_ ' ' ‘ ' “

lIllllllllllllllllllllIlllllllllllllllllllllllllllllIllllllllllllllllllllll
USOO5438086A

United States Patent [19] [11] Patent Number: 5,438,086

* .
Stevenson et al. [45 Date of Patent: Au . 1 3 1995

[54] HYDROLYTICALLY STABLE 4,290,976 9/1981 Hechenbleikner et a1. ...... .. 260/927

PENTAERYTHRITOL DIPHQSPHITES 4,299,885 11/1981 Sahajpal et a1. ........... .. 428/403
4,305,866 12/1981 York et a1. 524/120
[76] Inventors: Donald R- Stevenson, 1532 "Fremont, 4,312,818 1/1982 Maul et a1. ...... .. 260/976
Dover, Ohio 44622; Satyanarayana 4,331,585 5/1982 Valdisern' et a1. 524/120
Kodali, 31 candle Light La,, Dover, 4,385,145 5/1983 Horn, Jr. ......... .. 524/120
011,043,622 4,403,053 9/1983 Lewis .......... .. 524/120
. 4,413,078 11/1983 Lewis et a1. .. 524/120
[*] Not1ce: The portion of the term of this patent 4,440,696 4/1984 Maul ............ .. 260/976
subsequent to Nov. 15, 2011 has been 4,492,661 6/1985 Maul et a1. 260/976
disclaimed. 4,588,764 5/1986 Lee, Jr. ....... .. 524/120
4,665,211 5/1987 Martin et a1. . 558/78
[21] Appl- NO~= 232,950 4,754,077 6/1988 Mina ................... .. 568/662
- _ 4,855,345 8/1989 Rosenberger et a1. 524/120
[22] Filed‘ Apr‘ 25’ 1994 4,912,198 3/1990 Fontana .............. .. 528/370
_ _ 4,983,657 1/1991 Humplik et a1. .. 524/120
Related U-S- Appllwtlon Data 5,137,950 8/1992 Hobbs et a1. ...................... .. 524/120
[63] Continuation-impart of Ser. No. 108,658, Aug. 30,
1993’ Pat. Nu 5,364,895‘ FOREIGN PATENT DOCUMENTS
199997 5/1991 European Pat. Off. .
o o o o I o q - o o o o - o o o o o o 0
'

[52] us. C1. .................................. .. 524/120; 558/78

[58] Field Of Search ......................... .. 524/120; 558/78 Primary Examiner-Veronica P. Hoke
[56] References Cited Attorney, Agent, or Firm—Oldham, Oldham & Wilson
Co.
U.S. PATENT DOCUMENTS
2,847,443 8/1958 Hechenbleikner ................ .. 260/461 [57] ABSTRACT
3,192,243 6/ 1965 Gagliani --; ----------- - 260/461 A class of hydrolytically stable bis(aralkylphenyl)penta
312054250 9/1965 Hechenblelkner -- 260/461 erythritol diphosphites is disclosed, which is suitable as
3,845,142 10/1974 Gurvich .............. .. 260/619 . . . . . . .
4,064,100 12/1977 Hechenbleikner __ 524/120 an ant1ox1dant addmves 1n polyole?ns, particularly, in
4,064,101 12/1977 Mark ____ 524M120 polypropylene. The diphosphites are of low volatility,
4,066,511 1/197g Axelrod _ __ 524/120 have a high thermal decomposition temperature and
4,116,926 9/1978 York ............ .. 524/ 120 resist yellowing when blended into a polyole?n base. A
4,116,939 9/1973 Cooper et 81 528/215 preferred diphosphite is bis(2,4-dicumylphenyl)penta
4,187,212 2/1980 Zinke et a1. ..... .. 524/151 erythritol diphosphm
4,206,111 6/1980 Valdiserri et al. . ............... .. 520/120
4,259,534 3/1981 Gurvich et a1. .................. .. 568/720
4,261,880 4/1981 Fuji et a1. .......................... .. 224/120 14 Claims, 9 Drawing Sheets
US. Patent Aug. 1, 1995 Sheet 1 0f 9 5,438,086

Pass
1%
2Q
38

FIG-l
Bose

,w§\ \vnVA,r/pVW
PHOSPHITE
&rl/ymun Pass
IE
28
3E

Base 111
PHOSPHITE
V/ , /
l
I
/
l
r
1/

/
I
I
US. Patent Aug. 1, 1995 Sheet 2 0f 9 5,438,086

a Control
800.“ 0 Diphosphi're
75
$5,, 700 —
E
v 600-

‘3c 500-
c:
E 400-
300 - i - i a a a
0 IO 20 3O 4O 50
TIME (min)

cxControl
o Diphosphite
x 70-
L5 ' 60-
Z
50-
312 4O—~
; 30"
3 2o—
.1
UJ [0-
>
O i i I I l
0 IO 20 3O 4O 50
TIME (min)
FIG-4
US. Patent Aug. 1, 1995 Sheet 3 of 9 5,438,086

a Control
A o Diphosphite V
g |200~——
c.”
5 moo-
DJ
3
g 1000-
O
F
900———

800 % i : : i a
0 IO 20 30
TIME (min)
F l G.- 5

1:: Control
0 Diphosphia‘e V
53
z
" 60-

3 50-
%g 40’“
.J 30-
d>.. 20'“
IO : : z : : :
0 IO 20 3O
TiME (min)
FIG-6
U.S. Patent Aug. 1, 1995 Sheet 4 of 9 5,438,086

AROE -
_
-

09
US. Patent Aug. 1, 1995 Sheet 5 0f 9 5,438,086

illflllllllllllllllllllfilllllllilllli
I20 H9 H8 H7 H6 _ H5 H4

ppm

FIG-7B
US. Patent Aug. 1, 1995 Sheet 6 of 9 5,438,086

‘JAIL

FlG.-8A
US. Patent Aug. 1, 1995 Sheet 7 0f 9 5,438,086

llllll‘llllllllliIlllllllliIIITIIXIllllllllllllllllliilllll!Ill
I20 H9 H8 H7 ' H6 H5

