BLENDING OF HIGH-PERFORMANCE LLDPEs WITH BUTENE-LLDPEs AND LDPEs

H. Mavridis, Equistar Chemicals, LP This article originally presented at SPE RETEC, February 25-28, 2001.

ABSTRACT
Several High-Performance LLDPE resins for film applications have been developed in the past few years, either through Advanced Ziegler-Natta or Single-Site catalysts. These new resins improve significantly on the film properties of conventional Ziegler-Natta resins, but they are generally more costly and/or more difficult to process. A relatively simple strategy for addressing the cost and processability issues is via post-reactor blending, either with buteneLLDPEs in order to reduce cost, or with LDPEs in order to improve processability. Blending of High-Performance resins has a generally detrimental effect on film strength properties, although there are exceptions in certain compositions. Viability of a certain blend composition then hinges on a cost versus performance evaluation of the properties of interest. The present work focuses on the performance aspect, through a study of the effect of blending butene-LLDPEs and LDPEs on the optical and mechanical properties of Advanced ZieglerNatta and metallocene-LLDPEs.

INTRODUCTION
A number of new resins have been introduced in the last decade for high-strength LLDPE film applications. In the area of hexene-LLDPE film resins, the two main categories [1] include metallocene-catalyzed (mLLDPE) or single-site-catalyzed (SSC) resins and Advanced Ziegler-Natta resins (commonly referred to as superhexenes or High Performance Hexenes, HPH, in the industry). A brief comparison of their relative merits in terms of film properties and blown film processability was recently presented in Ref.[2]. However, both families of LLDPE resins (using either single-site-catalysts or advanced Ziegler-Natta catalysts) still lack the extrusion processability of high-pressure LDPE resins. Blending LDPE into LLDPE is known to improve processability but compromise film properties [3]. It may be possible, in principle, to have a certain type of LLDPE that displays a relative advantage in blendability with LDPE. It is an objective of the present work to investigate the relative blendability of mLLDPEs and advanced Ziegler-Natta HPH-LLDPEs, in their blends with LDPE. By analogy to blending with LDPE for the purpose of improving processability, a second type of blending commonly employed in industry, is to blend standard Ziegler-Natta buteneLLDPEs so as to reduce cost (butene LLDPEs can be 10-20% cheaper than highperformance hexene-LLDPEs, thus the cost incentive). It is the second objective of the present work to investigate the relative blendability of mLLDPEs and advanced Ziegler-Natta HPH-LLDPEs, in their blends with standard Ziegler-Natta butene-LLDPE.

EXPERIMENTAL
MATERIALS The resins used in the present study are listed in Table 1, along with their fundamental polymer properties. HPH is a High-Performance-Hexene LLDPE from Equistar, made with an Advanced Ziegler-Natta catalyst and described elsewhere [5-6]. mLLDPE is a metallocene-catalyzed LLDPE without long chain branching [7]. C4-LLDPE is a standard Zielger-Natta butene-LLDPE and LDPE is a high-pressure LDPE with long chain branching. A comparison of the molecular weight distributions, short chain branching distributions, thermal characteristics and rheological behavior, is given in Figures 1 through 4, respectively. Figure 5 also shows a certain representation of the rheological data that highlights differences in MWD and/or LCB. The higher the Storage Modulus at low Loss Modulus in Figure 5, the broader the resin rheologically [4], which translates to better melt extrusion processability. As Figure 5 clearly shows, the LDPE is the broadest rheologically (also indicated by the ER number in Table 1, see also Ref.[4]), whereas the mLLDPE is the narrowest rheologically.

FILM FABRICATION AND TESTING Blown film extrusion was performed on a lab line equipped with a 4 spiral mandrel die with a 0.100" die gap and a dual lip air ring. A "hump" temperature profile was used for the barrel temperature settings in all cases. Output rate was held constant at 40 lb/hr. Blow up ratio and film gauge were held fixed at 2.5:1 and 1 mil, respectively. Each run condition was replicated 2 times. All films produced were conditioned and tested per the standard ASTM methods. Film property averages and standard deviations were determined on the basis of 2replicates.

