HINDERED BENZOATES AND HALS:

HIGH PERFORMANCE COMBINATIONS FOR POLYOLEFINS

LIGHT STABILIZATION.

Ivan Vulic1, Leonard H. Davis2, Jerry Eng2, Giacomo Vitarelli2, and Vincenzo

Malatesta3
1
Cytec Industries B.V., Botlek-Rotterdam, the Netherlands
2
Cytec Industries Italia s.r.l., Milan, Italy
3
Cytec Industries Inc., Stamford (CT), U.S.A.

Abstract
Formulations containing two UV stabilizers and a UV absorber provide
synergistic stabilization of polypropylene slit tapes at concentration level well
below the FDA sanctioned values. A combination of a photostable antioxidant
and monomeric HALS provided good stabilization of pigmented
polypropylene (PP) and thermoplastic polyolefins (TPO's). A non-HALS UV
stabilizer gives excellent stabilization of polypropylene articles containing
halogenated flame retardants.

Introduction
Polyolefins are markedly susceptible to oxidative deterioration initiated by both
heat and light. The key intermediates involved in the oxidative degradation are
now reasonably well understood [1]. Processing stabilization is usually achieved
with a combination of high molecular mass phenolic antioxidants with phosphites
or phosphonites that act as chain breaking H-donors (CB-D) and hydroperoxide
decomposers (HD) respectively [2]. The earliest technology used to improve the
light stability of polyolefins was by using UV absorbers (UVA's) such as 2-
hydroxy, -benzophenones, -phenylbenzotriazoles and nickel phenolates. These
compounds provide light stabilization by absorbing harmful UV radiation and
converting it to heat [1,3-5].
Hindered amine light stabilizers (HALS) have been used for decades as highly
efficient inhibitors of polymer photooxidation. Scavenging of alkyl and peroxy
radicals is generally considered to be the mechanism by which HALS work [6]
and they are referred to as chain-breaking acceptors (CB-A). Recent
investigations have demonstrated that they are also effective as thermal
antioxidants (HAS) [7].
Hindered hydroxybenzoates are used commercially on a large scale to impart UV
stabilization to polyolefins. Their efficacy is second only to HALS [7] and may
effectively replace HALS in some stabilizing formulations containing compounds
that may hinder the stabilization efficacy of one of the components. Indeed, acids
will impair the protection given by HALS if used in the stabilization of acid
catalyzed cross-linked automotive coatings, halogenated flame-retardant plastics
and agricultural films exposed to pesticides. The stabilizing efficacy of hindered
hydroxybenzoates is unaffected under these conditions. The performance of the
aliphatic hydroxybenzoates in HDPE and PP has been suggested to be due to
the multifaceted radical-scavenging properties of this class of phenolic stabilizers
that are also endowed with a unique resistance to photo-dimerization and
consequent photo-yellowing [8].
PP slit tapes are widely used in packaging, building and construction.
Furthermore, PP is established, together with polyester, as one of major
technical fibers worldwide. PP and PET represent about 20% of the world total
fiber consumption with PP being stronger in the Western world.
Product applications for thermoplastic olefins (TPO's) and polypropylene (PP)
continue to grow and many of the newer applications require improved
performance over traditional polyolefins formulations. It is interesting to note,
however, that no new class of stabilizers having efficiency comparable to that of
HALS has been commercialized so far, but higher efficacy has been obtained
with combination of UV stabilizers that in many instances have provided
interesting synergistic results.
In this paper we present some new formulations containing CB-D and CB-A
stabilizers that overcome the shortcomings of traditional stabilization packages
and provide synergistic stabilization of PO's, in particular of PP slit tapes and
flame retarded pigmented PP articles [9]. Interesting low water carry over value
and/or excellent stabilization have been obtained.
Experimental
Formulations -
PP Tapes:
UV: 0.3% UV-2908/UV-3346/UV-531, UV-3346, UV-783, UV-770, UV-791, AO:
0.05% AO-XS4 vs. 0.05% each AO-330 + P-168
FR Stadium Seats:
UV: 0.5% UV-2908 + 0.5% UV-531 + 0.5% P-619
Pigment: Phthalo Blue 15:1 (Cu Phthalocyanine)
Flame Retardant: 3:1 FR-800 (halogenated aromatic FR) + Sb2O3
Processing
The stabilizer systems were all dry blended with powdered virgin resins and the
resulting formulations were compounded on a one and one quarter (1 1/4") inch
single screw extruder. For injection molded HDPE and PP, the resulting pellets
were converted by injection molding on an Arburg Injection Molding Machine into
2"x2"x0.060" plaques for accelerated aging studies. The pellets from the
corresponding formulations were examined for color, gas fade, melt and thermal
stability.
The process or melt stability of each formulation was determined by
compounding the materials on the single screw Killion Extruder using typical
polyolefin temperature parameters and following the ASTM D-1238 test method.
Once the materials were compounded, the extruder temperature profile was
increased by approximately 20 percent and then multiple passes were performed
to examine the melt and color stability of the antioxidant system.

