Beruflich Dokumente
Kultur Dokumente
~. 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
INTRODUCTION EXPERIMENTAL
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Habicher, W. D., unpublished).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 ~. Chmela et al.
iiI i
(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
! I
compounds in a polymer than when H A L S and 0 500 1000 1500
phosphite are bound in one molecule. The IRRADIATION TIME (h)
complete absence of any interaction in the Fig. 5. The rates of photooxidation of PP films (0-15 ram)
mixture of H A L S and phosphite at a given ratio containing: +, no additive; O, P-3, 3-57 10-3 mol/kg; I~,
and considerable synergism of the combined 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
H A L S - p h o s p h i t e stabilizer leads to the conclu- 10 3moi/kg; and &, HALS-2+P-3, 10-7 10 3+3.57x
sion that a special type of synergism is involved 10-3 mol/kg; processing temperature; 190C.
which might be called 'intramolecular synergism'.
The influence of the ratio of H A L S to for the N-oxyl derivative (HALS-2, Fig. 5). These
phosphite on the efficiency was investigated for data indicate m o r e or less the trend in the interac-
the pairs 2,2,6,6-tetramethyl-4-hydroxypiperidine tion of H A L S and its derivatives and phosphite.
(HALS-1) or 2,2,6,6-tetramethyl-4-hydroxypiper- In order to understand this interaction better,
idine-l-oxyl (HALS-2) and tris(2,4-di-tert.butyl- additional data using different structures and
phenyl) phosphite (P-3). The course of PP concentrations of H A L S and phosphite are
photooxidation is shown in Figs 4 and 5. No syner- needed. Nevertheless, 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. Moreover, this interaction
amine and N-oxyl respectively. A t a higher H A L S - also depends upon the chemical structures of the
to-phosphite ratio, namely 3:1, a weak antag- components. 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, Fig. 4) while slight synergism was seen 1:1 results in a noticeable antagonistic effect
(Fig. 6). This behaviour was rather unexpected,
J / /
0.2
/
A
g~ o.1
=
o
6
m
" 0.1
J
/
0 500 1000 1500
IRRADIATION TIME (h )
500 10'00 1500 2000
Fig. 4. The rates of photooxidation of PP films (0-15 mm) IRRADIATION TIME (h)
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 Fig. 6. The rates of photooxidation of PP film (0.15 mm)
10 3moi/kg; I , H A L S - I + P - 3 , 3-57x10 -3+3.57x containing: +, no additive; A, HALS-1, 3-57x
10 3mol/kg; O, HALS-1+ P-3, 7.14 10-3 + 3.57 10-3mol/kg; D, HALS/PI, 3.57x 10 3mol/kg; and O,
10 -3 mol/kg; and A, HALS-1 + P-3, 10.7 x 10-3 + 3.57 x HALS-1 + HALS/P I, 3-57 10-3 + 3.57 x 10-3 mol/kg;
10-3 mol/kg; processing temperature: 190C. processing temperature: 190C.
HALS-phosphite combinations as stabilizers for polypropylene 371