Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
;
- iOS1~52
1 It is generalty believed that to provide the best ther~al
2 stability to polyolefins such as polypropylène, it is necessary to
3 provide a free radical chain stopping agent such as a phenol or an
4 amine which can serve to donate a hydrogen radical to the polymeric
free radical, thus stopping the chain reaction. The phenol or amine
6 is generally substituted such that the resulting radical from the phenol
7 or the amine is relatively stable. In addition to the chain stopping
8 agents, stabilizers, such as thiodipropionates, which act to decom-
9 pose peroxides and hydroperoxides by a non-free radical mechanism,
10 are often used. The two types of stabilizers often interact syner- -
11 gistically to give an extremely effective stabili~ing system.
12 Polyolefin compositions stabilized against both oxidation
13 and u1traviolet degradation by incorporating therein effective ad-
14 d1tiYe quantities of a novel polycarbonate, which is prepared by a
noYel process.
16 The present invention is directed to new compositions of
17 matter which act as antioxidant and light stabilizers; and in parti-
i8 cular is an improvement over U. S. 3,510,507, which discloses the
19 use of polycarbonate condensation products as especially effective
stabilizers for polyolefins.
21 The present invention may be briefly described as composi-
22 tions of matter having the following structural formula:
23 R"" R "' R "' R"" -
26 Y I O ~ X ~ ~ ' t Z
27 ~' R" R" R' n
28 Where:
. ,
29 1) x is
~; 30 a) -s-, or
- 31 b) R
l 3 2 R""'
.,
: - 2 -
''' ~ '`
.:
1051452
1 Where: R and R""' are selected from hydrogen, a Cl to
2 C18 alkyl, and an aryl.
3 c) O
4 -C-
d) -C-C-; and
6 e) -C-A-C-
7 Where: A is selected from Cl to Cl6 alkylene and an
8 arylene.
9 2) R' is selected from C4 to C12 tertiary alkyls
~0 and C3 to C12 secondary alkyls. -
11 R" is hydrogen.
12 R"' is selected from hydrogen and a Cl to Cs
13 alkyl.
14 R"" is selected from hydrogen and hydrogen
and a Cl to C2 alkyl.
16 3) Y is selected from carbophenoxy,
17 and substituted carbophenoxy.
18 4) Z is selected from
19 - a) Phenoxy,
b) Substituted phenoxy and
21 c) R"" R"' R"' R"" `
22 ~ O ~ X ~ OH
23 R' R" R" R'
24 Where: R, R'j R", R"', R"", and X are the same as previously
7`.~
selected;
26 5) n has a vaIue from 1 to 10
27 The preferred composition of matter for stabili~ing
; 28~ polyolefin, such as polypropylene, are those where
,: :
29 a) X is R
3~
31 R""'
.: ~
~ - 3 -
;~ ~ .`.,
10S1452
l b) Y is O
2 <~co_
3 c) n is 4 to 8, and
4 d? R, R', R", R"', R"", R""', and Z are the same as
previously selected.
6 The compositions of matter of the present invention are as
7 good if not better than known stabilizers in imparting theroal or
8 oxidative stability; have the advantage over known stabilizers due to
g their ability to also function as light stabilizers; and ha~e numerous
advantages in important properties over known stabilizers and especially
11 over the polycarbonate stabilizers disclosed in U. S. 3,510,507 in -
12 that the ends of the polymer chains of the compositions of matter can
13 be capped, which results in a material having few or no free hydroxyl
. . .
14 g~oups attached to aromatic rings. -
The compositions of matter of the present invention are
16 unique in that they do not need to have free hydroxyl groups in order
17 to function essentially as one-to-one replacements for the ~ost often
18 used hindered phenols. A further indication of the ability of the
19~ compositions of matter to function as hindered phenols is in providing
thermal stability for polyolefins is the fact that the compositions of
21 matter interact synergistically with diesters of thiodipropionic acid
22 to provide excellent oxidative stability to polyolefins-
23 The ability to substitute the compositions of matter that do
4 ~not contain free hydroxyl groups for hindered phenols that ~o contain
free hydroxyl~groups is not only surprising; but it imparts several
26 important advantages to the compositions of matter. Color teYelopment
27~ ~in mater~als stabilized with hindered phenols or aromatic amines very
28 often isa severe problem that arises due to interaction of the free
29 ~hydroxyl group~with oxygen, acid or base, or metal ions. Usually
stabilizing effectiveness is lost due to these interactions at the same
31 time that color is developing.
