Polymer Degradation and Stability 39 (1993) 367-371

HALS-phosphite combinations as light and

heat stabilizers for polypropylene
Dedicated to Prof. Dr K. Schwetlick on the occasion of his 60th birthday.

~. C h m e l a , W . D . H a b i c h e r , b U . H~ihner ~ & P . H r d l o v i ~
a Polymer Institute, Slovak Academy of Sciences, CS-842 36 Bratislava, Dt~bravskd cesta 9, Czech and Slovak Federal
Republik
b Technische Universitiit Dresden, Institut fiir Organische Chemie und Farbenchemie, 0-8027 Dresden, Mommsenstrasse 13,
Germany

(Received 29 November 1991; accepted 16 December 1991)

Organic phosphites combined with Hindered Amine Light Stabilizers (HALS)

were used as stabilizers in the photo- and thermoxidation of polypropylene
film. The efficiency of the mixture of HALS and phosphite was compared with
the efficiency of the combination of HALS and phosphite in one molecule. A
strong synergistic effect was observed for the molecule with HALS and
phosphite moieties. Generally, the mixture of HALS and phosphite exhibited
synergistic, antagonistic or additive effects. The efficiency of the mixture
depends upon the chemical structure of the phosphite and HALS structural
units as well as on the ratio of the components.

INTRODUCTION EXPERIMENTAL

Most commercial stabilized plastics contain a Combined HALS-phosphite stabilizers were

combination of stabilizers. Deterioration is due
to the combination of various agents like light,
heat, oxygen and stress, and a combination of
stabilizers is therefore more efficient in coping
with the various types of deterioration. The
choice of components to be combined has to be
made very carefully because of possible an-
tagonistic effects. On the other hand, synergistic
effects can bring some advantages by applying a
combination of stabilizers. ~'2 We have dealt with
these questions in connection with the stabilizing
system containing HALS (Hindered Amine Light
Stabilizers), phosphites with alkyl or aryl
substituents and a sterically hindered phenol. A
deeper insight into their interaction was achieved
by applying a stabilizing mixture of these
components on the one hand, and by using their
combination in one molecule on the other.
Polymer Degradation and Stability 0141-3910/93/$06.00
(~) 1993 Elsevier Science Publishers Ltd.
367
perpared by reaction of PCI3 with the appropriate
phenol or alcohol and with 2,2,6,6-tetramethyl-4-
hydroxypiperidine in the presence of triethyl-
amine.3'4 The combined stabilizers have the follow-
ing structures (Scheme 1): [bis(2,2,6,6-tetramethyl-
piperidin-4-yl)-(2,6-ditert.butyl-4-methylphenyl)]-
phosphite (HALS/P I), m.p. 126-127C,
31p NMR: 146.1 ppm.; [2,2,6,6-tetramethyl-
piperidin-4-yl-neopentyl]phosphite (HALS/P II),
m.p. 94-95C; [bis(2,2,6,6-tetramethypiperi-
din-4-yl)-(2-tert.butyl-5-methylphenyl)]phosphite
(HALS/PIII), m.p. 63-64C, 31PNMR: 134.1
ppm.
The alkyl aryl phosphites were prepared
by standard methods (H~ihner, V. & Habicher,
W. D., unpublished). The products P-l:
[bis(isopropyl)-2,6-ditert.butylphenyl]phosphite
and P-2: [monoisopropyl-neopentyl]phosphite
were yellow viscous liquids. [tris(2,4-
ditert.butylphenyl]phosphite (P-3) was the com-
mercial product Irgafos 168 (Ciba-Geigy, Basel,
368
HALS/P I
HsC CH3
HALS/P I I
H3C CH3
H3C,~.IcH3
~H=p ( H3C CHa
HALS/P III -- i O - ~ N - H
CH= L HaC CH=
Scheme1.
Switzerland) used without purification.
The low molecular weight HALS stabilizers