ppm

FIG-8B
 5,438,086
1 2
coloration, crosslinking, and deterioration of other pol
HYDROLYTICALLY STABLE ymer properties will occur.
PENTAERYTHRITOL DIPHOSPHITES When a free radical is formed, a chain reaction begins
that initiates Spolymeric oxidation. Subsequent reaction
This application is a continuation-in-part of applica 5 of the radical with an oxygen molecule yields a peroxy
tion Ser. No. PCT 93/00499, ?led Jan. 20, 1993 and U.S. radical, which then reacts with an available hydrogen
Ser. No. 08/108,658, ?led Aug. 30, 1993, now U.S. Pat. atom to form an unstable hydroperoxide and another
No. 5,364,895. free radical. In the absence of an antioxidant, these
reactions become self-propagating, and lead to polymer
TECHNICAL FIELD degradation.
The invention described herein pertains generally to There are two basic types of antioxidants, primary
a new class of phosphites, i.e., a bis(aralkylphenyl)pen and secondary. Primary antioxidants intercept and sta
taerythritol diphosphites with improved hydrolytic bilize free radicals by donating active hydrogen atoms.
stability, and their ability to be used as a stabilizer for Hindered phenols and aromatic amines represent the
several polymers, e. g., polypropylene, polyesters, poly 15 two main types of primary antioxidants. Secondary
carbonates, polyamides, polyurethanes, polysulfones, antioxidants prevent formation of additional free radi
polyimides, polyphenylene ethers, styrenic polymers, cals by decomposing the unstable hydroperoxides into a
acrylic polymers, polyacetals, halide-containing poly stable product. Phosphites and thioesters are secondary
mers and copolymers therof. antioxidants that function by decomposing hydroperox
BACKGROUND OF THE INVENTION
20 ides, thus preventing free-radical formation. Secondary
antioxidants are often used along with primary antioxi~
Plastics are used in a myriad of widely diverse appli dants, but can be used alone, especially if they contain a
cations, in automobile parts, in components for houses hindered phenolic group within their structure. To
and buildings, and in packaging from food to electronic gether they decrease the discoloration of the polymer
parts. Plastics would not be able to perform such di 25 and may also regenerate the primary antioxidant.
verse functions without the assistance of a very broad There are several commercially available phosphites
range of plastics additives. Without them, some plastics that are used to stabilize polymer materials against color
would degrade during processing and, over time, the degradation and melt flow degradation. One product
polymers would lose impact strength, discolor, and which has been found to be especially useful is a bis(2,4
become statically charged, to list just a few problems. di-t-butylphenyl)pentaerythritol diphosphite as shown
Additives not only overcome these and other limita by formula (I) described in U.S. Pat. No. 4,305,866 to
tions, but also can impart improved performance prop York, with an initial acid value of ~1.1.

t-Bu

erties to the ?nal product. Another product which has been mentioned in the liter
Formulating with plastics additives has always been a ature is bis(2-t-butyl-4-{a,a’-dimethylbenzyl})pentaery
tricky business. Incorporating additives into a polymer thritol diphosphite as shown by formula (II), described
requires a ?ne balance between the properties of the in U.S. Pat. No. 4,983,657 to Humplik.

CH 0 0 CH (11)
I 3 / \ I 3

I \ / |
CH3 0 0 CH3
t-Bu t-Bu

polymer and the additive. Formulating a plastic for

enhanced ultraviolet light resistance, for example, can
have an impact on the polymer’s color stability and 55
retention of its functional characteristics. Formulators
need to choose additives carefully, so that the additive
not only possesses a speci?c functionality, but that it
also minimizes the effect on other additives and the Both phosphites of formulas (I) and (II) have problems
formulated plastic. in that they are hygroscopic, and therefore, are not
Antioxidants are but one class of additives applicable hydrolytically stable. On exposure to moisture for a
in polyolefm and other polymer resins. These additives period of time, they have a tendency to lump and be
retard the oxidative degradation of a plastic. Degrada come a sticky mass.
tion is initiated when free radicals, (highly reactive Additionally, symmetrical triarylphosphites (e.g.,
species with an unpaired electron), are created in the 65 tris-(2,4-di-t-buty1phenyl)phosphite) stabilization sys
polymer by heat, ultraviolet radiation, mechanical tems have been described for polyole?ns in U.S. Pat.
shear, or metallic impurities. Without the protection of No. 4,187,212 to Zinke et al., as shown for example in
antioxidants, loss of molecular weight, brittleness, dis formula (III)
 5,438,086
4
possible thereby indicating that the additive has limited
t-Bu t-Bu t-Bu (In)
the amount of degradation of the polymer under pro
cessing conditions.
It is yet another object of this invention to maintain
the melt-?ow index of the polymer thereby indicating
that the additive has limited the amount of degradation
of the polymer under processing conditions.
It is a further object of this invention to provide a
method for synthesizing a bis(aralkylphenyl)pentaery
thritol diphosphite in improved yield.
It is yet a further object of this invention to demon
strate that a bis(aralkylphenyl)pentaerythritol di
t-Bu phosphite can be used in combination with a class of
hindered phenols and UV. stabilizers to maintain both
While this phosphite does possess good hydrolytic 15 color and minimize melt-degradation of the polymer in
stability, it is not as effective as desired for color stabil a synergistic manner.
ity and melt-?ow stabilization. Pentaerythritol di These and other objects of this invention will be
phosphites such as shown in formulas (I) and (II) are evident when viewed in light of the detailed description
more effective in maintaining color stability. and appended claims.
Additionally, phosphonites are used as commercial 20 DETAILED DESCRIPTION OF THE
resin additives as shown by generic formula (VI). DRAWINGS
CH3 (VI)
C'—CH3
CH3

