U.S. patent application number 13/588532 was filed with the patent office on 2013-08-29 for alkylphenol free - liquid polymeric polyphosphite polymer stabilizers.
This patent application is currently assigned to Dover Chemical Corporation. The applicant listed for this patent is Michael Jakupca, Jacob M. Lance, Donald Stevenson. Invention is credited to Michael Jakupca, Jacob M. Lance, Donald Stevenson.
Application Number | 20130225736 13/588532 |
Document ID | / |
Family ID | 44483219 |
Filed Date | 2013-08-29 |
United States Patent
Application |
20130225736 |
Kind Code |
A1 |
Jakupca; Michael ; et
al. |
August 29, 2013 |
ALKYLPHENOL FREE - LIQUID POLYMERIC POLYPHOSPHITE POLYMER
STABILIZERS
Abstract
An alkylphenol-free liquid polymeric polyphosphite is described
of general Structure IV illustrated below ##STR00001## wherein each
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be the same or different
and independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers, and or Y--OH; Y is selected from the group
consisting of C.sub.2-40 alkylene, C.sub.2-40 alkyl lactone,
--R.sup.7--N(R.sup.8)--R.sup.9--, wherein R.sup.7, R.sup.8 and
R.sup.9 are independently selected from the group previously
defined for R.sup.1, R.sup.2, R.sup.3 and R.sup.4, now further
including H; m is an integral value ranging from 2 to 100
inclusive; and x is an integral value ranging from 1 to 1,000 and
further in which by controlling a molar ratio of reactants, the
number of terminal hydroxyl groups is minimized. The
alkylphenol-free liquid polymeric phosphite is useful in reducing
phosphite migration within polymers.
Inventors: |
Jakupca; Michael; (Canton,
OH) ; Lance; Jacob M.; (Dover, OH) ;
Stevenson; Donald; (Dover, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Jakupca; Michael
Lance; Jacob M.
Stevenson; Donald |
Canton
Dover
Dover |
OH
OH
OH |
US
US
US |
|
|
Assignee: |
Dover Chemical Corporation
Dover
OH
|
Family ID: |
44483219 |
Appl. No.: |
13/588532 |
Filed: |
August 17, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US2010/053207 |
Oct 19, 2010 |
|
|
|
13588532 |
|
|
|
|
61306014 |
Feb 19, 2010 |
|
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Current U.S.
Class: |
524/128 ;
558/156 |
Current CPC
Class: |
C08K 5/524 20130101;
C08L 85/02 20130101; C08K 2201/014 20130101; C08G 79/04
20130101 |
Class at
Publication: |
524/128 ;
558/156 |
International
Class: |
C08L 85/02 20060101
C08L085/02; C08G 79/04 20060101 C08G079/04 |
Claims
1. An alkylphenol-free liquid polymeric polyphosphite which
comprises: ##STR00017## wherein each R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 can be the same or different and independently selected
from the group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.3-40 cycloalkyl, C.sub.3-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers and Y--OH as an
end-capping group; each Y is independently selected from the group
consisting of C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers, C.sub.2-40 alkylene, C.sub.3-40 alkyl lactone,
and --R.sup.7--N(R.sup.8)--R.sup.9--; R.sup.7, R.sup.8 and R.sup.9
are independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene and H; m is an integral value ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are terminated with an hydroxyl group.
2. The polymeric polyphosphite of claim 1 wherein no more than one
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are terminated with an
hydroxyl group.
3. The polymeric polyphosphite of claim 1 wherein essentially all
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are terminated by an alkyl
group.
4. The polymeric polyphosphite of claim 1 wherein said polymeric
polyphosphite is comprised of a polyalkylene glycol.
5. The polymeric polyphosphite of claim 4 wherein said polyalkylene
glycol is selected from the group consisting of polyethylene glycol
and polypropylene glycol.
6. The polymeric polyphosphite of claim 1 wherein each R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are aliphatic and which further
comprises an alkanolamine.
7. An alkylphenol-free liquid polymeric polyphosphite which
comprises: ##STR00018## wherein each R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 can be the same or different and independently selected
from the group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers, and Y--OH as
an end-capping group; each Y is independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl,
C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers,
C.sub.3-20 alkyl glycol ethers, C.sub.2-40 alkylene, C.sub.2-40
C.sub.3-40 alkyl lactone, and --R.sup.7--N(R.sup.8)--R.sup.9--;
R.sup.7, R.sup.8 and R.sup.9 are independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene and H previously
defined for R.sup.1, R.sup.2, R.sup.3 and R.sup.4, now further
including H; m is an integral value ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are difunctional having two reactive terminal groups and a
remainder are monofunctional with one reactive terminal group.
8. The polymeric polyphosphite of claim 7 wherein no more than one
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is difunctional having two
reactive terminal groups and a remainder are monofunctional with
one reactive terminal group.
9. The polymeric polyphosphite of claim 8 wherein essentially all
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are terminated by an alkyl
group.
10. The polymeric polyphosphite of claim 1 wherein said polymeric
polyphosphite is comprised of a polyalkylene glycol.
11. The polymeric polyphosphite of claim 10 wherein said
polyalkylene glycol is selected from the group consisting of
polyethylene glycol and polypropylene glycol.
12. The polymeric polyphosphite of claim 1 wherein each R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are aliphatic and which further
comprises an alkanolamine.
13. A process for stabilizing a polymer, as indicated by
essentially matching or lowering the Yellowness Index of a polymer
when compared to a polymeric composition using a tris(nonylphenyl)
phosphite, comprising the step of adding an alkylphenol-free liquid
polymeric polyphosphite which comprises: ##STR00019## wherein each
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be the same or different
and independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.3-40 cycloalkyl, C.sub.3-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers and Y--OH as an end-capping group; each Y is
independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, C.sub.3-20
methoxy alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers,
C.sub.2-40 alkylene, C.sub.3-40 alkyl lactone, and
--R.sup.7--N(R.sup.8)--R.sup.9--; R.sup.7, R.sup.8 and R.sup.9 are
independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene and H; m is an integral value ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are terminated with an hydroxyl group.
14. The polymeric polyphosphite of claim 13 wherein no more than
one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are terminated with an
hydroxyl group.
15. The polymeric polyphosphite of claim 13 wherein essentially all
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are terminated by an alkyl
group.
16. The polymeric polyphosphite of claim 13 wherein said polymeric
polyphosphite is comprised of a polyalkylene glycol.
17. The polymeric polyphosphite of claim 16 wherein said
polyalkylene glycol is selected from the group consisting of
polyethylene glycol and polypropylene glycol.
18. The polymeric polyphosphite of claim 13 wherein each R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are aliphatic and which further
comprises an alkanolamine.
19. The process of claim 13 which comprises: adding between 0.01-2
weight percent of said polymeric polyphosphite to at least one
polymer.
20. The process of claim 16 wherein said polymer is a carbon-based
polymer.
21. The process of claim 16 which further comprises the step of
adding at least one other additive selected from the group
consisting of a hindered phenol, a hindered amine light stabilizer,
a benzotriazole, a thioester, a second phosphite, a metal stearate
and a hydrotalcite.
22. An alkylphenol-free liquid polymeric polyphosphite which
comprises: ##STR00020## wherein each R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 can be the same or different and independently
selected from the group consisting of C.sub.1-20 alkyl, C.sub.2-22
alkenyl, C.sub.3-40 cycloalkyl, C.sub.3-40 cycloalkylene,
C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20 alkyl glycol
ethers and A-OH and B--OH as an end-capping group; each A and B is
independently selected from the group consisting of C.sub.2-40
alkylene, C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers, C.sub.3-40 alkyl lactone, and
--R.sup.7--N(R.sup.9)--R.sup.9-- wherein R.sup.7, R.sup.9 and
R.sup.9 are independently selected from the group previously
defined for R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5; m and n
are integral values ranging from 2 to 100 inclusive; x is an
integral value ranging from 1 to 1,000; and further wherein no more
than two of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are
terminated with an hydroxyl group.
23. The polymeric polyphosphite of claim 22 wherein no more than
one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are
terminated with an hydroxyl group.
24. The polymeric polyphosphite of claim 23 wherein essentially all
of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are terminated by
an alkyl group.
25. The polymeric polyphosphite of claim 22 wherein said polymeric
polyphosphite is comprised of a polyalkylene glycol.
26. The polymeric polyphosphite of claim 25 wherein said
polyalkylene glycol is selected from the group consisting of
polyethylene glycol and polypropylene glycol.
27. The polymeric polyphosphite of claim 22 wherein each R.sup.1,
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are aliphatic and which
further comprises an alkanolamine.