were 2,2,6,6- tetramethyl- 4- hydroxypiperidine
(HALS-1) and 2,2,6,6-tetramethyl-4-hydroxy-
piperidine-l-oxyl (HALS-2) as used previously, s
2,6-Ditert.butyl-4-methylphenol (A-l) (AO4K,
Istrochem s.e., Bratislava, SFR) was used as
processing stabilizer.
Thermal stability was measured on a Perkin-
Elmer TGS-1, thermobalance (Norwalk, USA)
at a heating rate of 10/min in air.
Polypropylene (PP) powder (Tatren HPF,
Slovnaft s.e., Bratislavia, SFR) and the
additives were mixed and homogenized in a
Brabender Plastograph (Duisburg, FRG) at
175C or 190C for 5min in air. The bulk
polymer was then pressed into c. 0.15- or 0-2-mm
films in an electrically heated laboratory press
(Fontune, Vlaardingen, Netherlands) at 200C
for 1 min.
Photooxidation was carried out in apparatus
equipped with a 125 W medium pressure mercury
arc (Tesla n.e. Hole~ovice, (~SFR) described
elsewhere. 6 The temperature of the system was
held at 30 + 2C. Thermooxidation was carried
out in a laboratory oven without circulation at
90 + 2C or 110 + 2C. The course of photo- and
thermooxidation was followed by monitoring the
increase in the absorption of carbonyl oxidation
products in the region between 1700 and
1740cm -1 (Specord IR-75, Carl Zeiss Jena,
FRG) as described previously. 4'6
;{. Chmela et al.
RESULTS AND DISCUSSION
For testing the efficiency of the combined
HALS-phosphite stabilizers and for studying the
interactions of the individual parts of a molecule,
we used in the first case stabilizing mixtures
containing, besides the stabilizers being eva-
luated, processing antioxidant 2,6-di-tert.-butyl-4-
methylphenol (A-l) and calcium stearate. This
system is most often used for testing. Figure 1
shows plots of the increase of carbonyl
absorption versus the time of irradiation. The
empty points denote the combined H A L S -
phosphite stabilizers, i.e. H A L S / P I, H A L S / P II,
H A L S / P I I I and control film containing A-1.
HALS/P I shows the highest efficiency. Slightly
lower efficiency was achieved by H A L S / P II in
spite of the absence of a phenolic group in its
molecule. The change of position of substituents
in the phenolic part of the stabilizer,
HALS/P III, and the reduction of the hindrance
of the phenolic group as compared with
H A L S / P I led to a rapid decrease in the
efficiency of this additive in PP.
Since the processing antioxidant A-1 was
present in the tested films and several authors
have described the antagonistic effect between
HALS and phenolic stabilizers, 2 the actual
stabilizing effect was determined by testing the
PP films containing the combined HALS-
phosphite stabilizer only. Figure 1 shows the
results as full points. All three additives exhibited
increased efficiency in the absence of A-1. This
indicates the antagonistic interaction between
A-1 and the additives used. The antagonistic
effect may be ascribed to the reaction between
nitroxyl radicals ( ~ N O ' ) formed from the HALS
<
0.1
o ~oo 800 12oo 1too
IRRADIATION TIME (h)
Fig. 1. The rates of photooxidation of PP films (0-2 mm)
containing combined HALS-phosphites with A-1 (0.1 wt %)
and calcium stearate (0-15wt %)--empty points; without
A-1 and CaSt--full points. Composition of films: V,
control; EJ, HALS/P I; ZX,HALS/P II; and C), HALS/P III.
Concentration of additive: 0.2wt%; processing tempera-
ture: 175C.
 HALS-phosphite combinations as stabilizers for polypropylene 369

