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 perpared by reaction of PCI3 with the appropriate
to the combination of various agents like light, phenol or alcohol and with 2,2,6,6-tetramethyl-4-
heat, oxygen and stress, and a combination of hydroxypiperidine in the presence of triethyl-
stabilizers is therefore more efficient in coping amine.3'4 The combined stabilizers have the follow-
with the various types of deterioration. The ing structures (Scheme 1): [bis(2,2,6,6-tetramethyl-
choice of components to be combined has to be piperidin-4-yl)-(2,6-ditert.butyl-4-methylphenyl)]-
made very carefully because of possible an- phosphite (HALS/P I), m.p. 126-127°C,
tagonistic effects. On the other hand, synergistic 31p NMR: 146.1 ppm.; [2,2,6,6-tetramethyl-
effects can bring some advantages by applying a piperidin-4-yl-neopentyl]phosphite (HALS/P II),
combination of stabilizers. ~'2 We have dealt with m.p. 94-95°C; [bis(2,2,6,6-tetramethypiperi-
these questions in connection with the stabilizing din-4-yl)-(2-tert.butyl-5-methylphenyl)]phosphite
system containing HALS (Hindered Amine Light (HALS/PIII), m.p. 63-64°C, 31PNMR: 134.1
Stabilizers), phosphites with alkyl or aryl ppm.
substituents and a sterically hindered phenol. A The alkyl aryl phosphites were prepared
deeper insight into their interaction was achieved by standard methods (H~ihner, V. & Habicher,
by applying a stabilizing mixture of these W. D., unpublished). The products P-l:
components on the one hand, and by using their [bis(isopropyl)-2,6-ditert.butylphenyl]phosphite
combination in one molecule on the other. and P-2: [monoisopropyl-neopentyl]phosphite
were yellow viscous liquids. [tris(2,4-
Polymer Degradation and Stability 0141-3910/93/$06.00 ditert.butylphenyl]phosphite (P-3) was the com-
(~) 1993 Elsevier Science Publishers Ltd. mercial product Irgafos 168 (Ciba-Geigy, Basel,
367

e. Hole~ovice.butyl-4-methylphenol (A-l) (AO4K. in the phenolic part of the stabilizer.~¢.6. control. This Slovnaft s. H A L S / P I. All three additives exhibited Polypropylene (PP) powder (Tatren HPF. Since the processing antioxidant A-1 was piperidine-l-oxyl (HALS-2) as used previously. results as full points. USA) phosphite stabilizer only. Slightly HALS/P III -.. 1740cm -1 (Specord IR-75.1 wt %) increase in the absorption of carbonyl oxidation and calcium stearate (0-15wt %)--empty points.2wt%.and Fig. HALS/P I.{. (~SFR) described elsewhere. The antagonistic Brabender Plastograph (Duisburg.e.368 . The bulk nitroxyl radicals ( ~ N O ' ) formed from the HALS polymer was then pressed into c. Photooxidation was carried out in apparatus < equipped with a 125 W medium pressure mercury 0. Concentration of additive: 0. 2 the actual processing stabilizer. and C). 6 The temperature of the system was held at 30 + 2°C. of the phenolic group as compared with The low molecular weight HALS stabilizers H A L S / P I led to a rapid decrease in the were 2. The rates of photooxidation of PP films (0-2 mm) thermooxidation was followed by monitoring the containing combined HALS-phosphites with A-1 (0. The course of photo. thermobalance (Norwalk. Figure 1 shows plots of the increase of carbonyl H3C CH3 absorption versus the time of irradiation. H A L S / P II. SFR) and the indicates the antagonistic interaction between additives were mixed and homogenized in a A-1 and the additives used. FRG) at effect may be ascribed to the reaction between 175°C or 190°C for 5min in air. Vlaardingen.i O .2. 0. PP films containing the combined HALS- Elmer TGS-1.6. 4'6 ture: 175°C. Composition of films: V.6-Ditert. ~H=p ( H3C CHa HALS/P I shows the highest efficiency. have described the antagonistic effect between Istrochem s.1 arc (Tesla n.e. s present in the tested films and several authors 2.6. we used in the first case stabilizing mixtures containing. This HALS/P I I system is most often used for testing.6-di-tert. processing tempera- FRG) as described previously.H lower efficiency was achieved by H A L S / P II in CH= L HaC CH= spite of the absence of a phenolic group in its molecule. (HALS-1) and 2. RESULTS AND DISCUSSION HALS/P I For testing the efficiency of the combined HALS-phosphite stabilizers and for studying the interactions of the individual parts of a molecule.