CH3

CH3
While this phosphonite possesses good thermal and
hydrolytic stability, its oxidative stability is considered 40
as moderate, consistent with the general observation
that the oxidative stability decreases as the number of The invention may take physical form in certain parts
phosphorus-carbon bonds increases. and arrangements of parts, a preferred embodiment of
To date, there still exists a need to 5provide a phos which will be described in detail in the speci?cation and
phite product, based on pentaerythritol, which is slower 45 illustrated in the accompanying drawings which form a
to absorb moisture, thereby maintaining its effectiveness part hereof, and wherein:
for longer periods of time in humid conditions. FIG. 1 is a plot of Yellowness Index as a function of
several phosphites in linear low density polyethylene
SUMMARY OF THE INVENTION
using the following formulations (100 2parts LLPE, 250
In accordance with the present invention, there is ppm CaS+Irganox 1010, and 500 ppm phosphite at
provided more hydrolytically stable bis(aralkylphenyl) 480° F.: (A) base case—no phosphite added; (B) tris
pentaerythritol diphosphites, which are suitable as an (2,4-di-t-butylphenyl)phosphite (formula III); (C) 2,4
antioxidant additive in polyole?ns, particularly polyeth di-t-butylphenyl)pentaerythritol diphosphite (formula
ylene and polypropylene, in polycarbonates, polyesters, I); (D) Sandostab ® PEPQ phosphonate (formula VI);
particularly in polyethylene terephthalate, polyatnides, 55 and (E) bis(2,4-dicumylphenyl)pentaerythritol di
particularly in nylons, polystyrene, impact polystyrene, phosphite (formula V).
polyphenyIene ether, ABS-type graft copolymers, FIG. 2 is a plot of Melt Index vs. the phosphorus
polyurethanes, polysulfone, polyacrylates and halide based additives described previously for FIG. 1;
containing polymers. ' FIG. 3 is a plot of Torque (meter grams) vs. time
It is an object of this invention to provide a thermally (minutes) of the addition of 0.2% of the diphosphite
stable polymer additive of low volatility, which pos described as (E) in FIG. 1 to polybutylene terephthalate
sesses a high thermal decomposition temperature. (PET) in comparison to a control sample with no di
It is another object of this invention to provide a phosphite added;
polymer additive which is resistant to phosphite hydro FIG. 4 is a plot of Yellowness Index vs. time (min
lysis upon exposure to moisture for an extended period 65 utes) using the same comparatives shown for FIG. 3;
of time, thereby remaining granular and free-?owing. FIG. 5 is a plot of Torque (meter grams) vs. time
It is still another object of this invention to maintain (minutes) of the addition of 0.2% of the diphosphite
the Hunter yellowness color index number as low as described as (E) in FIG. 1 to polycarbonate;
 5,438,086
5
FIG. 6 is a plot of Yellow Index vs. time (minutes)
using the same comparatives shown for FIG. 5;
FIG. 7A is a 31P NMR spectra of the diphosphite de
scribed as (E) in FIG. 1 run in deuterated benzene at 300
MHZ;
FIG. 7B is an expanded section of the 31P NMR spec
tra shown in FIG. 7;
FIG. 8A is a —P NMR spectra of the diphosphite de
scribed as (E) in FIG. 1 run in deuterated benzene at 300
MHZ;
FIG. 8B is an expanded section of the — P NMR spec
tra shown in FIG. 8;
FIG. 9A is a Fourier Transform Infra-Red (FTIR)
plot of absorbance vs. wavenumbers (cm-1) for the
diphosphite described as (E) in FIG. 1; 15
FIG. 9B is a plot of the same information described for
FIG. 9A for the diphosphite described as (C) in FIG. 1;
and
FIG. 9C is a plot of the same information as that
previously described for FIGS. 9A and 9B for 2,4‘
dicumylphenol.
DETAILED DESCRIPTION OF THE
INVENTION are more hydrolytically stable than prior art penta
erythritol diphosphites, and therefore require less pre~
Polymer degradation is the deterioration in the physi 25
cautions to be taken in their handling, and are more
cal properties of a polymer caused by chemical reac desirable as additives.
tions involving the backbone of the polymer chain. Specifically, within the pentaerythritol-based di
Symptoms of degradation are yellowing, loss of tensile phosphite of formula (IV), R1, R2, R4, R5, R7, R8, R10
strength, loss of impact strength, changes in melt-?ow, and R11 are selected independently from the group
and poor processability. This degradation can be caused consisting of hydrogen and alkyl radicals of generic
by contamination in the polymer, residual catalyst (po formula CmI-I2m+1 wherein m ranges from 1 to 4; Rn3,
tentially causing depolymerization), temperature, and Rn?, RH9 and R,,12 are selected independently from the
light. Degradation tends to occur under the following group consisting of hydrogen, halogens and alkyl radi
conditions: polymer drying; polymer pelletizing and cals of generic formula CmI-I2m+1 wherein in ranges
compounding; polymer storage and shipment; polymer from 1 to 4, and further wherein n ranges from 0 to 3,
fabrication processing; and during recycling. and the substituent is located at a position ortho, meta or
One technique which ameliorates some of the above para to the bridging methylene radical. The halogens
problems is through the use of an additive, in particular, are preferably selected from the group consisting of
a phosphite additive. One of the problems with the chlorine and bromine and anticipated to impart some
addition of pentaerythritol phosphite stabilizers has 4-0
additional degree of tire retardancy to the polymer.
been their tendency to absorb moisture, thereby de In particular, a preferred embodiment of the inven
creasing the product’s ability to flow freely. Another tion, is a diphosphite in a spiro conformation of formula
problem has been the experience that at high tempera (V), a bis(2,4~dicumylphenyDpentaerythritol diphosph
tures (typically greater than 480° F.), some phosphites
ite,

CH 0 0 on (V)
I 3 / \ i 3

65
are not particularly effective. It has been found, that although depending upon synthetic methods and condi
pentaerythritol-based diphosphites of the invention, tions employed, a minor amount of the cage conforma
shown in genetic form as formula (IV), tion, as is shown below in formula (V ’)
 5,438,086
7 8
TABLE I
(V') TGA“) Comparison
TemErature at % of Weight Loss
5 Temp.
T Cc.) T ("0.) T (Q) T (“0.)
Percent Phosphite
C_CH3 weight loss (I) (III) (v) (II)
CH3 CH3 s 250 258 250 314
\C 10 10 275 265 275 332
20 300 282 300 343
CH3 30 315 293 318 350
40 320 297 329 354
0\ 61-120 so 327 303 336 365
CH3 P__0CH2_C_CH2O_P 80 345 318 364 375
15 (DDuPont 2000 TGA using a heating rate of 10‘ C. from room temperature to 800'
H3C—C O CHzO C. under nitrogen

As shown in Table I, the bis(2,4-dicumylphenyl)penta

erythritol diphosphite (V) exhibited good high tempera
H3C 20 ture stability and low volatility in comparison to the
C_CH3 bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite of
formula (I) and the unsubstituted symmetrical tri
phenylphosphite, tris-(2,4-di-t-butylphenyl)phosphite)
of formula (III) and similar characteristics to the bis(2-t
25 butyl-4-{a,a’-dimethylbenzyl})pentaerythritol di
can be present. Of course, it is possible to include larger phosphite of formula (II).
All phosphites will eventually react with water and
amounts of cage conformation in the ?nal product, with hydrolyze. As this reaction occurs, an acidic species is
the preparation of 10-15% cage conformation possible. produced which is titratable. In the ?rst stage of hydro
As shown in the 300 MHz 31P-NMR shown in FIGS. 30 lysis, the phosphite reacts with a molecule of water to
7-8, wherein the samples were dissolved in deuterated form an alcohol or substituted phenol and dialkyl or
benzene, the ratio can be maximized in favor of the dialkylaryl phosphite. The dialkyl or dialkylaryl phos
phite once again reacts with water to form a monoester
spiro conformation in relationship to the cage confor
and once more with water to yield the dibasic phospho
mation. In FIG. 8A, the spiro conformation represents 35 rous acid. By monitoring a phosphite for the alcohol or
99.94% while the cage is 0.07%, shown down at 95 ppm phenol and acid content, the extent of hydrolysis can be
on the spectrum. No thiaryl phosphite was detected at determined and thereby gauge the product’s ?tness for
all. In FIG. 7A, the spiro conformation represents use.

