U.S. patent application number 10/037543 was filed with the patent office on 2002-09-05 for functionalised polymers.
Invention is credited to Evans, Samuel, Herbst, Heinz, Hoffmann, Kurt, Pfaendner, Rudolf, Steinmann, Alfred.
Application Number | 20020123577 10/037543 |
Document ID | / |
Family ID | 8225738 |
Filed Date | 2002-09-05 |
United States Patent
Application |
20020123577 |
Kind Code |
A1 |
Pfaendner, Rudolf ; et
al. |
September 5, 2002 |
Functionalised polymers
Abstract
This invention relates to a process for stabilizing and at the
same time phase compatibilising plastics or plastic compositions by
incorporating polymeric compounds obtainable by reacting a compound
selected from the group consisting of the sterically hindered
phenols, sterically hindered amines, lactones, sulfides,
phosphites, benzotriazoles, benzophenones and
2-(2-hydroxyphenyl)-1,3,5-triazines, which compounds contain at
least one reactive group, with a compatibilisator.
Inventors: |
Pfaendner, Rudolf; (Rimbach,
DE) ; Herbst, Heinz; (Heppenheim, DE) ;
Hoffmann, Kurt; (Weitenau-Steinen, DE) ; Evans,
Samuel; (Marly, CH) ; Steinmann, Alfred;
(Praroman, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8225738 |
Appl. No.: |
10/037543 |
Filed: |
November 9, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10037543 |
Nov 9, 2001 |
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09284840 |
Apr 21, 1999 |
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6362278 |
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09284840 |
Apr 21, 1999 |
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PCT/EP97/05782 |
Oct 20, 1997 |
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Current U.S.
Class: |
525/431 ;
524/721; 524/740; 524/741; 525/903 |
Current CPC
Class: |
C08K 5/34 20130101; C08K
5/0008 20130101; Y10T 428/31913 20150401; C08K 5/005 20130101; C08F
8/00 20130101; Y10T 428/31928 20150401; C08F 8/00 20130101; C08F
20/00 20130101; C08F 8/00 20130101; C08F 22/00 20130101; C08F 8/00
20130101; C08F 10/00 20130101 |
Class at
Publication: |
525/431 ;
525/903; 524/740; 524/741; 524/721 |
International
Class: |
C08G 077/08 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 31, 1996 |
EP |
96810726.8 |
Claims
What is claimed is:
1. A process for stabilising and at the same time phase
compatibilising plastics or plastic compositions by incorporating
polymeric compounds obtainable by reacting a compound selected from
the group consisting of the sterically hindered phenols, sterically
hindered amines, lactones, sulfides, phosphites, benzotriazoles,
benzophenones and 2-(2-hydroxyphenyl)-1,3,5-triazines, which
compounds contain at least one reactive group, with a
compatibilisator.
2. A process according to claim 1, wherein the sterically hindered
phenols are compounds of formula I 58R.sub.1 and R.sub.2 are each
independently of the other hydrogen, C.sub.1-C.sub.25alkyl,
phenyl-C.sub.1-C.sub.3alkyl which is unsubstituted or substituted
once or several times at the aromatic ring by OH or/and
C.sub.1-C.sub.4alkyl, unsubstituted or
C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, or
phenyl; n is 1, 2 or 3; E is OH, SH, NHR.sub.3, SO.sub.3H, COOH,
--CH.dbd.CH.sub.2, 59m is 0 or 1; R.sub.3 is hydrogen or
C.sub.1-C.sub.9alkyl; R.sub.4 is C.sub.1-C.sub.12alkyl, or phenyl
which is unsubstituted or substituted by one or several
C.sub.1-C.sub.4-alkyl, halogen or/and C.sub.1-C.sub.18alkoxy; A if
E is OH, SH or --CH.dbd.CH.sub.2, is --C.sub.xH.sub.2x--,
--CH.sub.2--S--CH.sub.2CH.sub.2--,
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--,
--C.sub.qH.sub.2q--(CO)--N- H--C.sub.pH.sub.2p-- or
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--S--C.-
sub.qH.sub.2q--; x is a number from 0 to 8; p is a number from 2 to
8; q is a number from 0 to 3; R.sub.1 and n are as defined above;
or A if E is --NHR.sub.3, is --C.sub.xH.sub.2x-- or
--C.sub.qH.sub.2q--(CO)--NH--C.sub- .pH.sub.2p--, wherein x, p and
q have the meanings cited above; or A if E is COOH or SO.sub.3H, is
--C.sub.xH.sub.2x--, --CH.sub.2--S--CH.sub.2-- or
--CH.sub.2--S--CH.sub.2CH.sub.2--, wherein x has the meaning cited
above; or A if E is 60is a direct bond,
--C.sub.qH.sub.2q--(CO).sub.m--O- --CH.sub.2-- or
--C.sub.xH.sub.2x--S--CH.sub.2--, wherein q, m, x, R.sub.1 and
R.sub.2 are as defined above; A if E is 61is --CH.sub.2--.
3. A process acording to claim 1, wherein the sterically hindered
amines are compounds of formula II, IIa or Iib 62R.sub.8 is
hydrogen, C.sub.1-C.sub.25alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20alkoxy,
phenyl-C.sub.1-C.sub.3alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.5-C.sub.8cycloalkoxy, phenyl, naphthyl, hydroxyethyl,
CO--C.sub.1-C.sub.25alkyl, CO-phenyl, CO-naphthyl,
CO-phenyl-C.sub.1-C.sub.3alkyl, O--CO--C.sub.1-C.sub.20alkyl or
C.sub.1-C.sub.6alkyl-S--C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-O--C.s- ub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-(CO)--C.sub.1-C.sub.6alkyl, 63w is a number
from 1 to 10; Y is a single bond, C.sub.1-C.sub.25alkylene,
phenylene, biphenylene, naphthylene, --O--C.sub.1-C.sub.25alkylene,
--NR.sub.9--, --O-- or 64Z is hydrogen, --COOR.sub.9, --NH.sub.2,
--OR.sub.9, hydroxyethyl, 65R.sub.9 is hydrogen or
C.sub.1-C.sub.12alkyl; R.sub.10 has the same definition as
R.sub.8.
4. A process according to claim 1, wherein the lactones are
compounds of formula III 66R.sub.11, R.sub.12, R.sub.12a and
R.sub.13 are each independently of one another hydrogen,
C.sub.1-C.sub.25alkyl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.5-C.sub.12cycloalkyl or phenyl; and G is OH,
OCH.sub.2CH.sub.2OH, 67or --OCH.sub.2COOH.
5. A process according to claim 1, wherein the sulfides are
compounds of formula IV R.sub.15 S--R.sub.16 (IV), wherein R.sub.15
is C.sub.1-C.sub.18alkyl, benzyl, phenyl or 68and R.sub.16 is
--CH.sub.2CH.sub.2OH, 69, --CH.sub.2COOH or --CH.sub.2CH.sub.2COOH;
and R.sub.17 is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl.
6. A process according to claim 1, wherein the phosphites are
compounds of formula V 70R.sub.16a is --CH.sub.2CH.sub.2OH or
--CH.sub.2CH.sub.2COOH; and R.sub.17a is C.sub.1-C.sub.18alkyl or
unsubstituted or C.sub.1-C.sub.4alkyl-substituted phenyl.
7. A process according to claim 1, wherein the benzotriazoles,
benzophenones and 2,4,6-triaryl-1,3,5-triazines are compounds of
formula VI, VIa, VIb or VIc 71R.sub.18 is
--(CH.sub.2).sub.t--R.sub.20 72or NH.sub.2; R.sub.19 is
C.sub.1-C.sub.12alkyl, .alpha.,.alpha.-dimethylbenz- yl or a
radical 73R.sub.20 is --OH, --SH, --NHR.sub.30, --SO.sub.3H,
--COOR.sub.21, --CH.dbd.CH.sub.2, 74or
--(CO)--NH--(CH.sub.2).sub.u--NCO- ; R.sub.21 is hydrogen, 75or
--CH.sub.2--CH(OH)--CH.sub.2--O--(CO)--R.sub- .22; R.sub.22 is
C.sub.1-C.sub.4alkyl or phenyl; R.sub.23 and R.sub.24 are each
independently of the other hydrogen or C.sub.1-C.sub.4alkyl;
R.sub.25 is hydrogen, --(CH.sub.2).sub.u--OH,
76--(CH.sub.2).sub.uCOOH or --(CO)--NH--(CH.sub.2).sub.u--NCO;
R.sub.26 is hydrogen, OH or C.sub.1-C.sub.12alkoxy; R.sub.27 is
hydrogen or OH; R.sub.28 is hydrogen or 77R.sub.29 is hydrogen or
halogen; R.sub.30 is hydrogen or C.sub.1-C.sub.9alkyl; m is 0 or 1;
t is a number from 0 to 6; u is a number from 2 to 12.