-butyl-4- methylphenol (A-l) and calcium stearate. Bratislavia. processing antioxidant 2.4.~ N . stabilizing effect was determined by testing the Thermal stability was measured on a Perkin.6-tetramethyl-4-hydroxy. H3C.HALS/P II.or 0-2-mm films in an electrically heated laboratory press (Fontune. HALS/P III.. i. Chmela et al. The empty points denote the combined H A L S - phosphite stabilizers. Carl Zeiss Jena.hydroxypiperidine efficiency of this additive in PP.IcH3 H A L S / P I I I and control film containing A-1. The change of position of substituents Scheme1.2.15. SFR) was used as HALS and phenolic stabilizers. Bratislava.e. . HALS/P III. Figure 1 shows the at a heating rate of 10°/min in air. 1.tetramethyl. besides the stabilizers being eva- HsC CH3 luated. EJ. ZX. Thermooxidation was carried o ~oo 800 12oo 1too out in a laboratory oven without circulation at IRRADIATION TIME (h) 90 + 2°C or 110 + 2°C. and the reduction of the hindrance Switzerland) used without purification. increased efficiency in the absence of A-1. without products in the region between 1700 and A-1 and CaSt--full points. Netherlands) at 200°C for 1 min.

For H A L S / P III it was 4% at isopropyl (Fig. 2. 0-2wt % corresponds to of 10°/min was 1% at 175°C and 2% at 190°C for 7.57 x 10-3mol/kg. 175°C.6.6-tetramethyl-4-hydroxy piperidine used derivatives of HALS/P II. The rates of photooxidation of PP films (0-2 mm) thermooxidation of paraffin at 150°C in air. 5% at 190°C and 20% at 230°C. the Brabender Plastograph for 5 min at 175°C to No interaction of HALS and phosphite was 190°C. compound B) and phosphite with observed at 250°C. B(HALS-1). The molecule contains two active IRRADIATIONTIME (hl HALS units so that the concentration of Fig. 0 x l 0 . The experiments were carried out for additives H A L S / P I and H A L S / P II. of HALS and phosphite. compounds A). The rates of photooxidation of PP films for 2. B (HALS-1). Figures 2 and 3 175°C. the containing O. 3. O. and A. then as the effectiveness was 70% of the value exhibited a mixture of two unbonded molecules. i.e. HALS-phosphite stabilizer (H/ihner. In spite of this the efficiency of antagonistic. A remarkable synergistic effect is study their interaction.57 x 10 -3 mol/kg. A marked decrease. Moreover. either synergistic or probably lower. When H A L S / P I was used to inhibit Fig.6-Tetramethyl- 4-hydroxypiperidine (HALS 1) was used as a free HALS molecule. iRRADIATION TIME (h) tion. phosphite with an isopropyl substituent (Fig. the quinone radical can react with another ~ N O " molecule forming an z 0. ~7.2. 2. & Habicher. the concentration of 0-2wt % cor- responds to a molar concentration of 3-5 × 0 ~QO 800 1200 10 -3 mol/kg. was (Fig. 3. 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). 2.4 sensitizer. HALS/P I. namely 30% at 175°C and 52% at both cases in the order: 190°C. induction period was 15 h and then phosphate and A.2). x.0 × 10 -3 mol/kg and was used for pure HALS H A L S / P I . W. control film. A + B . In the case of phosphite we used an isopropyl substituent instead of the 2. x. 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. unpublished). 20%.1 -~N # B= HO H adduct which lowers the concentration of the 3 effective ~ N O " radicals. For H A L S / P I . control film. show the results for the photooxidation of PP H A L S / P I I exhibited a much higher weight films. 3. (3-5 + 7. to the precise sum of the efficiencies of free In order to evaluate contributions from the HALS and phosphite.0 x 10-3moi/kg.e.2. A + B. . 