“New stabilizer solutions for polyolefin film grades”

by

Dr. Florian Stricker

Ciba Specialty Chemicals
Basel, Switzerland
[email protected]

Murray Horton
Ciba Specialty Chemicals
Macclesfield, Cheshire, UK
[email protected]

European Tappi PLACE Conference

May 12 - 14, 2003
Rome, Italy

Ciba
NEW STABILIZER SOLUTIONS FOR POLYOLEFIN FILM GRADES
Dr. Florian Stricker and Murray Horton; Ciba Specialty Chemicals Corporation

ABSTRACT

Over the years the plastic industry is launching a variety several new polyolefin products, including metallocene-
based and bimodal polyethylenes and polypropylenes. Nevertheless the industry has matured quite considerably
over the past 30 years. In such a mature industry, there are still many incumbent products which have established
positions in existing markets. These products have been successful in meeting the most important needs in their
markets but there still remains areas where performance can be improved or where deficiencies exist. These
opportunities could encompass processing improvements, reduction of defects, reduced discoloration, or product
stewardship concerns. Successful attempts to make improvements upon these incumbent products seem to depend
from a technical stand point on two factors: a wide spectrum of products from which to choose (toolbox) and people
with knowledge of the chemistries and the technologies they will be applied to. This paper will describe two
examples of new approaches to base stabilization of polyolefins.

INTRODUCTION

Base stabilization of polyolefins is necessary to protect the polymer from degradation during melt processing and
conversion. Beside processing stability base stabilizers provide long-term thermal stability in use. But today’s
requirements in polyolefin applications demand more and many other constraints must be taken into account in real
world situations. Figure 1 shows some of the constraints, which may apply to specific situations. In any given
situation, some of the considerations listed may impose limitations on the chemistries which can be applied.

Polymer Production
• resin type PE/ PP/ EVA Cost
• production process and catalyst residues constraints
• molecular weight distribution and rheology
Compounding Potential defects
• feeding, temperature blooming
• mixing / shear and residence time gels
• chemical interactions discoloration
Polymer Modification organoleptics
• visbreaking sub-optimum physicals
• crosslinking foreign matter/ black specs
Transportation and Storage
• moisture Treatments/ processing
• combustion gases surface treatments
• temperature, time paintability
Conversion lamination/ adhesion
• processing window foaming
• chemical interactions color yield
• time and temperature recycle/ rework
• melt fracture, die lip buildup sterilization
• volatiles (smoke)
End use application regulatory requirements
• heat, light interactions with other additives/ effects
• chemicals, air pollutants consumer sensitivities
• extraction media
Figure 1: Aspects relevant to optimize stabilization systems for a given polymer grade
Stabilizers are by nature reactive chemicals and sometimes tend to give undesired reactions and effects. Examples
are blooming or die build up as well as the tendency of phenolic antioxidants to discolor when exposed to active
catalyst residues and exhaust gasses from combustion processes.

Two factors are key in being able to optimally formulate base stabilization packages. One is having access to a
diverse toolbox of additives from which to choose. Having several degrees of freedom in the selection and
combination of additives allows for a much greater possibility of meeting primary requirements and constraints.
Fortunately, there exists a quite broad portfolio of stabilizers from which to choose. In particular, new chemistries
like hydroxylamine and lactone or recently available ones like vitamin E, significantly improve the ability to reach a
peak performance in a given situation. Perhaps even more important is having the knowledge and experience to
apply the use of additives to different situations. This experience comes over many years as customer problems are
worked though and needs are recognized. Many of the new chemistries which are now available came about via
attempts to meet more demanding needs.

Some of the important constraints are listed in the Figure 1. With regard to the resin, certainly the amount and type
of catalyst residue that remains after production and catalyst deactivation are known to have an effect on the
stabilization of the polymer during melt processing. In addition, other trace constituents like free radicals or
oligomers can have an influence on the type and degree of molecular weight changes which are likely to occur
during subsequent processing.

Compounding is usually the most straightforward step however issues can still arise. For instance, accurate feeding
of all additives can sometimes be a challenge. In such cases, preblends can often improve the situation but care
must be taken to insure proper stability of the blend. Other parameters such as processing temperature ‘window’ can
constrain the stabilizer selection.

Often polymer modification such as PP visbreaking or PE crosslinking is practiced. These free radical initiated
processes can be very sensitive to additive selection. Stabilizers will in general interact with the radicals and care is
needed in selecting appropriate additives for specific situations. Some representative examples of pitfalls that can
occur include degradation of properties like color or organoleptics, reduction of physical integrity or interference
with the cross link density. In addition, a poor selection of stabilizers can result in increased cost for chemicals or
treatment needed to achieve the desired property.