8. A process according to claim 1, wherein the compatibiliser
compound is a polymer containing acid groups, acid anhydride
groups, ester groups, epoxy groups or alcohol groups or wherein the
compatibiliser compound is a copolymer or terpolymer of
polyethylene, polypropylene, vinyl acetate or styrene with acrylic
acid.
9. A process according to claim 8, wherein the compatibiliser
compound is a polymer with acrylic acid (M) function, glycidyl
methacrylate (G MA) function, methacrylic acid (MM) function,
maleic anhydride (MAH) function or vinyl alcohol (VA) function.
10. A process according to claim 8, wherein the compatibiliser
compound is a copolymer consisting of polyethylene acrylic acid
(PE-AA), polyethylene glycidyl methacrylate (PE-GMA), polyethylene
methacrylic acid (PE-MAA) or polyethylene maleic anhydride (PE-MAH)
or a terpolymer of polyethylene and vinyl acetate with acrylic acid
or a terpolymer of polyethylene and acrylates with acrylic
acid.
11. A process according to claim 8, wherein the compatibiliser
compound is a grafted polyethylene or polypropylene copolymer
selected from the group consisting of maleic anhydride grafted to
polyethylene vinyl acetate (MAH-g-PE-vinyl acetate), maleic
anhydride grafted to low density polyethylene (MAH-g-LDPE), maleic
anhydride grafted to high density polyethylene (MAH-g-HDPE), maleic
anhydride grafted to linear low density polyethylene (MAH-g-LLDPE),
acrylic acid grafted to polypropylene (AA-g-PP), glycidyl
methacrylate grafted to polypropylene (GMA-g-PP), maleic anhydride
grafted to polypropylene (MAH-g-PP), maleic anhydride grafted to
ethylene/propylene terpolymer (MAH-g-EPDM), maleic anhydride
grafted to ethylene/propylene rubber (MAH-g-EPM) and maleic
anhydride grafted to polyethylene/polypropylene copolymer
(MAH-g-PE/PP).
12. A process according to claim 8, wherein the compatibiliser
compound is a grafted styrene co- or terpolymer selected from the
group consisting of styrene/acrylonitrile grafted with maleic
anhydride (SAN-g-MAH), styrene/maleic anhydride/methyl
methacrylate, styrene/butadiene/styrene block copolymer grafted
with maleic anhydride (SBS-g-MAH),
styrene/ethylene/propylene/styrene block copolymer grafted with
maleic anhydride (SEPS-g-MAH), styrene/ethylene/butadiene/styrene
block copolymer grafted with maleic anhydride (SEPS-g-MAH) and
acrylic acid/polyethylene/polystyrene terpolymer
(AA-PE-PS-terpolymer).
13. A process according to claim 8, wherein the compatibiliser
compound is a vinyl alcohol copolymer.
14. A process according to claim 1, wherein the polymers to be
stabilised are at least two different polymers.
15. A process according to claim 1, wherein the polymers to be
stabilised are recycled material.
16. A compound obtainable by reacting sterically hindered phenols
of formula I 78R.sub.1 and R.sub.2 are each independently of the
other hydrogen, C.sub.1-C.sub.25alkyl, phenyl-C.sub.1-C.sub.3alkyl
which is unsubstituted or substituted once or several times at the
aromatic ring by OH or/and C.sub.1-C.sub.4alkyl, unsubstituted or
C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, or
phenyl; n is 1, 2 or 3; E is OH, SH, NHR.sub.3, SO.sub.3H, COOH,
--CH.dbd.CH.sub.2, 79m is 0 or 1; R.sub.3 is hydrogen or
C.sub.1-C.sub.9alkyl; R.sub.4 is C.sub.1-C.sub.12alkyl, phenyl
which is unsubstituted or substituted by one or several
C.sub.1-C.sub.4 alkyl, halogen or/and C.sub.1-C.sub.18alkoxy; A if
E is OH, SH or --CH.dbd.CH.sub.2, is --C.sub.xH.sub.2x--,
--CH.sub.2--S--CH.sub.2CH.sub.2--,
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--,
--C.sub.qH.sub.2q--(CO)--N- H--C.sub.pH.sub.2p-- or
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--S--C.-
sub.qH.sub.2q--; x is a number from 0 to 8; p is a number from 2 to
8; q is a number from 0 to 3; R.sub.1 and n are as defined above;
or A if E is --NHR.sub.3, is --C.sub.xH.sub.2x-- or
--C.sub.qH.sub.2q--(CO)--NH--C.sub- .pH.sub.2p--, wherein x, p and
q have the meanings cited above; or A if E is COOH or SO.sub.3H, is
--C.sub.xH.sub.2x--, --CH.sub.2--S--CH.sub.2-- or
--CH.sub.2--S--CH.sub.2CH.sub.2--, wherein x has the meaning cited
above; or A if E is 80is a direct bond,
--C.sub.qH.sub.2q--(CO)--O--CH.s- ub.2-- or
--C.sub.xH.sub.2x--S--CH.sub.2--, wherein q, m, x, R.sub.1 and
R.sub.2 are as defined above; A if E is 81is --CH.sub.2--; or
sterically hindered amines of formula II, IIa or IIb 82R.sub.8 is
hydrogen, C.sub.1-C.sub.25alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20alkoxy,
phenyl-C.sub.1-C.sub.3alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.5-C.sub.8cycloalkoxy, phenyl, naphthyl, hydroxyethyl,
CO--C.sub.1-C.sub.25alkyl, CO-phenyl, CO-naphthyl,
CO-phenyl-C.sub.1-C.sub.3alkyl, O--CO--C.sub.1-C.sub.20alkyl or
C.sub.1-C.sub.6alkyl-S--C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-O--C.s- ub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-(CO)--C.sub.1-C.sub.6alkyl, 83w is a number
from 1 to 10; Y is a single bond, C.sub.1-C.sub.25alkylene,
phenylene, biphenylene, naphthylene, --O--C.sub.1-C.sub.25alkylene,
--NR.sub.9--, --O-- or 84Z is hydrogen, --COOR.sub.9, --NH.sub.2,
--OR.sub.9, hydroxyethyl, 85R.sub.9 is hydrogen or
C.sub.1-C.sub.12alkyl; R.sub.10 has the same definition as R.sub.8;
or lactones of formula III 86R.sub.11, R.sub.12, R.sub.12a and
R.sub.13 are each independently of one another hydrogen,
C.sub.1-C.sub.25alkyl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.5-C.sub.12cycloalkyl or phenyl; and G is OH,
OCH.sub.2CH.sub.2OH, 87or --OCH.sub.2COOH; or sulfides of formula
IV R.sub.15--S--R.sub.16 (IV), wherein R.sub.15 is
C.sub.1-C.sub.18alkyl, benzyl, phenyl or 88and R.sub.16 is
--CH.sub.2CH.sub.2OH, 89--CH.sub.2COOH or --CH.sub.2CH.sub.2COOH;
and R.sub.17 is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl; or phosphites of formula V
90R.sub.16a is --CH.sub.2CH.sub.2OH or --CH.sub.2CH.sub.2COOH; and
R.sub.17a is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl; or benzotriazoles,
benzophenones or 2,4,6-triaryl-1,3,5-triazines of formula VI, VIa,
VIb or VIc 91R.sub.18 is --(CH.sub.2).sub.t--R.sub.20, 92or
NH.sub.2; R.sub.19 is C.sub.1-C.sub.12alkyl,
.alpha.,.alpha.-dimethylbenzyl or a radical 93R.sub.20 is --OH,
--SH, --NHR.sub.30, --SO.sub.3H, --COOR.sub.21, --CH.dbd.CH.sub.2,
94or --(CO)--NH--(CH.sub.2).sub.u--NCO; R.sub.21 is hydrogen, 95or
--CH.sub.2--CH(OH)--CH.sub.2--O--(CO)--R.sub.22; R.sub.22 is
C.sub.1-C.sub.4alkyl or phenyl; R.sub.23 and R.sub.24 are each
independently of the other hydrogen or C.sub.1-C.sub.4alkyl;
R.sub.25 is hydrogen, --(CH.sub.2).sub.u--OH,
96--(CH.sub.2).sub.uCOOH or --(CO)--NH--(CH.sub.2).sub.u--NCO;
R.sub.26 is hydrogen, OH or C.sub.1-C.sub.12alkoxy; R.sub.27 is
hydrogen or OH; R.sub.28 is hydrogen or 97R.sub.29 is hydrogen or
halogen; R.sub.30 is hydrogen or C.sub.1-C.sub.9alkyl; m is 0 or 1;
t is a number from 0 to 6; u is a number from 2 to 12; with a
compatibiliser compound.
