Note: Descriptions are shown in the official language in which they were submitted.
Case 1999CH118 CA 02392152 2002-05-30
MIXTURES OF PHOSPHANES AND CHROMANE DERIVATIVES
The invention relates to synergistic mixtures which comprise phosphanes,
(diloligo)-
phosphanes, cyclophosphanes as component 1 and 6-hydroxychromane derivatives
as
component 2, and also to a process which uses these mixtures to stabilize
polymers with
respect to degradation initiated by heat or by mechanical stress.
When polymers are processed to give the final products they are exposed, inter
olio, to high
temperatures. This can have adverse effects on the melt viscosity and physical
properties of
the polymers, and also on the appearance of the final products produced from
them. Suitable
stabilizers or stabilizer systems are therefore required in order to minimize
oxidation, chain
breakage or discoloration.
However, many of the known stabilizers or stabilizer systems have
disadvantages, e.g.
insufficient efficacy and shortcomings with respect to other requirements,
e.g. inadequate
stability with respect to hydrolysis, tendency to develop colour, very limited
compatibility with
the polymers to be stabilized and restricted thermal stability. Due to limited
compatibility, it is
desirable to have lower concentrations of these stabilizers in the polymers,
this being
achievable by using more efficacious stabilizer systems.
An object of the present patent application is therefore to provide novel
stabilizer systems
which give better performance.
This object is achieved by way of the synergistic stabilizer mixture of the
invention, which is
an improved processing stabilizer for polymers since even when used in small
amounts it
inhibits the damaging reactions caused by heat.
The invention provides a mixture comprising
a) at least one compound from the group of compounds of the formulae (I) to
(IV)
[hereinafter termed component 1 J
i.
CA 02392152 2002-05-30
Cass 1999CH118
Replacement Sheet
2
R~
~P-R ~ (I)
R~
R~\ ~R~
/P-D P\ (II)
R' R'
Rz\ ~R~
/P P\ (III)
R, Rz
P-R~ (IV)
* f
and
b) at least one compound of the general formula (V) [hereinafter termed
component 2]
R~
HO
R ; (V)
R / O- _R
b a
Rs
where, independently of one another,
R, is C,-C24-alkyl (linear or branched), CS-C3o-cycloalkyl C ,-C3o-alkylaryl,
Cs-C24-aryl, C,-C24-heteroaryl, C6-C24-aryl or C4-Cz4-heteroaryl (mono- or
polysubstituted by the groups C,-C,8-alkyl (linear or branched)), CS-C,z-
cycloalkyl or C,-C,8-alkoxy;
Case 1999CH118 CA 02392152 2002-05-30
Replacement Sheet
3
Rz is C4-Cz4-alkyl (linear or branched), C5-C3o-cycloalkyl, C,-C3o-alkylaryl,
C6-Cz4-aryl, C4-Cz4-heteroaryl, C6-C2,-aryl or C4-CZ4-heteroaryl (mono- or
polysubstituted by the groups C,-C,8-alkyl (linear or branched)), CS-C,2-
cycloalkyl or C,-C,8-alkoxy;
R3 is hydrogen, C,-Cz4-alkyl (linear or branched), C3-C,2-cycloalkyl, C,-C2o
alkenyl (mono- or polyunsaturated, linear or branched);
R4, R5, Rs, R, are hydrogen, C,-C24-alkyl (linear or branched), C3-C,2-
cycloalkyl, C,-CZa-
alkenyl (mono- or polyunsaturated, linear or branched), carboxy groups
-COORS, succinyl groups -CH(COORB)-CHZ-COORS;
Re is hydrogen, C,-C2o-alkyl (linear or branched), C4-C,2-cycloalkyl or CZ-CZO-
polyethylene glycol groups;
D is C,-C3o-alkylene (linear or branched), Cz-C3o-alkylidene C5-C,2-cyclo-
alkylene or C6-Cz4-arylene or C4-C2,-heteroarylene, Ce-CA4-arylene or C4-
C24-heteroarylene (mono- or polysubstituted by C,-C,8-alkyl (linear or
branched)), CS-C,2-cycloalkyl or C,-C,8-alkoxy;
q is from 1 to 5;
r is from 3 to 6, the groups P-R, in the formula (IV) being a constituent of a
phosphacycle indicated by * on the bonds emanating from P.