part in the stabilizing process and A-1.

Hydroxylamine ( ) N O H ) is formed from N-oxyl __ O-CH(CH3
radical ( ~ N O ' ) and quinone radical is formed CH3

from A-1 which is considered to be a powerful ,4

sensitizer. Moreover, the quinone radical can
react with another ~ N O " molecule forming an z 0.1 -~N
# B= HO H
adduct which lowers the concentration of the 3
effective ~ N O " radicals. The absence of the
processing antioxidant in the control film 0 500 1000 1500
naturally accelerates the course of its degrada- iRRADIATION TIME (h)

tion. When H A L S / P I was used to inhibit Fig. 2. The rates of photooxidation of PP films (0-2 mm)
thermooxidation of paraffin at 150C in air, the containing O, HALS/P I, 3.57 x 10 -3 mol/kg; I~, A (P-l),
3.57 x 10-3mol/kg; V, B (HALS-1), 7.0 x 10-3moi/kg;
induction period was 15 h and then phosphate and A, A + B, (3-5 + 7.0) x 10-3 mol/kg; x, control film;
started to be formed from the combined processing temperature: 175C.
HALS-phosphite stabilizer (H/ihner, U. &
Habicher, W. D., unpublished). Weight decrease compound A) was 3-5 x 10-3mol/kg. For the
measured on the thermobalance at a heating rate derivative H A L S / P II, 0-2wt % corresponds to
of 10/min was 1% at 175C and 2% at 190C for 7.0 10 -3 mol/kg and was used for pure HALS
H A L S / P I . A marked decrease, 20%, was (Fig. 3, compound B) and phosphite with
observed at 250C. For H A L S / P III it was 4% at isopropyl (Fig. 3, compounds A). Figures 2 and 3
175C, 5% at 190C and 20% at 230C. show the results for the photooxidation of PP
H A L S / P I I exhibited a much higher weight films. The efficiency of the additives increases in
decrease, namely 30% at 175C and 52% at both cases in the order:
190C. These results suggest that the concentra-
tions of H A L S / P I and H A L S / P I I I are not phosphite < HALS < phosphite + HALS
changed while the mixture is being processed on << HALS-phosphite.
the Brabender Plastograph for 5 min at 175C to
No interaction of HALS and phosphite was
190C. The actual concentration of H A L S / P II is
observed in their mixtures, either synergistic or
probably lower. In spite of this the efficiency of
antagonistic, and the efficiency was almost equal
HALS/P II is rather high.
to the precise sum of the efficiencies of free
In order to evaluate contributions from the
HALS and phosphite. A different situation arises
individual parts of the combined HALS-
if HALS and phosphite moieties are bound in
phosphite stabilizers to the overall efficiency or to
one molecule. A remarkable synergistic effect is
study their interaction, we have tested the
evident in both cases (HALS/P I and
efficiency of the individual parts of the molecule
H A L S / P II). It is interesting that the increase in
separately, i.e. of HALS and phosphite, then as
the effectiveness was 70% of the value exhibited
a mixture of two unbonded molecules. The
by the mixtures of HALS and phosphite for both
results were compared with the efficiency of a
combined HALS-phosphite, i.e. both com-
ponents were bound in one molecule. The
experiments were carried out for additives
H A L S / P I and H A L S / P II. 2,2,6,6-Tetramethyl-
4-hydroxypiperidine (HALS 1) was used as a free
HALS molecule. In the case of phosphite we
used an isopropyl substituent instead of the
2,2,6,6-tetramethylpiperidin-4-yl substituent. For
H A L S / P I , the concentration of 0-2wt % cor-
responds to a molar concentration of 3-5 0 ~QO 800 1200
10 -3 mol/kg. The molecule contains two active IRRADIATIONTIME (hl