Stabilization Principles

As a brief review [1], the autoxidation cycle for olefin polymers is shown in Figure 2. In this cycle, which is
representative of various stages of the life cycle of the polymer, the polymer is subjected to a variety of damaging
stresses. This includes high temperatures and shear rates from the multiple melt compounding steps as the product
is transformed from reactor powder (melt) → pelletized product → formulated compound → finished article. In
addition to temperature and shear, catalyst residues, entrapped oxygen, and other types of impurities might also play
a role in promoting further degradation of the polymer.
R· Alky Radical
R-H Energy; Shear
RO· Alkoxy Radical
(Polymer) Melt Processing
HO· Hydroxy Radical
Catalyst Residues
ROO· Peroxy Radical
ROOH Hydroperoxide

Oxygen

R·
RO· + ·OH Cycle II + Cycle I ROO·
ROOH

Figure 2: Auto-oxidation cycle for polyolefins.

During these repeated heat histories, free radicals are initiated via C-C and C-H bond scission. Once the free radical
cycle is initiated, the resultant carbon centered free radicals not only react with other polymer molecules, but also
feed on the oxygen that is entrapped in the system, leading to the formation of peroxy radicals. The peroxy radicals
react with the polymer generating hydroperoxides; concomitantly, a new carbon centered free radical site is formed.
The carbon centered free radical feeds back into Cycle I.

The formation of unstable hydroperoxides, which can be decomposed by heat, UV light, catalyst residues, or other
metallic impurities, ultimately leads to the formation of alkoxy and hydroxy radicals, as depicted in Cycle II.
Oxygen centered radicals can react further with the polymer, leading to the formation of more carbon centered free
radicals, which feed back into Cycle I. The reactions leading to free radicals being formed on the polymer
backbone results in chain linking and/or chain scission reactions in an effort to quench the free radicals.

These chain linking and chain scission reactions result in fundamental changes to the molecular architecture of the
polymer in regard to molecular weight (MW), MW distribution (MWD), as well as the nature of chain branching on
the polymer backbone. Most, if not all of these changes are unwelcome in that they can change the physical
properties, melt processability and the final utility of the polymer during its life cycle. Considering the costs
associated with the design put into the development of the polymer (catalyst; polymerization process; etc.), it is
undesirable for indiscriminate changes in the molecular architecture of the polymer (remodeling) to take place.

In an effort to eliminate these type of negative reactions that lead to the unwelcome “remodeling of the molecular
architecture of the polymer”, a variety of stabilization chemistries have been developed [2,3] and commercialized
over the last four decades. A phenolic antioxidant, typically in combination with a phosphite melt processing
stabilizer, can be used at various loadings and ratios to meet most requirements of a given end-use application. The
role of the phenolic antioxidant is to scavenge oxygen centered free radicals, such as alkoxy, hydroxy and peroxy
type species, while the role of the phosphite is to decompose the hydroperoxides into relatively inert products
(before they can split back into oxygen centered free radicals); see Figure 3.

R-H
(Polymer) Energy; Shear
Melt Processing
Catalyst Residues

Oxygen

R·
RO· + ·OH Cycle II + Cycle I ROO·
ROOH

Phenolic AOs react with Phosphites react with Phenolic AOs react with
free radicals to yield inactive hydroperoxides to yield oxygen centered radicals
products (ROH and H20) inactive products (ROH)

Path of Degradation Path of Stabilization

Figure 3: Traditional inhibited auto-oxidation cycle for polyolefins.

Where limitations have been encountered regarding the desired level of stabilizer performance, the judicious re-
selection of the phenolic antioxidant and/or phosphite, combined with adjustments in the concentration and ratio of
the stabilizers could usually resolve the problem. In addition, acid acceptors can be used to fine tune the
performance of the stabilizers, and work to assure a synergistic functioning of the stabilizers [4].

Trends in Polymers and Stabilization

Over the last few years, a variety of new catalyst systems and polymerization processes have been developed. The
relative performance of the polymers derived from these recent developments has shown a path of continuous
improvement. New polymers have been, and continue to be, developed for a variety of new end-use applications
that give improved performance and often serve as replacements for metal, paper and glass.

In addition, subtle features (not necessarily associated with the intrinsic physical properties of the polymer), such as
initial color, color maintenance, compatibility, resistance to discoloration due to pollution, clarity, cling, taste and
odor, have also become key measures with regard to specific applications. Thus, there always seems to be room for
improvement in the field of stabilization, whether it is associated with maintaining or improving physical properties
(MW and MWD), or with the subtle aesthetic features as described above.

Along with these technology driven developments, the demands and expectations being made on the polymer and
the stabilizer system have been significantly increased as well. In order to address these more demanding
applications, antioxidant systems have been improved through the development of new and novel chemistries for
polymer stabilization. The primary objective for bringing these new stabilizers forward to commercialization was to
provide new solutions for polymer stabilization based on the escalating demands being made on the polymer during
melt processing; such as high temperature or high shear.