28. A process to control the molecular weight and hydroxyl
termination of an alkylphenol-free liquid polymeric polyphosphite
of formula (IV) ##STR00021## wherein each R.sup.1, R.sup.2, R.sup.3
and R.sup.4 can be the same or different and independently selected
from the group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.3-40 cycloalkyl, C.sub.3-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers and Y--OH as an
end-capping group; each Y is independently selected from the group
consisting of C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers, C.sub.2-40 alkylene, C.sub.3-40 alkyl lactone,
and --R.sup.7--N(R.sup.8)--R.sup.9--; R.sup.7, R.sup.8 and R.sup.9
are independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene and H; m is an integral value ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are terminated with an hydroxyl group comprising the steps
of: reacting a triphosphite with a limiting molar amount of a
dihydroxy-terminated reactant with a molar excess of a
monofunctional chain stopper; adding a base; heating said
triphosphite, dihydroxy-terminated reactant and monofunctional
chain stopper and base; and isolating said alkylphenol-free liquid
polymeric polyphosphite.
29. The alkylphenol-free liquid polymeric polyphosphite of claim 28
wherein said triphosphite comprises a triphenylphosphite; said
dihydroxy-terminated reactant comprises at least one polyalkylene
glycol; and said monofunctional chain stopper comprises at least
one alcohol group.
30. A process to control the molecular weight and hydroxyl
termination of an alkylphenol-free liquid polymeric polyphosphite
of formula ##STR00022## wherein each R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 can be the same or different and independently
selected from the group consisting of C.sub.1-20 alkyl, C.sub.2-22
alkenyl, C.sub.3-40 cycloalkyl, C.sub.3-40 cycloalkylene,
C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20 alkyl glycol
ethers and A-OH and B--OH as an end-capping group; each A and B is
independently selected from the group consisting of C.sub.2-40
alkylene, C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20
alkyl glycol ethers, C.sub.3-40 alkyl lactone, and
--R.sup.7--N(R.sup.9)--R.sup.9-- wherein R.sup.7, R.sup.9 and
R.sup.9 are independently selected from the group previously
defined for R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5; m and n
are integral values ranging from 2 to 100 inclusive; x is an
integral value ranging from 1 to 1,000; and further wherein no more
than two of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are
terminated with an hydroxyl group. comprising the steps of:
reacting a triphosphite with a limiting molar amount of at least
two dihydroxy-terminated reactants with a molar excess of a
monofunctional chain stopper; adding a base; heating said
triphosphite, at least two dihydroxy-terminated reactants and
monofunctional chain stopper and base; and isolating said
alkylphenol-free liquid polymeric polyphosphite.
31. The alkylphenol-free liquid polymeric polyphosphite of claim 30
wherein said triphosphite comprises a triphenylphosphite; said
dihydroxy-terminated reactant comprises at least two polyalkylene
glycols; and said monofunctional chain stopper comprises at least
one alcohol group.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application
national stage United States Patent Office filing under 35 U.S.C.
.sctn.111(a) and claims priority to and incorporates by reference,
International Patent Application PCT/US2010/053207 filed on 19 Oct.
2010 and published as WO 2011/102861 A1 which claims the benefit of
and priority to U.S. Patent Application Ser. No. 61/306,014 filed
on 19 Feb. 2010.
TECHNICAL FIELD
[0002] The invention described herein pertains generally to an
improved polymer composition which contains at least one liquid
polymeric polyphosphite additive which is selected from the group
of all alkyl polymeric polyphosphites as antioxidant additives and
a method for the preparation thereof.
BACKGROUND OF THE INVENTION
[0003] At least one purpose associated with the addition of a
stabilizer to a polymeric resin is to prevent deterioration of the
polymers derived from the resin during processing at high
temperatures and also to permit the manufacture of products with
increased intrinsic quality attributable at least in part to
increased resistance to thermal and light degradation during their
intended use.
[0004] Many organic phosphites have been used as stabilizers, and
most are based on alkylphenols. Among them are the commercially
significant phosphites, tris(nonylphenyl) phosphite (TNPP) and
tris(2,4-di-t-butylphenyl) phosphite. Historically, TNPP has been
the primary low cost liquid phosphite stabilizer used in the
plastic and rubber industry. Recently, however, plastic and rubber
manufactures have been reluctant to use TNPP in their formulation
due to concerns that one of the degradation product of TNPP
(nonylphenol) may be xenoestrogen.
[0005] U.S. Pat. No. 6,541,549 B2 and U.S. Pat. No. 7,199,170 B2
disclose phosphite compounds having a general Structure I as
non-xenoestrogenic stabilizers for polymers, although they are
still based on an alkylphenol.
##STR00002##
[0006] U.S. Pat. No. 7,186,853 B2 discloses phosphites comprising
substituted or unsubstituted tricyclodecylmethyl groups. The
phosphites disclosed also comprise certain alcohols which can be
aliphatic, arylalkyl and alkylaryl.
[0007] U.S. Pat. No. 7,468,410 B2 and WO 07 009,916 disclose
tris-(mono-alkyl)phenyl phosphites or a mixture of the general
Structure II where each R is the same or different alkyl group
having 1 to 8 carbon atoms. Again this is a low molecular weight
monophosphite still based on an alkylphenol.
[0008] The problem with the mono phosphites or lower molecular
weight phosphites described in the mentioned patents are that, the
phosphites are still based on an alkylphenol of some type and lower
molecular weight phosphites can be extracted easily from the
polymer. Alkylphenols are of concern as potential skin irritants or
having xenoestrogenic activity. Being easily extracted from a
polymer means the phosphite or its degradation products can easily
migrate into foods that come into contact with polymer that maybe
stabilized with the lower molecular weight or mono phosphites.
##STR00003##
[0009] WO 08 028,858 discloses liquid polymeric phosphites of the
general structure III wherein L is a linkage between the repeated
unit n, comprising C.sub.1-C.sub.24 alkylene, C.sub.2-C.sub.24
alkenylene, and oxygen, sulfur or substituted nitrogen (N--R)
interrupted C.sub.2-C.sub.24 alkenylene. The integer m is 0 and
1.
##STR00004##
[0010] A disadvantage of the polymeric phosphites of this
disclosure is that all the polymeric phosphites are based on an
alkylphenol of some type. It is preferable to have a polymeric
phosphite that does not contain an alkylphenol.
SUMMARY OF THE INVENTION
[0011] The present invention is directed to novel liquid polymeric
phosphites of the general Structure IV as stabilizers for polymers
during processing.
##STR00005##
[0012] wherein [0013] each R.sup.1, R.sup.2, R.sup.3 and R.sup.4
can be the same or different and independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers, and or Y--OH
(serving as an end capping moiety) [0014] Y is selected from the
group consisting of C.sub.2-40 alkylene, C.sub.2-40 alkyl lactone,
(e.g., ethylene, propylene, caprylactone),
--R.sup.7--N(R.sup.8)--R.sup.9-- (e.g., C.sub.2-40 alkyl diamines
and C.sub.2-40 alkyl triamines), [0015] wherein R.sup.7, R.sup.8
and R.sup.9 are independently selected from the group previously
defined for R.sup.1, R.sup.2, R.sup.3 and R.sup.4, now further
including H; [0016] m is an integral value ranging from 2 to 100
inclusive; [0017] x is an integral value ranging from 1 to 1,000;
further wherein [0018] no more than two of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are terminated with an hydroxyl group.
[0019] Depending on reaction conditions and components, it is also
possible to synthesize Structure V, and be within the scope of this
invention:
##STR00006##
[0020] wherein [0021] each R.sup.1, R.sup.2, R.sup.3, R.sup.4, Y,
and m are as defined previously.
[0022] The novel, polymeric phosphites of the general Structures IV
or V are suitable for stabilization of organic materials against
oxidative, thermal or actinic degradation.
[0023] The most preferred polymeric diphosphites or polymeric
phosphites are the ones that do not have or contain aromatic groups
or alkylphenol groups.
[0024] The advantages of the liquid high molecule weight dimeric
and the polymeric phosphites are very low volatility, no migration
out of the polymer being stabilized, very difficult to extract from
the polymer being stabilized. These advantages can translate into
no plate out during polymer extrusion (no die lip build up) and no
migration into food from polymers that are used in food packaging.
It is extremely advantageous to have a liquid polymeric phosphite
that has excellent hydrolytic stability and one that is not based
on alkylphenols.
[0025] These and other objects of this invention will be evident
when viewed in light of the drawings, detailed description and
appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The best mode for carrying out the invention will now be
described for the purposes of illustrating the best mode known to
the applicant at the time of the filing of this invention. The
examples and figures are illustrative only and not meant to limit
the invention, as measured by the scope and spirit of the
claims.