Preference is given to mixtures in which the radicals R and the alphabetical
characters in the
formulae relating to compounds (I) to (V) have the following meanings:
R,' is C$-C2,-alkyl (linear or branched), C6-C,2-cycloalkyl, CZ-C24-alkylaryl,
C6-C24-aryl or C4-C,8-heteroaryl, Cs-CZ4-aryl or heteroaryl (mono- or
polysubstituted by the groups C,-C,2-alkyl (linear or branched)), CS-C8-
cycloalkyl or C,-C,2-alkoxy;
0 1
Case 19$9CH118 CA 02392152 2002-05-30
Replacement Sheet
4
R2' is C6-C,8-alkyl (linear or branched), C5-C,2-cycloalkyl C,-C,e-alkylaryl,
C6-Cz4-aryl, C4-C,e-heteroaryl, Cs-C24-aryl or C4-C,8-heteroaryl (mono- or
polysubstituted by the groups C,-C,z-alkyl (linear or branched)), CS-C8-
cycloalkyl or C,-C,2-alkoxy;
R3' is C,-CZO-alkyl (linear or branched), C4-Ca-cycloalkyl, C,-CZO-alkenyl
(mono-
or polyunsaturated, linear or branched);
R4', RS', R6', R,' are hydrogen, C,-C2o-alkyl (linear or branched), C4-C8-
cycloalkyl, C,-Czo-
alkenyl (mono- or polyunsaturated, linear or branched), carboxy groups,
-COOR$', succinyl groups -CH(COORB )-CHZ-COORB';
R8' is hydrogen, C,-C,2-alkyl (linear or branched), C4-C8-cycloalkyl or C4-C,s-
polyethylene glycol groups;
D' is C,-C24-alkylene (linear or branched), C2-Cz4-alkylidene, CS-C8-cyclo-
alkylene, or C6-Cz4-arylene or C,-C,e-heteroarylene, C6-C;Z4-arylene or
C4-C,e-heteroarylene (mono- or polysubstituted by C,-C,8-alkyl (linear or
branched)), CS-CB-cycloalkyl or C,-C,2-alkoxy;
q' is from 1 to 4;
r' is from 4 to 5, the groups P-R, in the formula (IV) being a constituent of
a
phosphacycle indicated by * on the bonds emanating from P.
Particular preference is given to mixtures in which the radicals R and the
alphabetic
characters in the formulae relating to compounds (I) to (V) have the following
meanings:
R," is C6-C24-aryl or C4-C,e-heteroaryl, Cs-C24-aryl or C,-C,e-heteroaryl
(mono-
or polysubstituted by the groups C,-C,2-alkyl (linear or branched)), CS-CB-
cycloalkyl or C,-C,z-alkoxy;
RZ" is Ce-C,8-alkyl (linear or branched), C5-C8-cycloalkyl, C,-C,e-alkylaryl,
Cs-C,2-aryl, C4-C,e-heteroaryl, C6-C,2-aryl or C4-C,8-heteroaryl (mono- or
polysubstituted by the groups C,-C,2-alkyl (linear or branched)), C6-C8-
cycloalkyl or C,-Ce-alkoxy;
R3" is C,-C,s-alkyl (linear or branched), CS-CB-cycloalkyl, C,-C,6-alkenyl
(mono-
or polyunsaturated, linear or branched);
Case 1999CH118 CA 02392152 2002-05-30
Replacement Sheet
Ra", R5", R6", R," are hydrogen, C,-C,6-alkyl (linear or branched), CS-C8-
cycloalkyl, C,-C,6-
alkenyl (mono- or polyunsaturated, linear or branched); -COORe",
-CH(COORB")-CH2-COORS";
R8" is hydrogen, C,-C8-alkyl (linear or branched), CS-C8-cycloalkyl or Cs-C,2-
polyethylene glycol groups;
D" is C,-C,e-alkylene (linear or branched), Cz-Cz4-alkylidene., C5-Ce-cyclo-
alkylene, or C6-C24-arylene or C4-C,e-heteroarylene, C6-Cz4-arylene or
C,,-C,e-heteroarylene (mono- or polysubstituted by C,-C,H-alkyl (linear or
branched)), CS-Ce-cycloalkyl or C,-C,2-alkoxy;
q" is from 1 to 4;
r" is from 4 to 5, the groups P-R, in the formula (IV) being a constituent of
a
phosphacycle indicated by * on the bonds emanating from P.