3. HALS/P II. A (P-l). Weight decrease compound A) was 3-5 x 10-3mol/kg.2.6. For the measured on the thermobalance at a heating rate derivative H A L S / P II. It is interesting that the increase in separately. i.. U.6-tetramethylpiperidin-4-yl substituent. The concentration of 10-3mol/kg. V. The actual concentration of H A L S / P II is observed in their mixtures.0) x 10-3 mol/kg. I~. The absence of the processing antioxidant in the control film 0 500 1000 1500 naturally accelerates the course of its degrada. processing temperature. concentration: 7-0x was 7 . D. and the efficiency was almost equal HALS/P II is rather high. The by the mixtures of HALS and phosphite for both results were compared with the efficiency of a combined HALS-phosphite. started to be formed from the combined processing temperature: 175°C. A(P . HALS-phosphite combinations as stabilizers for polypropylene 369 part in the stabilizing process and A-1.6. E3. 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 . 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 efficiency of the additives increases in decrease.3 m o l / k g . 3. 7. both com- ponents were bound in one molecule.

3 . 3-57 × 10-3 + 3.57x containing: +. In order to understand this interaction better. Nevertheless. 3.15 mm) 10 3moi/kg. 5). HALS-1+ P-3. 10-7× 10 3+3. namely 3:1. which might be called 'intramolecular synergism'.57x 10-3 mol/kg. HALS-1.57 x HALS-1 + HALS/P I. where A is phosphite J / / 0. O. The rates of photooxidation of PP film (0. E v e n addition of free HALS-1 to onistic effect was observed for parent amine the combined stabilizer H A L S / P I in the ratio (HALS-1. 7. 2) which is roughly the sum of the contributions of the individual parts (A + B. 10.1 = o 6 m "¢ 0. needed.. 3-57 × 10-3mol/kg. and &.14 × 10-3 + 3. 10. a weak antag. The same increase in efficiency.7 x 10-3 + 3. P-3.57x sion that a special type of synergism is involved 10-3 mol/kg. also depends upon the chemical structures of the to-phosphite ratio. 3. HALS-1 + P-3. The rates of photooxidation of PP films (0-15 ram) mixture of H A L S and phosphite at a given ratio containing: +. Fig. I-7.57 × 10-3mol/kg. A.57x 10 3mol/kg.I + P . 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 IRRADIATION TIME (h) complete absence of any interaction in the Fig. (HALS-1) or 2. 4) while slight synergism was seen 1:1 results in a noticeable antagonistic effect (Fig. 3-57x 10 3mol/kg. Chmela et al.57 x 10 3 mol/kg. HALS/PI. derivatives. additional data using different structures and phenyl) phosphite (P-3). I .1 J / 0 500 1000 1500 IRRADIATION TIME (h ) 500 10'00 1500 2000 Fig. idine-l-oxyl (HALS-2) and tris(2. this interaction amine and N-oxyl respectively. I .. HALS-2+P-3. processing temperature: 190°C. 190°C.7× Fig. and O. These phosphite on the efficiency was investigated for data indicate m o r e or less the trend in the interac- the pairs 2. O. P-3. The influence of the ratio of H A L S to for the N-oxyl derivative (HALS-2.2.4-di-tert. / especially in comparison with the results based on the efficiency of the mixture (Fig.butyl. o. H A L S . no additive. A. HALS-1. 6. 3. 10.6. components. The course of PP concentrations of H A L S and phosphite are photooxidation is shown in Figs 4 and 5. A t a higher H A L S .6-tetramethyl-4-hydroxypiper. 3-57 × 10-3 mol/kg. O. led to the conclusion that the synergism is caused by the presence of both H A L S and phosphite in one molecule. 10-3 mol/kg. 6). 370 ~.7x 10-3mol/kg.6-tetramethyl-4-hydroxypiperidine tion of H A L S and its derivatives and phosphite. the results indicate that gistic or antagonistic effects are observable at the this interaction depends upon the ratio of the molar ratio H A L S : phosphite = 1:1 using parent components involved. No syner. 3-57×10 -3+3. Moreover. A. 10 -3 mol/kg. 3-57x10 -3+3. Fig. 4. and considerable synergism of the combined HALS-2. The rates of photooxidation of PP films (0-15 mm) IRRADIATION TIME (h) containing: +. and A. processing temperature: 190°C. .2 / A g~ o.2. in spite of the chemically different substituents iiI i (substituted aryl in H A L S / P I and alkyl in H A L S / P I I ) . HALS-1. processing temperature. HALS-2+P-3. D.57x H A L S .6. HALS-2. This behaviour was rather unexpected. 10 3moi/kg. no additive. no additive.57 x 10-3 mol/kg. The extent and the possibility of interaction is smaller for a mixture of the two ! • I compounds in a polymer than when H A L S and 0 500 1000 1500 phosphite are bound in one molecule. I~. 5.p h o s p h i t e stabilizer leads to the conclu.