99.49% of the sample , whereas the remainder indicated 40 The acid number was determined by weighing out a
one gram phosphite sample. Approximately 75 ml of
that 0.25% of the sample was of the cage conformation
methylene chloride was neutralized with 0.02N sodium
with 0.26% thiaryl phosphite. butylate to a blue-green endpoint using about 4-6 drops
By using the synthetic procedures outlined in this of a 0.1% bromothymol blue indicator solution. The
application, high purity samples can be obtained. Using 45 neutralized methylene chloride was added to the phos
differential scanning calorimetry to plot heat ?ow vs. phite sample and dissolved. The solution was immedi~
temperature, a melting point of 232.35“ C. was shown, ately titrated with 0.02N sodium butylate to a blue
green endpoint. '
the data of which, when plotted on a Van Hofft plot,
A hydrolytic stability comparison was made between
indicated the purity to be 99.63%. the prior art products, formulas (I) and (II) in compari
Cost and time prohibit real-life testing of stabilizer son to new formula (V), by exposing the 5 g samples of
systems, therefore laboratory tests have been developed the phosphites to 85% relative humidity at about 25° C.
to simulate conditions under which degradation occurs. for various periods of time, and noting when the pow
Thermal gravimetric analysis (TGA) is a sensitive tech 55 der changed its physical characteristics to either non
powdery or became sticky and lumpy. Without being
nique used to follow the weight change of a sample as a
held to any particular theory, it is proposed that the
function of temperature, thereby providing information hydrolytical stability of formula (V) is due to the large
about the thermal stability, volatility and decomposition bulky groups adjacent to the phosphorus. This provides
temperature of the material studied. The test simulates a good deal of steric hindrance to hydrolysis.
conditions which the polymer would experience during TABLE II
manufacturing and compounding. Phosphite Hydrolysisu)
As shown in Table I, TGA scans were used to mea Hours _

sure the thermal stability of a series of phosphite stabi 0 67 163 consistency

Phosphite acid numbera) after 163 hrs
lizers shown previously by formulas (I), (II), (HI) and
(I) 0.06 0.01 21.9 sticky
(V). The percentage weight loss of the starting phos (II) 0.08 0.12 10.1 sticky
phite was determined as a function of temperature. (V) 0.67 2.36 6.13 granular &
 5,438,086
9 . 10
TABLE II-continued sure, the polymer is prepared into samples which can be
Phosphite Hydrolysis“) used for physical property, color, and viscosity testing.
Hours
A Brabender plasticorder PL2000, multipurpose instru
0 67 I63 consistency
ment was used to study the viscosity or ?ow properties
Phosphite acid numberm after 163 hrs of polymer materials under various temperatures and
free ?owing shear rates. For testing, samples were prepared by accu
(“exposure phosphites to 85% relative humidity at 25° C.
rately weighing additives to be added to the polymer
macid number (mg KOH/G) in a function of time (hours) (e. g., polypropylene). They were dry blended in a plas
tic 1000 ml beaker by shaking for approximately 5 min
As can be seen in Table II, diphosphites of formulas (II) utes.
and (V) exhibit a lower acid number for longer periods The Brabender consisted essentially of a measuring
of time, and additionally, for the case of formula (V), head with roller blades, drive control and measuring
the diphosphite remains granular and free-flowing even unit. For the series of tests Sperformed, the temperature
after exposure to extremely elevated moisture levels for was set at 200° C. and the speed was 100 rpm. The
more than 163 hours. 15 sample weight was 39 g. The length of the time of the
In a more rigorous test, involving exposure of several test was approximately 12-40 minutes. The sample to be
commercially available diphosphites, i.e., bis(2,4 evaluated was charged to the mixer head by means of a
dicumylphenyl)pentaerythritol diphosphite (formula V) loading chute ram on a 5 kg weight. The Brabender
and bis(2-t-butyl-4-{a,a’-dimethylbenzy1})Pentaery then continuously recorded torque, which is a measure
thritol diphosphite (formula II), a trisubstituted sym of viscosity at a constant temperature of 200° C. over a
metrical phosphite, i.e., tris-(2,4-di-t-butylphenyl) time period varying from 0-40 minutes. Torque and
phosphite (formula III) and one diphosphonate, i.e., temperature were continuously monitored. Torque
Sandostab ® PEP-Q, the improved performance of the gives an indication of the viscosity of the polymer. For
diphosphite of formula (II) can once again be seen. most polymers, as the polymer degrades, the viscosity
25
TABLE III decreases and the torque decreases. Immediately upon
Hydrolytic Stability conclusion of the test, the measuring head was re
at 40° C. and 100% Relative Humidity moved. Using a brass knife, a sample was quickly re
Phosphorus Additive (V) (III) (II) (V1) moved to be used for color determination from the
Initial TGA (°C.) 50% 412 351 330 384 30 mixing head and placed on a clean stainless steel plate.
weight loss The sample was measured for color determination.
TGA (°C.) weight loss 389 275 188 213 When cool, the sample was placed between two pol
after hydrolysis
Exposure Time 700 650 50 250 ished plates and inserted in a Carver press for 6 minutes
(hours) at 5 metric tons of pressure and a temperature of about
Comments free caked slushy sticky/fused
35 150° C. After pressing the plates containing the samples,
?owing they were cooled for 6 minutes, the sample removed
and the color read on a Hunter Colorimeter. The Bra
The exposure temperature effect can be seen with bender also computed the speci?c energy imparted to
reference to Table IV, wherein a TGA weight loss the sample over the period of time the evaluation was
comparison after exposure to 100% Relative Humidity carded out. The higher the speci?c energy for a given
at 40° C. is shown at a series of temperatures. The per period of time, the less the polymer degraded.
formance of several commercially available diphosph Melt indexes were measured in accordance with the
ites, i.e., bis(2,4-dicumylphenyl)pentaerythritol di requirements of Condition L of ASTM D 1238. The test
phosphite (formula V) and bis(2-t-butyl- 4-{a,a’-dime method covers measurement of the rate of exudation of
thylbenzyl})pentaerythritol diphosphite (formula II), a 45 molten resin through a die of a speci?ed length and
trisubstituted symmetrical phosphite, i.e., tris-(2,4-di-t diameter under prescribed conditions of temperature
butylphenyl)phosphite (formula HI) and one diphos and load. The results of this test give some indication of
phonate, i.e., Sandostab® PEP-Q, were once again the molecular weight of the polymer. For polypropyl
i measured. ene, as the polymer is degraded and the molecular
TABLE IV 50 weight decreases, the melt index or ?ow through the
ori?ce increases. For Condition L, the temperature is
TGA Comparison Weight Loss after Exposure to
40° C. and 100% Relative Humidity 230° C. with a load of 2.16 kg. Melt index or melt flow
Phosphorus Additive (V) (III) (II) (VI) is given in numbers of g/l0 minutes.
Color measurements were determined using a Hunter
100° C. 0.23 0.73 0.80 1.60
150° C. 0.54 6.20 13.50 10.80 55 Lab D25-PC2 Delta Processor. This processor calcu
200° C. 1.65 10.80 55.30 42.60 lates the yellowness index per ASTM D1925 and
250° C. 4.31 27.80 62.50 65.40 ASTM E3 13. Theindustrial standard for measuring
300° C. 5.68 88.60 67.90 71.80 color for polymer such as polyethylene and polypropyl
350° C. 9.52 95.20 70.70 75.00
400“ C. 57.78 95.90 74.70 79.30 ene is the yellowness index. Visually, yellowness can be
Exposure Time (hrs) 700 650 50 250 associated with scorching, soiling and general product
Comments free caked slushy sticky/fused degradation by light, chemical exposure or processing
?owing variables. Yellowness Index, ASTM D1925 is used to
measure these types of degradation for plastics and
Tests which simulate compounding and fabrication paint industries. The test is carried out by comparing
include measurements of the polymers’ torque rheome 65 the yellowing of the sample to a white standard. The
try using a Brabender and multiple pass extrusions. lower the number YI, the whiter the sample and the less
These tests subject the molten polymer to heat and degradation. The higher the YI, the yellower the sam
shear for extended periods of time. After the test expo ple and indicates more degradation.
 5,438,086
11 12
Typically polymers such as polypropylene, polysty equally effectively to that of a known state-of-the-art
rene, polyethylene terephthalates (PET), polyalklylene products, formulas (I) and (HI), and signi?cantly better
terephthalates, and polycarbonates will tend to break than formula (lID in discoloration.
down or chain scission as they are processed at higher The improvement resides therefore, in the ability to
temperatures for a period of time. This will result in an 5 outperform phosphites, such as formula (I) and (II) in its
increase in melt index. Polyethylene on the other hand, resistance to hydrolysis, as indicated in Table (II) and
can increase in molecular weight due to crosslinking additionally, in its inherent thermal stability as indicated
and oxidation. When evaluating polyethylene by melt in Table (I).
index, and basically for all polymers, it is desirable that A multi-extrusion study was performed using phos
the melt index not change from the beginning to the phite (V), a bis-2,4-dicumylpentaerythritol diphosphite,
end. with several other phosphites using polypropylene in
In regard to the yellowness index, the more the poly accordance with the amounts shown in Table IV. The
nier is processed, the higher the yellowness index or the samples were blended and extruded at 210° C. through
darker the material becomes. Again, it is desirable that a twin-screw extruder. The extruded material was pel
there be minimal change in this index during processing. 15 letized and a small sample was retained for melt-?ow
and color resting. The remaining pellets were extruded
TABLE V
Evaluation of Phosphites in Polypropylene
Torguem gm-grams!
Polymer composition 12 min 24 min 36 min Hunter YI yellowness color index
base?) 875 550 375 40.8
base + (1)0) 1075 720 395 17.5
base + (me) 1025 700 375 17.6
base + 00(2) 1075 725 375 15.5
base + (11mm 1000 685 375 44.3
(1) base formulation (a) 100 parts polypropylene, Profax TM 6501 produced by
Himont, an isotactic homopolymer with a melt-index
of 4, a density of 0.9 g/crn , a tensile strength of 5,000
psi, and elongation at yield of 12%.
(b) 0.10 parts Irganox 1076 (octadecyl 3-(3',5’-di-t
butyl-4'-hydroxyphenyl)propionate), formula (VII)

