SINGLE SITE CATALYSTS AND DUAL REACTOR TECHNOLOGY CREATE MORE FREEDOM IN PE ROTOMOLDING RESIN AND PRODUCT DESIGNS

XiaoChuan (Alan) Wang, Mark Weber, Henry Hay, Marlee Cossar NOVA Chemicals Corporation Calgary, Alberta, Canada Abstract
While polyethylene continues to be the resin of choice for rotational molding, advancements in material design are still required. From a structure-property perspective, a thinner lamellar thickness of a polyethylene resin may lead to a higher tie chain formation probability. It is also believed that longer polymer chains with proper comonomer incorporation enhance this probability. Single site catalysts and octene comonomer usage enable the design of rotomolding resins with superior properties compared with conventional Ziegler-Natta resins. This paper combines our fundamental understanding of this topic with experimental data. information such as the tie chain formation probability and relative concentration of tie chains, etc. [9, 10, 11]. However, the true quantity of tie chains has not been fully confirmed by experimental results for a given resin and it is expected to be very difficult from an experimental perspective, although there have been some attempts to correlate the experimental or calculated results with enduse properties. In this work, an experimental method has been used to infer the relative amount of tie chains. From a morphology point of view (Figure 1), the tie chains must pass through the interfacial region. As a result, they may be counted as part of the interfacial phase if measured by an experimental method. With this fundamental understanding in mind, for a similar polyethylene resin category (e.g., roughly HDPE or MDPE), the measured amount of the interfacial phase may be used as a relative indication of the amount of tie chains, although not their exact amount, since this phase includes at least loose chain loops and chain ends as well. For this objective, therefore, laser (514.5 nm) Raman spectroscopy internal mode analysis of band intensities has been applied to quantitatively characterize the polyethylene three-phase structure, with respect to interfacial phase characterization and hence the information about tie chains.

Introduction
High performance octene polyethylene products produced by single site catalysts (SSC) have been discussed previously for high performance films [1], and rotomolding products with enhanced processability [2]. With respect to rotomolding products, the objective of this work is to provide more fundamental understandings versus comparable Ziegler-Natta (ZN) hexene rotomolding resins. It has been well known that for semi-crystalline polyethylene, at least three phases must be considered to describe its solid-state morphology, i.e., crystalline, amorphous, and interfacial phases, as illustrated in Figure 1 [3,4,5,6,7]. Here, the interfacial phase is defined to be that part of the non-crystalline material that represents a transition zone between the surface of the crystal and that point at which the presence of the crystal is no longer significant in terms of affecting amorphous phase molecular motion and conformation. This disordered phase mainly includes loose chain loops, chain ends and tie chains or molecules. It is widely believed that tie chains in polyethylenes play key roles in affecting the end-use physical properties such as toughness and environmental stress crack resistance (ESCR). This is because tie chains are the molecular chains connecting the lamellae together, and their integrity is critical in order for the ductile-type behavior to occur. Attempts have been made to infer the relative amount of tie chains by experimental methods, such as Fourier Transform Infrared Spectroscopy [8]. Calculation methods have also been suggested to infer the

Experimental
Polymers and Characterizations The solution octene HDPE and MDPE rotomolding resins examined here were produced on a commercial plant using NOVA Chemicals Advanced SCLAIRTECH Technology and proprietary single site catalyst. The bench mark hexene HDPE and MDPE rotomolding resins were produced by a gas phase process and a Ziegler-Natta catalyst. Analytical temperature rising elution fractionation (A-TREF) fractions were obtained by an analytical TREF system built in-house. Melt Index (MI or I2) was measured in accordance with ASTM D-1238, condition F (190oC/2.16kg). Density was obtained in accordance with ASTM D-1505. Polyethylene Three-Phase Characterizations Raman spectra were collected from a 514.5 nm laser Raman Spectroscope at the Research Laboratory Canmet Energy Technology Centre, Devon, Alberta, Natural Resources Canada. The principle for using Raman