HALS units so that the concentration of Fig. 3. The rates of photooxidation of PP films for
2,2,6,6-tetramethyl-4-hydroxy piperidine used derivatives of HALS/P II. O, HALS/P II; E3, A(P - 2); ~7,
B(HALS-1); and A, A + B ; concentration: 7-0x
was 7 . 0 x l 0 - 3 m o l / k g . The concentration of 10-3mol/kg; x, control film; processing temperature;
phosphite with an isopropyl substituent (Fig. 2, 175C.
 370
derivatives. The same increase in efficiency, in
spite of the chemically different substituents
(substituted aryl in H A L S / P I and alkyl in
H A L S / P I I ) , led to the conclusion that the
synergism is caused by the presence of both
H A L S and phosphite in one molecule. A n o t h e r
possible explanation is that synergism is caused
by the interaction of transformation products of
the additive in the course of the stabilization
process. The extent and the possibility of
interaction is smaller for a mixture of the two
compounds in a polymer than when H A L S and
phosphite are bound in one molecule. The
complete absence of any interaction in the
mixture of H A L S and phosphite at a given ratio
and considerable synergism of the combined
H A L S - p h o s p h i t e stabilizer leads to the conclu-
sion that a special type of synergism is involved
which might be called 'intramolecular synergism'.
The influence of the ratio of H A L S to
phosphite on the efficiency was investigated for
the pairs 2,2,6,6-tetramethyl-4-hydroxypiperidine
(HALS-1) or 2,2,6,6-tetramethyl-4-hydroxypiper-
idine-l-oxyl (HALS-2) and tris(2,4-di-tert.butyl-
phenyl) phosphite (P-3). The course of PP
photooxidation is shown in Figs 4 and 5. No syner-
gistic or antagonistic effects are observable at the
molar ratio H A L S : phosphite = 1:1 using parent
amine and N-oxyl respectively. A t a higher H A L S -
to-phosphite ratio, namely 3:1, a weak antag-
onistic effect was observed for parent amine
(HALS-1, Fig. 4) while slight synergism was seen
o,,. / especially in comparison with the results based
g~ o.1
6
0 500 1000
IRRADIATION TIME (h )
Fig. 4. The rates of photooxidation of PP films (0-15 mm)
containing: +, no additive; O, P-3, 3-57 10-3mol/kg; I-7,
HALS-1, 3.57x 10-3 mol/kg; A, HALS-1, 10.7
10 3moi/kg; I , H A L S - I + P - 3 , 3-57x10 -3+3.57x
10 3mol/kg; O, HALS-1+ P-3, 7.14 10-3 + 3.57
10 -3 mol/kg; and A, HALS-1 + P-3, 10.7 x 10-3 + 3.57 x
10-3 mol/kg; processing temperature: 190C.
~. Chmela et al.
iiI i
! I
0 500 1000 1500
IRRADIATION TIME (h)
Fig. 5. The rates of photooxidation of PP films (0-15 ram)
containing: +, no additive; O, P-3, 3-57 10-3 mol/kg; I~,
HALS-2, 3.57 x 10 3 mol/kg; A, HALS-2, 10.7x
10-3mol/kg; I , HALS-2+P-3, 3-5710 -3+3.57x
10 3moi/kg; and &, HALS-2+P-3, 10-7 10 3+3.57x
10-3 mol/kg; processing temperature; 190C.
for the N-oxyl derivative (HALS-2, Fig. 5). These
data indicate m o r e or less the trend in the interac-
tion of H A L S and its derivatives and phosphite.
In order to understand this interaction better,
additional data using different structures and
concentrations of H A L S and phosphite are
needed. Nevertheless, the results indicate that
this interaction depends upon the ratio of the
components involved. Moreover, this interaction
also depends upon the chemical structures of the
components. E v e n addition of free HALS-1 to
the combined stabilizer H A L S / P I in the ratio
1:1 results in a noticeable antagonistic effect
(Fig. 6). This behaviour was rather unexpected,
on the efficiency of the mixture (Fig. 2) which is
roughly the sum of the contributions of the
individual parts (A + B, where A is phosphite
J / /
0.2
/
A
=
o
m
" 0.1
J
/
1500
500 10'00 1500 2000
IRRADIATION TIME (h)
Fig. 6. The rates of photooxidation of PP film (0.15 mm)
containing: +, no additive; A, HALS-1, 3-57x
10-3mol/kg; D, HALS/PI, 3.57x 10 3mol/kg; and O,
HALS-1 + HALS/P I, 3-57 10-3 + 3.57 x 10-3 mol/kg;
processing temperature: 190C.
 HALS-phosphite combinations as stabilizers for polypropylene
with two isopropyl substituents and B is
HALS-1). The substitution of the two isopropyl
groups by 2,2,6,6-tetramethyl-4-piperidyl leads to
much higher efficiency for this c o m p o u n d w h e n it
is used alone. In the mixture with free HALS-1,
the antagonistic effect was monitored. The data
show that the interaction of the mixture of H A L S
and phosphite depends upon their ratio as well as
on the chemical structures of the individual
components. The extent of interaction can differ
greatly for various pairs and different ratios.
Most H A L S - t y p e stabilizers are used as light
stabilizers because their efficiency as heat
stabilizers is not sufficient. The presence of
phosphite in combined H A L S - p h o s p h i t e mole-
cules also p r e d e t e r m i n e s their use as light and
heat stabilizers. Results indicate that their
light-stabilizing activity is quite good. Qualita-
tively similar results were obtained in the
thermooxidation of PP films at 90C and ll0C.
The synergistic effect of the H A L S - p h o s p h i t e
combination was m o r e clearly d e m o n s t r a t e d as a
function of the type of substituents. For the alkyl
substituent, i.e. for H A L S / P II, the increase in
the efficiency was 200% c o m p a r e d with a 70%
increase when it was used as a light stabilizer.
The time to reach an absorbance of 0.2 in the
carbonyl region was c. 4 0 0 h for the mixture,
while for combined H A L S / P II it was 1200 h at
90C. For the H A L S / P I mixture, the time to
reach A = 0.2 was 700h. It was 4700h for the
combined H A L S / P I , which is an increase in
efficiency of m o r e than 600% at 90C.
371
CONCLUSIONS
Our data show that the light- and heat-stabilizing
efficiencies of H A L S and phosphite are preserved
by applying t h e m as a mixture in the p r o p e r
ratio. The interaction in the complex system
depends upon the ratio of the c o m p o n e n t s and
their structures. Variations in the composition of
the mixture may bring about slight synergistic or
antagonistic effects or have no effect at all. The
products which contain a H A L S - p h o s p h i t e
structural unit in one molecule exhibit a strong
synergistic effect. It was clearly d e m o n s t r a t e d
that the combined H A L S - p h o s p h i t e s are able to
function both as good light- and excellent heat
stabilizers.
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1. Allen, N. S., Chem. Soc. Rev., 15 (1986) 373 and
references therein.
2. Chirinos-Padr6n, A. J., J. Photochem. Photobiol., A:
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Schwetlick, K., P r o c . Chemiedozenten tagung,
Muhlhausen, Chemische Gesellschaft, Germany, 1990, p.
137.
4. Chmela, S. & Habicher, W. D., Proc. Microsymposium
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Star~i Lesnd, 1990, p. 136.
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