interesting to note that the Mw/Mn ratios of ZN catalysts. Consequently, a Keltan ACE EPDM with similar

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all polymers are within the range 3-3.5 (table 2), supporting ethylene content as its ZN counterpart would have a higher
good processing behavior. Typically, EPDM polymers pro-
duced with metallocene catalysts show very low Mw/Mn ra-

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tios (<2.5), resulting in poor mixing and extrusion characteris- Figure 4 - comparison of mixing behavior
tics, which in turn results in lower filler dispersion and/or (energy uptake as function of time) for
Keltan ACE versus Ziegler Natta EPDMs

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longer mixing times.
The monomer composition of the ZN-ACE analogues indi-
cates similar levels of ENB content to ensure similar cure 60
rates, crosslink densities and physical properties after vulcani-

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50

40
Figure 3 - loss angle versus frequency Power (kW)
curves as determined with dynamic 30

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mechanical spectrometry (125°C) for

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20
Keltan ACE versus Ziegler Natta EPDMs
10 1ZN
1ACE
45 0
40 1ZN
35 0 1 2 3 4 5
30 1ACE
Delta (°)

Time (min.)

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25
20
15
10 50
5

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0 40
Power (kW)

0.01 0.1 1 10 100 1,000

Frequency (rad/s) 30
45
40 2ZN 20
35 2ACE
30 2ZN
Delta (°)

25 10
20 2ACE
15 0
10 0 1 2 3 4 5
5
0 Time (min.)
0.01 0.1 1 10 100 1,000
50
Frequency (rad/s)
50 40
45 3ZN
40 3ACE
Power (kW)

30
Delta (°)

35
30
25 20
20
15 10 3ZN
10
5 3ACE
0 0
0.01 0.1 1 10 100 1,000 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Frequency (rad/s) Time (min.)

Reprinted with permission from Rubber World

 Figure 5 - comparison of sulfur Figure 6 - comparison of median tensile
vulcanization kinetics as determined with curves as determined with tensile testing
rheometry (MDR 2000E rheometer at 180°C) for Keltan ACE versus Ziegler Natta
for Keltan ACE versus Ziegler Natta EPDMs EPDMs

18 12
16
10
14
12 8
Torque (dNm)

Stress (MPa)
10
6
8

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6 4

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1ZN 2 1ZN
2 1ACE 1ACE
0

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0
0 5 10 15 20 0 100 200 300 400 500
Time (min.) Strain (%)
18 14

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16
12
14
10
12
Torque (dNm)

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Stress (MPa)

10 8

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8 6
6
4
4 2ZN
2 2ZN

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2 2ACE 2ACE
0 0
0 5 10 15 20 0 100 200 300 400 500

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Time (min.) Strain (%)
16 20
14 18
12 16
14
Torque (dNm)

10
Stress (MPa)

12
8 10
6 8
4 6
3ZN 4 3ZN
2
3ACE 2 3ACE
0 0
0 5 10 15 20 0 100 200 300 400 500 600 700
Time (min.) Strain (%)

(ethylene) crystallinity and, therefore, different low-tempera- The DSC data in table 2 show that they also have similar crys-
ture characteristics (e.g., higher compression sets at low tem- tallization temperatures and heats of crystallization (∆Hc).
peratures) and different tensile properties (e.g., higher tensile Clearly, lowering the ethylene content by approximately 5
strength at room temperature). From the DSC cooling curves, weight % results in Keltan ACE EPDMs with similar crystal-
shown in figure 2, it can be concluded that the ZN and ACE linity as their ZN counterparts.
EPDM polymers show very similar crystallization behavior. Finally, the LCB level completes the list of important