Slit Tapes
Slit tapes for the WCO and UV studies were prepared using a resin system of
PP/HDPE (100/15) containing 0.12% AO. The UV stabilizer package was
incorporated via masterbatch.
Slit tapes for the AO study were prepared in a Unipol homopolymer PP, 5 MI.
AO and acid scavenger (DHT-4A) were added to the virgin PP powder on a twin
screw extruder.
Water carryover was determined by measuring the water height in centimeters
carried on the un-stretched PP tapes, dimensions 130 micron X 39 mm. Speed
of the line was fixed at 16 m/min. The effect of water carryover on processability
of PP tapes was also determined by the maximum line speed that could be
achieved.
UV stability (QUV-313, and Xenon Arc WOM) was determined for stretched
tapes (7:1 to 10:1 ratio at 170-185 degrees C oven temp.), dimensions 80 micron
X 4 mm, speed of the line was fixed at 11.5 m/min.

PP Stadium seats
The stadium seat samples were prepared from a masterbatch containing the blue
pigment and stabilizers. The flame-retardant was also prepared as a masterbatch
and all the components were extruded into polypropylene in a twin screw
extruder and pelletized. The pelletized formulations were then injection molded
into micro tensile bars and plaques for accelerated weathering. The molded
plaque samples were characterized for initial color (Macbeth Color-Eye 7000
colorimeter) and gloss (Gardner/Neotec Glossgard II 60º glossmeter). The
molded micro-tensile bars were characterized for initial physical properties using
an Instron at a crosshead speed of 2 inches per minute. The samples were
mounted and exposed in a Xenon Arc WOM operated at standard ASTM G-155
conditions (formerly ASTM G-26).
Test criteria:
General appearance color, gloss and tensile properties of samples were
determined at equal intervals until physical failure, determined as 50% loss of
initial tensile strength for PP slit tapes, and 50% loss of initial elongation for FR-
PP microtensile bars.
Gas fade measurements were done by exposing compounded pellets of the
stabilized resin to the combustion products of natural gas in a controlled
environment following AATCC Method 23. Pellets containing the different
antioxidant systems were exposed in a United States Testing Co. Atmospheric
Fume Chamber (Model 8727). The chamber was maintained between 57-60oC.
The color of compounded pellets (multipass extrusion, gas fade) was determined
using a Macbeth Color-Eye 7000 colorimeter. Yellowness Index was calculated
according to ASTM E313.
Mechanical Testing of Slit Tapes:
Tensile strength was determined using an Instron tensile tester according to
ASTM method D-638.
Accelerated Aging:
We exposed the single tapes to UV light, not woven fabric as required by EN
277.
The polypropylene test samples (slit tapes, injection molded FR-PP microtensile
bars and plaques) were exposed in a Ci65 Atlas Xenon Arc WOM according to
the ASTM G-155 test method (formerly G-26). The test method parameters
consisted of a black panel temperature of 63oC, relative humidity of 35 ± 10 %
and an irradiance of 0.35 W/m² @ 340 nm. The samples were also sent to
Florida (45° south direct) for outdoor weathering.
The polypropylene tape samples were also exposed in Q-Lab’s QUV-313
weather-o-meter following ASTM G-154 (formerly ASTM G-53). The
light/condensation cycle consisted of 8 hours UV light followed by 4 hours of
condensation and black panel temperature was set at 70oC.
Results and discussion
PP slit tapes