32 ~The compositions of matter, since they can be made such that
4 _
-`` ~OS145;~
1 no free hydroxyl grou~ps are present, avoid these problems.
2 In some applications it is desirable to maintain a completely
3 neutral medium due to undesirable reactions that can be cata-
4 lyzed by the presence of acidic or basic additives such as
hindered p~enols or aromatic amines. The compositions of
6 matter can be made completely neutral to avoid such problems.
7 When the compositions of matter of the present in-
8 vention are added to polyolefin polymers, they are advantageous
9 over known stabilizers in that the polymers have improved
color, increased stability, and superior odor. The additives
ll of the present invention have marked decreased volatility over
12 known stabilizers for polyolefins and are, therefore, advan-
13 tageous for high temperature applications. The polyolefins
14 containing the stabilLzers of the present invention may be
" .
; 15 used in preparing films, dishes, automobile parts, etc.
16 In the stabilization of polyolefins, particularly
17 those polymerized from alpha-olefins using a Ziegler-type `~
18 polymerization catalyst, the compositions of matter according
l9 to the present invention are especially advantageous since
i
they have excellent solubility and compatability characteris-
21 tics with the polyolefins, and they are not tied up with metal
22 residues in the polyolefins. The compositions of matter des-
23 cribed herein are mostly crystalline white or colorless solids
2~ which are easily powdered giving the additional advantage of
being able to add the compositions of matter in a dry stabilizer
26 addition system.
27 The present invention may be further described as a
28 method for preparing the compositions of matter set forth
j 29 herein. The compositions of matter are obtained as condensation
! 30 products of the reaction of a bisphenol with phosgene or
31 diphenyl carbonate. The condensation products are a mixture
32 of the compositions of matter of the present invention and
~: ^ 5 -
.
lOS145Z
1 have molecular wei~hts which depend on the mole ratio of
2 starting materials, the presence ~f monofunction chain stop-
3 ping and capping materials, and the degree to which the
4 reaction is carried to completion by the removal of one of
the reaction products.
6 The desirability of producing a product havin~ no free
7 hydroxyl groups by mixture of the ends of the polycarbonate chains
8 being capped with aryloxy groups is extremely advantageous in the methods
g used for preparing the compositions of matter set forth herein.
In the reaction of bisphenols with phosgene, the ends of the
11 of the chains can be capped either by addition of a monofunctional
12 phenol to the reaction mixture after the polymerization has been com-
13 pleted, but before workup of the product or more preferably by carrying
14 out the polymerization between the bisphenol and phosgene directly
in the presence of the monofunctional phenol. In the latter case,
16 the desirability of producing a capped chain with free hydroxyl groups
17 also has the advantage of all'owing a very efficient means of controlling
18 molecular weight.
19 In the'preferred'reaction of bisphenols with diphenyl
carbonate, use of an excess of diphenyl carbonate over the bisphenol
21 insures that all chain ends are capped. In addition, however, by
22 controlling the ratio of excess diphenyl carbonate to bisphenol, the
23 molecular weight of the product is easily controlled. Improved color
.
24 relative to the compositions of matter of U. S. 3,510,507 also results
~5 from use of an excess of diphenyl carbonate because the color forming
26 side reaction of the Kolbe - Schmitt type are thereby prevented. The
27 bisphenol and diphenyl carbonate may be reacted in a molar ratio from
28 about 1:2 to about 1:1. Preferably the ratio is about 10:11.