[0027] As used herein, and unless otherwise stated, the term
"alkyl" means straight and branched chain saturated acyclic
hydrocarbon monovalent groups; said alkyl group may further
optionally include one or more suitable substituents independently
selected from the group consisting of amino, halogen, hydroxy,
sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting
examples of straight-chain or branched alkyl groups are C.sub.1-20
alkyls, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl groups. It
is recognized that the alkyl may be interrupted with oxygen, sulfur
or nitrogen, examples for which include:
CH.sub.3--O--CH.sub.2CH.sub.2--, CH.sub.3--S--CH.sub.2CH.sub.2--,
CH.sub.3--N(CH.sub.3)--CH.sub.2CH.sub.2--,
CH.sub.3--O--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--,
CH.sub.3--(O--CH.sub.2CH.sub.2--).sub.2O--CH.sub.2CH.sub.2--,
CH.sub.3--(O--CH.sub.2CH.sub.2--).sub.3O--CH.sub.2CH.sub.2-- or
CH.sub.3--(O--CH.sub.2CH.sub.2--).sub.4O--CH.sub.2CH.sub.2--.
[0028] As used herein, and unless otherwise stated, the term
"alkenyl" means straight and branched chain unsaturated acyclic
hydrocarbon monovalent groups; said alkenyl group may further
optionally include one or more suitable substituents independently
selected from the group consisting of amino, halogen, hydroxy,
sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting
examples of the straight-chain or branched alkenyl groups are those
having 2 to 30 carbon atoms wherein the position of the double bond
may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl,
nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl groups. It
is once again, recognized that the alkenyl may be interrupted with
oxygen, sulfur or nitrogen, examples for which include:
--CH.sub.2--O--CH.sub.2--, --CH.sub.2--S--CH.sub.2--,
--CH.sub.2--N(CH.sub.3)--CH.sub.2--,
--CH.sub.2--O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--(O--CH.sub.2CH.sub.2--).sub.2O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--(O--CH.sub.2CH.sub.2--).sub.3O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--(O--CH.sub.2CH.sub.2--).sub.4O--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2-- or
--CH.sub.2CH.sub.2--N(CH.sub.3)--CH.sub.2CH.sub.2--.
[0029] As used herein, and unless otherwise stated, the terms
"cycloaliphatic" refer to a mono- or polycyclic saturated
hydrocarbon monovalent group having from 3 to 10 carbon atoms, or a
C.sub.7-10 polycyclic saturated hydrocarbon monovalent group having
from 7 to 10 carbon atoms. Specific non-limiting examples of the
cycloaliphatic or cyclic alkyl groups which may have substituents
are cycloalkyl groups having 5 to 7 carbon atoms such as
cyclopentyl, cyclohexyl and cycloheptyl groups, and the
alkylcycloalkyl groups having 6 to 11 carbon atoms wherein the
position of the alkyl group may vary, such as methylcyclopentyl,
dim ethylcyclopentyl, methylethylcyclopentyl, dim ethylcyclopentyl,
methylcyclohexyl, dim ethylcyclohexyl, methylethylcyclohexyl,
diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl,
methylcycloheptyl, and diethylcycloheptyl groups. It is once again,
recognized that the cycloaliphatic may be interrupted with oxygen,
sulfur or nitrogen.
[0030] As used herein, and unless otherwise stated, the term
"heterocyclic" means a mono- or polycyclic, saturated or
mono-unsaturated or poly-unsaturated monovalent hydrocarbon group
having from 2 up to 15 carbon atoms and including one or more
heteroatoms in one or more rings, each of said rings having from 3
to 10 atoms (and optionally further including one or more
heteroatoms attached to one or more carbon atoms of said ring, for
instance in the form of a carbonyl or thiocarbonyl or
selenocarbonyl group, and/or to one or more heteroatoms of said
ring, each of said heteroatoms being independently selected from
the group consisting of nitrogen, oxygen, sulfur, selenium and
phosphorus, heterocyclic groups, including all possible isomeric
forms thereof, wherein each carbon atom of said heterocyclic ring
may be independently substituted with a substituent selected from
the group consisting of halogen, nitro, C.sub.1-7 alkyl (such as
above defined, in particular methyl), C.sub.3-7 alkenyl,
trifluoromethyl, C.sub.3-10 cycloalkyl, hydroxyl, sulfhydryl,
alkoxy (such as above defined, in particular methoxy), thio
C.sub.1-7 alkyl, thio C.sub.3-10 cycloalkyl, cyano, carboxylic acid
or esters. depending upon the number of unsaturations in each of
said rings, heterocyclic groups may be sub-divided into
heteroaromatic (or "heteroaryl") groups and non-aromatic
heterocyclic groups; when a heteroatom of the said non-aromatic
heterocyclic group is nitrogen, the latter may be substituted with
a substituent selected from the group consisting of C.sub.1-7
alkyl, C.sub.3-10 cycloalkyl, aryl, arylalkyl and alkylaryl (each
of said groups being as defined herein).
[0031] As used herein, and unless otherwise stated, the term
"alkoxy" refer to substituents wherein an alkyl group is attached
to an oxygen atom through a single bond.
[0032] As used herein, and unless otherwise stated, the terms
"halo" or "halogen" means any atom selected from the group
consisting of fluoro, chloro, bromo and iodo.
[0033] As used herein, and unless otherwise stated, the term "acyl"
refers to a substituent derived from an acid such as an organic
monocarboxylic acid, a carbonic acid, a carbamic acid (resulting
into a carbamoyl substituent) or the thioacid or imidic acid
(resulting into a carbamidoyl substituent) corresponding to said
acids, wherein said acids comprise an aliphatic, aromatic or
heterocyclic group in the molecule. A more specific kind of "acyl"
group within the scope of the above definition refers to a carbonyl
(oxo) group adjacent to an alkyl, a cycloalkyl, an aryl, an
arylalkyl or a heterocyclic group, all of them being such as herein
defined.
[0034] The present invention is directed to novel liquid polymeric
phosphites of the general Structure IV as stabilizers for polymers
during processing.
##STR00007##
[0035] wherein [0036] each R.sup.1, R.sup.2, R.sup.3 and R.sup.4
can be the same or different and independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers, and or Y--OH
(serving as an end capping moiety); [0037] Y is selected from the
group consisting of C.sub.2-40 alkylene, C.sub.2-40 alkyl lactone,
(e.g., ethylene, propylene, caprylactone),
--R.sup.7--N(R.sup.8)--R.sup.9-- (e.g., C.sub.2-40 alkyl diamines
and C.sub.2-40 alkyl triamines), [0038] wherein R.sup.7, R.sup.8
and R.sup.9 are independently selected from the group previously
defined for R.sup.1, R.sup.2, R.sup.3 and R.sup.4, now further
including H; [0039] m is an integral value ranging from 2 to 100
inclusive; [0040] x is an integral value ranging from 1 to 1,000;
further wherein [0041] no more than two of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are terminated with an hydroxyl group.
[0042] Depending on reaction conditions and components, it is also
possible to synthesize Structure V, and be within the scope of this
invention:
##STR00008##
[0043] wherein [0044] each substituent is defined as with Structure
(IV).
[0045] Synthesis of the compositions typically involve
transesterification in which triphenyl phosphite (or any other
suitable alkyl or aryl phosphite) is allowed to react with an alkyl
or alkenyl alcohol or polyethylene or polypropylene glycol-ether
and a diol or a polymeric diol H(OY).sub.mOH wherein Y and m are as
previously defined with a suitable base catalyst at temperature
between 20.degree. C. and 250.degree. C., and more preferred at
temperature between 50.degree. C. and 185.degree. C. Non-limiting
examples of mono alkyl or alkenyl alcohols include: decyl,
isodecyl, lauryl, tridecyl, isotridecyl, myristyl, pentdecyl,
palmyl, stearyl, isotearyl, oleic alcohol, momo hydroxyl
glcolethers, etc.
[0046] Suitable base catalysts include sodium hydroxide, sodium
methoxide, sodium phenolate, potassium hydroxide, and potassium
carbonate. The amount of the base catalyst used is within the range
of 0.01 to 10 weight percent based on the total amount of reactants
charged. In a preferred embodiment, the amounts are within 0.1 to
1.0 weight percent of the reactants.
[0047] The mole ratio of alkyl alcohol or glycol-ether (containing
no alkylphenols) and a polymeric diol used in forming the
diphosphite of general Structures IV or V, with regard to triphenyl
phosphite, is from about 1.9 to 2.2 moles of the phenol or alcohol
or glycol-ether per mole of triphenyl phosphite and 0.3 to 0.6 mole
of the diol per mole of triphenyl phosphite. In a preferred
embodiment, the mole ratio is 2.0 to 1.0 of an alkyl or alkenyl
alcohol or a glycol ether per mole of triphenyl phosphite and the
mole ratio of a diol to triphenyl phosphite is 0.5 to 1.0.