Particularly suitable mixtures are all of those which can be formed by
combining one or more
of the components 1 and 2 mentioned below:
~ CA 02392152 2002-05-30
Case 1999CH118
6
~ Component 1
i _
I - triphenylphosphane
I
- tris(2-methylphenyl)phosphane
- tris(4-methylphenyl)phosphane
- tris(2-methoxyphenyl)phosphane
- tris(4-methoxyphenyl)phosphane
- tetracyclohexylcyclotetraphosphane
- tetra-tent-butylcyclotetraphosphane
- tetrabiphenylylcyclotetraphosphane
- tetraphenylcyclotetraphosphane
- pentaphenylcyclopentaphosphane
- pentabiphenylylcyclopentaphosphane
tetraphenyldiphosphane
- tetrac clohex Idi hos have
Y Y P P
- bis(diphenylphosphino)methane
- 1,2-bis(diphenylphosphino)ethane
- 1,3-bis(diphenylphosphino)propane
- 1,4-bis(diphenylphosphino)butane
- 1,5-bis(diphenylphosphino)pentane
1,6-bis(diphenylphosphino)hexane
- 1,8-bis(diphenylphosphino)octane
- 1,3-bis(diphenylphosphino)-2,2-dimethylpropane
1,1,1-tris(diphenylphosphinomethyl)methane
- 1,1,1-tris(diphenylphosphinomethyl)ethane
- 1,1,1-tris(diphenylphosphinomethyl)propane
- 1,1,1-tris(diphenylphosphinomethyl)butane
- 1,1,1-tris(diphenylphosphinomethyl)-1-phenylmethane
- 1,3-bis(diphenylphosphinomethyl)-2,2-diphenylphosphinopropane
1,3-bis(diphenylphosphinomethyl)-2,2-diethylphosphinopropane
- 1,3-bis(diphenylphosphino)-2-methylpropane
,r
Case 1999CH118 CA 02392152 2002-05-30
7
Component 2
- 2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltridecyl)chroman-6-of (a-
tocopherol)
- 2,5,8-trimethyl-2-(4',8',12'-trimethyltnidecyl)chroman-6-of ((3-tocopherol)
- 2,7,8-trimethyl-2-(4',8',12'-trimethyltridecyl)chroman-6-of (y-tocopherol)
- 2,8-dimethyl-2-(4',8',12'-trimethyltridecyl)chroman-6-of (8-tocopherol)
- 3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-of
- 6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid (Trolox)
Among these mixtures, very particular preference is given to the following
mixtures of
components 1 and 2:
A) where component 1 is triphenylphosphane and component 2 is a-tocopherol;
B) where component 1 is tniphenylphosphane and component 2 is 3,4-dihydro-
2,2,5,7,8-
pentamethyl-2H-1-benzopyran-6-ol;
C) where component 1 is tris(4-methylphenyl)phosphane and component 2 is a-
toco-
phenol;
D) where component 1 is tris(4-methylphenyl)phosphane and component 2 is 3,4-
dihydro-
2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol;
E) where component 1 is tris(4-methoxyphenyl)phosphane and component 2 is a-
toco-
phenol;
F) where component 1 is tris(4-methoxyphenyl)phosphane and component 2 is 3,4-
di-
hydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol;
G) where component 1 is tris(2-methylphenyl)phosphane and component 2 is a-
toco-
phenol;
H) where component 1 is tris(2-methylphenyl)phosphane and component 2 is 3,4-
dihydro-
2, 2, 5, 7, 8-pentamethyl-2H-1-benzopyran-6-ol;
I) where component 1 is tris(2-methoxyphenyl)phosphane and component 2 is a-
toco-
phenol;
J) where component 1 is tris(2-methoxyphcnyl)phosphane and component 2 is 3,4-
di-
hydro-2, 2, 5, 7, 8-pentamethyl-2H-1-benzopyran-6-ol;
K) where component 1 is tetracyclohexylcyclotetraphosphane and component 2 is
a-tocopherol;
L) where component 1 is tetracyclohexylcyclotetraphosphane and component 2 is
3,4-di-
hydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol;
1
Case 1999CH118 CA 02392152 2002-05-30