Representative examples of these new chemistries are based on traditional functional groups, such as phosphites. [5]
In one sense phosphites are traditional, since they are based on P(III) → P(V) hydroperoxide decomposition
chemistry which is well known. However, it must be made clear that each phosphite is not “just a phosphite”. Upon
more careful analysis, these individual molecules have specific properties that have a positive effect on important
ancillary properties in various polyolefin substrates. These can be, improved initial color and color maintenance;
enhanced long term thermal stability; improved compatibility in linear lower density olefin copolymers; excellent
hydrolytic stability and inhibition of discoloration during hot water contact. They also possess low melting points as
well as outstanding solubility in process solvents. Therefore, beyond the traditional retention of MW & MWD via
hydroperoxide decomposition chemistry, the ancillary properties of the new phosphorus based stabilizers can be
translated into real end use applications. Stabilizer performance can be optimized based on key measures, such as:
good color maintenance for color critical applications; better maintenance of cling properties; improved handling in
hot/humid environments, better color maintenance in hot water contact applications; as well as molten systems for
the topical addition of additives.

In 1997, a fundamentally new chemistry was introduced, that not only inhibits the autoxidation cycle, but attempts
to shut it down as soon as it starts [6,7,8]. The exceptional stabilizer activity of L-1 is due to the ready formation of
a stable lactone (benzofuranyl) radical by donation of the weakly bonded benzylic hydrogen atom; see Figure 4.

R = Carbon or Oxygen Centered Radical

O O O
R R-H
O H O R1 O R1

Highly Stabilized Radical

Figure 4: Proposed stabilization mechanism of arylbenzofuranones.

The resonance stabilized lactone (benzofuranyl) radicals can either reversibly dimerize or react with other free
radicals. Model experiments have demonstrated that this class of chemistry behaves as a powerful hydrogen atom
donor and are also effective scavengers of carbon centered and oxygen centered free radicals [9]. While the
sterically hindered phenols react preferentially with oxygen centered radicals like peroxy and alkoxy rather than
with carbon centered radicals, lactones (benzofuranones) can scavenge both types of radicals. Accordingly, the
lactone, can be repeatedly positioned at key locations around autoxidation cycle to inhibit the proliferation of free
radicals. The combination of phenolic, phosphite and lactone represents an extremely efficient stabilization system
since all three components provide a specific function.

In Figure 5, the hindered phenolic antioxidant functions as a scavenger of oxygen centered radicals and provides
melt processing and long term thermal stability. The phosphite functions as a hydroperoxide decomposer and
provides melt processing stability and color maintenance. The lactone and its radical intermediates persistently
inhibit the propagation of polymer radicals. It has also been observed that the lactone can also donate hydrogen
atoms to the phenoxy radical to regenerate the phenolic AO [9]. This mechanism allows the phenolic to extend its
use as a long term thermal stabilizer.

Lactone chemistry reacts with

R-H carbon centered radicals
(Polymer) Energy; Shear
Melt Processing
Catalyst Residues

Oxygen

R·
RO· + ·OH Cycle II + Cycle I ROO·
ROOH

Phenolic AOs react with Phosphites react with Phenolic AOs react with
free radicals to yield inactive hydroperoxidesto yield oxygen centered radicals
products (ROH and H20) inactive products (ROH)
Path of Degradation Path of Stabilization

Figure 5: Revised inhibited auto-oxidation cycle for polyolefins

Film Converting

Producers of polyolefin film grades, as well as the downstream film converters, often look for new developments in
polymer stabilization technology to make sure that they can provide the best products with the most value while
minimizing costs. Additives, or combinations of additives, represent tools that can be used for adjusting product
performance (improved physical and aesthetic properties). Examples of such improvements might include better
maintenance of melt flow rates, lower YI color, improved long term thermal stability, inhibition of gas fade
discoloration, enhanced additive compatibility, reduced taste and odor, resistance to irradiation induced oxidation,
as well as the suppression of ‘gels’ and other extrusion related imperfections [10]. More difficult to demonstrate, but
of significant economic value, stabilization can often influence the processing window. Processing window refers to
the range of machine parameters over which acceptable quality parts can be produced. Generally speaking, a
polymer and additive formulation that yields a wider processing window will translate into a more robust process at
the converter. One which will be less sensitive to small perturbations in the system. Improvements in processing
window might translate to higher onstream time, faster line speeds, better quality, less sensitivity to process upsets,
etc. Identification and exploitation of these kinds of opportunities usually requires cooperation between the
converter, resin producer, and additive supplier.

The identification of new stabilizing additives that can deliver these type of desirable improvements usually begins
with the development of novel molecules; or clever ways to use known, but under-utilized molecules. New
stabilizer chemistries are compared to “established” systems. Unfortunately, acceptance of new stabilizer
chemistries takes a long time from initial concept to commercial success. Qualification begins with standard lab
scale extrusion experiments, where typical measures such as a) melt flow rates and b) color maintenance are the key
measures. As the qualification moves forward, key measures are shifted to ones that are considered to be more
relevant in the final end-use application. There are many steps between initial lab testing and final qualification.
Nevertheless, if the new chemistries solve real problems, the implementation process is usually accelerated.