A light stability superior to that obtainable using HALS or combination of HALS

has been observed for PP slit tapes containing a ternary stabilizing formulation
HALS/hindered hydroxybenzoate/UVA, namely UV-3346/UV-2908/UV-531, when
aged by exposure to QUV-B (Fig.1-2).
For all of these applications the stabilizers loading was well below the maximum
level sanctioned by FDA (21 CFR 178.2010 and 21 CFR 177.1520).
It must be noted that polypropylene slit tape processes are crucial for additive
selection. Stabilizers can cause a phenomenon called “water carry-over” where
the stabilizers can affect the surface tension of the polyolefin and cause water to
be carried over into the take-up rolls.
For PP slit tapes the water carry over (WCO) values were lower for the ternary
HALS/hindered hydroxybenzoate/UVA formulation (Fig. 3-4) as compared to
single or binary HALS stabilization packages, the advantage being, for this
particular application, a higher production speed and less line breakage.
Combination of UV-2908 and UV-3853 gave the same performance vs.
incumbent stabilization packages in the stabilization of pigmented injection
molded PP and TPO's at considerably lower loading (Fig. 5-8). Furthermore
the mechanical properties were not adversely affected by the absence of
oligomeric HALS.
The binary mixture (UV-3346+UV-2908) yielded a better performance than that
obtained for UV-3346 alone (Fig.9) when the tapes were aged by exposure in a
Xenon-arc WOM.
Flame retarded PP
Formulations based on hindered hydroxybenzoate (UV-2908), 2-hydroxy-4-n-
octoxybenzophenone (UV-531) and an aliphatic phosphite (P-619) gave
excellent stabilization to flame retarded, pigmented PP injection molded stadium
seats as shown in Figures 10-11. The radical scavenger hindered
hydroxybenzoate (UV-2908) afforded excellent UV stabilization in an application
where HALS, because of their basicity, would be inactivated by the acid released
during the degradation of the halogenated flame retardant used.
A synergistic effect between the hexadecyl ester (BZ-2) and the distearyl
pentaerythritol diphosphite (P-619) has been observed [9]. This combination has
retained over 70 % of its breaking strength for greater than 31 months as
compared to failure (<50%) after 20 months for the single component UV-2908.
These results were generated with half the UV-2908 concentration in the two
component system (0.25 % of UV-2908 + 0.25 % of P-619) compared to the 0.5
% of UV-2908 single component system. This synergistic effect led to the
conclusion that aliphatic phosphites show stronger synergy with the hexadecyl
ester compound than aromatic phosphites. Therefore, the more aliphatic the
phosphite, the greater the synergy in the two component system.
Conclusions
Combinations of UV stabilizers may provide unexpected advantages in light
stabilization of polyolefins due to synergistic effects. Selection of appropriate UV
stabilizers is based on the demonstrated performance properties of low volatility
during processing, low color contribution, good compatibility with polyolefins,
good long-term light and thermal stability, and low toxicity. The hexadecyl ester
of 3,5-di-t-butyl-4-hydroxybenzoic acid (UV-2908) meets these criteria and in
addition has little or no known chemical interaction with other co-additives.
Indeed UV-2908 does not interact with the acidic species formed by degradation
of halogenated flame retardants and conveniently replaces HALS by providing
excellent UV stabilization in these demanding applications.
Acknowledgments
The authors acknowledge the contribution of Brent Sanders and thank the
management of Cytec Industries Polymer Additives Department for allowing
them to present this paper.
References
[1] Gugumus, F., Plastic Additives, Gaechter, R. and Muller, H. (Eds)., 3rd Edition,
Hanser publisher, Munich, 1990.
[2] Schwarzenbach, K., et al.: Plastic Additives Handbook, Zweifel, H., (Ed), 5th
Edition, Hanser Publisher, 2001, 1-140.
[3] Heller, H. I. & Blattmann, H.R., Pure Applied Chemistry, 1973, 36, 141-161.
[4] Rieken, J. et al., Journal Chemical Physics, 1992, 96, 10225-10234.
[5] Gugumus, F., Polymer Degradation & Stability, 1993, 39, 117-135.
[6] Step, E. N., Turro, N. J., Klemchuck, P. P., & Gande, M. E.; Angewandte
Makromoleculare Chemie, 1995, 232, 65-83 and references therein.
[7] Gensler, R. et al., Polymer Degradation & Stability, 2000, 67, 195-208.
[8] Allen, N. S. & McKellar, J.F., Chem. Soc. Revs., 1975, 4, 533-566.
[9] Davis, L., Sanders, B., Stretanski, J.; SPE RETEC 2000, Color & Appearance
Division and Polymer Modifiers and Additives Division co-sponsors, Sept. 17-19,
2000, Washington, DC.
 Figures