8
M) where component 1 is bis(diphenylphosphino)methane and component 2 is a-
toco-
pherol;
N) where component 1 is bis(diphenylphosphino)methane and component 2 is 3,4-
di-
hydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol;
O) where component 1 is 1,3-bis(diphenylphosphino)propane and component 2 is
a-tocopherol;
P) where component 1 is 1,3-bis(diphenylphosphino)propane and component 2 is
3,4-di-
hydro-2, 2, 5, 7, 8-pentamethyl-2H-1-benzopyran-6-ol;
Q) where component 1 is 1,3-bis(diphenylphosphino)-2,2-dimethylpropane and
component 2 is a-tocopherol;
R) where component 1 is 1,3-bis(diphenylphosphino)-2,2-dimethylpropane and
component 2 is 3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol;
S) where component 1 is 1,1,1-tris(diphenylphosphinomethyl)ethane and
component 2 is
a-tocopherol;
T) where component 1 is 1,1,1-tris(diphenylphosphinomethyl)ethane and
component 2 is
3, 4-dihydro-2, 2, 5, 7, 8-pentamethyl-2H-1-benzopyran-6-ol;
U) where component 1 is 1,1,1-tris(diphenylphosphinomethyl)propane and
component 2 is
a-tocopherol;
V) where component 1 is 1,1,1-tris(diphenylphosphinomethyl)propane and
component 2 is
3,4-dihydro-2,2,5,7,8-pentamethyl-2H-1-benzopyran-6-ol.
Known mixtures based on commercially available stabilizers
(phosphiteslphosphonites)
cannot achieve sufficient stabilization. In contrast, it is possible to use
very small amounts of
the components of the mixtures of the invention, sometimes less than 0.01 ~/o
by weight,
based on the polymeric material. Producers and users of these stabilized
polymers can
achieve an advantage in both economic and environmental terms through these
markedly
reduced usage concentrations of stabilizers.
Depending on the requirements profile placed upon the final products and the
nature of the
polymers to be stabilized, ideal stabilization can be achieved by varying the
ratio of the two
components.
The quantitative proportions of component 1 to component 2 in the mixture of
the invention
are preferably in the range from 50:1 to 2:1, with preference from 20:1 to
1.5:1, particularly
preferably from 15:1 to 1:1.
Case 1999CH118 CA 02392152 2002-05-30
9
Each of the components 1 and 2 may be composed either of one or of two or more
compounds of the same component group.
Based on the polymeric material to be stabilized, the amounts used of the
mixtures of
components 1 and 2 are from 0.001 to 2% by weight, preferably from 0.005 to 1
% by weight,
particularly preferably from 0.0075 to 0.75% by weight.
Mixtures of components 1 and 2 may be prepared by simple mixing, by mixing in
the melt, by
dissolving or dispersing one component in the other liquid or molten
component, by mixing
two melts or by melting the materials together, where necessary, with a
subsequent cooling
step in each case. Mixtures of the invention are likewise obtained by mixing
solutions of the
components in suitable solvents and concentrating these by evaporation. The
mixtures may
be prepared either by a batch process in suitable apparatus, e.g. various
mixers or reactors,
etc., or else continuously, e.g. in extruders, continuous mixers, kneaders or
roll mills. A
suitable commercial form may then be prepared - if this further process is
necessary - by
compacting, pelletization, pressing, extrusion, or some other method.