Polym. & Hrdlovi6. Chmela. Chirinos-Padr6n.. Deg. For the H A L S / P I mixture. H~ihner. It was 4700h for the Star~i Lesnd. S. Hrdlovi6. & efficiency of m o r e than 600% at 90°C. The interaction in the complex system show that the interaction of the mixture of H A L S depends upon the ratio of the c o m p o n e n t s and and phosphite depends upon their ratio as well as their structures. P. Variations in the composition of on the chemical structures of the individual the mixture may bring about slight synergistic or components.and heat-stabilizing much higher efficiency for this c o m p o u n d w h e n it efficiencies of H A L S and phosphite are preserved is used alone. 5. the increase in references therein. & The time to reach an absorbance of 0. 1990. 1990. i...and excellent heat cules also p r e d e t e r m i n e s their use as light and stabilizers. W. Proc. S. heat stabilizers. Qualita- tively similar results were obtained in the thermooxidation of PP films at 90°C and ll0°C. HALS-phosphite combinations as stabilizers for polypropylene 371 with two isopropyl substituents and B is CONCLUSIONS HALS-1). Z. for H A L S / P II. S. The substitution of the two isopropyl groups by 2..p h o s p h i t e mole- function both as good light.p h o s p h i t e Most H A L S . Habicher. S. while for combined H A L S / P II it was 1200 h at 4. carbonyl region was c. . which is an increase in 6. Muhlhausen. B. A: the efficiency was 200% c o m p a r e d with a 70% Chem.6. & Mafidsek. Allen. 38 (1984) 199. P r o c . Photochem. N. The data ratio. It was clearly d e m o n s t r a t e d stabilizers is not sufficient. 3. Noack..... 137. Soc. REFERENCES The synergistic effect of the H A L S . & Habicher. Chmela. W. Photobiol. Chmela.e. increase when it was used as a light stabilizer.2. reach A = 0. p. The greatly for various pairs and different ratios.2 was 700h. p. Rev. combined H A L S / P I . P. Stab. 11 (1985) 233.p h o s p h i t e s are able to phosphite in combined H A L S .. U.6-tetramethyl-4-piperidyl leads to Our data show that the light. the time to 'Degradation Stabilization and Combustion of Polymers'. Chmela. Chem. 15 (1986) 373 and substituent. 136.2 in the Schwetlick. Results indicate that their light-stabilizing activity is quite good. Papers. In the mixture with free HALS-1. The extent of interaction can differ antagonistic effects or have no effect at all. products which contain a H A L S .. J. Germany.t y p e stabilizers are used as light structural unit in one molecule exhibit a strong stabilizers because their efficiency as heat synergistic effect.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. The presence of that the combined H A L S . A. 49 (1989) 1 and references therein. S. Chemiedozenten tagung. D. J.... 4 0 0 h for the mixture. 2. For the alkyl 1. Microsymposium 90°C. Chem. K. by applying t h e m as a mixture in the p r o p e r the antagonistic effect was monitored. D.. Chemische Gesellschaft.