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technique to characterize the interfacial phase and hence to infer the relative amount of tie chains is as follows. Since the total integrated intensity Iref of the CH2 twisting band at 1298 cm-1 is irrelevant to the conformations of molecular chains, it can be used as an internal intensity reference. The curve-fitting technique was performed using Grams AI (Version 7.00). The total integrated intensity Iref at 1298 cm-1 was measured using the integrate program in the Grams AI where the integrate area from 1352 cm-1 to 1253 cm-1 was used. The band at 1416 cm-1 arises from crystalline regions. A curve fitting program was used to obtain I1416 in which three peaks at 1461, 1442 and 1416 cm-1 were fitted in the area between 1550 cm-1 to 1400 cm-1 region using a 100% Gaussian distribution and iterated until convergence. From the integrated intensity of this band (I1416), the fraction of CH2 units in the crystalline orthorhombic phase, or the crystallinity of the sample can be calculated:

of this paper, only the maximum impact strength achievable with 100% ductility (prior to the point where the effects of possible thermal and oxidative degradation/crosslinking are evident) is reported here and will be explained below. The environmental stress crack resistance of compression-molded plaques at constant tensile load (abbreviated as CTL-ESCR) recommended by ARM was evaluated at 300C, a stress level of 4.5 MPa, 20% notch depth, and 10% Igepal concentration.

Results and Discussion

Polymer Properties Table 1 shows the molecular characteristics of the SSC and ZN rotomolding resins examined in this paper. Two groups can be defined according to the catalyst and comonomer type, i.e., SSC/octene (SSC-A and SSC-C) vs. ZN/hexene (ZN-B and ZN-D). Note that within the same group (SSC-A vs. SSC-C, and ZN-B vs. ZN-D), the change in weight average molecular weight (Mw) is similar, in the range of about 22000, and the molecular weight distribution (MWD) remains relatively unchanged. Also note that the SSC/octene resins have narrower molecular weight distributions than their ZN/hexene counterparts (SSC-A vs. ZN-B in HDPE resin category, and SSC-C vs. ZN-D in MDPE resin category). It is well known that a fundamental difference between a SSC and ZN resin is in their comonomer distribution uniformity. A SSC resin has a uniform comonomer distribution while that of a ZN resin is heterogeneous. This is reflected by the comonomer distribution breadth index (CDBI) measured by A-TREF in Table 1. A higher value of CDBI is indicative of a more homogeneous comonomer distribution. Other molecular parameters being similar, it is believed that a more uniform comonomer distribution helps reduce the lamellar thickness and hence increases the probability to form tie chains. Three-Phase Measurements by Laser Raman As an example, Figure 2 shows the de-convoluted crystalline phase at the band of 1416 cm-1 in the crystalline orthorhombic phase, and the de-convoluted amorphous phase between the region of 1400 and 1250 cm-1 for ZNB. Table 2 summarizes the measured amounts of the crystalline, amorphous and interfacial phases, and other physical properties. It can be seen from Tables 1 and 2 that for the comparable resins in the same resin category (MDPE or HDPE), a SSC/octene resin has a comparable or higher amount of the interfacial phase than its ZN/hexene counterpart, even under the condition of increased density or stiffness. This is significant, as one would normally expect a smaller interfacial region for resins with higher crystallinity, or density. For the above two groups, comonomer distribution uniformity and comonomer type have impacts on the

c =

I 1416
0.46 I ref

(1)

where the constant 0.46 is measured from the spectrum of fully crystalline polyethylene using 514.5 nm laser Raman spectroscopy [12,13]. In the CH2 twisting vibration region, i.e., the region of 1400 and 1250 cm-1, a mixed 60% Gaussian and 40% Lorentzian curve-fitting program was used to obtain I1303 in which the two peaks at 1303 cm-1 and 1298 cm-1 were fitted, the position of 1303 cm-1 was limited between 1303 cm-1 and 1305 cm-1 region and iterated until being converged. The fraction of amorphous phase can then be calculated:

a =

I 1303 I ref

(2)

where the constant 1.0 is measured from the spectrum of fully amorphous polyethylene using 514.5 nm laser Raman spectroscope [12,13]. Finally, the mass fraction of the interfacial region is given by:

b =

1 c a

(3)