t-Bu

HO
t-Bu
(VII)
(2) 0.2% phosphites added to the base
(3) Brabender temperature 200° C. - 100 rpm

As shown in Table III, without the addition of any again, up to a total of ?ve extrusions.
TABLE VI
Multi-Pass Extrusion Stud
melt melt
new") new“) YI(5) YI(5)
base?) Additives 1st 5th 1st 5th
polymer Ca(2) phenol(3) phosphite pass pass pass pass
#1 PP 0.05% 0% 0% 26.9 208.3 4.6 6.7
#2 PP 0.1% 0% 7.0 12.2 4.5 6.3
#3 PP 0.1% (V) 0.05% 5.9 7.8 4.5 5.4
#4 PP 0.1% (I) 0.05% 3.9 4.8 4.0 6.1
#5 PP 0.1% (II) 0.05% 3.5 4.8 4.0 6.1
#6 PP 0.1% (III) 0.05% 6.0 54.6 4.3 5.4
#7 PP 0.1% (V) 0.05% 4.0 5.1 4.0 4.6
#8 PP 0.05% (V) 0.10% 3.9 15.0 4.1 4.4
(“polypropylene (PP) '
calcium stearate
(Dhindered phenol (I-1076 of formula (vn))
(“melt flow (grams/l0 minutes)
<5>Hunter Yellowness Color Index