17. Use of compounds according to claim 16 as stabilisers and at
the same time as phase compatibilisers in plastics or plastic
compositions.
Description
[0001] The present invention relates to stabilising plastics and
plastic compositions (virgin materials or recyclates, optionally
blended with virgin materials) while at the same time improving the
mechanical properties by incorporating specific
compatibilisers.
[0002] The preparation of polymer blends is an established method
for producing plastics having novel properties. As is known,
however, polymers of different structures usually cannot be blended
with each other, i.e. processing two different plastics gives a
macroscopical mixture having insufficient mechanical properties. To
improve the compatibility and therefore also the properties of the
plastic blends, so-called compatibilisers are commercially
available. These compatibilisers are polymers which prevent or
reduce the separation of two- or multi-component systems or which
improve the dispersion, thereby producing a homogeneous blend of
different plastics which has good mechanical properties.
[0003] The known compatibilisers are predominantly based on
polymers of polar and nonpolar structures which are produced by
customary polymerisation reactions.
[0004] Compatibilisers are used in virgin plastic compositions and
also, increasingly, in recyclates. In this case, the production
process, or the used plastics collection, often results in plastic
compositions the mechanical properties of which are only adequate
for new applications if compatibilisers are added to them. In
Kunststoffe 83 (1993), 10, 820-822 and in Kunststoffe 85 (1995) 4,
446-450, K. Hausmann discusses the problem of recycling
incompatible plastics such as polyethylene/polyethylene
terephthalate (PEIPET) and polyamidelpolyethylene (PA/PE). For
recycling, compatibilisers are used. In Kunststoffe 83 (1993) 5,
369-372 R. -E. Grutzner, R. Grtner and H. -G. Hock published
research on similar systems (PE/PA composite foils). R. Muhlhaupt
and J. Rosch report on phase compatibilisers for
polypropylene/polyamide (PP/PA) alloys in Kunststoffe 84 (1994) 9,
1153-1158. In Kunststoffe 83 (1993) 11, 926-929, G. Obieglo and K.
Romer also describe compatibilisers for use in plastic recycling.
In Recycle '91, 8/5-1 and Recycle '95, 6/4-3, S. Fuzessery presents
compatibilisers and polymer modifiers for virgin and recycled
thermoplastics. It is known to bind stabilisers to a polymer to
obtain a better blend in the product to be stabilised and to
prevent the stabiliser from migrating therefrom. This has been
suggested, inter alia, by M. Minagawa in Polymer Degradation and
Stability 25 (1989), 121-141 or by
[0005] H. Yamaguchi, M. Itoh, H. Ishikawa and K. Kusuda in
J.M.S.-Pure Appl. Chem., A30(4), (1993), 287-292. In Die Angewandte
Makromolekulare Chemie 158/159 (1988), 221-231, in Advances in
Polmer Science 101, pages 65-167, Springer-Verlag Berlin
Heidelberg, 1991 and in Jan Pospisil, Peter P. Klemchuck, Oxidation
Inhibition in Organic Materials, Vol.1 (1989), 193-224, Jan
Pospisil presents a survey of "functionalised" polymers, i.e.
polymers containing an effective antioxidant, antiozonant, metal
deactivator, light stabiliser or biostabiliser group. EP-A 306 729
discloses antioxidants bound to polymers, said polymers being
obtained by reacting an anhydride-functionalised polymer with a
hydrazide-functionalised antioxidant or with a copolymer consisting
of N-substituted imides of cyclic .alpha.,.beta.-unsaturated
dicarboxylic acid anhydrides (with antioxidant function) and
ethylenic or vinylic aromatic monomers.
[0006] Stabilising plastic compositions against heat and light
poses a special problem because, depending on the polarity of the
components, a nonuniform distribution of the stabiliser compounds
is obtained in the polyphase polymer system (stabiliser
partitioning). This is described, inter alia, by D. M. Kulich, M.
D. Wolkowicz and J. C. Wozny in Makromol. Chem., Macromol. Symp.
70/71, 407-418 (1993). The distribution equilibrium of the
stabilisers is additionally influenced by the compatibilisers used
which are moreover often the least stable component of the
composition. Thermal or photooxidative damage of the compatibiliser
then results in a very rapid breakdown of the entire composition
because the compatibilising component is impaired.
[0007] Accordingly, it is desirable to provide compounds which
improve the compatibility of the components in polymer blends as
well as the mechanical properties and which also ensure protection
against oxidative and photooxidative damage.
[0008] It has now been found that specific polymers with
corresponding stabiliser side groups possess these properties.
[0009] Accordingly, this invention relates to a process for
stabilising and at the same time phase compatibilising plastics or
plastic compositions by incorporating polymeric compounds
obtainable by reacting a compound selected from the group
consisting of the sterically hindered phenols, sterically hindered
amines, lactones, sulfide, phosphites, benzotriazoles,
benzophenones and 2-(2-hydroxyphenyl)-1,3,5-triazines, which
compounds contain at least one functional reactive group, with a
compatibiliser.
[0010] Suitable sterically hindered phenols which contain at least
one reactive group and which are reacted with the compatibiliser
compound are compounds of Formula I 1
[0011] R.sub.1 and R.sub.2 are each independently of the other
hydrogen, C.sub.1-C.sub.25alkyl, phenyl-C.sub.1-C.sub.3alkyl which
is unsubstituted or substituted once or several times at the
aromatic ring by OH or/and C.sub.1-C.sub.4alkyl, unsubstituted or
C.sub.1-C.sub.4alkyl-substituted C.sub.5C.sub.12cycloalkyl, or
phenyl;
[0012] n is 1, 2 or 3;
[0013] E is OH, SH, NHR.sub.3, SO.sub.3H, COOH, --CH.dbd.CH.sub.2,
2
[0014] m is 0 or 1;
[0015] R.sub.3 is hydrogen or C.sub.1-C.sub.9alkyl;
[0016] R.sub.4 is C.sub.1-C.sub.12alkyl, or phenyl which is
unsubstituted or substituted by one or several
C.sub.1-C.sub.4-alkyl, halogen or/and C.sub.1-C.sub.18alkoxy;
[0017] A if E is OH, SH or --CH.dbd.CH.sub.2, is
--C.sub.xH.sub.2x--, --CH.sub.2--S--CH.sub.2CH.sub.2--,
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.s- ub.2p--,
--C.sub.qH.sub.2q--(CO)--NH--C.sub.pH.sub.2p-- or
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--S--C.sub.qH.sub.2q--;
[0018] x is a number from 0 to 8;
[0019] p is a number from 2 to 8;
[0020] q is a number from 0 to 3;
[0021] R.sub.1 and n are as defined above; or
[0022] A if E is --NHR.sub.3, is --C.sub.xH.sub.2x-- or
--C.sub.qH.sub.2q--(CO)--NH--C.sub.pH.sub.2p--, wherein x, p and q
have the meanings cited above; or
[0023] A if E is COOH or SO.sub.3H, is --C.sub.xH.sub.2x--,
--CH.sub.2--S--CH.sub.2-- or --CH.sub.2--S--CH.sub.2CH.sub.2--,
wherein x has the meaning cited above; or
[0024] A if E is 3
[0025] is a direct bond,
--C.sub.qH.sub.2q--(CO).sub.m--O--CH.sub.2-- or
--C.sub.xH.sub.2x--S--CH.sub.2--, wherein q, m, x, R.sub.1 and
R.sub.2 are as defined above;
[0026] A if E is 4
[0027] , is --CH.sub.2--;
[0028] C.sub.1-C.sub.25alkyl is linear or branched and is typically
C.sub.1-C.sub.20-, C.sub.1-C.sub.18-, C.sub.1-C.sub.12-,
C.sub.1-C.sub.9-, C.sub.1-C.sub.6- or C.sub.1-C.sub.4alkyl. Typical
examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,
iso-butyl, tert-butyl, pentyl, 1,1-dimethylpropyl, hexyl, heptyl,
2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl,
dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl, icosyl, docosyl or pentacosyl.
[0029] C.sub.1-C.sub.9Alkyl and C.sub.1-C.sub.4alkyl have, for
example, the meanings cited above up to the corresponding number of
carbon atoms.
[0030] C.sub.2-C.sub.6Alkenyl radicals can be mono- or
polyunsaturated and are typically allyl, methallyl,
1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl
or 5-hexenyl. Allyl is preferred. R.sub.3 defined as
C.sub.2-C.sub.6alkenyl is, for example, C.sub.2-C.sub.4alkenyl.
[0031] C.sub.1-C.sub.4Alkoxy is a linear or branched radical and is
methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,
iso-butyloxy or tert-butyloxy.