Rotational Molding Trials and Testing The resins were molded with a Ferry Industries Inc. RS-160 rotational molding machine using 30.530.535.6 cm3 cast aluminum molds, under the conditions of 5600F oven temperature and forced air cooling. The oven time was changed to optimize the state of cure and hence the physical properties. The impact strength at 400C of the rotomolded part was evaluated using the method recommended by the Association of Rotational Molders (ARM) International. For the purpose

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amount of the interfacial phase. Recall that within the same group (SSC-A vs. SSC-C, and ZN-B vs. ZN-D), the change in Mw is similar, and MWD remains relatively unchanged. It can been seen that, within the SSC/octene resin group, an increase in octene content of 0.8 mol.% results in a decrease in crystallinity (c) of 8.75 wt.%. However, this trend is not so significant within the ZN/hexene resin group, mainly due to its heterogeneous comonomer distribution and hence reduced ability to decrease crystallization. For example, within the ZN/hexene group, an increase in a similar amount of comonomer (0.9 mol.%, but it is hexene comonomer) leads to only 5.0 wt.% reduction in crystallinity. Within SSC/octene resin group, the amorphous (a) and interfacial (b) amounts increase by 6.04 wt.% and 2.71 wt.% respectively, while for ZN/hexene resin group, the increase in amorphous phase amount is similar (5.95 wt.%), however the interfacial amount seems to increase by only 0.96 wt.%. Therefore, with the similar change in comonomer content of about 0.8 mol.%, the change in the amount of the interfacial phase within SSC/octene resin group is about 2.8 times that within the ZN/hexene resin group for the resins examined here. This is attributed to a combination of the comonomer distribution uniformity of a SSC resin, certain molecular species produced by the multiple reactor process technology, and possibly the longer chain length of octene comonomer. Within either the HDPE or MDPE resin category in Table 2, why are higher amorphous contents (a) for these ZN rotomolding resins observed? This is probably because conventional ZN catalyst and its process technology create more short polymer chains with many short chain comonomer branches. A good example is in Figure 3 that shows the analytical temperature rising fractionation profiles for SSC-A and ZN-B. The weight fractions between 25 to 900C elution temperatures are shown in Table 2. It can be seen that ZN-B has a much higher amount of chains with many branches that typically have lower molecular weight. It is known that polyethylene chains having comonomer branches normally do not enter the tightly packed lamellar lattice. Depending on their comonomer content and distribution, molecular weight and crystallization conditions, these chains may enter either amorphous or interfacial regions. For the ZN/hexene group, the lower molecular weight molecules with many branches seem to be concentrated mainly in the amorphous phase, and this has be detected by laser Raman spectroscopy. Contrary to the ZN/hexene resin group, the use of single site catalysts reduces the formation of those chains having low molecular weight and many branches. As a result, their amorphous region amount seems to be less if compared with those of their ZN/hexene counterpart examined here. Nevertheless, the higher molecular weight of some species helps to increase the tie chain formation