29 The phenols which may be used in the condensation reactions
are selected from the 4,4'-butylidenebis (3-methyl-6-t-butylphenol);
31 4,4. _ Methylenebis (3-methyl-6-t-butylphenol); 4,4' - thiobis (3-methyl-
6-t-butylphenol); 4~' - methylenebis (3-methyl-6-t-butylphenol);
- 6 -
105i4~Z
1 4,4'-isopropylidenebisphenol; 4,4' is~propylidenebis (~-
2 isopropylphenol); 4,4' methylenebis (2-methyl-6-t-butyl-
3 phenol). Other 4,4'-bisphenols whic~ may be used are the
4 reaction products of substituted phenols and aldehydes of
ketones.
6 The monofunctional phenols which may be used to cap the chai~
7 ends are widely varied. Illustrative are: phenol, 2,4-di-t-butyphenol
8 and p-cresol.
g When the condensation reaction is carried out betl~een a bis-
phenol and phosgene, at least an equivalent amount of a suitable
11 weak base such as pyridine is used. This reaction may be carried out
12 in an inert solvent such as dichloromethane with an equivalent a~ount o~
13 slight excess of the weak base, or alternatively this reaction ~ay
14 be carried out using the weak base, such as pyridine, as the solvent,
in which case an excess is used.
16 When the condensation reaction is carried out bet~leen the
17 bisphenol and d;phenyl carbonate, it is preferable to use a basic
18 catalyst. Suitable catalysts are the alkali metals, sodium, potassium,
19 or lithium; tetra-n-butyl ammonium hydroxide; sodium hydroxide;
potassium t-butoxide; sodium methoxide; lithium hydride;and the like.
21 The basic catalyst is used in effective amounts from about 0.001 to
22 about 0.05 weight percent based on the total reactants employed.
23 According to one embodiment of the present invention wherein
24 diphenYl carbonate is used, a mixture of the new compositions of matter
are obtained under conditions wherein the condensation reaction is
26 driven to completion by removal of phenol. Accordingly, the conditions
27 for the condensation reaction may vary from temperatures in excess of
,: ,.0
182C. at atmospheric pressures (the boiling point of phenol) to a
29 temperature wherein the phenol or phenolic-type reaction product will
be evolved using a vacuum of about 1 to 2 mm. Hg. Since in most
31 instances the removal of the phenol or phenolic-type reaction product 7S
32 not easily separated from the starting mater;als, it is preferred to
. - 7 -
':
~051452
1 utilize te~peratures within the range of about 160 to about 200C. as
2 well as evacuating the reactor in which the condensation reaction is
3 taking place. Suitable conditions for carrying out the reaction are 2
4 about 180C. and a vacuum of about l mm. Hg.
S The mixture of the new compositions of matter obtained from
6 the condensation of a bisphenol with diphenyl carbonate is obtained
7 as a clear glass which may easily be pulverized to give a white solid
8 This solid mixture may be used as is for obtaining the excellent
9 stability the compositions of matter provide; but purification steps
may be taken to improve odor and color. The preferred method of puri-
11 fication is to slurry the powder in methanol and stir the mixture at
12 room temperature for a short time. The product can then be collected
13 by filtration to give an odorless and colorless solid.
14 The invention will be further illustrated by the following
spec~fic examples which are given by way of illustration and not as
16 limitations of the scope of the invention.
17 Example I - -~
18 2,2-bis-(4-hydroxy-3-t-butylphenyl) propane, 9,52 9. (0.028
19 mole), was dissolved in 175 ml. of pyridine and the solution was place~
in a three-necked flask equipped with a mechanical stirrer, a gas
21 inlet tube under the level of the liquid, and a condenser. Phosgenè
22 59. (0.051 mole), was slowly bubbled in over a period of 30 minutes a~
23 room temperature. The reaction mixture was then allowed to stir for
.
24 an additional 90 minutes whereupon the solution was poured into water.
An oily semisolid formed and was separated by decanting off the liquid
26 ~ayer. The oily product was dissolved in dichloromethane and the
27 resulting solution was extracted with 5% aqueous hydrochloric acid
28 and then water until a neutral wash was obtained. Dichloromethane was
29 then removed by evaporation under reduced pressure to give 10.45 g. of
a solid material. This material was ground into a powder, slurried in
31 a methanol and filtered. 4.42 g. of the product as a fine white
3~ powder, m.p. 210-214C., was collected and dried.