[0032] Phenyl-C.sub.1-C.sub.3alkyl is typically benzyl,
phenylethyl, .alpha.-methylbenzyl or
.alpha.,.alpha.-dimethyl-benzyl.
[0033] Benzyl is preferred.
[0034] C.sub.5-C.sub.12Cycloalkyl is typically cyclopentyl,
cyclohexyl, cyclooctyl, cyclododecyl, in particular cyclopentyl and
cyclohexyl, preferably cyclohexyl. C.sub.1-C.sub.4Alkyl-substituted
C.sub.5-C.sub.12cycloalkyl is typically 1-methylcyclohexyl.
[0035] Halogen is fluoro, chloro, bromo and iodo, in particular
chloro and bromo, preferably chloro.
[0036] Mono- or polysubstituted phenyl is typically substituted one
to five times, for example one, two or three times, preferably one
or two times, at the phenyl ring.
[0037] Substituted phenyl is, for example, substituted by linear or
branched C.sub.1-C.sub.4alkyl, such as methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, s-butyl or t-butyl, or by linear or
branched C.sub.1-C.sub.4alkoxy, such as methoxy, ethoxy, n-propoxy,
i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, or by halogen,
such as fluoro, chloro, bromo or iodo.
[0038] Phenyl is preferably substituted by, in particular, methyl,
t-butyl, methoxy, and chloro.
[0039] Suitable compounds are those of formula I, wherein R.sub.1
and R.sub.2 are C.sub.1-C.sub.4alkyl.
[0040] Other compounds to be mentioned are those of formula I,
wherein R.sub.1 and R.sub.2 are in ortho-position to the phenolic
OH group.
[0041] Particularly suitable compounds are those, wherein A is
--C.sub.xH.sub.2x--, typically
6-tert-butyl-2,4-dimethyl-3-hydroxymethylp- henol,
2,6-di-tert-butyl-4-(3-hydroxypropyl)phenol or
2,6-di-tert-butyl-4-(2,2-dimethyl-3-hydroxypropyl)phenol.
[0042] x is typically a number from 0 to 6, preferably from 0 to
4.
[0043] Those compounds of formula I also mert mention, wherein A is
a group --CH.sub.2--S--CH.sub.2-- or
--CH.sub.2--S--CH.sub.2CH.sub.2--, typically
2,6-di-tert-butyl-4-(4-hydroxy-2-thiabut-1-yl)phenol or
6-tert-butyl-2,4-dimethyl-3-(4-hydroxy-2-thiabut-1-yl)phenol.
[0044] Other important compounds of formula I are those, wherein A
is --C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--, p is a number
from 2 to 5, and q is 1 to 2, such as 5
[0045] Other suitable compounds are 6
[0046] 2,6-di-tert-butyl-4-(3-aminopropyl)phenol,
2,6-di-tert-butyl-4-(2,2- -dimethyl-2-amino-ethyl)phenol or
2,4,6-trimethyl-3-aminomethylphenol.
[0047] If E is COOH, x is preferably 2 or 3.
[0048] Preferred compounds are, for example,
2,6-di-tert-butyl-4-(2-carbox- yethyl)phenol,
2-tert-butyl-6-methyl-4-(2-carboxyethyl)phenol and
2,6-di-tert-butyl-4-(3-carboxy-2-thiaprop-1-yl)phenol.
[0049] If E is 7
[0050] R.sub.4 is e.g. C.sub.1-C.sub.4alkyl, preferably methyl or
ethyl, such as 8
[0051] Particularly preferred examples of compounds of formula I
with epoxy function are 9
[0052] wherein x is as defined above.
[0053] Particularly preferred examples of compounds of formula I
with OH--, SH-- or NHR.sub.3 function are 10
[0054] wherein x is a number from 1 to 8.
[0055] The preparation of sterically hindered phenols is known to
the skilled person and is described, inter alia, in DE-A-42 13 750,
DE-A-25 12 895, EP-A463 835, U.S. Pat. No. 5,189,088, DE-A-24 14
417, U.S. Pat. No. 4,919,684, DE-A-42 42 916, DE-A-20 37 965 and in
numerous other publications.
[0056] Suitable sterically hindered amines which contain at least
one reactive group and which are reacted with the compatibiliser
compound are the compounds of formula II, IIa or IIb 11
[0057] R.sub.8 is hydrogen, C.sub.1-C.sub.25alkyl,
C.sub.2-C.sub.20alkenyl- , C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20alkoxy, phenyl-C.sub.1-C.sub.3a- lkyl,
C.sub.5C.sub.12cycloalkyl, C.sub.5-C.sub.8cycloalkoxy, phenyl,
naphthyl, hydroxyethyl, CO--C.sub.1-C.sub.25alkyl, CO-phenyl,
CO-naphthyl, CO-phenyl-C.sub.1-C.sub.3alkyl,
O--CO--C.sub.1-C.sub.12alkyl or
C.sub.1-C.sub.6alkyl-S--C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-O--- C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-(CO)--C.sub.1-C.sub.6alkyl 12
[0058] w is a number from 1 to 10;
[0059] Y is a single bond, C.sub.1-C.sub.25alkylene, phenylene,
biphenylene, naphthylene, --O--C.sub.1-C.sub.25alkylene,
--NR.sub.9--, --O-- or 13
[0060] Z is hydrogen, --COOR.sub.9, --NH.sub.2, --OR.sub.9,
hydroxyethyl, 14
[0061] R.sub.9 is hydrogen or C.sub.1-C.sub.12alkyl;
[0062] R.sub.10 has the same definition as R.sub.8.
[0063] C.sub.1-C.sub.25Alkyl, phenyl-C.sub.1-C.sub.3alkyl and
C.sub.5-C.sub.12cycloalkyl have, for example, the meanings given
above for formula I. C.sub.1-C.sub.12Alkyl also has these meanings
up to the corresponding number of carbon atoms.
[0064] C.sub.1-C.sub.25Alkylene is linear or branched, such as
methylene, ethylene, propylene, isopropylene, n-butylene,
sec-butylene, iso-butylene, tert-butylene, pentylene, hexylene,
heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene,
heptadecylene or octadecylene. Y is in particular
C.sub.1-C.sub.12alkylene, for example C.sub.1-C.sub.8alkylene,
preferably C.sub.1-C.sub.4alkylene.
[0065] Particularly preferred examples of compounds of formula II
with epoxy function are 15
[0066] wherein R.sub.9 is C.sub.1-C.sub.12alkyl.
[0067] Particularly preferred examples of compounds of formula II
with OH-- or NH.sub.2 function are 16
[0068] wherein R.sub.9 is C.sub.1-C.sub.12alkyl.
[0069] The skilled person is familiar with the preparation of
suitable sterically hindered amine compounds, which is described,
inter alia, in EP-A-634 450, EP-A-634 449, EP-A-434 608, EP-A-389
419, EP-A-0 634 399, EP-A-0 001 835 or by Luston and Vass,
Makromolekulare Chemie, Macromol. Symp. 27, 231 (1989) and other
publications.
[0070] Suitable lactones which contain at least one reactive group
and which are reacted with the compatibiliser compound are
compounds of formula III 17
[0071] R.sub.11, R.sub.12, R.sub.12, and R.sub.13 are each
independently of one another hydrogen, C.sub.1-C.sub.25alkyl,
phenyl-C.sub.1-C.sub.3alk- yl, C.sub.5-C.sub.12cycloalkyl or
phenyl; and
[0072] G is OH, 18
[0073] --OCH.sub.2CH.sub.2OH or OCH.sub.2COOH.
[0074] The meanings of C.sub.1-C.sub.25alkyl,
C.sub.1-C.sub.12alkyl, phenyl-C.sub.1-C.sub.3alkyl,
C.sub.5-C.sub.12-cycloalkyl and C.sub.1-C.sub.25alklene correspond
to those given for formulae I, II and IIa.
[0075] Preferred compounds are those of formula III, wherein G is a
radical OH.
[0076] Particularly suitable compounds of formula III are those,
wherein R.sub.11, R.sub.12, R.sub.12a and R.sub.13 are hydrogen,
C.sub.1-C.sub.10alkyl, phenyl-C.sub.1-C.sub.3alkyl or
cyclohexyl.
[0077] R.sub.11, R.sub.12, R.sub.12a and R.sub.13 are preferably
C.sub.1-C.sub.4alkyl, in particular methyl and tert-butyl.
[0078] Preferred examples of compounds of formula III are, for
example, 19
[0079] It is also possible to use mixtures of positional isomeric
compounds.
[0080] The preparation of suitable lactones is known to the skilled
person and is described, inter alia, in EP-A-591 102 and other
publications.