0.30% UV-3346
0.10% UV-3346, 0.10% UV-2908, 0.10% UV-531

100
80
60
40
20
0
0 100 200 300 400 500 600
Hours (QUV-313 Weathering)

Figure 1. UV Stabilization of PP Slit Tape (PP/HDPE 100/15), EN-277: European

Standard*, 80 micron x 4 mm, AO: 0.12% AO, FDA Formulations, ASTM G-154
*(EN 277 Standard for woven fabric)

0.10% UV-3346, 0.10% UV-2908, 0.10% UV-531

0.30% UV-783
100

80

60

40

20

0
0 100 200 300 400 500 600
Hours (QUV-313 Exposure)

Figure 2. UV Stabilization of PP Slit Tape (PP/HDPE 100/15), EN-277: European

Standard*, 80 micron x 4 mm, AO: 0.12% AO, FDA Formulations, ASTM G-154
*(EN 277 Standard for woven fabric)
 9
8
centimeter (cm) 7 NOT
6 FDA
5 Sanctioned
4
3 FDA
2 Sanctioned
1
0
0.10% UV-3346, 0.30% UV-791
0.10% UV-2908,
0.10% UV-531

Figure 3. Polypropylene Tape (PP/HDPE - 100/15, 130 micron X 39 mm,

unstretched), Water Carry-Over, Film Speed - 16 m/minute.

10
Not
centimeter (cm)

8
FDA
6 Sanctioned
4
FDA
2 Sanctioned
0
0.10% UV-3346 0.10% 0.30% UV-770
UV-2908, 0.10% UV-
531
Figure 4. Polypropylene Tape (PP/HDPE 100/15,130 micron X 39 mm,
unstretched), Water Carry-Over, Film Speed - 16 m/minute.
 0.15% UV-3853 0.30 UV-770
0.30% UV-791 0.225% UV-3853/UV-2908
0.11% UV-3853/UV-2908

100
80
60
40
20
0
0 1000 2000 3000 4000 5000 6000
Hours

Figure 5. UV stabilization of pigmented green PP: Gloss, 60 degree. WOM ASTM

G155 wet.