- 8 -
1(~51~52
The product mainly contained a mixture of noncapped polycarbonates having
the following structure:
H0- ~ -C ~ -0 - C-0 ~ C ~ OH
CH3 CH3
n ~l
.. . .
with the average de2ree of polymerization, n ~lO.
Example II
Same as Example I, except that the reaction mixture was quenched
by the addition of 50 ml. of methanol before pouring into water. The
product was a tan powder, 11.25 g., m.p. = 166-172C.
The predominant component of the product was identified as:
'' ~C--~--o-C3--0CH3
., CH3 ~ _ :
.3 _ n
with n ''' 10.
Example III
I Same as Example I, except that 2, 4-di-t-butylphenol, 1.65 g. -
$ (0.008 mole), was added to the reaction mixture before the addition of the
phosgene was begun. 11.15 g. of a tan powder was obtained, m.p. - 185 C.
The product was substantially identified as:
i.?~
C~o c~o-~
n
~ with n = 2.6.
'1, ~;
_g_
* r. hereinafter represents the tertiary alkyl group
I CH3
H C C CH
~'r: -
lOS145Z
Example IV
4,4' -Butylidenebis (3-methyl-6-t-butylphenol), 120.27 g.
(0.31 mole) was dissolved in 1000 ml. of dichloromethane. 59.75 g.
(0.75 mole) of pyridine was added and the solution was placed in a 2000 ml.
three-necked round bottomed flask equipped with a mechanical stirrer, an
inset tube for gas addition, and a condenser. 31.10 g. (0.31 mole) of
phosgene was bubbled in over a period of 4 hours. During this time the
temperature was maintained between 25 and 29 C. with an ice water bath.
After phosgene addition was complete, the solution was extracted once with
10% aqueous hydrochloric acid and four times with distilled water, the final
wash was neutral and chloride free. The solution was concentrated to
600 ml. and was dropped into methanol to give 110 g. of a slightly off-
white colored precipitation with m.p. = 155-170C. and a molecular weight
of 4120.
The product was identified predominantly as:
, CH3 CH3
,~ CH2 CH2
20HO - ~ CH ~ O ~ CH ~ -OH
~, H3 ~13 H3 I CH3
, . n~l
with n = 9.8.
Example V
Same as Example II except that 4,4' -butylidenebis (3-methyl-
~ 6-t-butylphenol), 10 7 g. (0.028 mole), was used.
7 The product was identified predominantly as:
CH3 ..
, , .
CH2
o~ ~ CH2 ~ 3 with n = 9 . 8 .
CH3 CH3 n
--10--
~,
.
, ~ - -.
1051452
Example VI
4,4' -Butylidenebis (3-methyl-6-t-butylphenol), 47.82 g.
(0.125 mole) and 2,4-di-t-butylphenol, 10.32 g. (0.050 mole) was dissolved
in 650 ml. of dry pyridine and reacted at room temperature with phosgene
~ntil a reddish color formed in the reaction mixture. The reaction mixture
was thereupon dumped into water. The gum that formed was collected by
decanting off the aqueous layer. The gum was then subjected to repeated
; triturations with distilled water until a solid powder formed. This powder
- was collected by filtration, washed an additional time with water, and dried
to give a very light brown powder having a molecular weight of 1075.
Analysis showed 79.74% carbon, 9.06% hydrogen, and 11.20% oxygen by weight.
The product was identified predominantly as:
~13
~o-ctO~ c~
with n ~ 2.6.
Example VII
4,4' -Butylidenebis (3-methyl-6-t-butylphenol), 20.20 g.
(0.053 mole), diphenyl carbonate, 17.13 g. (0.080 mole), and lithium
hydrlde, 0.001 g., were mixed together in a 500 ml. round-bottomed flask.