[0048] The structure composition of the polymeric phosphites of the
Structure IV depends on the reaction conditions, for example the
temperature, the sequence how the reactants are added, alkyl or
alkenyl alcohol or glycol ether or a mixture or alkyl or alkenyl
alcohol or glycol ether or a combination of some or all are used,
the mole ratio and the concentration of the alkyl or alkenyl
alcohols or glycol ether and the polymeric diols, and the molecular
weight of the polymeric diols chosen. For example, the phosphorus
content of the polymeric phosphite can be adjusted by the molecular
weight of the diol and the alkyl or alkenyl alcohol or glycol ether
chosen. The viscosity of the polyphosphite, again, can be adjusted
by the molecular weight, the length and the structure, whether it
is straight or branched, of the diol used, and as well as the
molecular weight of the phenol alkyl or alkenyl alcohol or glycol
ether used.
[0049] The preferred alkyl alcohols used are C.sub.12 to C.sub.18.
The preferred alkenyl alcohols used are the C.sub.16 and C.sub.18.
And the preferred glycol ethers used are Carbowax 350
(monomethylether of polyethylene glycol MW 350, and tripropylene
glycol monobutylether.
[0050] The polymeric diols used in the process are those which are
commercially available, known as poly glycols. The preferred poly
glycols are polyethylene or polypropylene glycols, having molecular
weight ranging from 200 to 3000, and existing as liquids at room
temperature. The most preferred are polyethylene glycols, having
molecular weight 300 to 400, and polypropylene glycols, having
molecular weight of 300 to 1000.
[0051] The polymeric diphosphites of the general Structure IV and
the polymeric phosphites of general Structure V are suitable for
stabilization of organic materials against oxidative, thermal or
actinic degradation.
[0052] The organic materials are preferably synthetic polymers.
Non-limiting illustrative examples of such polymers include:
[0053] Polymers of monoolefins and diolefins for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyvinylcyclohexane, 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), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE), and blends of the polymers described above, regardless of
the method of preparation.
[0054] Mixtures of the polymers above, for example, mixtures of
polypropylene with polyisobutylene, polypropylene with polyethylene
(for example PP/HDPE, PP/LDPE) and mixtures of different types of
polyethylene (for example LDPE/HDPE).
[0055] Copolymers of monoolefins and diolefins with each other or
with other vinyl monomers such as 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,
ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin
copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins
copolymers, where the 1-olefin is generated in-situ;
propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate
copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl
acetate copolymers 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 previously, for example
polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl
acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers
(EAA), LLDPE/EVA, LLDPE/EAA and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0056] Hydrocarbon resins, (for example C.sub.5-C.sub.9) including
hydrogenated modifications thereof (e.g. tackifiers) and mixtures
of polyalkylenes and starch.
[0057] Homopolymers and copolymers from the above and which may
have any stereostructure including syndiotactic, isotactic,
hemi-isotactic or atactic. Stereoblock polymers are also
included.
[0058] Polystyrene and poly(p-methylstyrene) and
poly(.alpha.-methylstyene).
[0059] Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, .alpha.-methylstyrene, all
isomers of vinyl toluene, especially p-vinyltoluene, all isomers of
ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene,
and vinyl anthracene, and mixtures thereof. Homopolymers and
copolymers may have any stereostructure including syndiotactic,
isotactic, hemi-isotactic or atactic. Stereoblock polymers are also
included. Copolymers are included, such as vinyl aromatic monomers
and comonomers selected from ethylene, propylene, dienes, nitriles,
acids, maleic anhydrides, maleim ides, vinyl acetate and vinyl
chloride or acrylic derivatives and mixtures thereof, for example
styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
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 ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene. Hydrogenated aromatic polymers
derived from hydrogenation of polymers mentioned above are
included, especially including polycyclohexylethylene (PCHE)
prepared by hydrogenating atactic polystyrene, often referred to as
polyvinylcyclohexane (PVCH). Further included are hydrogenated
aromatic polymers derived from hydrogenation of polymers mentioned
previously. The homopolymers and copolymers may have any
stereostructure including syndiotactic, isotactic, hemi-isotactic
or atactic. Stereoblock polymers are also included.
[0060] Graft copolymers of vinyl aromatic monomers, such as 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 above, for example
the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
[0061] Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfo-chlorinated 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 copolymers. such as
styrene on polybutadiene, styrene and alkylacrylates or
methacrylates on butadiene, styrene and acrylonitrile on
ethylene/propylene/diene terpolymers, styrene and acrylonitrile on
polyacrylates or polymethacrylates, styrene and acrylonitrile on
acrylate/butadiene copolymers, and copolymer blends known as ABS,
MBS, and AES polymers.
[0062] 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.
[0063] Copolymers of the monomers mentioned in the preceding
paragraph 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.
[0064] 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 above.
[0065] Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0066] Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0067] Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0068] Polyurethanes derived from hydroxyl-terminated polyethers,
polyesters or polybutadienes on the one hand and aliphatic or
aromatic polyisocyanates on the other, as well as precursors
thereof.
[0069] 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,-trimethylhexamethylene
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).
[0070] Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0071] 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, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS.
[0072] Polycarbonates and polyester carbonates.
[0073] Polysulfones, polyether sulfones and polyether ketones.
[0074] Crosslinked polymers derived from aldehydes on the one hand
and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0075] Drying and non-drying alkyd resins.
[0076] 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.
[0077] Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0078] Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0079] Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0080] Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and their derivatives.
[0081] Blends and alloys of the aforementioned polymers
(polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA,
PVC/ABS, PVC/MBS, PC/ABS, PC/Polyester, PBTP/ABS, PC/ASA, PC/PBT,
PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic
PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,
PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
[0082] Naturally occurring and synthetic organic materials which
are pure monomeric compounds or mixtures of such compounds, for
example mineral oils, animal and vegetable fats, oil and waxes, or
oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates or trimellitates) and also mixtures of
synthetic esters with mineral oils in any weight ratios, typically
those used as spinning compositions, as well as aqueous emulsions
of such materials.
[0083] Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers.
[0084] In general the polymeric diphosphites and the polymeric
phosphites of this invention are added to the organic material to
be stabilized in amounts from about 0.001 wt % to about 5 wt % of
the weight of the organic material to be stabilized. A more
preferred range is from about 0.01% to 2.0%. The most preferred
range is from 0.025% to 1%.
[0085] The stabilizers of this invention may be incorporated into
the organic materials at any convenient stage prior to manufacture
of the shaped article using techniques known in the art.
[0086] The stabilized polymer compositions of the invention may
also contain from about 0.001% to 5%, preferably from 0.01% to 2%,
and most preferably from 0.025% to 1% of other conventional
stabilizers, a non-limiting exemplary list is provided below.
[0087] Hindered phenolic antioxidants such as
2,6-di-tert-butyl-4-methylphenol; octadecyl
3,5-di-tert-butyl-4-hydroxy-hydrocinnamate; tetrakis methylene
(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane; and
tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate.
[0088] Thioesters, a non-limiting exemplary list including dilauryl
thiodipropionate and distearyl thiodipropionate.
[0089] Aromatic amine stabilizers, a non-limiting exemplary list
including as N,N'-diphenyl-p-phenylene-diamine.
[0090] Hindered amine light stabilizers, known as HALS, a
non-limiting exemplary list including
bis-(2,2,6,6-tetramethylpiperidyl) sebacate, condensation product
of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and
4,4-octylamino-2,6-dichloro-s-triazine, and the condensation
product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine
and 4-N-morpholinyl-2,6-dichloro-s-triazine.
[0091] UV absorbers, a non-limiting exemplary list including
2-hydroxy-4-n-octyloxybenzophenone,
2(2'-hydroxy-5'-methylphenyl)-benzotriazole, and
2(2'-hydroxy-5-t-octylphenyl)-benzotriazole.
[0092] Phosphites, a non-limiting exemplary list including
tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol
diphosphite, and 2,4-dicumylphenyl pentaerythritol diphosphite.
[0093] Acid neutralizers, a non-limiting exemplary list including
calcium stearate, zinc stearate, calcium lactate, calcium stearyl
lactate, epoxidized soybean oil, and hydrotalcite (natural and
synthetic).
[0094] Other additives such as lubricants, antistatic agents,
antiblocking agents, slip agents, fire retardants, nucleating
agents, impact modifiers, blowing agents, plasticizers, fillers,
dyes, and pigments may be used in an amount appropriate and in
combination of the invented polymeric diphosphites to modify a
selected property of the polymer, such as alkanolamines, a
non-limiting exemplary list including triethanolamine and
triisopropanolamine.
[0095] The novel, polymeric phosphites of the structures IV and V
can be used in particular with combination of phenolic
antioxidants, light stabilizers and/or processing stabilizers.
[0096] In addition to the liquid polymeric compounds of the
formulas IV and V, the novel compositions can comprise further
additives, such as for example the following:
[0097] Antioxidants:
[0098] Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethyl-phenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
linear or branched in the side chains, for example
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0099] Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctyl-thiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol.