500 hrs 1000 hrs 2000 hrs 3000 hrs 4000 hrs

10 8.5
8.1 7.9
8
6 4.5
3.7
4
2
0
0.15% UV- 0.30 UV-770 0.30% UV- 0.225% UV- 0.11% UV-
3853 791 3853/UV- 3853/UV-
2908 2908

Figure 6. UV stabilization of blue pigmented PP: ∆E, WOM ASTM G155 wet.
 0.15% UV-3853 0.30 UV-770
0.30% UV-791 0.225% UV-3853/UV-2908
0.11% UV-3853/UV-2908

100
80
60
40
20
0
0 1000 2000 3000 4000 5000 6000
Hours

Figure 7. UV stabilization of blue pigmented PP: Gloss, 60 degree. WOM, ASTM

G155 wet.

Green Blue

100
80
60
40
20
0
0.15% UV- 0.30 UV-770 0.30% UV- 0.225% UV- 0.11% UV-
3853 791 3853/UV- 3853/UV-
2908 2908

Fig.8. UV stabilization of blue and green pigmented PP: % Retained tensile

strength after 2500 hours in xenon arc WOM for different formulations and
pigments.
 0.3% UV-3346
0.2% UV-3346 + 0.1% UV-2908
0.3% UV-783

3500
3000
2500
2000
1500
1000
500
0
T-70% T-50%

Figure 9 .UV Stabilization of PP Slit Tape (PP/HDPE 100/15), General Outdoor

Applications, 65 micron, ASTM G-155 with spray cycle

0 hrs 1000 hrs 1500 hrs 2000 hrs

120
100
80
60
40
20
0
FR PP Control FR PP UV System
UV System: 0.5% each UV-2908/UV-531/P-619
Flame Retardant: FR-800 + antimony trioxide (3:1)

Figure 10. Percent of original elongation of blue V-2 flame-retardant UV-

stabilized PP stadium seats, ASTM G-155.
 500 hrs
25
1000 hrs
20 1500 hrs
2000 hrs
15 2500 hrs
3000 hrs
10 3500 hrs

0
FR PP Control FR PP UV System
UV System: 0.5% each UV-2908/UV-531/P-619
Flame retardant: FR-800+ antimony trioxide (3:1)

Figure 11. Total color change of UV-stabilized blue V-2 flame-retardant PP

stadium seats, ASTM G-155.
 Chemical Structures

Chemical Structure Trade Name

[CAS Number] (Producer)
Ethanox E330
OH (Albemarle)

HO

OH

AO-330
[1709-70-2]
C18H37 O O C18H37 Weston 619
O P P O (G. E. Specialty Chemical)
O O
P-619
[3806-34-6] + [122-20-3]
C(CH3)3
Irgafos 168
(Ciba Specialty Chemical)
(H3C)3C C(CH3)3
O O
P
O
C(CH3)3

(H3C)3C C(CH3)3

P-168
[31570-04-4]
O CYASORB UV-2908 Light Stabilizer
OC16H33 (Cytec Industries Inc.)
HO

UV-2908
[67845-93-6]
 CYASORB UV-3346 Light Stabilizer
O (Cytec Industries Inc.)
H
N
N

N N
N
* N N
*

N
H
n

UV-3346
[82451-48-7]
O OH CYASORB UV-531 Light Absorber
(Cytec Industries Inc.)

OC8H17

UV-531
[1843-05-6]
Chimassorb 944
H
H N (Ciba Specialty Chemicals)
N

N N
N
* N N
*

N
H n

UV-944
[70624-18-9]
Tinuvin 622
O
O
(Ciba Specialty Chemicals)
* O N C2 H4 O C2 H4 O CH 3

UV-622
[65447-77-0]
Tinuvin 770
O
O NH
(Ciba Specialty Chemicals)
O
HN O

UV-770
[52829-07-9]
UV-944 + UV-622 1:1 Mixture Tinuvin 783
UV-783 (Ciba Specialty Chemicals)

UV-944 + UV-770 1:1 Mixture Tinuvin 791

UV-791 (Ciba Specialty Chemicals)