RESULTS AND DISCUSSION

BUTENE-LLDPE BLENDS Comparative plots of film properties versus blend composition for HPH/C4-LLDPE blends and mLLDPE/C4-LLDPE blends are given in Figures 6-12. The impact strength of the blends is shown to decrease precipitously as function of C4-LLDPE content. However, for the mLLDPE/C4-LLDPE blends where the C4-LLDPE is the minor component (<50%) the mLLDPE blends maintain substantial film impact strength. Beyond the level of 50 wt% C4LLDPE, the film impact strength is at the level seen with ordinary hexene-LLDPEs and, therefore the choice of the blend composition will need to take into account specific cost factors of the blend components. Similarly to the film impact strength, the tear strength of the mLLDPE blends is flat as a function of C4-LLDPE content, up to 50% C4-LLDPE (Fig.8-9). Examination of other film properties (haze in Fig.10 and heat seal strength in Fig.11) shows no other detrimental effects of C4-LLDPE addition into mLLDPE. Therefore, it appears that diluting mLLDPE with C4LLDPE for up to 50%, maintains substantially the film impact and tear of mLLDPE. The blendability of HPH with C4-LLDPE is slightly different. The film impact of the HPH/C4-LLDPE blends shows a steep reduction upon C4-LLDPE addition, even at low C4LLDPE content (see Fig.6). The Elmendorf tear strength, on the other hand, varies more gradually with C4-LLDPE content (Fig. 8-9). Note that the tear strength of the HPH/C4LLDPE blends is higher than that of the mLLDPE/C4-LLDPE blends. Therefore the relative viability of HPH/C4-LLDPE blends versus mLLDPE/C4-LLDPE blends, must be examined in the context of the specific film properties desired and the specific cost structure associated with the blend composition in question.

LDPE BLENDS Comparative plots of film properties versus blend composition for HPH/LDPE blends and mLLDPE/LDPE blends are given in Figures 14-20. The processability enhancement upon LDPE addition is shown in Figure 13, which plots the extruder amps as a function of blend composition. There is clearly a reduction in extruder amps with increasing LDPE content, which in turn relates to the reduction in high-shear-rate viscosity (see for example Table 1). There is no significance difference in the extrudability of the HPH and mLLDPE blends. The impact strength of the blends is shown to decrease precipitously as function of LDPE content (Figure 14). The mLLDPE/LDPE blends do maintain an advantage over HPH/LDPE blends, which may relate to the lower film modulus of the mLLDPE/LDPE blends (shown in Figure 15. Film impact strength is inversely related to film modulus, generally). However, in MD-Tear strength, all differentiation between mLLDPE/LDPE and HPH/LDPE blends is lost (Figure 16): the effect of LDPE addition is to decrease the MD-Tear dramatically, as also observed in the past [5]. In contrast to the catastrophic effect of LDPE addition on MD-Tear, the effect on optical properties is synergistically positive (Figures 18-19). Again, all differentiation between mLLDPE/LDPE and HPH/LDPE blends is lost, but now both types of blends have optical properties better than any of the pure components. Finally, in terms of resistance to slow puncture (Figure 20), the mLLDPE/LDPE blends have a slight advantage over HPH/LDPE blends (higher puncture energy). This may be, at least partly, due to the difference in surface friction characteristics of the films (as illustrated by the higher coefficient of friction, COF, of the mLLDPE/LDPE blends in Figure20). It is known that the puncture resistance of polyethylene films, as measured in ASTM-5748, shows a pronounced dependence on COF.