The invention also provides a process which stabilizes polymeric materials
with respect to
thermooxidative degradation. This process encompasses the addition and
incorporation of a
stabilizing amount of the mixture of the invention in solid or molten form, in
solution
(preferably as liquid concentrate), in a mixture with other additives in
the~form of powder
blends, in extrudates or in other commercial forms, as a compounded material
(mixture of a
polymer with a mixture of the invention and other additives, e.g. acid
scavengers (e.g. metal
soaps, dihydrotalcites, etc.), or with sterically hindered phenols, in the
form of powder blends,
extrudates or other commercial forms) or else as a solid masterbatch
composition in
amounts which achieve a stabilizer concentration of from 0.001 to 2% by
weight, preferably
from 0.005 to 1% by weight, particularly preferably from 0.0075 to 0.75% by
weight, based
on the polymeric material to be stabilized.
A liquid concentrate here encompasses from 10 to 80% by weight of a mixture of
the
invention and from 90 to 20% by weight of a solvent.
A masterbatch composition here (also termed solid base-compound) encompasses
from 5 to
80% by weight, preferably from 10 to 70% by weight, particularly preferably
from 15 to 40%
by weight, of a mixture of the invention and from 95 to 20% by weight,
preferably from 90 to
30% by weight, particularly preferably from 85 to 60% by weight, of a
polymeric material
Case 1999CH118 CA 02392152 2002-05-30
which is identical or compatible with the polymeric material to be stabilized.
The weights of
the mixture of the invention present in a corresponding compounded material
are the same
as those in a masterbatch composition, but there is a reduction in the weight
of the polymeric
material corresponding to the amount of the other additives.
All of the components of the mixture of the invention may be prepared from
known
compounds using known methods.
The mixtures of the invention made from components 1 and 2 may be used as
processing
stabilizers for polymeric materials, preferably for
polymers of mono- and diolefins, e.g. polypropylene, polyisobutylene, poly-1-
butene,
poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and also polymers of
cycloolefins, e.g. of cyclopentene or norbornene; also polyethylene (where
appropriate
crosslinked), e.g. high-density polyethylene (HDPE), low-density polyethylene
(LDPE),
linear low-density polyethylene (LLDPE), branched low-density polyethylene
(VLDPE).
Polyolefins, i.e. polymers of monoolefins, in particular polyethylene and
polypropylene,
may be prepared by various processes, in particular using the following
methods:
a) free-radical polymerization (normally under high pressure and at elevated
temperature)
b) catalytic polymerization using a catalyst that normally contains one or
more
metals of group IVb, Vb, Vlb or VIII of the Periodic Table. These metals
usually
have one or more ligands, such as oxides, halides, alcoholates., esters,
ethers,
amines, alkyls, alkenyls and/or aryls that may be either rr- or Q-coordinated.
These metal complexes may be in the free form or fixed on substrates, for
example on activated magnesium chloride, titanium chloride, alumina or silicon
oxide. These catalysts may be soluble or insoluble in the polymerization
medium.
The catalysts can be active as such in the polymerization or further
activators
may be used, for example metal alkyls, metal hydrides, metal alkyl halides,
metal
alkyl oxides or metal alkyloxanes, the metals being elements of groups la, Ila
and/or Illa of the Periodic Table. The activators may be modified, for
example,
with further ester, ether, amine or silyl ether groups. These catalyst systems
are
usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),
metallocene or single site catalysts (SSC).
Case 1999CH118
CA 02392152 2002-05-30
11
2. Mixtures of the polymers mentioned under 1 ), e.g. mixtures of
polypropylene with
polyisobutylene, polypropylene with polyethylene (e.g. PP/HDPE, PP/LDPE,
PPILLDPE) and mixtures of various grades of polyethylene (e.g. LDF'EIHDPE).