The flask was placed on an all-glass rotary evaporator with the flask
resting ln an oil bath. The oil bath was heated to a temperature of 145C.
whlle the reaction mixture was subjected to 15-20 torr of pressure. As
soon as the contents of the flask formed a clear melt, the vacuum was
increased and the temperature was increased until the oil bath reached
r
~ 180-190 C. with a pressure of less than 1 torr. After one hour the. : : ~ :
~ vacuum was released and the reaction flash was removed. The reaction
mixture had lost 9.05 g. in weight while the trap attached to the rotary
iO5~45Z
evaporator had gained 9.05 g. in weight~ By nmv the material collected
in the trap was 95% phenol. The material in the reaction flask solidified
upon cooling to room temperature to form a clear glass. The glass was
easily pulverized to give 28.4 g. of a pure white powder, m.p. 105-110 C.
(softening range = 58-70 C.) and molecular weight of 680.
The product was identified predominantly as:
CH3
CH2
~0~O-~ -CH--~-O-C~O- ~>
CH3 CH3 _ :
n
with n = 1.1.
Example VIII
Same as Example VII except that 15.24 g. (0.071 mole) of
diphenyl carbonate was used. 8.38 g. of phenol was collected. The product
s formed a clear glass, which when pulverized formed 27.2 g. of a white
powder, m.p. 161C. (softening range = 78-95 C.) and malecular weight of
850.
Example IX
Same as Example VII except that 14.21 g. (0.066 mole) of
diphenyl carbonate was used. 8.54 g. of phenol was collected. The product
formed a clear glass, which when pulveri~ed formed 25.9 g. of a white
powder, m.p. - 217C. (softening range = 107-127C.) and molecular weight
of 935.
~ ~ Example X
:Ss ~ ` Same as Example VII except that 13.7 g. (0.064 mole) of
~ diphenyl carbonate was used. 10.02 g. of phenol were collected. The
s ~ product formed a clear glass, which when pulverized formed 24.0 g. of a
white powder, m.p. 240 C. (softening range = 131-152C.).
~ -lla-
~9~ , ..... .
lO5i~52
Example XI
Same as Example VII except that 50.0 g. (0.23 mole) diphenyl
carbonate and 81.2 g. (0.21 mole) 4,4' -butylidenebis (3-methyl-6-t-
butylphenol) were used. Product lost 38.48 g. phenol. The clear glass
was pulverized to give a white powder, which was slurried in methanol for
one hour, then filtered and dried. The resulting product had m.p. 255 C.
(softens at 150C.) and a molecular weight of 1952.
; Example XII
Same as Example XI except that 54.8 g. (0.26 mole) of diphenyl
carbonate was used. Product lost 38.92 g. phenol. After pulverizing and
slurrying with methanol, the white powder had m.p. = 248 C. (softens at
145 C.) and molecular weight of 1650.
Examples VII to XII above show that the polymerization of the
instant invention is conducted with an excess of diphenyl carbonate.
Further polymerlzation became difficult due to the increased viscosity as
the degree of polymerization went up, which made the reaction products so
thick that phenol could not be removed with ease.
The foregoing examples illustrate the various methods and con-
ditions for preparing the compositions of matter of the present invention.
However, it is to be noted that each method must be characterized as
producing a "mixture" of the compositions of the present invention. The
'` term "mixture" is used herein to mean that the products of the foregoing
examples will contain compositions of matter of the present invention which
j~ differ only by a difference in the number of repetitive groups and thus in
a marked degree in molecular weight. The methods of preparation set forth
also produce a "mixture" wherein one composition of matter differs from
.
others in the "mixture" by the terminal group. These "mixtures" produced
~ appear to follow a probability
{ ~
-llb-
,~,,
lOS~4~;Z
1 distribution, and as shown in the examples, are subject to change
2 depending on the conditions; e.g. using an excess of phenol or condens-.rg
3 agent. The distribution in the "mixtures" is reproducible. The indi-
4 vidual compositions of matter may be separated from the "mixtures" by
known methods. The compositions of matter are effective stabilizers
6 when usedP, however, as a "mixture". The average molecular weisht of
7 the products produced by the methods of preparation are bet:,een about
8 600 and 8000 or higher. The preferred average molecular weight of the
9 compositions of matter of the present invention as stabilizers is be-
tween about 800 and 3000.