[0081] Suitable sulfides which contain at least one reactive group
and which are reacted with the compatibiliser compound are
compounds of formula IV
R.sub.15--S--R.sub.16 (IV),
[0082] wherein
[0083] R.sub.15 is C.sub.1-C.sub.18alkyl, benzyl, phenyl or 20
[0084] and
[0085] R.sub.16 is --CH.sub.2CH.sub.2OH, 21
[0086] --CH.sub.2COOH or --CH.sub.2CH.sub.2COOH; and
[0087] R.sub.17 is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl.
[0088] The meanings of C.sub.1-C.sub.18alkyl and of
C.sub.1-C.sub.4alkyl-substituted phenyl are the same as those given
above for formula I.
[0089] R.sub.15 is preferably C.sub.8-C.sub.12alkyl, benzyl or
phenyl, in particular C.sub.8-C.sub.12alkyl. R.sub.16 is preferably
--CH.sub.2CH.sub.2OH or 22
[0090] Typical examples are 23
[0091] or C.sub.12H.sub.25--S--CH.sub.2CH.sub.2OH.
[0092] Also suitable are compounds of formula IV, wherein R.sub.15
is 24
[0093] preferably 25
[0094] The preparation of suitable sulfides is known to the skilled
person and is described, inter alia, in Abh. Akad. Wiss. DDR Abt.
Math., Naturwiss., Tech. (1987), Vol. Oct. 1986 (IN), 511-5;
EP-A-166 695, EP-A-413 562 and other publications.
[0095] Suitable phosphites which contain at least one reactive
group and which are reacted with the compatibiliser compound are
compounds of formula V 26
[0096] (V), wherein
[0097] R.sub.16a is --CH.sub.2CH.sub.2OH or --CH.sub.2CH.sub.2COOH;
and
[0098] R.sub.17a is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl.
[0099] The meanings of C.sub.1-C.sub.18alkyl and of
C.sub.1-C.sub.4alkyl-substituted phenyl are the same as those given
above for formula I.
[0100] Particularly suitable phosphites are those of formula 27
[0101] The skilled person is familiar with the preparation of
suitable phosphites which is described, inter alia, in Khim.-Famy.
Zh. (1988),22(2), 170-4 and other publications.
[0102] Suitable benztriazoles, benzophenones and
2-(2-hydroxyphenyl)-1,3,5- -triazines which contain at least one
reactive group and which are reacted with the compatibiliser
compound are compounds of formula VI, VIa, VIb or VIc 28
[0103] wherein
[0104] R.sub.18 is --(CH.sub.2).sub.t--R.sub.20, 29
[0105] or NH.sub.2;
[0106] R.sub.19 is C.sub.1-C.sub.12alkyl,
.alpha.,.alpha.-dimethylbenzyl or a radical 30
[0107] R.sub.20 is --OH, --SH, --NHR.sub.30, --SO.sub.3H,
--COOR.sub.21, --CH.dbd.CH.sub.2, 31
[0108] or ----(CO)--NH--(CH.sub.2).sub.u--NCO;
[0109] R.sub.21 is hydrogen, 32
[0110] or --CH.sub.2--CH(OH)--CH.sub.2--O--(CO)--R.sub.22;
[0111] R.sub.22 is C.sub.1-C.sub.4alkyl or phenyl;
[0112] R.sub.23 and R.sub.24 are each independently of the other
hydrogen or C.sub.1-C.sub.4alkyl;
[0113] R.sub.25 is hydrogen, --(CH.sub.2).sub.u--OH, 33
[0114] --(CH.sub.2).sub.uCOOH or
--(CO)--NH--(CH.sub.2).sub.u--NCO;
[0115] R.sub.25 is hydrogen, OH or C.sub.1-C.sub.12alkoxy;
[0116] R.sub.27 is hydrogen or OH;
[0117] R.sub.28 is hydrogen or 34
[0118] R.sub.29 is hydrogen or halogen;
[0119] R.sub.30 is hydrogen or C.sub.1-C.sub.9alkyl;
[0120] m is 0 or 1;
[0121] t is a number from 0 to 6;
[0122] u is a number from 2 to 12.
[0123] C.sub.1-C.sub.4Alkyl is typically linear or branched and is
methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or
tert-butyl. Methyl is preferred.
[0124] Particularly suitable compounds are, for example,
hydroxy-substituted benzophenones such 35
[0125] These compounds can be further substituted at the aromatic
rings, for example with additional hydroxyl groups or alkoxy.
Benzotriazoles of formula 36
[0126] are also suitable. In addition to the epoxy-functionalised
radical, the hydroxyphenyl group can also contain alkyl
substituents. Particularly suitable triazine compounds are, for
example, those of formula 37
[0127] wherein the phenyl groups can additionally be substituted by
methyl.
[0128] The preparation of suitable benztriazoles is known to the
skilled person and is described, inter alia, in EP-A-693 483;
Polymer (1995), 36(17), 3401-8 and other publications.
[0129] The preparation of suitable
2-(2-hydroxyphenyl)-1,3,5-triazines is known to the skilled person
and is decribed, inter alia, in EP-A-434 608; CA-A-2062217 and
other publications.
[0130] The preparation of suitable benzophenones is known to the
skilled person and is described, inter alia, in EP-A-693 483;
EP-A-538 839; Zh. PrikI. Khim. (Leningrad) (1976), 49(5), 1129-34;
JP-A-Hei 3 31235 (=Chemical Abstract No. 115:49102) and other
publications.
[0131] This invention also relates to compounds which are
obtainable by reacting sterically hindered phenols of formula I
38
[0132] R.sub.1 and R.sub.2 are each independently of the other
hydrogen, C.sub.1-C.sub.25alkyl, phenyl-C.sub.1-C.sub.3alkyl which
is unsubstituted or substituted once or several times at the
aromatic ring by OH or/and C.sub.1-C.sub.4alkyl, unsubstituted or
C.sub.1-C.sub.4alkyl-substituted C.sub.5C.sub.12cycloalkyl, or
phenyl;
[0133] n is 1, 2 or 3;
[0134] E is OH, SH, NHR.sub.3, SO.sub.3H, COOH, --CH.dbd.CH.sub.2,
39
[0135] m is 0 or 1;
[0136] R.sub.3 is hydrogen or C.sub.1-C.sub.9alkyl;
[0137] R.sub.4 is C.sub.1-C.sub.12alkyl, phenyl which is
unsubstituted or substituted by one or several
C.sub.1-C.sub.4-alkyl, halogen or/and C.sub.1-C.sub.18alkoxy;
[0138] A if E is OH, SH or --CH.dbd.CH.sub.2, is
--C.sub.xH.sub.2x--, --CH.sub.2--S--CH.sub.2CH.sub.2--,
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.s- ub.2p--,
--C.sub.qH.sub.2q--(CO)--NH--C.sub.pH.sub.2p-- or
--C.sub.qH.sub.2q--(CO)--O--C.sub.pH.sub.2p--S--C.sub.qH.sub.2q--;
[0139] x is a number from 0 to 8;
[0140] p is a number from 2 to 8;
[0141] q is a number from 0 to 3;
[0142] R.sub.1 and n are as defined above; or
[0143] A if E is --NHR.sub.3, is --C.sub.xH.sub.2x-- or
--C.sub.qH.sub.2q--(CO)--NH--C.sub.pH.sub.2p--, wherein x, p and q
have the meanings cited above; or
[0144] A if E is COOH or SO.sub.3H, is --C.sub.xH.sub.2x--,
--CH.sub.2--S--CH.sub.2-- or --CH.sub.2--S--CH.sub.2CH.sub.2--,
wherein x has the meaning cited above; or
[0145] A if E is 40
[0146] is a direct bond, --C.sub.qH.sub.2q--(CO)--O--CH.sub.2-- or
--C.sub.xH.sub.2x--S--CH.sub.2--, wherein q, m, x, R.sub.1 and
R.sub.2 are as defined above;
[0147] A if E is 41
[0148] is --CH.sub.2--;
[0149] or sterically hindered amines of formula II, IIa or Iib
42
[0150] R.sub.8 is hydrogen, C.sub.1-C.sub.25alkyl,
C.sub.2-C.sub.20alkenyl- , C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20alkoxy, phenyl-C.sub.1-C.sub.3a- lkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.5-C.sub.8cycloalkoxy, phenyl,
naphthyl, hydroxyethyl, CO--C.sub.1-C.sub.25alkyl, CO-phenyl,
CO-naphthyl, CO-phenyl-C.sub.1-C.sub.3alkyl,
O--CO--C.sub.1-C.sub.20alkyl or
C.sub.1-C.sub.6alkyl-S--C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-O--- C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkyl-(CO)--C.sub.1-C.sub.6alkyl, 43
[0151] w is a number from 1 to 10;
[0152] Y is a single bond, C.sub.1-C.sub.25alkylene, phenylene,
biphenylene, naphthylene, --O--C.sub.1-C.sub.25alkylene,
--NR.sub.9--, 44
[0153] Z is hydrogen, --COOR.sub.9, --NH.sub.2, --OR.sub.9,
hydroxyethyl, 45
[0154] R.sub.9 is hydrogen or C.sub.1-C.sub.12alkyl;
[0155] R.sub.10 has the same definition as R.sub.8;