Reprinted with permission from Rubber World

 lecular weight polymers or addition of very low viscosity
Table 3 - comparison of Ziegler Natta versus EPDM). However, the resulting engineered polymer will
Keltan ACE technology, showing EPDM require significant alterations in the compound formulation
compound and vulcanizate properties as well as in the processing conditions when replacing the
“original” ZN version.
EPDM 1ZN 1ACE 2ZN 2ACE 3ZN 3ACE
compound
CML (1+4) @100°C 59 57 61 61 71 75 Mixing, rheometry and physical properties
t5, min. @ 125°C 29 30 29 31 37 32 The EPDM compounds were mixed in a Shaw K-1 batch
Rheometer data @ 180°C mixer with the formulations shown in table 1. It should be
ts2, min. 1.2 1.2 1.2 1.2 1.5 1.5 noted that the ZN EPDM products consisted of compressed
t90, min. 4.7 4.8 3.8 3.7 5.3 5.4
MH-ML, dNm 15 15 15 14 11 11 crumb (commercial EPDM bales), whereas the Keltan
CR, Nm/min. 4.3 4.1 5.7 5.4 2.8 2.9 ACE EPDM polymers produced in the pilot unit consisted
Cured properties of slabs. The mixing curves of the ZN and ACE compounds

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HS, IRHD 64 63 64 65 55 54 are shown in figure 4. Prior to the actual mixing, the poly-
HS ag, IRHD 69 68 68 70 61 61 mer was crumbled for 1-1.5 minutes, which resulted in a
M 100%, MPa 2.8 2.9 3.2 3.3 1.9 1.8
relatively small power peak. After the polymer crumbling,

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M 300%, MPa 10 10 11 11 7 7
TS, MPa 14 15 13 13 18 18 the oil and fillers were added, resulting in a power peak
EB, % 486 469 375 394 613 628 which is identical in shape and height for the ZN and ACE
M 100% ag, MPa 4.2 4.2 4.3 4.7 3.2 3.2 analogues. After a so-called sweeping step (ram moved up

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M 300% ag, MPa 13 13 13 13 12 12 and down to clean shaft), the mixing was continued for one
TS ag, MPa 14 13 13 13 13 14
EB ag, % 360 311 303 295 338 346 minute. From figure 4, it can be concluded that the com-
Tear, N 42 44 42 45 43 42 pound mixing behavior of the ZN and ACE analogues is

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Tear ag, N 40 43 39 44 31 30 very similar. The differences in EPDM sample structure
CS -25°C, % 33 33 25 32 83 77 (bale or slab) did not affect the power uptake during the
CS 100°C, % 18 24 15 17 35 34 polymer crumbling phase.

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The compound Mooney viscosities of the ZN and ACE
EPDM polymer characteristics. High levels of LCB have a polymer analogues are very similar. Obviously, this is the re-

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positive effect on compound processing (mixing and extrusion sult of the development of EPDM analogues with similar a)
[including collapse resistance]), whereas low levels of LCB polymer Mooney viscosity, b) MWD and c) LCB level. The
enhance elasticity, since less dangling polymer ends result in a details on rheometry data and cured properties can be found in
more elastic network. The Δδ value decreases with increasing table 3. Rheometer data were used to evaluate the curing char-
degrees of LCB. The presence of branched molecules will acteristics and crosslink densities (defined as the maximum

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decrease the δ value specifically at low frequencies because of rheometer torque difference, MH-ML) of the EPDM com-
decreased polymer chain dynamics. The δ value at high fre- pounds. In figure 5, the rheometer curves of all ZN and ACE
quencies is governed by the average molecular weight of the compounds are shown. Clearly, the observed differences in