3. Copolymers of monoolefins and diolefins with each other ar with other vinyl
monomers,
for example ethylene-propylene copolymers, linear low-density polyethylene
(LLDPE)
and mixtures thereof with low-density polyethylene (LDPE), propylene-but-1-ene
copolymers, propylene-isobutylene copolymers, ethylene-but-1-ene copolymers,
ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-
heptene
copolymers, ethylene-octene copolymers, propylene-butadiene copolymers,
isobutylene and isoprene copolymers, ethylene-alkyl acrylate copolymers,
etliylene-
alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their
copolymers
with carbon monoxide, or ethylene-acrylic acid copolymers and their salts
(ionomers)
as well as terpolymers of ethylene with propylene and a diene such as
hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers
with one
another and with polymers mentioned under 1 ), for example polypropylene-
ethylene-
propylene copolymers, LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-
acrylic acid copolymers, LLDPE-ethylene-vinyl acetate copolymers, l_LDPE-
ethylene-
acrylic acid copolymers and alternating or random polyalkylene-carbon monoxide
copolymers and mixtures thereof with other polymers, for example palyamides.
4. Hydrocarbon resins (for example CS-C9) including hydrogenated modifications
thereof
(e.g. tackifier resins) and mixtures of polyalkylenes and starch.
5. Polystyrene, polyp-methylstyrene), poly(b'-methylstyrene).
6. Copolymers of styrene or d-methylstyrene with dienes or acrylic
derivatives, for
example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate,
styrene-
butadiene-alkyl acrylate, styrene-butadiene-alkyl methacrylate, styrene-
malefic
anhydride, styrene-acrylonitrile-methyl acrylate; mixtures of high impact
strength of
styrene copolymers and another polymer, for example a polyacrylate, a diene
polymer
or an ethylene-propylene-diene terpolymer; and black copolymers of styrene,
such as
styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-
styrene or styrene-ethylenelpropylene-styrene.
7. Graft copolymers of styrene or t~-methylstyrene, for example styrene on
polybutadiene,
styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers,
styrene
and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and
Case 1999CH118 CA 02392152 2002-05-30
12
methyl methacrylate on polybutadiene; styrene and malefic anhydride on
polybutadiene;
styrene, acrylonitrile and malefic anhydride or maleimide on polybutadiene;
styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or alkyl methacrylates
on
polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene
terpolymers,
styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates,
styrene and
acrylonitrile on acrylate-butadiene copolymers, as well as mixtures thereof
with the
copolymers mentioned under 6), for example the copolymer mixtures known as
ABS,
MBS, ASA or AES polymers.
8. Halogen-containing polymers, such as polychloroprene, chlorinated rubber,
chlorinated
or sulphochlorinated polyethylene, copolymers of ethylene and chlorinated
ethylene,
epichlorohydrin homo- and copolymers, especially polymers of halogen-
containing vinyl
compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride,
polyvinylidene fluoride; as well as copolymers thereof such as vinyl chloride-
vinylidene
chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
9. Polymers derived from b',3-unsaturated acids and derivatives thereof, such
as
polyacrylates and polymethacrylates, polyacrylonitriles, polyacrylamides and
polymethyl methacrylates impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with
other
unsaturated monomers, for example acrylonitrile-butadiene copolymers,
acrylonitrile-
alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers,
acrylonitrile-
vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene
terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl
derivatives or
acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl
stearate,
polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate
or polyallyl
melamine; as well as their copolymers with olefins mentioned in section 1.
12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene
glycols,
polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl
ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which
contain
comonomers, for example ethylene oxide; polyacetals modified with
thermoplastic
polyurethanes, acrylates or MBS.
h
CA 02392152 2002-05-30
Case 1999CH118
13
14. Polyphenylene oxides and sulphides, and mixtures thereof with styrene
polymers or
polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and
polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on
the
other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids
andlor
from aminocarboxylic acids or the corresponding lactams, such as polyamide 4,
6, 616,
6/10, 6/9, 6112, 4/6, 12112, 11 and 12, aromatic polyamides starting from m-
xylene,
diamine and adipic acid; polyamides prepared from hexamethylenediamine and
isophthalic andlor terephthalic acid and with or without an elastomer as
modifier, for
example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene
isophthalamide, block copolymers of the aforementioned polyamides with
polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted elastomers; or
with
polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene
glycol. As well as polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and dialcohols andlor from
hydroxycarboxylic acids or the corresponding lactones, such as polyethylene
terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane
terephthalate, polyhydroxybenzoates, as well as block polyether-esters derived
from
hydroxyl-terminated polyethers; and also polyesters modified with
polycarbonates or
MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulphones, polyether sulphones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols,
urea or
melamine on the other hand, such as phenollformaldehyde resins,
urea/formaldehyde
resins and melaminelformaldehyde resins.