[0156] or lactones of formula III 46
[0157] R.sub.11, R.sub.12, R.sub.12a and R.sub.13 are each
independently of one another hydrogen, C.sub.1-C.sub.25alkyl,
phenyl-C.sub.1-C.sub.3alk- yl, C.sub.5-C.sub.12cycloalkyl or
phenyl; and
[0158] G is OH, OCH.sub.2CH.sub.2OH, 47
[0159] or --OCH.sub.2COOH;
[0160] or sulfides of formula IV
R.sub.15--S--R.sub.16 (IV),
[0161] wherein
[0162] R.sub.15 is C.sub.1-C.sub.18alkyl, benzyl, phenyl or 48
[0163] and
[0164] R.sub.16 is --CH.sub.2CH.sub.2OH, 49
[0165] --CH.sub.2COOH or --CH.sub.2CH.sub.2COOH; and
[0166] R.sub.17 is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl;
[0167] or phosphites of formula V 50
[0168] R.sub.16a is --CH.sub.2CH.sub.2OH or --CH.sub.2CH.sub.2COOH;
and
[0169] R.sub.17a is C.sub.1-C.sub.18alkyl or unsubstituted or
C.sub.1-C.sub.4alkyl-substituted phenyl;
[0170] or benzotrazoles, benzophenones or
2,4,6-triaryl-1,3,5-triazines of formula VI, VIa, VIb or VIc 51
[0171] R.sub.18 is --(CH.sub.2).sub.t--R.sub.20 52
[0172] or NH.sub.2;
[0173] R.sub.19 is C.sub.1-C.sub.12alkyl,
.alpha.,.alpha.-dimethylbenzyl or a radical 53
[0174] R.sub.20 is --OH, --SH, --NHR.sub.30, --SO.sub.3H,
--COOR.sub.21, --CH.dbd.CH.sub.21, 54
[0175] or --(CO)--NH--(CH.sub.2).sub.u--NCO;
[0176] R.sub.21 is hydrogen, 55
[0177] or --CH.sub.2--CH(OH)--CH.sub.2--O--(CO)--R.sub.22;
[0178] R.sub.22 is C.sub.1-C.sub.4alkyl or phenyl;
[0179] R.sub.23 and R.sub.24 are each independently of the other
hydrogen or C.sub.1-C.sub.4alkyl;
[0180] R.sub.25 is hydrogen, --(CH.sub.2).sub.u--OH, 56
[0181] --(CH.sub.2).sub.uCOOH or
--(CO)--NH--(CH.sub.2).sub.u--NCO;
[0182] R.sub.26 is hydrogen, OH or C.sub.1-C.sub.12alkoxy;
[0183] R.sub.27 is hydrogen or OH;
[0184] R.sub.28 is hydrogen or 57
[0185] R.sub.29 is hydrogen or halogen;
[0186] R.sub.30 is hydrogen or C.sub.1-C.sub.9alkyl;
[0187] m is 0 or 1;
[0188] t is a number from 0 to 6;
[0189] u is a number from 2 to 12;
[0190] with a compatibiliser compound.
[0191] To prepare the novel compounds, compatibilisers with
specific reactive groups are suitable. These compatibilisers are
polymers containing acid groups, acid anhydride groups, ester
groups, epoxy groups or alcohol groups. Copolymers or terpolymers
of polyethylene, polypropylene, vinyl acetate or styrene with
acrylates are also suitable. Typical examples are polymers with
acrylic acid (AA) function, glycidyl methacrylate (GMA) function,
methacrylic acid (MAA) function, maleic anhydride (MAH) function or
vinyl alcohol (VA) function.
[0192] Preferred compatibilisers are, for example, copolymers
consisting of polyethylene acrylic acid (PE-AA), polyethylene
glycidyl methacrylate (PE-GMA), polyethylene methacrylic acid
(PE-MAA), polyethylene maleic anhydride (PE-MAH) or terpolymer of
polyethylene and vinyl acetate with acrylates (e.g.
PE-AA-acrylate).
[0193] Also suitable as compatibilisers are grafted polyethylene or
polypropylene copolymers selected from the group consisting of
maleic anhydride grafted to polyethylene vinyl acetate
(MAH-g-PE-vinyl acetate), maleic anhydride grafted to low density
polyethylene (MAH-g-LDPE), maleic anhydride grafted to high density
polyethylene (MAH-g-HDPE), maleic anhydride grafted to linear low
density polyethylene (MAH-g-LLDPE), acrylic acid grafted to
polypropylene (M-g-PP), glycidyl methacrylate grafted to
polypropylene (GMA-g-PP), maleic anhydride grafted to polypropylene
(MAH-g-PP), maleic anhydride grafted to ethylene/propylene
terpolymer (MAH-g-EPDM), maleic anhydride grafted to
ethylene/propylene rubber (MAH-g-EPM) and maleic anhydride grafted
to polyethylene/polypropylene copolymer (MAH-g-PE/PP).
[0194] Other suitable compatibiliser components are grafted styrene
co- or terpolymers selected from the group consisting of
styrene/acrylonitrile grafted with maleic anhydride (SAN-g-MAH),
styrene/maleic anhydride/methyl methacrylate,
styrene/butadiene/styrene block copolymer grafted with maleic
anhydride (SBS-g-MAH), styrene/ethylene/propylene/sty- rene block
copolymer grafted with maleic anhydride (SEPS-g-MAH),
styrene/ethylene/butadiene/styrene block copolymer grafted with
maleic anhydride (SEPS-g-MAH) and acrylic
acid/polyethylene/polystyrene terpolymer (AA-PE-PS-terpolymer).
[0195] Important compatibilisers are those containing anhydride
units. Illustrative examples of suitable anhydrides are itaconic
acid anhydride, citraconic acid anhydride,
bicyclo[2.2.2]-5-octene-2,3-dicarboxylic acid anhydride,
bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid anhydride or maleic
anhydride. Maleic anhydride is preferred.
[0196] Particularly suitable as compatibilisers are copolymers or
terpolymers having one anhydride. Typical examples are
ethylene/vinyl acetate/maleic anhydride terpolymers,
ethylene/ethyl-acrylate/maleic anhydride terpolymers,
ethylene/acrylic acid/maleic anhydride terpolymers, styrene/maleic
anhydride copolymer or styrene/maleic anhydride/methyl methacrylate
terpolymer.
[0197] Such polymers and their preparation are known and are
described, inter alia, by P. J. Flory in Principles of Polymer
Chemistry, 1964, Cornell University Press, Ithaca, N.Y., as well as
in Compatibilizers and polymer modifiers for virgin and recycled
thermoplastics including multipolymer and multilayer materials,
Maack Business Services, Study MBS No. 10, September 1990,
Zurich.
[0198] Also preferred as compatibiliser component are copolymers or
terpolymers containing a grafted anhydride, such as maleic
anhydride grafted to polypropylene, maleic anhydride grafted to
polyethylene, maleic anhydride grafted to ethylene/vinylacetate
copolymer, styrene/ethylene/propylene/styrene block copolmer
(SEPS), styrene/ethylene/butylene/styrene block copolmer (SEBS),
maleic anhydride grafted to ethylene/propylene terpolymer (EPDM),
maleic anhydride grafted to ethylene/propylene copolymer.
[0199] Such graft polymers and their preparation are known and are
described, inter alia, in H. -G. Elias, Makromolekule 1981, HOthig
& Wepf Verlag Heidelberg; or in Compatibilizers and polymer
modifiers for virgin and recycled thermoplastics including
multipolymer and multilayer materials, Maak Business Services,
Study MBS No. 10, September 1990, Zurich; as well as in M. Xanthos,
Reactive Extrusion, 1992, Oxford University Press, NY.
[0200] The maleic anhydride content is typically from 0.05-15%,
preferably from 0.1-10%.
[0201] Also suitable as compatibiliser component are copolymers or
terpolymers containing unsaturated carboxylic acid, typically
acrylic acid, methacrylic acid, crotonic acid, fumaric acid, vinyl
acetic acid, maleic acid, itaconic acid. Acrylic acid, methacrylic
acid, fumaric acid and maleic acid are preferred, and acrylic acid
and methacrylic acid are particularly preferred. Illustrative
examples of such copolymers or terpolymers are ethylene/acrylic
acid copolymer, propylene/acrylic acid copolymer or
ethylene/propylene/acrylic acid terpolymer. Such polymers and their
preparation are described, inter alia, in Compatibilizers and
polymer modifiers for virgin and recycled thermoplastics including
multipolymer and multilayer materials, Maak Business Services,
Study MBS No. 10, September 1990, Zurich.