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polymer. To ensure similar mixing and extrusion behavior of crosslink densities are very small and within experimental
the ACE polymers when compared to their ZN counterparts, it error. For this reason, it can be expected that a curing package
is essential that both polymers have a similar Δδ value (of used for a certain compound does not need any significant
course in combination with similar molecular weight and mo- adjustment when replacing a ZN EPDM by its Keltan ACE
lecular weight distribution). The DMS frequency sweep plots analogue.
of the three sets of polymers are shown in figure 3. It can be Most physical properties of rubber vulcanizates are strong-
concluded that the LCB levels of all three ZN-Keltan ACE ly correlated to the crosslink density, as obtained from a rhe-
EPDM combinations are identical. The DMS frequency sweep ometer curve. For EPDM vulcanizates, similar crosslink den-
plots of the 3ZN EPDM and its 3ACE analogue show a minor sities result in similar physical properties, provided the ethyl-
difference at low frequency. This difference can be explained ene crystallinity is at a similar level. The physical properties
by the slightly more branched structure of the ACE version. (hardness, tensile properties, tear and compression sets) are
However, this difference is very small and has no significant measured as a fingerprint of the EPDM vulcanizates. They
effect on processing characteristics and physical properties. By show very similar results for the compounds based on ZN and
changing the polymerization catalyst from ZN to ACE tech- ACE EPDM polymers (table 3). The tensile curves are pre-
nology, the capability to fine tune the structure of the polymer sented in figure 6. The fact that the tensile curves are identical
to the desired LCB level via a specific and controlled process is again solid proof that the polymer structure and crystallinity
can be maintained. Of course, methods to adjust the processing of the analogues are very similar. In general, small differences
behavior of EPDM polymers, produced with other advanced in polymer structure (i.e., LCB level) or in ethylene crystallin-
catalyst systems, do exist and are applied. For example, the ity will affect the tensile strength and elongation at break.
processing behavior of such metallocene EPDMs with their Also, the effect of heat aging (168 hours @ 100°C) on hard-
characteristically narrow MWD can be improved by molecu- ness, tensile properties and tear resistance of the vulcanized
lar engineering (e.g., solution blending of high and low mo- samples is not affected by the choice of polymer (ZN or ACE).

Reprinted with permission from Rubber World

Obviously, aging results in additional crosslinking initiated by 2. J.A. Riedel and R. Vander Laan, “Ethylene propylene rub-
thermo-oxidative reactions, as witnessed by an increasing bers” in The Vanderbilt Rubber Handbook, 13th ed.; R.T.
hardness, an increasing M100% and a decreasing EB. But Vanderbilt Co.: New York, 1973; p. 123.
these changes upon aging are identical for the ZN and ACE 3. J.W.M. Noordermeer, “Ethylene-propylene copolymers” in
combinations. Finally, the compression set results are at the Encyclopedia of Polymer Science and Engineering; John
same level for the various EPDM analogues, both at -25 and Wiley and Sons: New York, 1986; vol. 6, pp. 178-196.
+100°C. The fact that compression sets measured at -25°C are 4. P.S. Ravishankar, Rubber Chem. Technol. 85, 2012, 327.
similar for the ZN and ACE analogues shows that the adjust- 5. M. Gahleitner, L. Resconi and P. Doshev, MRS Bulletin 38,
ments in ethylene content indeed have led to the same levels 2013, 229.
of crystallinity. 6. E. IJpeij, M. Zuideveld, E. Arts, F. v.d. Burgt and G. van
Doremaele, WO2007/031295, to DSM Elastomers B.V. “Pro-
Conclusions cess for the preparation of a metal-organic compound com-
EPDM polymers produced with the most advanced (metallo- prising a spectator ligand.”

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cene) catalyst technologies have several limitations, i.e., 7. E. IJpeij, E. Arts, F. v.d. Burgt, G. van Doremaele and M.
Mooney viscosities (ML [1+4] 125°C) are restricted to the Zuideveld, WO2005/090418, to DSM Elastomers B.V., “Prep-
range of ~20-80 and the ENB content is usually below 7 aration of a polymer.”

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weight %. In contrast, Keltan ACE technology enables the 8. E. IJPeij, B. Coussens, M. Zuideveld, G. van Doremaele, P.
manufacturing of a full range of EPDM products, including Mountford, M. Lutz and A. Spek, Chem. Commun. 46, 2010,
(oil-extended) very high molecular weight polymers and poly- 3,339.

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mers with very high ENB content (up to 9 weight %). The 9. H.J.H. Beelen, Kautsch. Gummi Kunstst., 52, 1999, 406.
Keltan ACE technology is capable of producing polymers 10. M. Dees and M. van Duin, Rubber World, 238, 2008,
with identical polymer characteristics to their Ziegler Natta 19/38.

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counterparts and, consequently, identical compound and vul- 11. M. van Duin, M. Dees and H. Dikland, Kautsch. Gummi
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