22. Drying and non-drying alkyd resins.
i
Case 1999CH118 CA 02392152 2002-05-30
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23. Unsaturated polyester resins derived from copolyesters of saturated and
unsaturated
dicarboxylic acids with polyhydric alcohols and vinyl compounds as
crosslinking
agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for
example from epoxy
acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylic resins crosslinked with
melamine resins, urea
resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins which derive from polyepoxides, e.g. from bis-
glycidyl ethers
or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, natural rubber, gelatin and
derivatives thereof
which have been chemically modified in a polymer-homologous manner, for
example
cellulose acetates, cellulose propionates and cellulose butyrates, or the
cellulose
ethers such as methyl cellulose; as well as rosins and derivatives.
28. Mixtures (polyblends) of the aforementioned polymers, for example PPIEPDM,
polyamidelEPDM or ABS, PVCIEVA, PVCIABS, PVC/MBS, PC/ABS, PBTP/ABS,
PCIASA, PC/PBT, PVCICPE, PVC/acrylates, POMlthermoplastic PUR,
PClthermoplastic PUR, POM/acrylate, POMIMBS, PPOIHIPS, PPOIPA 6.6 and
copolymers, PAIPE-HD, PA/PP, PA/PPO.
29. Natural and synthetic organic substances which constitute pure monomeric
compounds
or mixtures thereof, examples being mineral oils, animal or vegetable fats,
oils and
waxes, or oils, waxes and fats based on synthetic esters (e.g. phthalates,
adipates,
phosphates or trimellitates), and also blends of synthetic esters with mineral
oils in any
desired proportion by weight, as are employed, for example, as spin finishes,
and
aqueous emulsions thereof.
30. Aqueous emulsions of natural or synthetic rubbers, such as natural rubber
latex or
latices of carboxylated styrene-butadiene copolymers.
Particularly preferred polymers to be stabilized are polyolefins,
polyurethanes and
polycarbonates.
CA 02392152 2002-05-30
Case 1999CH118
These polymers may comprise other additives, e.g. antioxidants, light
stabilizers (UV
absorbers and/or HALS compounds andlor UV quenchers), metal deactivators,
peroxide
degraders, polyamide stabilizers, basic co-stabilizers, nucleating agents,
fillers, reinforcing
agents, plasticizers, lubricants, emulsifiers, pigments and dyes, optical
brighteners, flame
retardants, antistats, blowing agents, peroxides, hydroxylamines,
polyalcohols, nitrones,
colour improvers, thiosynergists, rheology additives, dispersing agents, etc.
These further additives may be added to the polymers prior to, together with
or after the
addition of the mixture of the invention. The feed here of these additives,
and also of the
mixture of the invention, may be in the form of a solid, or a solution or
melt, or else in the
form of solid or liquid mixtures or masterbatches/concentrates, using batch
operation or else
continuously.
The invention also encompasses all of the products obtainable by moulding the
abovementioned polymers which comprise a mixture of the invention and comprise
at least
one of the abovementioned other additives.
The advantageous action of the mixture of the invention is illustrated by the
examples below.
FXOMPI F 1
To prepare a polymer stabilized according to the invention,
100.00 parts of polypropylene (Eltex P HL 001 PF, Solvay)
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant AG)
0.10 part of calcium stearate and
0.04 part of 1,3-bis(diphenylphosphino)-2,2-dimethylpropane (component 1) and
0.01 part of a-tocopherol (Ronotec 201, Hoffman-La Roche) (component 2)
are mixed in a Kenwood mixer and then homogenized by non-aggressive extrusion
in a
single-screw extruder (Collin, 210°C, 80 rpm, compression ratio 1:3,
die 4 mm), and the
resultant polymer extrudate is pelletized. To study melt flow stabilization
and colour
stabilization, the stabilized polymers are extruded five times at 270°C
in a single-screw
extruder (Gottfert Extrusiometer, 50 rpm, compression ratio 1:3, die 2 mm).