phosphite additive, the torque, which is a measure of

the polymer degradation, measured at 12 min. was sig
ni?cantly lower than the torque measured for samples The data clearly shows that the phosphite of formula
to which 0.2% phosphites had been added. Addition 65 (V) does improve the stability over the base polymer.
ally, the unstabilized polypropylene exhibited signi? The amount of phosphite added is well-known by those
cant discoloration as indicated by the high yellowish skilled in the art, but in general is guided 'by cost consid
color index number. The diphosphite (V) performed erations and FDA approval. Typical amounts added
 5,438,086
13 14
however, will generally range from 0.01% to about polybutylene terephthalate (PET), a semi-crystalline
0.5%. thermoplastic polyester that can be used in a wide vari
While only one hindered phenol is shown in Table ety of high performance applications, which include
IV, there are many different phenolic compounds both interior and exterior automotive parts including
which are equally suitable for use in the invention, and 5 electronic components, industrial manufacturing parts,
well-known to those skilled in the art. A non-inclusive and household appliance handles and housings. Ap
list of examples of such suitable phenolic~based com proximately 0.2% of the diphosphite of formula (V) was
pounds would be: Bisphenol TM A (Dow Chemical added to Ultradur® B4500 HF PBT, commercially
Co., 4,4’-isopropylidene-diphenol); TEN OX# BHA available from BASF, and the Torque Rheometer data
(Eastman Chemical, butylated hydroxyanisole); displayed wherein the test was run for 40 minutes at
ETHANOX TM 330 (Ethyl Corp., 1,3,5-trimethyl 240° C. and 100 rpm.
2,4,6-tris(3,5-di-di-t-butyl-4-hydroxybenzyl)benzene); The color stability of PET was also improved with
ETHANOX TM 702 (Ethyl Corp., 4,4'-methylene the addition of the diphosphite additive as shown in
bis(2,6-di-t-butylphenol)); MIXXIM# AO-30 (Fair FIG. 4, wherein the Yellowness Index was also mea
mount Chemical Co., 1,1,3-tris(2-methyl-4-hydroxy-5-t 15 sured on samples taken from the Torque Rheometer run
butylphenyDbutane); ANULLEX# BHEB, (Hodgson above.
Chemicals Ltd., 2,6~di~t~butyl-4-ethylphenol); HOS FIG. 5 shows that the addition of 0.2% of the bis(2,4
TANOX TM 03 (Hoechst Celanese Corp., bis-[3,3-bis dicumylphenyl)pentaerythritol diphosphite of formula
(4'-hydroxy-3'-t-butyl-phenylbutanoic acid]-glycol es— (V) to Lexan l5 1 branched polycarbonate results in a
ter)); TOPANOL# CA (ICI Americas Inc., 1, l,3-tris(2 20 signi?cant improvement in melt stability as shown by
methyl-4-hydroxy-5-t-butyl-phenyl)butane); SAN the Torque Rheometer data. The test was run for 25
TONOXTM (Monsanto Co., 4,4’-thio-bis(6-t-butyl-m minutes at 300° C. and 100 rpm.
cresol)); SANTONOX# (Monsanto Co., 4,4’-thio-bis(2 Similarly, the color stability of the polycarbonate was
t-butyl-m-cresol)); SANTOWHITETM (Monsanto also improved with the addition of the diphosphite
Co., 4,4’~butylidene-bis(2-t-butyl-m-cresol)); SUS 25 additive as shown in FIG. 5 wherein the Yellowness
TANETM BHT (UOP Biological & Food Products, Index was also measured on samples taken from the
2,é-di-t-butyl-p-cresol); VANOX TM 1320 (R. T. Van Torque Rheometer run above.
derbilt Co., Inc., 2,6-di-t-butyl-4-sec-butylphenol);
CYANOX# 425 (American Cyanamid Co., 2,2 EXAMPLES
'-methylene-bis(4-ethyl-6-t-butylphenol)); CYANOX# The best mode for carrying out the invention will
1790 (American Cyanamid Co., 1,3,5-(4-t-buty1-3 now be described for the purposes of illustrating the
hydroxy-Z,6-dimethylbenzyl)- l ,3,5-triazine-2,4,6 best mode known to the applicant at the time. The ex
(lH,3H,5G)-trione); CYANOX TM 2246 (American amples are illustrative only and not meant to limit the
Cyanamid Co., 2,2'-methylene-bis(4-methyl-6-t-butyl invention, as measured by the scope and spirit of the
phenol)); IRGANOX# 245 (Ciba-Geigy Corp., 1,6 35 claims.
hexamethylene-bis(3,S-di-t-butyl-4-hydroxyhydrocin
namate)); IRGANOX# 1010 (Ciba_Geigy Corp., tetra Example #1
kis ( methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)pro Preparation of bis(2,4-dicumylphenyl)pentaerythritol
pionate ) methane); IRGANOX TM 1076 (Ciba-Geigy diphosphite of formula (V)
Corp., octadecyl-3-(3'5'—di-t-butyl-4 ’-hydroxyphenyl) A glass reactor was ?tted with an agitator, re?ux
propionate); IRGANOX# 3114 (Ciba-Geigy Corp., condenser, and a gas outlet. The reactor was charged
1,3,5-tris(3,5-di-t-butyl-4hydroxybenzyl)isocyanurate); with 150 g of 2,4-dicumylpheno1, 100 g heptane and 100
and IRGANOX# 3 125 (Ciba-Giegy Corp., 3,5-di- - g toluene and heated to 35° C. After suf?cient mixing,
butyl-4hydroxyhydrocinnamic acid triester with 1,3,5 62.6 g of PCB were added and the reaction mixture
tris(2-hydroxyethyD-s-triazine-Z,4,6-(1H,3 H,S 45 heated to 90° C. After 0.5 hours at 90°—95° C., HCl was
H)trione). still evolving. The reaction is allowed to proceed for
The information presented in FIGS. 1 and 2 repre approximately 1.25 hours at 90°—95° C., followed by
sents similar data to that described previously for poly cooling to 45° C. with the addition of 31.4 g of penta
propylene in Table VI above, with the substitution of erythritol under vigorous agitation. The reaction is
linear low density polyethylene for polypropylene. The allowed to proceed with agitation for about 3 hours at
bis(2,4-dicumylphenyl)pentaerythritol diphosphite of 50° C. A nitrogen purge was initiated over the reaction
formula (V), with a signi?cant degree of aromaticity, and 120 g of additional heptane was added to the batch
was clearly shown to be superior to with heating to 100° C. for 8 hours. The product is a
several commercially available additives, such as that milky-white suspension. After cooling, ?ltering and
of bis(2-t-butyl-4-{a,a’-dimethylbenzyl})pentaery~ 55 drying, 129 g of bis(2,4-dicumylphenyl)pentaerythritol
thritol diphosphite (formula II) wherein an aliphatic diphosphite was recovered (66% yield). The acid num
substituent is positioned ortho to the diphosphite oxy ber varied from 2 to 6. The mother liquor can be recy
gen and an aralkyl substituent is positioned para to the cled into another batch to produce additional product if
same oxygen attachment point on the benzene ring, to desired.
bis(2,4-di-t-butyIphenyDpentaerythritol diphosphite 60
(formula I) wherein an aliphatic substituent is posi Example #2
tioned both ortho and para to the diphosphite oxygen Preparation of bis(2,4-dicumylphenyl)pentaerythritol
attachment to the benzene ring, and the phosphonite diphosphite of formula (V)with added trialkanolamine
formula (VI) wherein an alkyl substituent is positioned A glass reactor was ?tted with an agitator, reflux
both ortho and para to the phosphorus attachment to 65 condenser, and a gas outlet. The reactor was charged
the benzene ring. with 150 g of 2,4-dicumylphenol, 0.22 g of triethanol
FIG. 3 shows the evaluation of the bis(2,4-dicumyl amine, 100 g heptane and 100 g toluene and heated to
phenyl)pentaerythritol diphosphite of formula (V) in 35° C. After sufficient mixing, 62.6 g of PCI3 were
 5,438,086
15 16
added and the reaction mixture heated to 90° C. After C. or less as well as 2 additional grams of sodium metal
0.5 hours at 90°—95° C., HCl was still evolving. The for the transesteri?cation reaction. The reaction tem
reaction is allowed to proceed for approximately 1.25 perature was held at 175° C. for approximately 12 hours
hours at 90°-95° C., followed by cooling to 45° C. with under nitrogen atmosphere. By-product phenol was
the addition of 31.4 g of pentaerythritol under vigorous then distilled from the reaction solution at 200°-2 10° C.
agitation. The reaction is allowed to proceed with agita under 3 to 5 mm vacuum. After cooling the reaction
tion for about 3 hours at 50° C. A nitrogen purge was temperature to 175° C., 2,500 g of xylene (dry) were
initiated over the reaction and 120 g of additional hep added and the product crystallized through the addition
tane was added to the batch with heating to 100° C. for of 2,500 g of isopropanol (dry) at 60° C. After cooling
8 hours. The product is a milky-white suspension. After the product to room temperature, the crystallized prod
cooling, ?ltering and drying, 147 g of bis(2,4-dicumyl uct was solvent washed with isopropanol several times
phenyDpentaerythritol diphosphite was recovered and dried under vacuum at 70° C. The melting point of
(75.4% yield). The acid number varied from 1 to 6, and the bis(2,4-dicumylphenyl)pentaerythritol diphosphite
generally from 1 to 3. The mother liquor can be recy of formula (V) was 230°—232° C. with an acid number of
cled into another batch to produce additional product if 15 less than 1. The product appearance was white to off
desired. white free-?owing powder, of 98% +purity by differ
The addition of a trialkanol amine increasing the ential scanning calorimetry.
yield of bis(2,4—dicumylphenyl)pentaerythritol di In this synthetic procedure, 2,4-dicumylphenol is
phosphite from 66% to more than 75% as shown by used as a solvent and can be added from 0 to 100%
reaction Schematic 1. 20 molar excess. In a preferred embodiment, the molar