Regarding traditional measures of stabilization, improvements in melt flow rate control can be achieved using a
variety of approaches. For example, higher concentrations or the use of more powerful additives (per unit weight)
are two representative examples. Over the last several decades, a variety of phenolic AO and phosphite melt
processing stabilizers have been developed to meet new opportunities. Used in different ratios and concentrations,
blends of phenolic AO and phosphites can provide optimal performance based on the nature of the polymer, the
extrusion temperatures, and shear rates experienced during various types of extrusion processes.

TNPP FREE STABILIZATION OF LLDPE FILM GRADES

Tris-nonylphenylphosphite (TNPP) is a successful phosphite stabilizer for LLDPE due to its excellent
price/performance ratio and its good compatibility in PE. As a response to ecological concerns surrounding some
chemistries with similarities to nonylphenol, some organizations that serve the consumer market have taken the
cautious step of removing stabilizers based on nonyl phenol from their products. This has created a need for resin
producers and additive suppliers to devise new environmentally friendly formulations which are able to meet the
requirements of these markets without containing TNPP.

The data shown below in Figures 6 and 7 gives the results of an alternative stabilization system to replace an
existing formulation based on P-2. Any of these formulations could potentially replace the base formulation
containing P-2. The melt flow data shows that some of the formulations containing lower levels of phosphite are not
able to maintain melt flow control as well as the base formulation at the fifth extrusion pass. This may or may not be
a problem for a specific application. The situation could be improved by increasing the phosphite level. All of the
formulations are equivalent or better performing in terms of the resistance to discoloration during processing, but
also during oven aging and regarding gas fade. Any of these formulations could potentially be replacements for the
control formulation.

30
1st extrusion
3rd extrusion
melt flow ratio 21.6/2.16 Kg

29
5th extrusion
28

27

26

25

24
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1

Figure 6: Melt flow ratio (melt flow index obtained with a 21.6 kg weight divided by the MFI obtained with a 2.16
kg weight) during multiple pass extrusion of LLDPE. Melt flow ratio is usually a good indication of melt
processing stability in PE. Both melt flow readings were obtained at 190°F.
 14

12 5th extrusion

10 3rd extrusion
1st extrusion
8
YI

0
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1

Figure 7: Color during multiple pass extrusion (compression molded plaques)

Solubility and compatibility are important features of stabilizers as they have a strong influence on final product
performance. This is mainly related to migration behaviour of the additives and can result in blooming effects as
well as gel formation. Density and crystallinity of the polymer are two factors influencing the migration behaviour
as they have impact on solubility of the stabilizers. Solubilities of different phosphites are illustrated in figure 8,
showing significant differences. Common loadings of phosphites are in the range of 700 to 1500ppm but can be
even higher. P-1 has a solubility limit, which is significantly below theses common loadings of phosphites and
consequently can result in blooming effects and gel formation. The other phophites investigated all have a very
good solubility.

typical loading
P-1 of phosphites

P-2

P-3

P-4

0 0.1 0.2 0.3 0.4

solubility at 23°C

Figure 8: Solubility of phosphites in LLDPE (0.92 g/cm3)

Selection of formulations for further studies will most likely depend upon cost as well as some of the other factors
listed in Figure 1 like resistance to gel formation or processing window. The data shown in this study give sufficient
indication that there are solutions available with attractive performance in terms of processing stability and film
properties. Depending on process-specific demands on the stabilizer package further fine-tuning might be required
in order to fulfill all requirements on LLDPE film grades.
BOPP FILM STABILIZATION

BOPP film converters have an interest in improving the base stabilization of PP resins used in film production.
Film plants recycle trim strips to improve efficiency. The amount of recycle may vary from time to time and there is
value in having a robust stabilization system in order reduce sensitivity to different amounts or recycle. Also,
process improvements to increase throughput have resulted in higher temperatures in the extruder and increased
thermal stress on the polymer. At the slitting end and in the warehouse, there is an interest in improving color of the
film in order to provide a good-looking product.

Results of multiple pass extrusion experiments on polypropylene homopolymer are shown in Figure 9. The blend
containing the lactone L-1 is superior both in terms of maintaining melt flow rate and color. The new lactone
chemistry, L-1 has been shown to synergize very well with traditional phenol/ phosphite systems. In this case as
well as in the previous example, the ability of a new system to control melt flow and maintain color during multiple
pass extrusion is an indication that the molecular structure is being preserved, but does not directly imply that the
polymer will be better fit for use.