probability. As a result, even with higher density or stiffness, their interfacial phase amount and hence probable amount of tie chains seem to be equivalent or higher than their ZN/hexene counterparts. This increase in tie molecules is anticipated to improve the inter-lamellar failure resistance and be favorable to many physical properties such as toughness at low temperature. Meanwhile, it should be noted that the interfacial phase also contains other species such as loose chain loops and chain ends, in addition to tie chains. This has been hinted by the data in Table 2. Therefore, the use of the interfacial amount as a relative indication of tie chains should be done with caution, preferably within the similar resin category (e.g., HDPE or MDPE as an example here). Toughness at low temperatures For a rotomolded product, one of the key performance indicators is impact strength at low temperatures. Table 2 contains the maximum ARM impact strength (-400C) achievable with 100% ductility for the four resins examined. The rationale for using this value is as follows. Assuming that the resins are properly stabilized and the powders are fully sintered, one may postulate that this value reflects more about the intrinsic resin properties and hence the morphology. Within the similar HDPE or MDPE resin category, it can be seen that SSC-A and SSC-C have higher resin densities and hence higher stiffness than ZN-B and ZN-D respectively. For conventional commercial Ziegler-Natta rotomolding products, typically the increase in stiffness may lead to the subsequent decrease in toughness. However, even with higher stiffness in the HDPE resin category, the SSC/octene resin SSC-A appears to have statistically (test error not shown here) equivalent maximum impact strength compared to that of the ZN/hexene resin ZN-B having lower stiffness. It is believed that this is due to the increased amount of its interfacial phase (b) and hence probably higher amount of tie chains. This trend is further confirmed in the MDPE resin category with the data of SSC-C. It has a much higher density and hence stiffness than ZN-D. Nevertheless, its higher interfacial amount or more tie chains imparts a higher toughness than that for ZN-D, as seen in Table 2. Environmental Stress Cracking Resistance Another key performance indicator is environmental stress crack resistance (ESCR). Generally, environmental stress crack resistance (ESCR) of polyethylene may be evaluated at constant-strain tests (such as the bent-strip tests in ASTM D 1693); and constant load testing under the tensile mode. For the bent-strip test, there has long been a concern about its ability to isolate the yield-stress (it actually ought to be flexural modulus in the opinions of the authors in this paper) property as a parameter independent of the polymers stress-crack properties [14], since different moduli of samples may result in different initial

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and persistant stress levels when subjected to such a test. This can be understood from the test procedure. In the bent strip test, samples are stressed by bending them into a fixed-radius U-shape and holding them in place. Initial stress levels are dependent upon the stiffness of the resin, and long-term stress levels depend upon the creep characteristics of the resin. For constant-tensile-load tests with an automatic failure-detection mechanism, specimen stiffness also has a somewhat confounding effect, since different stiffness may lead to a different deformation under the constant load. Although there has been some ambiguity with the interpretation of ESCR results, it was surmised that environmental stress cracking in polyethylene takes place because of inter-lamellar failure, which in turn is caused by relaxation of tie molecules [14]. It was further deduced that the resistance to this failure mode can be best reflected through constant-tensile-load testing, while taking into account the differences in yield point among various polyethylenes [14]. In this work (Table 2), it is found that the relationship of the interfacial amount with either CTL-ESCR or toughness at low temperature indeed seem to be in line with the concept of an inter-lamellar failure mechanism, when compared within the similar resin category. Evidently, the higher interfacial amount and hence possibly the increased number of tie chains for SSC/octene resins seems to improve the ductile-brittle transition in either low temperature impact testing or constant-tensile-load ESCR testing, even under the conditions of higher stiffness.

meeting the practical needs in many rotomolding applications.

Acknowledgements
The authors acknowledge NOVA Chemicals Corporation for permission to publish this work.

Disclaimer
This information is furnished in good faith, without warranty, representation, inducement or license of any kind. All implied warranties and conditions (including warranties and conditions of quality and fitness for a particular purpose), are specifically excluded. No freedom from infringement of a patent owned by NOVA Chemicals or others is to be inferred.