After the 5th
pass the melt flow index (MFI) is determined to ASTM 1238 cond. L
(230°CI2.16 kg).
q 1
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EXAMPLE 2
Using a methodar to that of Example 1, another stabilized polymer
simil of the invention is
prepared from
100.00 parts polypropylene (Eltex P HL 001 PF, Solvay)
of
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant
AG)
0.10 part of calcium stearate and
0.04 part of 1,1,1-tris(diphenylphosphinomethyl)ethane (component
1 ) and
0.01 part of a-tocopherol (Ronotec 201, Hoffman-La Roche)
(component 2).
EXAMPLE 3
Using a methodar to that of Example 1, another stabilized polymer
simil of the invention is
prepared from
100.00 parts polypropylene (Eltex P HL 001 PF, Solvay)
of
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant
AG)
0.10 part of calcium stearate and
0.04 part of 1,1,1-tris(diphenylphosphinomethyl)propane (component
1 ) and
0.01 part of a-tocopherol (Ronotec 201, Hoffman-La Roche)
(component 2).
The following comparative mixtures are prepared:
EXAMPLE 4 (comparative mixture without component 1 )
Using a method based on Example 1, a polymer stabilized according to the prior
art is
prepared for comparative purposes from
100.00 parts of polypropylene (Eltex P HL 001 PF, Solvay)
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant AG)
0.10 part of calcium stearate and
0.05 part of a-tocopherol (Ronotec 201, Hoffman-La Roche).
n
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EXAMPLE 5 (comparative mixture without component 2)
Using a method based on Example 1, a polymer stabilized according to the prior
art is
prepared for comparative purposes from
100.00 parts of polypropylene (Eltex P HL 001 PF, Solvay)
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant AG)
0.10 part of calcium stearate and
0.05 part of 1,3-bis(diphenylphosphino)-2,2-dimethylpropane.
EXAMPLE 6 (comparative mixture without component 2)
Using a method based on Example 1, a polymer stabilized according to the prior
art is
prepared for comparative purposes from
100.00 parts of polypropylene (Eltex P HL 001 PF, Solvay)
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant AG)
0.10 part of calcium stearate and
0.05 part of 1,1,1-tris(diphenylphosphinomethyl)ethane.
EXAMPLE 7 (comparative mixture without component 2)
Using a method based on Example 1, a polymer stabilized according to the prior
art is
prepared for comparative purposes from
100.00 parts of polypropylene (Eltex P HL 001 PF, Solvay)
0.05 part of Hostanox O-10 (sterically hindered phenol, Clariant AG)
0.10 part of calcium stearate and
0.05 part of 1,1,1-tris(diphenylphosphinomethyl)propane.
The results obtained are given in the table below.
Case 1999CH118 CA 02392152 2002-05-30
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Table 1: Results of melt flow stabilization measurements on a polypropylene
stabilized
with 0.05 part of stabilizer (mixture).
Example Melt Flow Index
(230C, 2.16 kg) [g110
min]
5th pass
1 4.43
2 3.41
3 3.39
4 6.41
4.60
6 4.02
7 3. 99
The results show that when a prior art stabilizer (Ronotec 201, Example 4;
component 2)
which is in itself a relatively poor stabilizer is added to another prior art
stabilizer (Examples
5-7; component 1) the result is synergistic mixtures of the invention
(Examples 1-3) with
improved stabilization properties (corresponding to lower MFI values due to
reduced
degradation of the polypropylene chain). This is surprising, since if the
change in stabilizing
action were additive and therefore linear the activity of mixtures of
components 1 and 2
would have been expected to be poorer than that of pure component 1 (Examples
5-7).