11 The compositions of matter of the present invention are
12 useful as stabilizers to retard the thermal oxidative and photochemical
13 oxidative degradation of fats, hydrocarbons, and high molecular weight
14 polyolefins. The stabilizers of the present invention are added to
the materials to be stabilized in amounts from about 0.01 to about 1.5
16 percent by weight. The compositions of matter of the present inventior~
~7 are especially effective in high molecular weight solid polyolefins
18 where there is also added a dialkyl sulfide costabilier such as exemp-
19 flied by dilaurylthiodipropionate, distearyl thiodipropionate and
diabietyl thiodipropionate. It has been found that when the compositicns
21 of matter of the present invention and dialkyl sulfides are used, that
22 there is a stabilizing synergistic effect in high molecular ~eight
23 solid polyolefins.
24 The compositions of matter of the present invention are
especially effective in retarding the photochemical degradation of
26 high molecular weight polyolefins when used in combination with
27 dialkyl sulfides. Additional stabilization towards ultraviolet may
28 be obtained by adding an organic phosphite to the above named combi-
29 nation. The organic phosphite can be selected from either a tris
(alkylated pheny7) phosphite, such as tris (nonylphenyl) phosphite,
31 or a dialkyl pentaerythritol diphosphite, such as didGdicyl pent~cry-
32 thritol diphosphite.
- 12 -
1 The compositl1ons o~ matter of the present invention ~hen
2 used as stabilizers for high molecular weight polyolefins are used in
3 amounts from about 0.01 to about 1.0 weight percent of the ~olymer ~-
4 to be stabilized. Preferably the polymers are stabilized using amount,
from about 0.05 to about 0.20 percent by weight. The dialky~ sulfides
6 are used ;n amounts from about 0.05 to about 1.0 percent by ~eight with
7 a preferred amount from about 0.1 to about 0.5 percent by weight.
8 The organic phosphites are used in amounts from about 0.01 t~ about
9 1.0 percent by weight with a preferred amount from about 0.~5 to
about 0.20 percent by weight.
11 The polyolefin polymers stabilized or treated in accordance
12 with the present invention are polymers which are produced by the well-
13 known methods. The polymers may be illustrated by those produced by
14 the high pressure, low pressure, or Ziegler-type polymerization process.
The polyolef~n polymers are exemplified by polymers of o~olefins having
16 2 to 8 carbon atoms in the molecule and may be illustrated by polyethy-
17 lene, polypropylene, ethylenepropylene copolymers, ethyleneb~tene-1
18 copolymers, ethylenepentene 1 copolymers, and the like, having molecular
19 weights in the range from about 10,000 to about 1,000,000. The polymers
.20 which are specifically illustrated for treatment in accordance ~lith
21 the present invention were produced by polymerization of the correspond-
22 in olefins employing the Ziegler-type polymerization catalyst.
23 In employing the compositions of matter of the present
24 invention, they may suitably be added to a polyolefin in a solution of
an aromatic hydrocarbon. The solution may be sprayed over the pellets
2~ or particles of the polyolefSn and the resulting mixture then extruded
"
27 through a suitable extrusion device to form a homogeneous mixture.
28 The compos;tions of matter may also be added as a dry solid ~here the
29 compositions of matter so exist. After adding the compositions of
matter of the present invention to the polymer particles, the resultir~
31 mixture may be milled or extruded or passed through other mixing
3~ devices to intimately admix the polymer particles with the solid
- 13 -
lOS1452
1 compositions of matter of the present invention to forma ho~OEeneous
2 mixture. The dialkyl sulfides and organic p~o~phites employed ~ay als.
3 be added to the polymer particles in a manner similar to that of t~e
4 addition of the compositions of matter of the present inven~ion;
5To illustrate the stabilizing efficiency of the compositions
6 of matter of the present invention, they were incorporated into
7 polypropylene. The samples were prepared by dry blending the composi-
8tions with polypropylene powder containing a small amount (0.04-0.06
9 wt. %) of the processing stabilizer BHT. The composites were then
extruded and peletized.