[0100] Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0101] Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, 6-tocopherol and mixtures
thereof (vitamin E).
[0102] Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
[0103] Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane-
, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0104] O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dim ethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0105] Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat-
e,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hyd-
roxybenzyl)malonate.
[0106] Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0107] Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-tria-
zine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tr-
iazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5--
triazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0108] Benzylphosphonates, for example dim
ethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
[0109] Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0110] Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0111] Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
[0112] Esters of .beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0113] Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0114] Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenedia-
mide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenedia-
mide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de.
[0115] Ascorbic acid (vitamin C).
[0116] Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine, N,
N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0117] UV Absorbers and Light Stabilizers
[0118] 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlo-
robenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobe-
nzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyp-
henyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yl-
phenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
--[R--CH.sub.2CH.sub.2--COO--CH.sub.2CH.sub.2].sub.2--, where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)phenyl]benzotriazole.
[0119] 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0120] Esters of substituted and unsubstituted benzoic acids, for
example 4-tert-butylphenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate,
octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
[0121] Acrylates, for example ethyl
.alpha.-cyano-3,3-diphenylacrylate,
isooctyl-.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and N-(.beta.-carbomethoxy
.beta.-cyanovinyl)-2-methylindoline.
[0122] Nickel compounds, for example nickel complexes of
2,2'-thiobis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
[0123] Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethyl-piperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine, a condensate of
1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as
N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine,
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di-aza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid anhydride-.alpha.-olefin
copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine.
[0124] Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0125] 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-di-
methyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
l)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dim
ethyl-phenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-ethylethoxy)phenyl]-4,6-diphenyl-1,3,5-triazine.
[0126] Metal deactivators, for example N,N'-diphenyloxamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyldihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0127] Phosphites and phosphonites, for example triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosph-
ocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosp-
hocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,r-bi[rh-
o]henyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite-
,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0128] Phosphines, for example
1,3-bis(diphenylphosphino)-2,2-dimethyl-propane.
[0129] Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0130] Nitrones, for example N-benzyl-.alpha.-phenylnitrone,
N-ethyl-.alpha.-methylnitrone, N-octyl-.alpha.-heptylnitrone,
N-lauryl-.alpha.-undecylnitrone,
N-tetradecyl-.alpha.-tridecylnitrone,
N-hexadecyl-.alpha.-pentadecylnitrone,
N-octadecyl-.alpha.-heptadecylnitrone,
N-hexadecyl-.alpha.-heptadecylnitrone,
N-ocatadecyl-.alpha.-pentadecylnitrone,
N-heptadecyl-.alpha.-hepta-decylnitrone,
N-octadecyl-.alpha.-hexadecylnitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0131] Thiosynemists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0132] Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0133] Polyamide stabilizers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0134] Basic co-stabilizers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0135] Nucleating agents, for example inorganic substances, such as
talcum, metal oxides, such as titanium dioxide or magnesium oxide,
phosphates, carbonates or sulfates of, preferably, alkaline earth
metals; organic compounds, such as mono- or polycarboxylic acids
and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,
diphenylacetic acid, sodium succinate or sodium benzoate; polymeric
compounds, such as ionic copolymers (ionomers), e.g.,
1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyldibenzylidene)sorbitol, and
1,3:2,4-di(benzylidene)sorbitol.
[0136] Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0137] Other additives, for example plasticizers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents blowing agents and infrared (IR) adsorbers. Preferred IR
absorbers are for example pigments, dyes or organometallic
compounds.
[0138] Benzofuranones and indolinones, such as
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one-
], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one or
3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.
[0139] The synthetic polymers prepared in this way can be employed
in a wide variety of forms, for example as foams, films, fibers,
tapes, molding compositions, as profiles or as binders for coating
materials, especially powder coatings, adhesives, putties or
especially as thick-layer polyolefin moldings which are in
long-term contact with extractive media, such as, for example,
pipes for liquids or gases, films, fibers, geomembranes, tapes,
profiles or tanks.
[0140] In one non-limiting embodiment, the preferred thick-layer
polyolefin moldings have a layer thickness of from 1 to 50 mm, in
particular from 1 to 30 mm, for example from 2 to 10 mm.
[0141] The compositions according to the invention can be
advantageously used for the preparation of various shaped articles.
An exemplary non-limiting list of end-use applications include, but
are not limited to: Floating devices, marine applications,
pontoons, buoys, plastic lumber for decks, piers, boats, kayaks,
oars, and beach reinforcements; Automotive applications, in
particular bumpers, dashboards, battery, rear and front linings,
moldings parts under the hood, hat shelf, trunk linings, interior
linings, air bag covers, electronic moldings for fittings (lights),
panes for dashboards, headlamp glass, instrument panel, exterior
linings, upholstery, automotive lights, head lights, parking
lights, rear lights, stop lights, interior and exterior trims; door
panels; gas tank; glazing front side; rear windows; seat backing,
exterior panels, wire insulation, profile extrusion for sealing,
cladding, pillar covers, chassis parts, exhaust systems, fuel
filter/filler, fuel pumps, fuel tank, body side moldings,
convertible tops, exterior mirrors, exterior trim,
fasteners/fixings, front end module, glass, hinges, lock systems,
luggage/roof racks, pressed/stamped parts, seals, side impact
protection, sound deadener/insulator and sunroof; Road traffic
devices, in particular sign postings, posts for road marking, car
accessories, warning triangles, medical cases, helmets, tires;
Devices for plane, railway, motor car (car, motorbike) including
furnishings; Devices for space applications, in particular rockets
and satellites, e.g. reentry shields; Devices for architecture and
design, mining applications, acoustic quietized systems, street
refuges, and shelters.
[0142] The invention also has applicability in: Appliances, cases
and coverings in general and electric/electronic devices (personal
computer, telephone, portable phone, printer, television-sets,
audio and video devices), flower pots, satellite TV bowl, and panel
devices; Jacketing for other materials such as steel or textiles;
Devices for the electronic industry, in particular insulation for
plugs, especially computer plugs, cases for electric and electronic
parts, printed boards, and materials for electronic data storage
such as chips, check cards or credit cards; Electric appliances, in
particular washing machines, tumblers, ovens (microwave oven),
dish-washers, mixers, and irons; Covers for lights (e.g.
street-lights, lamp-shades); Applications in wire and cable
(semi-conductor, insulation and cable-jacketing); and foils for
condensers, refrigerators, heating devices, air conditioners,
encapsulating of electronics, semi-conductors, coffee machines, and
vacuum cleaners.
[0143] The invention further has applicability in: Technical
articles such as cogwheel (gear), slide fittings, spacers, screws,
bolts, handles, and knobs; Rotor blades, ventilators and windmill
vanes, solar devices, swimming pools, swimming pool covers, pool
liners, pond liners, closets, wardrobes, dividing walls, slat
walls, folding walls, roofs, shutters (e.g. roller shutters),
fittings, connections between pipes, sleeves, and conveyor belts;
Sanitary articles, in particular shower cubicles, lavatory seats,
covers, and sinks; Hygienic articles, in particular diapers
(babies, adult incontinence), feminine hygiene articles, shower
curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and
bed pans; Pipes (crosslinked or not) for water, waste water and
chemicals, pipes for wire and cable protection, pipes for gas, oil
and sewage, guttering, down pipes, and drainage systems; Profiles
of any geometry (window panes) and siding; Glass substitutes, in
particular extruded or co-extruded plates, glazing for buildings
(monolithic, twin or multiwall), aircraft, schools, extruded
sheets, window film for architectural glazing, train,
transportation, sanitary articles, and greenhouse; Plates (walls,
cutting board), extrusion-coating (photographic paper, tetrapack
and pipe coating), silos, wood substitute, plastic lumber, wood
composites, walls, surfaces, furniture, decorative foil, floor
coverings (interior and exterior applications), flooring, duck
boards, and tiles; Intake and outlet manifolds; and Cement-,
concrete-, composite-applications and covers, siding and cladding,
hand rails, banisters, kitchen work tops, roofing, roofing sheets,
tiles, and tarpaulins.
[0144] Still further applications include: Plates (walls and
cutting board), trays, artificial grass, astroturf, artificial
covering for stadium rings (athletics), artificial floor for
stadium rings (athletics), and tapes; Woven fabrics continuous and
staple, fibers (carpets/hygienic
articles/geotextiles/monofilaments; filters; wipes/curtains
(shades)/medical applications), bulk fibers (applications such as
gown/protection clothes), nets, ropes, cables, strings, cords,
threads, safety seat-belts, clothes, underwear, gloves; boots;
rubber boots, intimate apparel, garments, swimwear, sportswear,
umbrellas (parasol, sunshade), parachutes, paraglides, sails,
"balloon-silk", camping articles, tents, airbeds, sun beds, bulk
bags, and bags; and Membranes, insulation, covers and seals for
roofs, tunnels, dumps, ponds, dumps, walls roofing membranes,
geomembranes, swimming pools, curtains (shades)/sun-shields,
awnings, canopies, wallpaper, food packing and wrapping (flexible
and solid), medical packaging (flexible & solid),
airbags/safety belts, arm- and head rests, carpets, centre console,
dashboard, cockpits, door, overhead console module, door trim,
headliners, interior lighting, interior mirrors, parcel shelf, rear
luggage cover, seats, steering column, steering wheel, textiles,
and trunk trim.