12 1st extrusion 25
3rd extrusion
10 5th extrusion
melt flow (230°C/ 2.16kg)

20

8
color, YI

15
6

10
4

5
2

0 0
0.1% 0.15% 0.1% 0.1% 0.15% 0.1%
AO-1/ P-1 AO-1/ P-1 AO-1/ P-1/ L-1 AO-1/ P-1 AO-1/ P-1 AO-1/ P-1/ L-1

Figure 9: Changes in melt flow rate and color of polypropylene homopolymer during multiple pass extrusion

Similar formulations have been tested on a Brückner pilot film line. This line uses the tenter process with a two-step
orientation: first the film is stretched in the machine direction, and then in the transverse direction. Table 1 describes
the conditions run on the line. In addition to measuring physical and optical properties of the films, the machine
direction orientation stretching ratio and the web temperature in the transverse direction orientation section were
independently varied in order to determine the influence of stabilization on the processing window.

Table 1: Operating parameters for the Brückner pilot BOPP film line

Parameter Varied or Constant? Standard Value

Extrusion temperature Constant 250°C
Line Speed Constant 85 m/min
MDO Ratio Varied 4.5:1
TDO Ratio Constant 8:1
TDO Temperature Varied zone temps 172-172-159-150°C
 Coex Film Thickness Constant 20 micron (1/18/1)
Three formulations were compounded and cast into film on the Brückner pilot line. 1500ppm of a conventional
phenol/ phosphite blend of AO-1/ P-1 (1:2) was compared with lesser amounts of phenol phosphite blends boosted
with the lactone L-1. One of the new formulations uses the phosphite P-1 and the other uses the high performance
phosphite P-3. Table 2 shows the results of the processing window part of the study. It is interesting that even in the
case of this commercial resin, the improved stabilization shows a discernable improvement in the processing
window. These differences can be of significant value to converters for instance, a few extra degrees C of tolerance
on the transverse orientation can make a lot of difference when the line is being brought up and is not yet fully
under control.

Table 2 The influence of lactone blends on the processing window for BOPP film production

Formulation Machine Direction Orientation Transverse Direction Orientation

(highest ratio before break) (high/low before break)
Range % Increase Range (°C) % Increase
1500 ppm AO-1/ P-1 5.1:1 - 14 -
1000 ppm AO-1/ P-1/ L-1 5.7:1 12% 16 14%
800 ppm AO-1/ P-3/ L-1 5.4:1 6% 17 21%

Figure 10 shows another way of visualizing the processing window. In this graph, the difference between the upper
and lower data points for each formulation represent the variation in thickness that across the web from the thinnest
to thickest part of the sheet. The data point farthest to the right represents the last viable stretching ratio before the
film broke.

2
thickness variation (micron)
above or below standard

1 1500 ppm AO-1/P-1

1000 ppm AO-1/P-1/L-1

0
800 ppm AO-1/P-3/L-1

-1

-2
4 4.5 5 5.5 6
MDO Ratio

Figure 10: Maximum thickness variation measured by the thickness gauge on the Brückner line versus theMDO
stretching ratio

Figure 11 shows some physical properties of the films produced in the trial. All the formulations show
approximately the same elongation to break. However, the elastic modulus on the lactone-boosted formulations is
significantly higher than the control. This may be due in part to the better thickness control, which is achieved with
the lactone-boosted formulations. Optical properties were also measured on the films. For this resin, there was no
significant difference between the formulations. All films had haze values of 1% and clarity values of 98%.
 1500 ppm AO-1/P-1
1000 ppm AO-1/P-1/L-1
800 ppm AO-1/P-3/L-1
2500 140

120
2000
100

1500
N/mm2

80

%
60
1000
40
500
20

0 0
Emod (mdo) Emod (tdo) Elongation Elongation
N/mm2 N/mm2 (mdo), % (tdo), %

Figure 11: Elastic modulus and elongation data from theBrückner pilot trial.

It is known that the lactone boosted systems are better at suppressing polymer chain scission especially the longer
ones which are the most likely to be attacked. During drawing, the number and complexity of tie molecules between
crystallites is important to good performance. These tie molecules insure that as the film is drawn, there is a
compensating factor for the tendency of the film to neck down at weak points leading to stress concentration and
failure. When these tie molecules or crosslinks between crystallites are present during drawing, the resin will strain
harden, resulting in a more stable drawing process. It seems likely that the lactone boosted stabilization packages
are better able to preserve the rich web of tie molecules present in the resin and that this accounts for the
improvements observed in thickness uniformity and processing window.

By this study it has been able to demonstrate improvements in processability which result from optimizing the base
stabilization for this BOPP grade. Since this work was completed, commercial experience with the system has borne
out the suitability of the lactone boosted systems for this application. For instance, on stream time at high line
speeds has reportedly been increased. In addition, experience has shown that other operations like metallizing,
flame treatment, and printability are not adversely affected by the new system.