11To illustrate the thermal oxidative stabilizing efficiency
12 of the compositions of matter of the present invention, the co~posite
13 pellet samples were compression molded into 50 mil plaques and aged in
14 a forced air circulating Freas oven in accordance with the Asn~l
15méthod D 3012-72 for evaluating the thermal oxidative stability of
16 propylene plastics. These tests were carried out at 150 C. and the
17 days to failure of the test specimen determined. Fa~lure ~;as defined
18 as visual evidence of localized discoloration or crumbling on any
19 part of the specimen directly exposed to the air flow~
20To illustrate the stabilizing efficiency of the compositions
21 of matter towards the degradative effects of ultraviolet light, the
22 composite pellet samples were extruded into 6-mil monofila~ent and
,~ .
23 aged in an Atlas Xenon Are-Type Weatherometer in accordance with the
24ASTM method D-2565-70, procedure B. Failure of these speci~ens was
. .
7 ~ 25defined as the number of hours to degrade to 50% retention of the
.~ 26original tenacity.
~; 27The thermal oxidative stability data for the compositions of
28 matter of the present invention incorporated in polypropylene are
29 summarized in Tables I, II, and III. The data of Table I illustrates
the effectiveness of the compositions of matter of the present invention
- 31when used with a secondary stab;lizer or costabilizer, the co~bination
3~ giving a synergistic effect. The co-stabilizer used in the test ~as
~: ~
- 14 -
`` lOS1452
1 distearylthiodipropionate (DSTDP). The data further'illustrates the
2 effectiveness of the compositions in combination with DSTDP when com-
3 pared to two comnercially accepted phenolic stabilizers.
4 The data of Table II illustrates the effect of increasing the
molecular weight of the compositions of matter of the present invention.
6 Thus the oxidative stabilizer's effectiveness increases with increasing
7 molecular weight, examples VII through XI.
: 8 The data of Table III illustrate the effect of end groups on
9 the stabilizing effectives of the compositions of matter of the present
invention. Thus, the data show that the end group 2,4-di-t-butylphenol,
11 #4429 and #4427, is more effective than no end group, ~4431 and ~4164,
12 and that methanol as an end group, #4432 and #4435, is detrimental to
' 13 to the stabiliz;ng effectiveness of the composition. ' "''
; 14 The data of Table IY illustrate the excellent stability
towards photochemical 'degradation imparted by the compositions of
16 matter of the present invention to polypropylene.
, .
~ ,' '
.
, .
, ;
! ~
` :
~ ~ .
- 15 -
lOSl~SZ
a~ c~
~- ~
n ~ n oo u~
._ V ~ -- o C~l
X _ ~
o ~
V~
, . ~
:8 , ~ o o o o o o o o
~," L I O O O OO o O O O
.: W ~ Ln L L
,~ ~ ~ O O O C~
~_3
..
.,,. ,
~ ~) F
1 O , .
. J c
o o i~
N ~ $ ~ D ~ ~ Ln
7'~ L~o s l ~ v l
s l i~~ s _ ~, _
Ln ~ X ~ ~ X
L~¦ ~ ~ ~ ~ O ~
O et ~ Xo o ~) o)
': ~
,-, :
- 1 6-
10514SZ
1 'TABLE II
2 THERMAL OXIDATIVE STABILITY OF POLYPROPYLENE
3 Oxidative
4 Sample'No. Stabilizer System Weight Percent Stability, Days
4546 DSTDP, Example VII 0.25, 0.10 51
6 4547 DSTDP, Example VIII 0.25, 0.10 67
7 4548 DSTDP, Example IX 0.25, 0.10 98
8 4566 DSTDP, Example X 0.25, 0.10 118
9 4654 DSTDP, Example XI 0.25, Q.10 131
' 'TABLE III
., j ~ , . .