[0202] The acrylic acid content is typically from 0.1-30%,
preferably from 0.1-25%.
[0203] The preparation of the polymeric, copolymeric and
terpolymeric compatibilisers is carried out by conventional
polymerisation processes with which the skilled person is
familiar.
[0204] The preparation of carboxyl group-containing polymers has
been published, for example, by N. G. Gaylord in "Reactive
Extrusion; Principles and Practice", Polymer Processing Institute,
page 56 et seq., Hanser Veriag, Munchen, Wien, New York (1992). In
the same work, p. 116 et seq., S. Brown describes the preparation
of other carboxylated compatibilisers.
[0205] The reaction of the compatibiliser compound with a compound
selected from the group consisting of the sterically hindered
phenols, sterically hindered amines, lactones, sulfides,
phosphites, benzotriazoles, benzophenones and
2-(2-hydroxyphenyl)-1,3,5-triazines, containing at least one
functional reactive group, is carried out as a grafting reaction or
polymer-analogous reaction.
[0206] The reactions can be carried out in solution or in the melt,
depending on the reactants. Different reactors may be used in this
case, for example tanks, extruders, mixers and the like. Extrusion
is preferred.
[0207] The reactive extrusion has been described, inter alia, by M.
Xanthos in Reactive Extrusion, Principle and Practice, Polymier
Processing Institute, Hanser Verlag, Munchen 1992.
[0208] The reactants can be fed into the extruder premixed or
separate, i.e. via separate feeding devices, and can be reacted in
the extruder. Liquid components or low-melting components may also
be fed into the extruder via feeding pumps (side channel
proportioning). It may also be useful to degas the melt in the
extruder, in particular when low molecular products are obtained in
the reaction which are then preferably removed. To this purpose the
extruder needs to be equipped with a corresponding degassing
device. The preparation can be carried out on commercially
available single- or twin-screw extruders. Twin-screw extruders are
preferred. Compounding is carried out by the customary techniques,
for example granulating. It is also possible to prepare and use a
masterbatch (concentrate) from this compatibiliserlstabiliser by
the methods known in the art.
[0209] The ratio of the compatibiliser component to the stabiliser
component in the polymer-analogous reactions is, of course, limited
by the number of reactive groups present on the compatibiliser
component. A suitable compatibiliser/stabiliser weight ratio is
100:0.05 to 100:50, in particular 100:0.1 to 100:25, preferably
100:1 to 100:20.
[0210] The novel compatibiliser/stabiliser compounds can be used,
for example, for stabilising the following polymers and, in
particular, mixtures of such polymers.
[0211] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene (which optionally can be crosslinked), for
example high density polyethylene (HDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), low density
branched polyethylene (VLDPE).
[0212] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE, PP/HDPEILDPE,
PP/HDPE/LLDPEILDPE) and mixtures of different types of polyethylene
(for example LDPE/HDPE, LLDPEILDPE, HDPE/LLDPEILDPE).
[0213] 3. Copolymers of monoolefins and diolefins with each other
or 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, ethylenelmethylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/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-norbomene; and mixtures of such
copolymers with one another and with polymers mentioned in 1)
above, for example polypropylenelethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid
copolymers, LLDPE/ethylene-vinyl acetate copolymers,
LLDPE/ethy-lene-acrylic acid copolymers and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0214] 4. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0215] 5. Copolymers of styrene or .alpha.-methylstyrene with
dienes or acrylic derivatives, for example styrene/butadiene,
styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadienelalkyl
methacrylate, styrene/maleic 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 ethylenelpropylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0216] 6. Graft copolymers of styrene or .alpha.-methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and
maleic anhydride on polybutadiene; styrene, acrylonitrile and
maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or
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 listed under 5), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers.
[0217] 7. Halogen-containing polymers such as polychloroprene,
chlorinated rubber, chlorinated or chlorosulfonated 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.
[0218] 8. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0219] 9. Copolymers of the monomers mentioned under 8) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0220] 10. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example 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 1) above.
[0221] 11. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexame- thylene
terephthalamide or poly-m-phenylene isophthalamide; and also 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).
[0222] 12. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived
from hydroxyl-terminated polyethers; and also polyesters modified
with polycarbonates or MBS.
[0223] 13. Polycarbonates and polyester carbonates.
[0224] 14. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
PON/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PAJHDPE, PA/PP, PA/PPO,
PA/LDPE, PE/PET, PS/PE, PS/PP, PS/PE/PP, PE/PP/PET/PS.
[0225] The novel compatibiliser/stabiliser compounds are added to
the polymer to be stabilised in amounts of 0.5-30%, e.g. of 1-20%,
preferably of 2-15% (based on the amount of polymer to be
stabilised).
[0226] The amounts depend on the one hand on the number of active
stabiliser groups in the compounds and, on the other hand, on the
requirements of the polymers or polymer blends to be
stabilised.
[0227] The novel compatibiliser/stabiliser compounds are also used
for phase compatibilisation in plastic compositions where they act
at the same time as stabilisers. These plastic compositions can be
virgin plastic compositions (as described above) or also
recyclates.
[0228] The novel compatibiliserlstabiliser compounds can, in
principle, be used in all incompatible plastic compositions, virgin
materials or recyclates or in blends of virgin material and
recyclates. The plastic compositions can consist of two or more
components. The novel compounds are preferably added to mixtures of
polar and nonpolar plastics.
[0229] The nonpolar components of plastic compositions are, for
example, polyolefins, typically polyethylene (PE) and polypropylene
(PP). To be mentioned in particular are low density polyethylene
(LOPE), low density linear polyethylene (LLDPE) and high density
polyethylene (HDPE), and also copolymers, such as
ethylene/propylene (EPM) and ethylene/propylene/diene copolymers
(EPDM) as well as ULDPE and MDPE. Such nonpolar plastics also
include polystyrene (PS, EPS) and copolymers having a styrene
component (e.g. ABS, ASA, HIPS, IPS) and polyvinyl chloride (PVC),
as well as copolymers with a predominant vinyl chloride component
(e.g. CPE)
[0230] The polar components are, for example, polyesters, such as
polyethylene terephthalate (PET) or polybutylene terephthalate
(PBT), polyamides or polycarbonates.
[0231] Mixtures of polyethylene and polypropylene or of
polyethylene and polyamide are particularly preferred.
[0232] The novel compatibiliser/stabiliser compounds can be used,
for example, in recycled plastic compositions comprising 25-100% by
weight, preferably 35-95% by weight, e.g. 40-85% by weight, of
polyolefins, 0-25% by weight of polystyrene, 0-25% by weight of
polyvinyl choride and 0-25% by weight of other thermoplastics.
Non-thermoplastic materials may also be obtained in minor amounts
in the mixture.
[0233] Of the polyolefins, polyethylene (PE), in particular low
density polyethylene, usually dominates. Polystyrene (PS) is also
understood to be copolymers having a predominant styrene component
(e.g. ABS, HIPS), and polyvinyl chloride (PVC) is also understood
to be copolymers having a predominant vinyl chloride component
(e.g. CPE). Other thermoplastics present in the used material are,
in particular, polyethylene terephthalate (PET), and also
polyamides, polycarbonate, cellulose acetate and polyvinylidene
chloride. Non-thermoplastic materials can be present in minor
amounts of up to 5%, typically polyurethanes, formaldehyde resins
and phenolic resins or also typical aminoplastics, as well as
elastomers such as caoutchouc or rubber. Minor amounts of foreign
matter may also be present in used plastics, such as paper,
pigments, paint systems, printing inks, adhesives, which are often
difficult to remove. Minor amounts of cellulose or fibre materials
do not interfere with recycling either.
[0234] Blends of the novel compatibiliser/stabiliser compounds may
also be added to the plastic compositions to be stabilised and to
be made compatible. It is, for example, convenient to use compounds
having the same compatibiliser backbone but which are differently
functionalised as regards the stabiliser, typically mixtures of
compounds having a phenolic anti-oxidant function with compounds
having a benzotriazole function, mixtures of compounds having an
antioxidant function with compounds having a HALS function,
mixtures of compounds having a HALS function with compounds having
a UV absorber function or e.g. mixtures of compounds having an
antioxidant function with compounds having a HALS function and with
compounds having a UV absorber function.
[0235] The plastic compositions may additionally be mixed with
other additives known to the skilled person. These additional
additives are used in the customary amounts and combinations
detailed in the relevant literature (e.g. "Plastics Additives",
Gachter/Muller, Hanser Verlag, Munchen/Wien/New York, 3rd
edition).