References
1. 2. 3. 4. 5. N. Aubee, C. Dobbin, S. Marshall, T. Swabey, TAPPI 2004 H. Hay, M. Weber, R. Donaldson, I. Gibbons, C. Bellehumeur, ANTEC 2004 L. Mandelkern, J. Phys. Chem., 75, 3909 (1971) L. Mandelkern, Faraday Discuss. Chem. Soc., 68, 310 (1979) L.E. Alexander, X-Ray Diffraction Methods in Polymer Science, Krieger Publishing Co., New York, 1979 L. Mandelkern, M. Glotin and R.A. Benson, Macromolecules, 14, 22(1981) M. Glotin and L. Mandelkern, 14, 1394(1981) A. Lustiger, and N. Ishikawa, J. Polym. Sci., Part B, Polym. Phys., 29, 1047(1991) Y.L. Huang, and N. Brown, J. Polym. Sci., Part B, Polym. Phys., 29, 129(1991) R.M. Patel, K. Sehanobish, P. Jain, S.P. Chum, and G.W. Knight, J. Appl. Polym. Sci., 60, 749 (1996) R. Popli, and D. Roylance, Polym. Eng. Sci., 25(13), 828 (1985) M. Failla, R.G. Alamo and L. Mandelkern, Polymer Testing, 11, 151(1992) R. P. Paradkar, S.S. Sakhalkar, X. He, and M.S. Ellison, J. Appl. Polym. Sci., 88, 545 (2003) A. Lustiger, Understanding Environmental Stress Cracking in Polyethylene, Medical Plastics and Biomaterials, July/August, 12(1996)

6. 7. 8. 9. 10. 11. 12. 13. 14.

Conclusions
The amounts of the crystalline, amorphous and interfacial phases for comparable single site/octene and ZieglerNatta/hexene rotomolding resins have been measured by 514.5 nm laser Raman spectroscopy. The results indicate that the resins produced by single site catalyst and multiple reactor process technology, in conjunction with octene comonomer, seem to have higher interfacial amount and hence possibly more tie chains even under the conditions of higher density or stiffness, when compared within the similar resin category. This possible increase in the amount of tie molecules seems to improve the interlamellar failure resistance and is supported by the experimental data, such as toughness at low temperature and ESCR measured under a constant tensile load. Compared with Ziegler-Natta/hexene counterparts, the SSC/octene resins seem to have a better balance of higher stiffness and equivalent or even higher toughness, while

Keywords:

tie chain, interfacial, amorphous, crystalline, Raman, single site, Ziegler-Natta, rotational molding

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Table 1: Polymer Properties.

Sample Resin Catalyst Comonomer Category Mw M w/M n FTIR CDBI Conomomer content (mol.% ) 0.3 90.9 0.8 51 1.1 1.7 80.5 30 Nominal MI DSC T m Density (dg/min.) ( o C) (g/cm 3 ) 0.944 0.942 0.939 0.935 1.7 1.8 5.2 5 129.4 128.6 126.3 125.8 H m (J/g)

SSC-A ZN-B SSC-C ZN-D

HDPE HDPE M DPE M DPE

SSC ZN SSC ZN

Octene Hexene Octene Hexene

87500 87000 64500 66200

2.19 2.90 2.26 3.5

187.3 174.5 172 157.1

Table 2: Laser Raman Measurement Results, CTL-ESCR and ARM Maximum Impact Strength.
Sample AResin Catalyst Comonomer c TREF (wt.% ) Category (< 90 0 C fraction HDPE SSC Octene 7.1 71.59 HDPE ZN Hexene 28.7 68.4 MDPE MDPE SSC ZN Octene Hexene 41.5 43.3 62.84 63.41
a b

(wt.% )

(wt.% )

CTLESCR (hrs) 240 280 110 87

M ax 1% ARM Flexural Impact M odulus (J) (M Pa) 235 254 202 160 990 920 750 620

Tensile Yield Stress (M Pa) 23.5 21.1 19.9 17.4

SSC-A ZN-B SSC-C ZN-D

13.64 18.74 19.68 24.69

14.77 12.86 17.48 11.9

Figure 1: Illustration of Three-Phase Morphology of Polyethylene [3,4,5,6,7].

Figure 2: An Example of the Raman Spectra in the Crystalline and Amorphous Regions (ZN-B).
Z N -B

C r y s t a llin e P hase

A m o rp h o u s P hase

Figure 3: Comparison of Analytical Temperature-Rising Elution Fractionation Profiles of SSC-A and ZN-B. Resins.

0 .2 5

S S C -A , S S C /O c te n e Z N -B , Z N /H e x e n e

Absorbance

0 .2 0 0 .1 5 0 .1 0 0 .0 5 0 .0 0 20 30

40

50

60

70

80

90

100

110

(C )

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