[0145] Additional applications include: Films (packaging, dump,
laminating, agriculture and horticulture, greenhouse, mulch,
tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper,
stretch film, raffia, desalination film, batteries, and connectors;
Food packing and wrapping (flexible and solid), bottles; Storage
systems such as boxes (crates), luggage, chest, household boxes,
pallets, shelves, tracks, screw boxes, packs, and cans; and
Cartridges, syringes, medical applications, containers for any
transportation, waste baskets and waste bins, waste bags, bins,
dust bins, bin liners, wheely bins, container in general, tanks for
water/used water/chemistry/gas/oil/gasoline/diesel; tank liners,
boxes, crates, battery cases, troughs, medical devices such as
piston, ophthalmic applications, diagnostic devices, and packing
for pharmaceuticals blister.
[0146] Still additional applications may encompass: Extrusion
coating (photo paper, tetrapack, pipe coating), household articles
of any kind (e.g. appliances, thermos bottle/clothes hanger),
fastening systems such as plugs, wire and cable clamps, zippers,
closures, locks, and snap-closures; Support devices, articles for
the leisure time such as sports and fitness devices, gymnastics
mats, ski-boots, inline-skates, skis, big foot, athletic surfaces
(e.g. tennis grounds); screw tops, tops and stoppers for bottles,
and cans; Furniture in general, foamed articles (cushions, impact
absorbers), foams, sponges, dish clothes, mats, garden chairs,
stadium seats, tables, couches, toys, building kits
(boards/figures/balls), playhouses, slides, and play vehicles;
Materials for optical and magnetic data storage; Kitchen ware
(eating, drinking, cooking, storing); Boxes for CD's, cassettes and
video tapes; DVD electronic articles, office supplies of any kind
(ball-point pens, stamps and ink-pads, mouse, shelves, tracks),
bottles of any volume and content (drinks, detergents, cosmetics
including perfumes), and adhesive tapes; Footwear
(shoes/shoe-soles), insoles, spats, adhesives, structural
adhesives, food boxes (fruit, vegetables, meat, fish), synthetic
paper, labels for bottles, couches, artificial joints (human),
printing plates (flexographic), printed circuit boards, and display
technologies; and devices of filled polymers (talc, chalk, china
clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica,
nanocomposites, dolomite, silicates, glass, asbestos).
[0147] Still further applications may encompass are: compositions
comprising as component (a) fibers and fabrics used in nonwoven
medical fabric and related apparel (surgical gowns, drapes,
bandages), construction fabrics (house wrapping, roofing,
swimming-pool wrapping) and home furnishing (carpets, table linens,
shower curtains).
[0148] Thus, a further embodiment of the present invention relates
to a shaped article, in particular a film, pipe, profile, bottle,
tank or container, fiber containing a composition as described
above.
[0149] As evident from the above, the organic materials to be
protected are preferably organic polymers, particularly synthetic
polymers. Thermoplastic materials, in particular polyolefins, are
particularly advantageously protected. In particular, the excellent
effectiveness of the polymeric compounds of the formula IV as
processing stabilizers (heat stabilizers) should be emphasized. For
this purpose, they are advantageously added to the polymer before
or during processing thereof. However, other polymers (for example
elastomers) or lubricants or hydraulic fluids can also be
stabilized against degradation, for example light-induced or
thermo-oxidative degradation. Elastomers are given in the above
list of possible organic materials.
[0150] At least one aspect of the present invention is therefore
the use of a liquid polymeric compound of the Formula IV or Formula
V or a mixture of compositions resulting from the synthesis of
compositions covered by Formulas IV and/or V for protecting organic
materials against oxidative, thermal or light-induced degradation.
The novel liquid polymeric compounds are at least partially
distinguished by pronounced hydrolysis stability and advantageous
coloring behaviour, i.e. low discoloration of the organic materials
during processing.
[0151] The invention will now be described by a series of
examples.
Example #1
[0152] The apparatus in Example #1 was used. PPG 425 (55 g, 0.129
mol), triphenyl phosphite (45 g, 0.145 mol), Carbowax 350 (a
mono-methylether polyethylene glycol with an average MW of 350),
(63 g, 0.189 mol), and 0.8 grams of potassium hydroxide were added.
The mixture was mixed well and heated to 160-162.degree. C. under
nitrogen and held at the temperature for 1 hour. The pressure was
then gradually reduced to 0.3 mmHg and the temperature was
increased to 170-172.degree. C. over a course of 1 hour. The
reaction contents were held at 170-172.degree. C. under the vacuum
for 2 hours at which point no more phenol was distilling out. The
vacuum was then broken by nitrogen and the crude product was cooled
to 50.degree. C. The product was a clear, colorless liquid.
Example #2
[0153] The apparatus in Example #1 was used. PPG 400 (95 g, 0.237
mol), triphenyl phosphite (73 g, 0.235 mol), a mixture of lauryl
and myristyl alcohol with a hydroxyl number of about 280, (47 g,
0.235 mol), and 0.8 grams of potassium hydroxide were added. The
mixture was mixed well and heated to 160-162.degree. C. under
nitrogen and held at the temperature for 1 hour. The pressure was
then gradually reduced to 0.3 mmHg and the temperature was
increased to 170-172.degree. C. over a course of 1 hour. The
reaction contents were held at 170-172.degree. C. under the vacuum
for 2 hours at which point no more phenol was distilling out. The
vacuum was then broken by nitrogen and the crude product was cooled
to 50.degree. C. The product was a clear, colorless liquid.
Example #3
[0154] The apparatus in Example #1 was used. PPG 400 (48 g, 0.12
mol), triphenyl phosphite (73 g, 0.235 mol), lauryl alcohol, (47 g,
0.235 mol), dipropylene glycol (16 g 0.12 mol) and 0.8 grams of
potassium hydroxide were added. The mixture was mixed well and
heated to 160-162.degree. C. under nitrogen and held at the
temperature for 1 hour. The pressure was then gradually reduced to
0.3 mmHg and the temperature was increased to 170-172.degree. C.
over a course of 1 hour. The reaction contents were held at
170-172.degree. C. under the vacuum for 2 hours at which point no
more phenol was distilling out. The vacuum was then broken by
nitrogen and the crude product was cooled to 50.degree. C. The
product was a clear, colorless liquid.
Example #4
[0155] The apparatus in Example #1 was used. PPG 400 (50.22 g,
0.1256 mol), triphenyl phosphite (40 g, 0.129 mol), Carbowax 350 (a
mono-methylether polyethylene glycol with an average MW of 350),
(26 g, 0.074 mol), tri-isopropanol amine (4.5 g 0.023 mol), and 0.8
grams of potassium hydroxide were added. The mixture was mixed well
and heated to 160-162.degree. C. under nitrogen and held at the
temperature for 1 hour. The pressure was then gradually reduced to
0.3 mmHg and the temperature was increased to 170-172.degree. C.
over a course of 1 hour. The reaction contents were held at
170-172.degree. C. under the vacuum for 2 hours at which point no
more phenol was distilling out. The vacuum was then broken by
nitrogen and the crude product was cooled to 50.degree. C. The
product was a clear, colorless liquid.
Example #5
[0156] The apparatus in Example #1 was used. PPG 400 (100 g, 0.25
mol), triphenyl phosphite (78 g, 0.2516 mol), a mixture of cetyl
and stearyl alcohol with a hydroxyl number of about 211, (34 g,
0.1285 mol), tripropylene glycol butylether (32 g, 0.129 mol) and
0.8 grams of potassium carbonate were added. The mixture was mixed
well and heated to 160-162.degree. C. under nitrogen and held at
the temperature for 1 hour. The pressure was then gradually reduced
to 0.3 mmHg and the temperature was increased to 170-172.degree. C.
over a course of 1 hour. The reaction contents were held at
170-172.degree. C. under the vacuum for 2 hours at which point no
more phenol was distilling out. The vacuum was then broken by
nitrogen and the crude product was cooled to 50.degree. C. The
product was a clear, colorless liquid.