Schematic l
OH
e3
(I: OH + PCl3 +
CH3 CH3 OH
/

H3C-C C-CH3

Example #3 55 excess is approximately 50%. The intermediate di

Preparation of bis(2,4-dicumylphenyl)pentaerythritol phenyl pentaerythritol diphosphite is prepared initially
diphosphite of formula (V) using sodium metal as a catalyst, but other alkali cata
Dry triphenylphosphite (2,582 g) were charged into a lysts are also expected to be useful in the reaction. The
reactor at room temperature under a nitrogen atmo reaction temperature is generally carried out between
sphere. Pentaerythritol (mono) (566 g) were added 60 175°-200° C. followed by the distillation of phenol,
while slowly stirring the solution, as was ;phenol (40 g) which is recovered. After the phenol is distilled off, the
After the addition, 1 g of sodium metal were added to batch is cooled to 175° C. and xylene added. The batch
the reactor solution, with the evolution of hydrogen is further cooled to approximately 60° C. and ispropanol
gas. The batch was slowly heated to 120 to 125° C. and added to precipitate the product which is then ?ltered
held at that temperature for 5 hours, followed by subse 65 and dried. The product, with an acid number of less
quent cooling to 100° C. By-product phenol was dis than 1, has a high spiral content, anywhere from 90%,
tilled off at 3-4 mm vacuum at 125°-130° C. 2,4» to more typically greater than 98% as determined by
Dicumylphenol (dry, 95% +purity) was added at 125° phosphorus NMR.
 5,438,086
17 18
Schematic II