CONCLUSION

Two examples of development of new stabilization systems have been discussed. In both cases, an incumbent
stabilization system has existed and a new stabilization system has been found which better meets the needs of the
polyolefin producer and their markets. These success stories have each involved a clear set of needs expressed by
the converters or end users. They have also included direct involvement from the additive supplier and the resin
producer in attempting to identify new opportunities.

Within the area of base stabilization there are many opportunities for improving on incumbent products. These
improvements in stabilization have the potential for improving economics at converters and for improving the
properties and appeal of the final articles. In order for these possibilities to become realized, it requires good
communication between additives suppliers, resin producers, converters and end users. This is sometimes a tall
order, but there are representative examples in which it has been done successfully.
Key elements for success can be summarized:
The converter or end user must be motivated to make an improvement
The additive supplier and resin producer need to be aware of the opportunity
The existence of chemistries which can meet the needs
Knowledgeable scientists who are able to make the connection between needs and available
technologies.
Commitment on all sides to drive the project through to completion

ACKNOWLEDGEMENTS

The authors wish to thank the following scientists and their teams for completing these projects and for sharing their
results: Dave Horst, Dr.Jay Ghosh, Dr.Doris Eisermann, Andreas Thuermer, Dr.Rick King. Also to be thanked are
customers, converters, and end users who have partnered with Ciba Specialty Chemicals in these and other projects.

REFERENCES

[1] Gugumus, F., "Plastic Additives", Chapter 1; 3rd Ed., Hanser Publisher, New York, 1990.
[2] Moss, S., Pauquet J-R., Zweifel, H., "Degradation and Stabilization of Polyolefins During Melt Processing",
Int. Conf. Adv. in the Stabilization & Degradation of Polymers, Lucerne 1991, Conf. Prep. (A. Patsis, Ed.).
[3] Zweifel, H., Moss, S., "Degradation and Stabilization of High Density Polyethylene during Multiple
Extrusion", Polymer Degradation and Stability, 25 (1989), 217-245.
[4] Drake, W.O., Cooper, K.D., "Recent Advances in Processing Stabilization of Polyolefins", SPE Polyolefins
VIII Int. Conf., Feb. 1993, Houston TX.
[5] Cooper, K.D., "A New Process Stabilizer for Polyolefins", SPE RETEC 1995, Houston, pp. 653-669.
[6] Kröhnke, C., “A Major Breakthrough in Polymer Stabilization”, Polyolefins X Conference, Houston, Feb 97.
[7] Pauquet, J.R., Zingg, J., “Improving Polyethylene Processing Stability with Novel Synergistic Blends”, Spec.
Plastics 95, 11th Ann. World Congress, Zürich, Dec 95.
[8] Pauquet, J.R., King, R., Kröhnke, C., “Revolutionary Stabilizer Systems for Polyethylene”, Polyethylene ‘97
Maack Conference, Milan, May 1997.
[9] Nesvadba, P., Kröhnke, C. “A New Class of Highly Active Phosphorus Free Processing Stabilizers for
Polymers”, Additives 97, 6th International. Conf., New Orleans, Feb 97.
[10] R. E. King, “Stabilization of a Clarified Gamma Irradiated Controlled Rheology Polypropylene Random
Copolymer” South Texas Section of the SPE Int. Conference on Additives for Polyolefins; Feb 21-24, 1999
APPENDIX 1. Description of Stabilization Chemistries.

Code Molecular Structure Stabilizer Function

Class
Tradename
AO-1 Melt Processing Stability;
Phenolic O Long Term Thermal
Stability;
HO CH2 CH2 C O CH2 C
Irganox® 1010 Oxidative Induction Time;

AO-2 Melt Processing Stability;

Phenolic Long Term Thermal
O Stability;
Irganox 1076
HO CH2 CH2 C O C18H37

AO-3 Melt Processing Stability;

Phenolic HO Long Term Thermal
Stability;
Irganox E201
O

P-1 Melt Processing Stability;

Phosphite (secondary enhancements to
O P
the performance of the
®
Irgafos 168 phenolic AO)

3
P-2 Melt Processing Stability;
Phosphite (secondary enhancements to
C9H19 O ]3-P the performance of the
Irgafos TNPP phenolic AO
P-3 Melt Processing Stability;
Phosphite (secondary enhancements to
the performance of the
Irgafos 38 phenolic AO)
O P OC2H5

2
P-4 Melt Processing Stability;
Phosphite (secondary enhancements to
O
the performance of the
Irgafos PEPQ phenolic AO)
P

2
L-1 O Melt Processing Stability;
Lactone O H (secondary enhancements to
CH
3
the performance of the
Irganox HP-136 phenolic antioxidant and
CH phosphite)
3
New stabilizer solutions for
polyolefin film grades

Dr. Florian Stricker

Murray Horton
Ciba Specialty Chemicals Corporation

European TAPPI PLACE Conference 2003

Rome, Italy

Ciba
• Introduction
• TNPP-free stabilizer formulations for LLDPE film
grades
• BOPP film stabilization
 Base stabilization of polymers