Example #6
[0157] The apparatus in Example #1 was used. PPG 400 (100 g, 0.25
mol), triphenyl phosphite (78 g, 0.2516 mol), a mixture of cetyl
and stearyl alcohol with a hydroxyl number of about 211, (34 g,
0.1285 mol), oleyl alcohol (34 g, 0.126 mol) and 0.8 grams of
potassium carbonate were added. The mixture was mixed well and
heated to 160-162.degree. C. under nitrogen and held at the
temperature for 1 hour. The pressure was then gradually reduced to
0.3 mmHg and the temperature was increased to 170-172.degree. C.
over a course of 1 hour. The reaction contents were held at
170-172.degree. C. under the vacuum for 2 hours at which point no
more phenol was distilling out. The vacuum was then broken by
nitrogen and the crude product was cooled to 50.degree. C. The
product was a clear, colorless liquid.
Example #7
[0158] The apparatus in Example #1 was used. PPG 400 (95 g, 0.237
mol), triphenyl phosphite (73 g, 0.235 mol), Neodol 23 (a blend of
C.sub.12 and C.sub.13 alcohols) (57 g, 0.266 mol) and 0.8 grams of
potassium hydroxide were added. The mixture was mixed well and
heated to 160-162.degree. C. under nitrogen and held at the
temperature for 1 hour. The pressure was then gradually reduced to
0.3 mmHg and the temperature was increased to 170-172.degree. C.
over a course of 1 hour. The reaction contents were held at
170-172.degree. C. under the vacuum for 2 hours at which point no
more phenol was distilling out. The vacuum was then broken by
nitrogen and the crude product was cooled to 50.degree. C. The
product was a hazy, colorless liquid.
Example #8
[0159] The apparatus in Example #1 was used. PPG 400 (100 g, 0.25
mol), triphenyl phosphite (155 g, 0.5 mol), a mixture of lauryl and
myristyl alcohol with a hydroxyl number of about 280, (200 g, 1.0
mol), and 0.8 grams of potassium hydroxide were added. The mixture
was mixed well and heated to 160-162.degree. C. under nitrogen and
held at the temperature for 1 hour. The pressure was then gradually
reduced to 0.3 mmHg and the temperature was increased to
170-172.degree. C. over a course of 1 hour. The reaction contents
were held at 170-172.degree. C. under the vacuum for 2 hours at
which point no more phenol was distilling out. The vacuum was then
broken by nitrogen and the crude product was cooled to 50.degree.
C. The product was a clear, colorless liquid.
Example #9
[0160] The apparatus in Example #1 was used. 1,6 hexane diol (57 g,
0.48 mol), triphenyl phosphite (150 g, 0.48 mol), a mixture of
lauryl and myristyl alcohol with a hydroxyl number of about 280,
(97 g, 0.48 mol), and 0.8 grams of potassium hydroxide were added.
The mixture was mixed well and heated to 160-162.degree. C. under
nitrogen and held at the temperature for 1 hour. The pressure was
then gradually reduced to 0.3 mmHg and the temperature was
increased to 170-172.degree. C. over a course of 1 hour. The
reaction contents were held at 170-172.degree. C. under the vacuum
for 2 hours at which point no more phenol was distilling out. The
vacuum was then broken by nitrogen and the crude product was cooled
to 50.degree. C. The product was a hazy, colorless liquid.
Example #10
[0161] The apparatus in Example #1 was used. Poly THF 250MW (121 g,
0.48 mol), triphenyl phosphite (150 g, 0.48 mol), a mixture of
lauryl and myristyl alcohol with a hydroxyl number of about 280,
(97 g, 0.48 mol), and 0.8 grams of potassium hydroxide were added.
The mixture was mixed well and heated to 160-162.degree. C. under
nitrogen and held at the temperature for 1 hour. The pressure was
then gradually reduced to 0.3 mmHg and the temperature was
increased to 170-172.degree. C. over a course of 1 hour. The
reaction contents were held at 170-172.degree. C. under the vacuum
for 2 hours at which point no more phenol was distilling out. The
vacuum was then broken by nitrogen and the crude product was cooled
to 50.degree. C. The product was a hazy, colorless liquid.
Example #11
[0162] The apparatus in Example #1 was used. methyldiethanolamine
(58 g, 0.48 mol), triphenyl phosphite (150 g, 0.48 mol), a mixture
of lauryl and myristyl alcohol with a hydroxyl number of about 280,
(97 g, 0.48 mol), and 0.8 grams of potassium hydroxide were added.
The mixture was mixed well and heated to 160-162.degree. C. under
nitrogen and held at the temperature for 1 hour. The pressure was
then gradually reduced to 0.3 mmHg and the temperature was
increased to 170-172.degree. C. over a course of 1 hour. The
reaction contents were held at 170-172.degree. C. under the vacuum
for 2 hours at which point no more phenol was distilling out. The
vacuum was then broken by nitrogen and the crude product was cooled
to 50.degree. C. The product was a hazy, colorless liquid.
Example #12
[0163] The apparatus in Example #1 was used. 100 grams (0.125 mol)
of PPG 400 (polypropylene glycol having an average molecular weight
of 400), 8.4 grams (0.071 mol) of 1,6 hexane diol, triphenyl
phosphite (100 g, 0.323 mol), a mixture of lauryl and myristyl
alcohol with a hydroxyl value of about 280 (68 g, 0.35 mol), and
0.4 grams of potassium hydroxide were added. The mixture was mixed
well and heated to approximately 150 C under nitrogen and held at
the temperature for 1 hour. The pressure was then gradually reduced
to 0.3 mm Hg and the temperature was increased to 180.degree. C.
over a course of 1 hour. The reaction contents were held at
180.degree. C. under the vacuum for 2 hours at which point no more
phenol was distilling out. The vacuum was then broken by nitrogen
and the crude product was cooled to ambient temperature.
Example #13
[0164] The apparatus in Example #1 was used. 150 grams (0.375 mol)
of PPG 400 (polypropylene glycol having an average molecular weight
of 400), 60 g of triethyl phosphite, and 0.8 grams of potassium
hydroxide were added. The mixture was mixed well and slowly heated
up to 150.degree. C. while ethanol slowly boiled out. After 12 hrs
of heating at 150.degree. C. the reaction was cooled to ambient
temperature. The product was a clear liquid.
Example #14
[0165] The apparatus in Example #1 was used. 150 grams (0.375 mol)
of PPG 400 (polypropylene glycol having an average molecular weight
of 400), 60 g of triethyl phosphite, 55 g (0.42 mol) of octanol,
and 1.0 grams of potassium hydroxide were added. The mixture was
mixed well and slowly heated up to 150.degree. C. while ethanol
slowly boiled out. After 12 hrs of heating at 150.degree. C. the
reaction was cooled to ambient temperature. The product was a clear
liquid.
Example #15
[0166] The apparatus in Example #1 was used. 100 grams (0.125 mol)
of PPG 400 (polypropylene glycol having an average molecular weight
of 400), 30 grams (0.075 mol) polycaprolactone, triphenyl phosphite
(100 g, 0.323 mol), a mixture of lauryl and myristyl alcohol with a
hydroxyl value of about 280 (66 g, 0.35 mol), and 0.5 grams of
potassium hydroxide were added. The mixture was mixed well and
heated to approximately 150.degree. C. under nitrogen and held at
the temperature for 1 hour. The pressure was then gradually reduced
to 0.3 mm Hg and the temperature was increased to 180.degree. C.
over a course of 1 hour. The reaction contents were held at
180.degree. C. under the vacuum for 2 hours at which point no more
phenol was distilling out. The vacuum was then broken by nitrogen
and the crude product was cooled to ambient temperature.
[0167] Characteristics of the various synthesized additives may be
characterized at least in part by the following tables.
TABLE-US-00001 TABLE 1 Parameter Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex.
6 Ex. 7 Ex. 8 % P 3.7 4.9 5.9 4.7 4.5 4.4 4.8 4.9 CPS/25.degree. C.
960 3212 973 2156 3144 3894 642 215 AV 0.01 0.01 0.05 0.01 0.01
0.01 0.01 0.01 Parameter Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14
Ex. 15 % P 8.9 6.4 6.4 5.4 6.9 5.2 4.9 CPS/25.degree. C. 6528 659
37282 1284 233 16 1561 AV 0.01 0.01 0.01 0.03 0.01 0.01 0.01
TABLE-US-00002 TABLE 2 MW data Parameter Ex. 1 Ex. 2 Ex. 3 Ex. 4
Ex. 5 Ex. 6 MW range 1000-16,500 700-55,000 350-50,000 600-16,500
1,000-55,000 800-55,000 Average MW 6,125 9,111 7,250 6,155 21,243
10,666 Parameter Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 MW range
1200-55,000 630-6,500 800-320,000 630-16,500 850-8,000 558-278,910
Average MW 12,024 2,550 31,515 8,157 1,530 23,942 Parameter Ex. 13
Ex. 14 Ex. 15 MW range 145-11,738 210-6,469 514-147,610 Average MW
1,413 918 20,078
[0168] Polymeric phosphites of examples 1-15 are of great interest
because they are not based on alkylphenols.