[0236] The incorporation of the novel compatibiliser/stabiliser
compounds into the polymers or polymer blends to be stabilised can
be conveniently carried out as follows:
[0237] as emulsion or dispersion;
[0238] as dry mixture while blending additional components or
polymer blends;
[0239] by direct addition to the processing apparatus (e.g.
calender, mixer, kneader, extruder and the like), or
[0240] as solution or melt.
[0241] The plastic compositions can be prepared in a manner known
per se by mixing the novel compounds and further optional additives
with the plastic composition using appliances known per se, such as
the above-mentioned processing apparatus. The additional additives
can be added singly or in admixture or also in the form of
so-called masterbatches.
[0242] By adding a suitable monomeric functionalised stabiliser
compound and a radical initiator to the plastic composition direct
while processing the mixture, i.e. without previous separate
preparation of the compatibiliser/stabiliser compound, it is
furthermore possible to produce said compatibiliser/stabiliser
compound and the compatible plastic composition in one process
step. In similar manner it is possible to process a suitable
monomeric functionalised stabiliser compound and a corresponding
compatibiliser together with the polymer mixture so that the
compatibiliser compound reacts with the stabiliser compound without
prior processing, an improved compatibilised polymer blend being
obtained at the same time.
[0243] The plastic compositions obtainable according to this
invention can be brought into the desired shape in known manner.
Such processes are, for example, grinding, calendering, extruding,
injection moulding, sintering or spinning, and also extrusion blow
moulding or processing by the plastisol process.
[0244] The novel process comprises two different aspects, i.e. two
different aims are attained by using the novel polymeric
compatibiliser/stabiliser compounds.
[0245] On the one hand, polymers are made compatible with each
other in blends of different polymers (virgin material or
recyclates), which, without compatibilisers, would form several
phases, and-the polymer is stabilised at the same time.
[0246] On the other hand, the stabiliser is made compatible or its
solubility in the polymer is enhanced because the polymer backbone
of the compatibiliser/stabiliser compound is compatible with the
polymer to be stabilised.
[0247] This also reduces the migration of the stabiliser from the
polymer which is conceivable e.g. in extracting ambient media. This
is the case, for example, when said compounds are used for fuel
tanks, geotextiles, dry cleaning fibres (e.g. textiles, carpet
floors), pipes, applications with foodstuff contact and the
like.
[0248] The following Examples illustrate the invention in more
detail. Here as well as in the remainder of the description and in
the claims, parts and percentages are by weight unless otherwise
stated.
[0249] I. Preparation of the Functionalised Polymers
EXAMPLE A
[0250] On a twin-screw extruder (TW 100, of Haake, Germany), an
SEBS copolymer (styrene/ethylene/butadiene/styrene copolymer) is
extruded with maleic anhydride groups (Kraton.RTM. FG 1901, of
Shell) at a temperature of 210-230.degree. C. (heating zone 1-5)
and at 45 rpm with addition of 2% of 2,3-epoxypropyl
3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropiona- te.
[0251] Subsequent analysis by gas chromatography shows that the
additive can no longer be detected in its original form, i.e. it is
completely chemically bound to the polymer chain.
EXAMPLE B
[0252] In general analogy to Example A, a polyethylene/acrylic
acid/acrylate (Lucalen.RTM. A 3110 MX, of BASF) is extruded with 2%
of 2,3-epoxypropyl
3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropionate.
EXAMPLE C
[0253] The procedure of Example B is repeated, but using 4% of
2,3-epoxypropyl
3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropionate.
EXAMPLE D
[0254] In general analogy to Example A, SEBS copolymer with maleic
anhydride groups is reacted with 2% of
1,2,2,6,6-pentamethyl-4-(2,3-epoxy- propyloxy)piperidine.
EXAMPLE E
[0255] In general analogy to Example 8, polyethylene/acrylic
acid/acrylate is reacted with 2% of
1,2,2,6,6-pentamethyl-4-(2,3-epoxypropyloxy)piperid- ine.
EXAMPLES F, G, H
[0256] In general analogy to Example E, 4%, 6% and 8% each of
1,2,2,6,6-pentamethyl-4-(2,3-epoxypropyloxy)piperidine are
used.
[0257] II) Use of the Polymeric Stabilisers
EXAMPLES 1-3
Impact Strength as a Function of Oven Ageing
[0258] To test the products obtained, a mixture of 70% of LDPE, low
density polyethylene (Lupolen.RTM. 3026 F, of BASF) with polyamide
6 (Ultramid.RTM. B 30, pre-dried, of BASF) is compounded with the
functionalised compatibilisers prepared in the above Examples at
240.degree. C. and at 75 rpm (twin-screw extruder TW 100, of Haake,
Germany), granulated and then injection moulded at 240.degree. C.
to test samples. The impact strength of these test samples is
determined according to DIN 53 448 as a function of ageing at
100.degree. C. in a circulating air oven.
[0259] For comparison purposes, compositions comprising instead of
the functionalised compatibilisers the corresponding
unfunctionalised compounds were prepared and tested. The tested
compositions and the test results are given in the following Table
1. The higher the impact strength value, the more stable the tested
composition.
1 TABLE 1 Additive Impact strength [kJ/m.sup.2] Ex. 5% each of 0 h
500 h 1000 h 2500 h 5000 h 7725 h -- 292 158 161 113 60 53 Kraton
FG 1901 571 509 458 451 311 241 Lucalen A 3110 MX 673 476 361 195
145 112 1 cmpd. of Example A544 503 479 473 448 428 2 cmpd. of
Example B663 581 583 570 538 478 3 cmpd. of Example C692 580 578
571 538 419
[0260] The values obtained show that the functionalised
compatibilisers stabilise the polymer more effectively when aged
over a prolonger period of time than the of non-functionalised
compatibilisers.
EXAMPLES 4-8
Impact Strength as a Function of Artificial Weathering
[0261] In general analogy to the method described in Examples 1-3,
test samples are prepared and their impact strength is determined
as a function of artificial weathering. The weatherings are carried
out in a Weather-O-meter [Type Ci 65A, of Atlas, BPT (black panel
temperature) 63.degree. C., RH (relative humidity) 60%, water
spray].
[0262] The compositions and test results are shown in Table 2.
2 TABLE 2 Additive Impact strength [kJ/m.sup.2] Ex. 5% each of 0 h
1000 h 2000 h 5000 h -- 292 99 104 93 Kraton FG 1901 571 83 52 45
Lucalen A 3110 MX 673 122 97 55 4 cmpd. of Example D 569 456 408
283 5 cmpd. of Example E 702 651 503 249 6 cmpd. of Example F 635
588 485 269 7 cmpd. of Example G 668 670 533 362 8 cmpd. of Example
H 596 535 476 416
[0263] The values obtained show that the functionalised
compatibilisers stabilise the polymer more effectively when
weathered over a prolonged period of time than the
non-functionalised compatibilisers.
EXAMPLES 9-12
Impact Strength as a Function of Oven Ageing After Extraction
[0264] A mixture of 70% of low density polyethylene (LDPE)
(Lupolen.RTM. 3026 F, of BASF) with 30% of polyamide 6
(Ultramid.RTM. B36, pre-dried, of BASF) is compounded with the
novel compatibiliser/stabiliser compounds to be tested at
240.degree. C. and at 75 rpm in a twin-screw extruder. Test samples
are then injection moulded at 240.degree. C.
[0265] These test samples are stored in an extraction medium:
[0266] A) in white spirit for 25 days at room temperature,
[0267] B) in water with 1% of Igepal CO630 (nonoxynol 9) for 2
weeks at 40.degree. C.
[0268] The dried test samples are then aged at 100.degree. C. in a
circulating air oven. The impact strength is determined according
to DIN 53 448 as a function of ageing. The higher the impact
strength value and the less this value diminishes after ageing, the
most stable the tested composition. The tested compounds and the
test results for the extraction variant A are given in Table 3 and
those for variant B are given in Table 4.
3TABLE 3 LDPE/PA6 Impact strength alter extraction in white spirit
70:30 [kJ/m.sup.2] Ex. 0 h 503 h 723 h 1006 h 1990 h 4004 h 9 5% of
the 535 554 574 582 595 538 cmpd. of Ex. B 10 5% of the 547 542 557
541 567 515 cmpd. of Ex. C
[0269]
4TABLE 4 LDPE/PA6 Impact strength after extraction in 70:30
water/surfactant [kJ/m.sup.2 ] Ex. 0 h 235 h 498 h 750 h 1241 h
2995 h 11 5% of the cmpd. 636 579 591 600 591 578 of Ex. B 12 5% of
the cmpd. 661 539 575 563 580 555 of Ex. C
* * * * *