• protects polymer during compounding and conversion

• provides long-term thermal stability

Additional aspects:
– no undesired side effects
– no interference with other components in the formulation
– no interference with operations later in the life of the polymer
– can provide application-specific benefits
– must be commercially viable ….
Polymer Production
• resin type PE/ PP/ EVA
• production process
• catalyst residues
• molecular weight distribution
• rheology
Compounding
• feeding
• temperature
• mixing / shear
• residence time
• chemical interactions
Polymer Modification
• visbreaking
• crosslinking
Transportation and Storage
• combustion products (gas fading)
• incidental light exposure
• moisture
• temperature/ time
Conversion
• processing window
• start-up transients
• time and temperature
• melt fracture, die build-up
• water carry over
• volatiles (smoke)
• build-up
Treatments/ Processing
• flame/corona treatment
• paintability/ printability
• lamination/ adhesion
• foaming
• color yield
• recycle/ rework
• sterilization
Transportation and Storage
• combustion products (gas fading)
• incidental light exposure
• moisture
• temperature/ time
DIN
€

€
Base stabilizers as part of successful applications

• Market need • Toolbox of additives

• Knowledgeable people • Business commitment
• Communication • Considerable patience
• Database of experience • Good fortune

Innovative stabilizer solutions meeting requirements defined by

• production technology (dosing, compounding)
• molecular structure
• converting process
• end-use application
 Adding stabilizers during resin production

separation / storage
polymerization flash
reactor
•dry blended fluff
catalyst
deactivation

possible routes of
stabilizer additivation drying

•base stabilized pellets

•fully formulated pellets
Ultimate goal: Keep Molecular Architecture
Intact
Impact of stabilizers in the film value chain

• Polymer manufacturer
Consistency
¾ reactor product
¾ finishing step and pelletization Ease of use
¾ fill & ship railcars, trucks, boxes, etc.

• Film producer Processability

¾blown & cast film blowing
¾conversion to commercial products (print; seal; fold)
¾recycle ( edge trim; wide spec)

• Distribution
Durability
¾storage stability
Aesthetics
¾performance in application
Autoxidation cycle of polyolefins
R· Alkyl Radical
Energy; Shear; RO· Alkoxy Radical
Polymer
Melt Processing; HO· Hydroxy Radical
Catalyst Residues ROO· Peroxy Radical
ROOH Hydroperoxide

Polymer Oxygen

Cycle II Cycle I
R•
RO • + • OH + ROO •
ROOH

Energy (UV Light, Heat) Polymer

Catalyst Residues
Revised inhibited autoxidation cycle

Polymer Energy; Shear; Carbon centered radical

Melt Processing; traps improve efficiency of
Catalyst Residues traditional stabilizers

Oxygen

Cycle II Cycle I
R•
RO • + • OH + ROO •
ROOH

Phenolic AOs react with Phosphites react with Phenolic AOs react with
free radicals to yield inactive hydroperoxides to yield oxygen centered radicals
products (ROH and H20) inactive products (ROH)
TNPP-free stabilization of
LLDPE film grades
Requirements on LLDPE film grade stabilization

Film performance requirements:

Film processing • optical properties / color
requirements: • mechanical properties
• processing stability • organoleptics
• low gels and black specs • regulations
• sealability
LLDPE
• environment/health
film
grades

Relevant resin production requirements:

• additive handling
• additive and resin stability
• formulation costs and availability
Process stability essential for LLDPE film grades

Long Term Thermal Stability Melt Processing Stability

Hindered Amine

Hindered Phenol Processing

temperature
range of
Thiosynergist (&Phenol)
blown film lines

Phosphite
Hydroxylamine
Lactone
0 50 100 150 200 250 300

Temperature (°C)
 Common LLDPE stabilization based on AO-2/P-1 or P2

Scavenger of oxygene centered radicals Hydroperoxide decomposers

O P-1 O P

AO-2 HO CH2 CH2 C O C18H37

3

P-2
C9H19 O ]3-P

Scavenger of carbon centered radicals

P-3
HO
AO-3 O P OC2H5

O
2

O
O H P-4 O
L-1 CH
3
P

CH O
3

2
Processing stability during multiple pass extrusion

30
melt flow ratio 21.6/2.16 Kg

1st extrusion
3rd extrusion
29
5th extrusion
28

27

26

25

24
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1
Color generation during multiple pass extrusion

14

12
1st extrusion
10 3rd extrusion
5th extrusion
8
YI

0
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1
Color development during aging at 80°C

7 initial
+ 28 days
6
5
4
YI

3
2
1
0
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1
Gas fading performance

initial YI
7
+ 7 cycles
6

4
YI

0
1700ppm 1400ppm 1100ppm 1050ppm
AO-2/P-2 AO-2/P-1/P-3 AO-2/P-3/AO-3 AO-2/P-3/L-1
1400 ppm 1200ppm 1150ppm
AO-2/P-1/P-4 AO-2/P-1/AO-3 AO-2/P-1/L-1
Solubility of stabilizers effects blooming