(I)
P
0/ \o
+ HQ><:HO
HO HO

O
\l/Na O
/ \
O-P P-O
\ /
O 0

‘EH3
? OH
CH3 CH 3
Na H3 c- 0/

@5
In general, the synthetic procedures used to prepare
the bis(2,4-dicumylphenyl)pentaerythritol diphosphite
@
of formula (V) are shown in Schematics I and II. It is of /ABS or polyester plus some other impact modi?er
course recognized that while only one speci?c embodi— may also be used. Such polymers are available commer
ment is shown, others would be possible. For example, 45 cially or may be made by means well known in the art.
the benzene rings could contain alkyl, typically of C14 However, the diphosphosphites of the invention are
and/or halogen, typically chlorine and bromine, substit particularly useful in thermoplastic polymers, such as
uents, and still be within the spirit of the invention. polyole?ns, polycarbonates, polyesters, polyphenylene
Additionally, the reaction times, temperatures and use ethers and styrenic polymers, due to the extreme tem
of other solvents have not been maximized, the speci?c peratures at which the thermoplastic polymers are often
examples being the best known to the inventors as of the processed and/or used.
date of the application. Polymers of monoole?ns and diole?ns, for example
DISCUSSION
would include polypropylene, polyisobutylene, polybu
tene-l, polymethylpentene-l, polyisoprene or polybuta
While the present invention has been directed to just diene, as well as polymers of cycloole?ns, for instance
a few stabilized polymer compositions which are pri of cyclopentene or norbornene, polyethylene (which
marily polyole?ns, polycarbonates, polyesters, etc., optionally can be crosslinked), for example high density
there is no need to limit it to such. In fact, any of the polyethylene (HDPE), low density polyethylene
polymers known in the art, such as polyesters, polyure (LDPE) and linear low density polyethylene (LLDPE)
thanes, polyalkylene terephthalates, polysulfones, 60 may be used. Mixtures of these polymers, for example
polyimides, polyphenylene ethers, styrenic polymers, mixtures of polypropylene with polyisobutylene, poly
polycarbonates, acrylic polymers, polyamides, polyace propylene with polyethylene (for example PP/HDPE),
tals, halide containing polymers and polyole?n homo may also be used. Also useful are copolymers of mono
polymers and copolymers. Additionally included ole?ns and diole?ns with each other or with other vinyl
would be mixtures of different polymers, such as poly 65 monomers, such as, for example, ethylene/propylene,
phenylene ether/styrenic resin blends, polyvinyl LLDPE and its mixtures with LDPE, propylene/bu
chloride/ABS or other impact modi?ed polymers, such tene-l, ethylene/hexene, ethylene/ethylpentene,
as methacrylonitrile containing ABS, and polyester ethylene/heptene, ethylene/octene, propylene/butadi
 5,438,086
19 20
ene, isobutylene/isoprene, ethylene/alkyl acrylates, copolymer, vinyl chloride-vinylidene chloride copoly
ethylene/alkyl methacrylates, ethylene/vinyl acetate mer, vinyl chloride-styrene-maleic anhydride ter
(EVA) or ethylene/acrylic acid copolymers (EAA) and copolymer, vinyl chloride-styrene-acrylonitrile copoly
their salts (ionomers) and terpolymers of ethylene with mer, vinyl chloride-isoprene copolymer, vinyl chloride
propylene and a diene, such as hexadiene, dicyclopenta chlorinated propylene copolymer, vinyl chloride
diene or ethylidene-norbomene; as well as mixtures of vinylidene chloride-vinyl acetate tercopolymer, vinyl
such copolymers and their mixtures with polymers chloride-acrylic acid ester copolymers, vinyl chloride
mentioned above, for example polypropylene/ethylene maleic acid ester copolymers, vinyl chloride-methacry
propylene copolymers, LDPE/EVA, LDPE/EAA, lic acid ester copolymers, vinyl chloride-acrylonitrile
LLDPE/EVA and LLDPE/EAA. 10 copolymer and internally plasticized polyvinyl chlo~
Thermoplastic polymers may also include styrenic ride.
polymers, such as polystyrene, poly-(p-methylstyrene), Other useful thermoplastic polymers include homo
poly-(a-methylstyrene), copolymers of styrene or a polymers and copolymers of cyclic ethers, such as poly
methylstyrene with dienes or acrylic derivatives, such alkylene glycols, polyethylene oxide, polypropylene
as, for example, styrene/butadiene, styrene/acryloni oxide or copolymers thereof with bis-glycidyl ethers;
trile, styrene/alkyl methacrylate, styrene/maleic anhy polyacetals, such as polyoxymethylene and those poly
dride, styrene/budadiene/ethyl acrylate, styrene/a oxymethylene with contain ethylene oxide as a come
crylonitrile/methacrylate; mixtures of high impact nomer; polyacetals modi?ed with thermoplastic poly
strength from styrene copolymers and another polymer, urethanes, acrylates or methacrylonitrile containing
such as, for example, from a polyacrylate, a diene poly ABS; polyphenylene oxides and sul?des, and mixtures
mer or an ethylene/propylene/diene terpolymer; and of polyphenylene oxides with polystyrene or polyam
block copolymers of styrene, such as, for example, ides; polycarbonates and polyester-carbonates; polysul
styrene/butadiene/styrene, styrene/isoprene/styrene, fones, polyethersulfones and polyetherketones; and
styrene/ethylene/butylene/styrene or styrene/e polyesters which are derived from dicarboxylic acid
thylene/propylene/styrene. Styrenic polymers may 25 and diols and/or from hydroxycarboxylic acids or the
additionally or alternatively include graft copolymers corresponding lactones, such as polyethylene tere
of styrene or a-methylstyrene such as, for example, phthalate, polybutylene terephthalate, poly-1,4-dime
styrene on polybutadiene, styrene on polybutadiene-sty thyliol-cyclohexane terephthalate, poly-[2,2,4-(4
rene or polybutadiene-acrylonitrile; styrene and acrylo hydroxyphenyl)-propane]terephthalate and polyhy
nitrile (or methacrylonitrile) on polybutadiene; styrene droxybenzoates as well as block copolyetheresters de
and maleic anhydride or maleimide on polybutadiene, rived from polyethers having hydroxyl end groups.
styrene, acrylonitrile and maleic anhydride or malei Polyamides and copolyamides which are derived
mide on polybutadiene; styrene, acrylonitrile and from diamines and dicarboxylic acids and/or from
methyl methacrylate on polybutadiene, styrene and aminocarboxylic acids or the corresponding lactams,
alkyl acrylates or methacrylates on polybutadiene, sty 35 such as polyamide-4, polyamide-6, polyamide-6/6,
rene and acrylonitrile on ethylene/propylene/diene polyamide-6/l0, polyamide-6/9, polyamide-6/ 12,
terpolymers, styrene and acrylonitrile on polyacrylates polyamide-4/6, polyamide- ll, polyamide- 12, aromatic
or polymethacrylates, styrene and acrylonitrile on polyamides obtained by condensation of m-xylene, di
acrylate/butadiene copolymers, as well as mixtures of amine and adipic acid; polyamides prepared from hexa
with the styrenic copolymers indicated above. methylene diamine and isophthalic and/or terephthalic
Nitrile polymers are also useful in the polymer com acid and optionally an elastomer as modi?er, for exam
position of the invention. These include homopolymers _ ple, poly-2,4,4-trimethylhexamethylene terephthalam
and copolymers of acrylonitrile and its analogs such as ide or poly-m-phenylene isophthalamide may be useful.
methacrylonitrile, such as polyacrylonitrile, acryloni Further copolymers of the aforementioned polyamides
trile/butadiene polymers, acrylonitrile/alkyl acrylate 45 with polyolef'ms, ole?n copolymers, ionomers or chemi
polymers, acrylonitrile/alkyl methacrylate/butadiene cally bonded or grafted elastomers; or with polyethers,
polymers, acrylonitrile/butadiene/styrene (ABS), and such as for instance, with polyethylene glycol, polypro
ABS which includes methacrylonitrile. pylene glycol or polytetramethylene glycols, and poly
Polymers based on acrylic acids, such as acrylic acid, amides or copolyamides modi?ed with EPDM or ABS
methacrylic acid, methyl methacrylate acid and etha may be used.
crylic acid and esters thereof may also be used. Such The resulting stabilized polymer compositions of the
polymers include polymethylmethacrylate, and ABS invention may optionally also contain various conven
type graft copolymers wherein all or part of the tional additives, such as the following:
acrylonitrile-type monomer has been replaced by an (1) Antioxidants
acrylic acid ester or an acrylic acid amide. Polymers 55 (1.1) Alkylated monophenols, for example: 2,6-di-t
including other acrylic-type monomers, such as acro butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol,
lein, methacrolein, acrylamide and methacrylamide 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butyl
may also be used. phenol, 2,6~di-t-butyl-4-butylphenol, 2,6-di-cyclopen
Halogen-containing polymers may also be useful. tyl-4-methylphenol, 2(ct-methylcyclohexyl)-4,6-dirne
These include resins such as polychloroprene, epichlo 60 thylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri
rohydrin homopolymers and copolymers, polyvinyl cyclohexylphenol, and 2,6-di-t-butyl-4-methoxymethyl
chloride, polyvinyl bromide, polyvinyl ?uoride, polyvi phenol.
nylidene chloride, chlorinated polyethylene, chlori (1.2) Alkylated hydroquinones, for example, 2,6-di-t
nated polypropylene, ?uorinated polyvinylidene, bro butyl-4—methoxyphenol, 2,5-di-t-butyl-hydroquinone,
minated polyethylene, chlorinated rubber, vinyl chlo 65 2,S-di-t-amyl-hydroquinone, and 2,6—diphenyl-4
ride-vinylacetate copolymer, vinyl chloride-ethylene octadecyloxyphenol.
copolymer, .vinyl chloride-propylene copolymer, vinyl (1.3) Hydroxylated thiodiphenyl ethers, for example,
chloride-styrene copolymer, vinyl chloride-isobutylene 2,2’-thio-bis-(6-t-butyl-4-methylphenol), 2,2’-thio-bis-(4