11THERMAL OXIDATIVE STABILITY OF POLYPROPYLENE
~ 12 Oxidative
';~Y~ . 13 Sample No. Stabilizer System Weight PercentStabil~i~ty, Days
~ 14 4431 DSTDP, Example I 0.25, 0.10 108
. ~
4432 DSTDP? Example II 0.25, 0.10 17
~ 16 4429 DSTDP, Example III 0.25, 0.10 112
-~ ~; 17 . 4164 ' DSTDP, Example IV 0.25, 0.10 93
18 4435 DSTDP, Example V 0.25, 0.10 10
19 4427 DSTDP, Example VI 0.25, 0.10 108
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SUPPLEMENTA~Y DISCLOSURE
The stabilizer composition of matter may have the
following structural formula:
~"" ~ "' R "' R/"'
Y~ ~X 4~o-C~
R' R" R" R'
Where: 1) X is selected from the group consisting of
a) -S-
b) R
-C-
R
- where: R and R""' arè selected from the
group consisting of hydrogen, a C
to C18 alkyl and an aryl.
, c) O
-C-
; d) -¢-C-; and
e) -C-A-~-
where; A is selected from the group con-
sisting of a Cl to C16 alkylene and
an arylene.
2) R', R", R"' and R"" are selected from the
group consis~ing of hydrogen and Cl-Cl8 alkyl.
3) Y ~s selected from thegroup consisting of
carbophenoxy and substituted carbophenoxy.
, 4) Z is selected from a group consisting o:
a) phenoxy
b) Substituted phenoxy, and
R"" R"' R "' R""
~ _ X ~ OH
R'/ " R' ' 19
~ 0514S2
where: R', R", R"~, R"", and X are the same as
previously selected; and
5) n has a value from 1 to 15.
Non-hindered bisphenols, i.e. wherein only primary
alkyl groups can be substituents, may be condensed and capped
to yield the desired stabilizers. In the above formula R',
R", R"' and R"" may be selected from the group consisting of
hydrogen and primary alkyl, e.g., R' and R"" may be Cl to C2
alkyl and R" and R"' may be hydrogen.
EXAMPLE XIII
0.10 mole of Santowhite Powder and 0.122 mole of di-
phenyl carbonate were mixed together in a one-liter flask.
0.1 gram of potassium-t-butoxide was also added. The flask
was ~aced in a hot oil bath at abou~ 190C.; and its pressure
was lowered to a vacuum. A trap was placed in the vacuum line
to collect phenol released from the condensation reaction as
by-product. The reaction was allowed to continue until no more
phenol was captured. The flask was then cooled to room temper-
ature; and the residue in the flask, with m.p. ~ 150-155C.
and average M.W. ~ 1260, was recovered as the desired product.
The product was identified as:
CH3
- CH2 -
O-C I D~ C{2 ~_ O-C'. J o_~)
~ CH3 CH3 n
~ : .
with ~ ~ 2.5.
EXAMPLE XIV
The preparation procedure was the same as in Example XIII
except th~t the non-hindered bisphenol of the followin~ structure:
~ 20_
iOSi4S2
CH C 3
HO ~ C 3 ~ OH
; CH3/ CH3
was employed as a reactant.
The end product was characterized as m.p. - 160-166C.
and average M.W. ~ 2100; and identified as:
o , l c~H ~3 ~ o c L o~>
CH3 CH3 CH3
with n ' 2.8
TABLE ~A
Thermal aXidative Stability of Stabilized Polypropylene
Stabilizer S~stem Wei~ht Percent Oxidative Stability Days
DSTDP, ~xample XIII 0.30 0.10 108
DSTDP, Example XIV 0.30 0.10 161
~ A wide variety of polymeric hydrocarbons may be
-~ effectively stabilized against thermal and/or W degradation by
`~ employing the novel bisphenol derivatives. Such stabilizable
, materials may include polyolefins, particularly those polymerized
from alpha-olefins using a Ziegler-type polymerization catalyst,
e.g., polypropylene and polyethylene; polyvinyl chloride;
elastomers; polyca~bonate plastics, lubricants; fuels, naphtha,
greases; waxes; petroleum resins and the like.
. ~
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21-