CONCLUDING REMARKS
Advanced Ziegler-Natta catalyzed LLDPE (HPH) and metallocene-catalyzed LLDPE (mLLDPE) were compared in their relative blendability with butene-LLDPE and LDPE. Such blends are practiced in industry for cost reduction and/or processability enhancement. In this study we compared the relative merits of such blends, by selecting pure components of similar melt index and density. In the case of blends with butene-LLDPE, all film properties show a gradual change between the values of the pure components. The mLLDPE/C4-LLDPE blends have an advantage over HPH/C4-LLDPE blends in film impact strength, whereas the HPH/C4LLDPE blends have an advantage in Elmendorf tear strength, at C4-LLDPE levels below 50 wt%. Therefore the choice of one type of blend over another will depend on the particular set of film properties required and the specific cost structure of the components. In the case of blends with LDPE, the expected enhancement in processability upon LDPE addition is observed in both the HPH/LDPE and mLLDPE/LDPE blends. LDPE causes a dramatic reduction in film strength properties (impact and tear) and a synergistic improvement in optical properties. There is little differentiation between HPH/LDPE and mLLDPE/LDPE blends, with the minor exception film impact strength at <50 wt% LDPE, where the mLLDPE/LPDE blends have an advantage over HPH/LDPE blends.

REFERENCES
1. 2. 3. 4. M. Mack, New Polyethylene Advances via Next-Generation Single-Site Catalysts, METCON 2000, June 8-9, 2000, Houston, TX H. Mavridis, New LLDPE resins for film offer superior processing, Proc. Film Conference 99, 283-290, Dec.7-9, 1999 D.J. Falla, Physical properties of blends of various melt index LDPEs and LLDPEs, TAPPI PLC Conference Proc., 279-303 (1996) R. Shroff and H. Mavridis, New Measures of Polydispersity from Rheological Data on Polymer Melts, J. Appl. Polym. Sci., 57, 1605-1626 (1995)

3 2

5. 6. 7.

H. Mavridis, TAPPI PLC Conf. Proc., 413-422 (1998) H. Mavridis, SPE ANTEC Tech Papers, 41-45 (1999) R. Shroff and H. Mavridis, Macromolecules, 32, 8454-8464 (1999)

Table 1. List of resins used in the present study Resin Catalyst Melt Index, g/10min Resin Density, g/cc Comonomer Antiblock, ppm Slip, ppm Rheology (190 oC) ER, Ref.[4] * @100 rad/sec, kpoise * @=2*103 Pa, kpoise MWD Mw Mz/Mw Mw/Mn TREF Br/1000C DSC Tm1 Tm2 Tc Heat of fusion, J/g HPH Advanced Ziegler-Natta 0.66 0.916 Hexene 7500 1500 0.90 18.1 114 140,000 2.6 5.3 15.3 125.6 114.9 127.5 mLLDPE Metallocene 1.1 0.918 Hexene 4600 500 0.15 23.3 61.8 116,000 1.8 2.9 16.7 119.8 109.3 107.5 123.7 C4-LLDPE Ziegler-Natta 0.94 0.920 Butene 6300 1600 0.62 17.7 82.5 128,000 2.7 4.3 15.8 122.2 110.8 118.2 LDPE N/A 0.77 0.920 N/A 0 0 2.5 6.3 140 106,000 2.8 7.4 21.0 109.8 97.4 122.8

Figure 1. Molecular weight distributions (GPC) of the resins in this study (apparent MWD for LDPE no LCB correction).
1.2 1.0 0.8 0.6 0.4 0.2 0.0 1.E+03

dw/dlogM

HPH mLLDPE C4-LLDPE LDPE

mLLDPE HPH

LDPE

1.E+04

1.E+05

1.E+06

1.E+07

Molecular Weight (M)

Figure 2. Comonomer compositions distributions (SCB by TREF) for the resins of this study.
25.0

HPH
20.0

LDPE
HPH mLLDPE C4-LLDPE LDPE

dw/dlogM

15.0 10.0 5.0 0.0 0 10 20 30

40

50

Short Chain Branching, SCB/1000C

Figure 3. DSC (melting at 10C/min) for the resins of this study.

-1.0

Heat Flow (W/g)

-3.0

-5.0

-7.0

HPH mLLDPE C4-LLDPE LDPE

60 80 100 Temperature (deg.C) 120 140

-9.0

Figure 4. Rheology data (viscosity) at 190C, illustrating differences in melt strength and extrudability.