1700ppm AO-2/P-2
typical loading
1700ppm AO-2/P-1
of phosphites
P-1 22 1400ppm AO-2/P-1/P-3

film haze (%)

P-2 20

18
P-3
16
P-4
14
0 0.1 0.2 0.3 0.4 0 7 14 21 28

solubility at 23°C film storage at 60°C (days)

Hydrolytic stability of phosphites

% phenol
40 P-2

30
P-4

P-3
20

10
P-1
0
0 50 100 150

storage at 50°C/ 75% r.h. (h)

TNPP-free stabilization of LLDPE film grades

Processing stability:
• equivalent melt flow control
• better color performance possible

Film performance:
• compatibility issues can be avoided
• hydrolytic stability can be improved
• improved gas fade resistance possible

Attractive cost-performance alternatives possible

BOPP film stabilization
Influence of temperature of the BOPP process

Stenter frame process (sequential stretching)

Extrusion at 220-250°C

MD orientation, temperature 110-140°C

TD orientation
temperature 145-160°C
BOPP Film Stabilization

Major requirements on stabilizers:

• broad processing window
• low color
• excellent optical properties (transparency, gloss)
• maintain mechanical properties (stiffness) and shrinkage performance
• excellent organoleptic performance
• rework quality
• no negative impact on printing, flame/corona treatment, metallization
• formulation costs
Conventional BOPP stabilization based on AO-1/P-
1

O
P-1
P
O

AO-1 HO CH 2 CH 2 C O CH 2 C
3

P-3 O P OC2H5
O
O H

L-1
CH 2
3

CH
3

P-4 O

2
Effect of lactone chemistry on BOPP film grades

12 1st extrusion 25
3rd extrusion
melt flow (230°C/ 2.16kg)

10 5th extrusion 20

color, YI
15
6
10
4

5
2

0 0
0.1% 0.15% 0.1% 0.1% 0.15% 0.1%
AO-1/P-1 AO-1/P-1 AO-1/P-1/L-1 AO-1/P-1 AO-1/P-1 AO-1/P-1/L-1
Operating parameters for Brückner pilot BOPP line

Parameter Varied or Constant? Standard Value

Extrusion temperature constant 250°C

Line Speed constant 85 m/min

MDO Ratio varied 4.5:1

TDO Ratio constant 8:1

TDO Temperature varied zone temps 172-172-159-150°C

Coex Film Thickness constant 20 micron (1/18/1)

Effect of stabilization on BOPP processing window

Formulation Machine direction Transverse direction

orientation (MDO) orientation (TDO)
- highest ratio before break - high/ low before break
Range % Increase Range (°C) % Increase
1500 ppm AO-1/ P-1 5.1 : 1 - 14 -

1000 ppm AO-1/ P-1/ L-1 5.7 : 1 12% 16 14%

800 ppm AO-1/ P-3/ L-1 5.4 : 1 6% 17 21%

Stabilizer impact on thickness uniformity of BOPP
films
thickness variation (micron)

2
above or below standard

1 1500 ppm AO-1/P-1

1000 ppm AO-1/P-1/L-1
0
800 ppm AO-1/P-3/L-1
-1

-2
4 4.5 5 5.5 6
MDO Ratio
+2

20.3
Micron
-2 BRUECKNER BOPP PILOT LINE
Physical properties of BOPP films

1500 ppm AO-1/P-1

2500 140 1000 ppm AO-1/P-1/L-1
800 ppm AO-1/P-3/L-1
120
2000
100
N/mm2

1500 80

%
60
1000

40
500
20

0 0
Emod (mdo) Emod (tdo) Elongation Elongation
N/mm2 N/mm2 (mdo), % (tdo), %
BOPP Film Stabilization

9 extended processing window

9 improved color
9 equal or better optical properties
9 improved mechanical properties
9 cost equivalent
9 no difficulties with treatments,
printing and metalization
9 improved onstream time observed
In Summary

• base stabilization is easy

• base stabilization is complex

• opportunities for improvement

• taking into account requirements of
– end-use application
– resin production
– polymer type and molecular structure
 Stabilizers presented in this paper

AO-1 HO CH 2 CH 2 C O CH 2 C
P-1
O P

IRGANOX 1010
4
IRGAFOS 168
3

O
P-2
AO-2 HO CH2 CH2 C O C18H37 IRGAFOS TNPP
C9H19 O ]3-P

IRGANOX 1076

P-3 O P OC2H5
IRGAFOS 38
HO 2

AO-4 O
IRGANOX E
O
P-4 O

P
O H IRGAFOS PEPQ O

L-1
CH
3

CH 2
IRGANOX HP-136 3
Thanks for your
attention!