1.0E+06

Melt Strength
Viscosity (poise) 1.0E+05

Extrudability

1.0E+04

HPH mLLDPE C4-LLDPE LDPE

1.0E+00 1.0E+01 Frequency (1/sec) 1.0E+02 1.0E+03

1.0E+03 1.0E-01

Figure 5. Rheology data (storage versus loss modulus) at 190 C, illustrating differences in rheological polydispersity.
1.0E+07

Storage Modulus (dyn/cm )

1.0E+06

1.0E+05

1.0E+04

HPH mLLDPE C4-LLDPE LDPE

1.0E+03 1.0E+04

1.0E+05 1.0E+06 2 Loss Modulus (dyn/cm )

1.0E+07

Figure 6. Variation of film impact strength (Dart Drop) with blend composition for butene-LLDPE blends.

1200 1000 800 600 400 200 0 0 25 50 75 100

HPH mLLDPE

% Figure 7. Variation of film modulus withC4-LLDPE blend composition for butene-LLDPE blends.

Dart Drop
Film MD-Modulus (psi)

30000

28000

26000

HPH
24000

mLLDPE

22000 0 25 50 75 100

% C4-LLDPE

Figure 8. Variation of film Elmendorf MD-Tear Strength with blend composition for butene-LLDPE blends.
3.0 500
400 2.0 300 200 1.0 100

MD-Tear (g) Seal Strength @110C (lbf)

HPH HPH mLLDPE mLLDPE

0.0 0 0 0

25 25

% C4-LLDPE % C4-LLDPE

50 50

75 75

100 100

Figure 9. Variation of film Elmendorf TD-Tear Strength with blend composition for butene-LLDPE blends.
600 500

TD-Tear (g)

400 300 200 100 0 0 25 50 75 100

HPH mLLDPE

% C4-LLDPE

Figure 10. Variation of film optical properties (Haze) with blend composition for butene-LLDPE blends.

30.0 25.0 20.0

Haze

15.0 10.0 5.0

HPH mLLDPE

0.0 Figure 11. Variation of film heat seal strength with blend composition for 0 50 75 100 butene-LLDPE25 blends. % C4-LLDPE

8 7

1200 1000 800 600 400 200 0 0 25 50 75 100

HPH mLLDPE

Figure 12. Variation of slow puncture% LDPE and COF with blend composition energy for butene-LLDPE blends.

Dart Drop

1.50

HPH mLLDPE

COF and Slow Puncture Energy

1.25 1.00

(Joules)

0.75 0.50 0.25 0.00

COF

Figure 13.

Variation of extruder amps with blend composition for LDPE 0 25 50 75 100 blends. % C4-LLDPE

25

HPH
Extruder Amps
20

mLLDPE
15

10

Figure 14.

Variation of film impact strength (Dart Drop ) with blend 5 composition for LDPE blends.
0 25 50 75 100

% LDPE

900 800 700

TD-Tear (g)

600 500 400 300 200

HPH mLLDPE

Figure 15.

100 Variation of film modulus with blend composition for LDPE blends. 0 0 25 50 75 100

% LDPE

40000

Film MD-Modulus (psi)

35000

30000

HPH mLLDPE

25000

Figure 16.

20000

Variation of film Elmendorf MD-Tear composition for LDPE blends.

0 25 50

Strength
75

with
100

blend

% LDPE

500 400

HPH mLLDPE

MD-Tear (g)

300 200

Figure 17. Variation of film Elmendorf TD-Tear Strength with blend composition for LDPE blends. 100
0 0 25 50 75 100

% LDPE

10

1.50

COF and Slow Puncture Energy

1.25

HPH mLLDPE

Figure 18.

Variation of film optical properties (Haze) with blend composition 0.75 for LDPE blends.
0.50 0.25 0.00 0 25 50 75 100

(Joules)

1.00

COF

% LDPE

30.0 25.0 20.0

HPH mLLDPE

Haze

Figure 19.

15.0 Variation of film optical properties (Gloss) with blend composition for LDPE blends. 10.0 5.0 0.0 0 25 50 75 100

% LDPE

80.0 70.0 60.0

Gloss

50.0 40.0 Variation of film slow puncture energy and coefficient of friction HPH with blend composition for LDPE blends 30.0 20.0 10.0 0.0 0 25 50 75 100

Figure 20.

mLLDPE

% LDPE

11