[0169] The following tables detail the performance of some of the
polymeric phosphite stabilizers 1-18 in polyolefin's, (linear low
density polyethylene, either Exxon or Nova LLDPE was used). These
compounds show performance as plastic stabilizers that are
comparable to or better than that of TNPP. With regard to Melt Flow
Rate (MFR), a good plastic stabilizer will contribute to a low
initial MFR and then maintain the low MFR. For Hunter b Color
performance, a good plastic stabilizer will yield low initial color
and then maintain that low color.
Sample Preparation
[0170] The polyolefin powders (polyethylene, LLDPE); (high density
polyethyle HDPE) and (polypropylene, PP) are dry blended with the
stabilizer formulation using a Warring blender. The mixer is run at
approximately 60 rpm or a speed which does not cause the material
to splash out of the bowl for 30 seconds with shaking of blender
every 5 seconds. The master batch is then added to a preheated
co-rotating twin screw extruder where the plastic is homogeneously
mixed. Extrusion is typically performed at 260.degree. C. The
extruded plastic is cooled into a cold water bath, completely
dried, and pelletized. The collected polymer pellets are the result
of the first pass extrusion and are the starting material for all
subsequent test protocols. The isolated pellets are added to the
extruder repeatedly to generate the third and fifth pass
material.
Melt Flow Rate Analysis
[0171] The melt flow rate was performed using the ASTM 1238-90b
test method measured at 21.6 Kg/190.degree. C. The melt flow rate
was complete on a Tinius Olsen extrusion plastometer.
Color Analysis
[0172] Color analysis was performed on compression molded films or
plaques with a Hunter Lab Ulstrascan XE machine. Observations were
made with a D65 illuminant and 10.degree. observer. Yellowness
Index measurements were made in accord with ASTM D1925-70. The
lower the YI (yellowness index) the better the color.
Gas Fade Aging
[0173] Gas fade aging was performed based on methods in ASTM 1925
using a NOx gas oven. Analysis was performed on compression molded
plaques placed into a 60.degree. C. nitrogen oven. Observations
were made by measuring yellowness index for color development
during exposure to oxides of nitrogen.
[0174] The LLPE formulations were tested using 900 PPM of the
phosphite and 500 PPM of the primary antioxidant Dovernox 76 or at
1800 ppm phosphite, 300 ppm Dovernox 76, zinc stearate 200 ppm and
100 ppm DHT4A were used as neutralizers.
[0175] The HDPR formulations were tested using 900 ppm phosphite,
500 ppm Dovernox 76 and 500 pp calcium stearate.
[0176] The PP formulations were tested using 500 ppm phosphite, 500
ppm Dovernox 10 and 500 ppm calcium stearate.
TABLE-US-00003 TABLE 3 LLDPE, MFI High Load Melt Flow: 190.degree.
C./21.6 Kgs (LLDPE, Phosphite at 900 ppm and 500 ppm Dovernox 76,
extrusion temperature 260.degree. C.) Polymeric Phosphite 1.sup.st
pass 3.sup.rd pass 5.sup.th pass None 15.3 13.6 12.8 TNPP 18.1 16.4
14.4 Ex 1 18.3 14.9 13.3 Ex. 2 18.7 17.2 15.5 Ex. 4 17.1 14.4 12.9
Ex. 5 18.5 17.5 15.4 Ex. 7 18.0 16.5 14.4
[0177] The data shows that TNPP gives good MFI stability and so do
the polymeric phosphites. The polymeric phosphites either match or
in some cases exceed the performance of the TNPP.
TABLE-US-00004 TABLE 4 LLDPE YI Color Data Polymeric Phosphite
1.sup.st pass 3.sup.rd pass 5.sup.th pass none -3.7 -1.7 0.4 TNPP
-4.7 -2.9 -0.1 Ex. 1 -6.2 -3.3 -1.1 Ex. 2 -5.4 -2.9 0.0 Ex. 4 -4.6
-2.3 1.4 Ex. 5 -4.4 -2.6 0.6 Ex. 7 -5.3 -3.9 -2.2
[0178] The polymeric phosphites closely match or exceed the
performance of the TNPP in color stability (the lower the YI the
better the color).
TABLE-US-00005 TABLE 5 Gas Fade 60.degree. C. Using 1.sup.st Pass,
LLDPE, Days Phos- phite 0 days 6 days 12 days 19 days 22 days 29
days TNPP -1.2 7.0 26.5 34.5 362 39.6 Ex. 2 -5.4 3.8 16.8 25.1 27.4
31.8 Ex. 7 -6.0 0.7 14.0 23.6 26.7 33.1
[0179] The gas fade results are better for the polymeric
phosphites.
TABLE-US-00006 TABLE 6 High Load Melt Flow: 190.degree. C./21.6 Kgs
(HDPE: 900 ppm Phosphite, 500 ppm Dovernox 76, and 500 ppm calcium
stearate) Extrusion temperature 260.degree. C. Phosphite 1.sup.st
pass 3.sup.rd pass 5.sup.th pass none 25.1 22.4 20.8 TNPP 26.6 25.3
25.1 Ex. 2 26.1 25.8 22.9 Ex. 5 25.6 24.0 22.3
TABLE-US-00007 TABLE 7 Color, YI for HDPE Extrusion @ 260 C.
Phosphite 1.sup.st pass 3.sup.rd pass 5 pass none 5 9.6 12.6 TNPP
7.4 8.1 11.7 Ex. 2 -2.4 1.2 4.0 Ex. 5 -1.0 1.7 4.1
[0180] The polymeric phosphites show good performance as stabilizer
fo HDPE especially for color.
TABLE-US-00008 TABLE 8 Melt Flow: 190.degree. C./21.6 Kgs
(Polypropylene: 500 ppm Phosphite, 500 ppm Dovernox 10, and 500 ppm
calcium stearate) Extrusion temperature 260.degree. C. Phosphite
1.sup.st pass 2.sup.nd pass 3.sup.rd pass none 30.9 50.1 Too high
TNPP 18.0 25.2 36.2 Ex. 2 20.7 26.8 39.0 Ex. 5 18.9 28.2 46.9 Ex. 2
using Vitamin E in 18.25 20.9 23.2 place of Dovernox 10
TABLE-US-00009 TABLE 9 Color, YI (Polypropylene: 500 ppm Phosphite,
500 ppm Dovernox 10, and 500 ppm calcium stearate) Extrusion
temperature 260.degree. C. Phosphite 1.sup.st pass 2.sup.nd pass
3.sup.rd pass none 9.8 12.9 17.6 TNPP 9 13.4 16.6 Ex. 2 11.6 12.3
13.5 Ex. 5 5.6 9.9 13.2 Ex. 2 using Vitamin E in 10.4 14.5 18.9
place of Dovernox 10
[0181] The polymeric phosphites show good performance as a
stabilizer in PP. The use of Vitamin E as the primary anti-oxidant
in place of the Dovernox 10 greatly improves the melt flow index
("MFI").
[0182] The data shows that some of the polymeric phosphites perform
equal to or better than the TNPP. Besides giving good melt flow
stability and color stability during processing and in gas fade
testing, the polymeric diphosphite and the polymeric
poly-phosphites have excellent compatibility with LLDPE and they do
not migrate. Non migration is especial important for additives that
are used in polymer film or plastics that are used for food
contact. Non migration also reduces of eliminates and plate out on
cooling rolls or die build up due to volatile additives. The
polymeric poly-phosphites illustrated in the Examples are
especially good polymer stabilizers for food contact plastic since
they do not contain any alkylphenols and basically are made from
raw materials that are all biodegradable.
[0183] What has been illustrated is the ability to synthesize a
liquid polymeric polyphosphite in which the substituent groups are
essentially all aliphatic. The liquid phosphite is preferably a
polyphosphite, in which the segments between the phosphite moieties
are preferably polyalkylene glycols, more preferably a polyethylene
glycol or a polypropylene glycol. During the synthesis, a
combination of monohydroxy and dihydroxy reactants are employed
with the triphosphite reactant in a molar ratio which minimizes the
number of end-capping hydroxyl groups. Without being held to any
theory of reaction, an illustrative stylized reaction schematic
depiction is illustrated below for Example #1.
##STR00009##
[0184] By controlling the molar ratio of reactants, the amount of
hydroxy termination is correspondingly controlled. The preferred
ratio is approximately 1:1:1 while a more preferred ratio will have
the dihydroxy-terminated reactant as the limiting reagent with a
slight molar excess of the monofunctional chain stopper. While the
graphic depiction is stylized and believed to be an accurate
description, the unpredictable nature of chemical reactions
prohibits any depiction with absolutely certainty. What is
illustrated however, is that while it is possible to have some
hydroxy termination in the polyphosphite, i.e., some of the above
Carbowax 350 moieties may be replaced by PPG 425 moieties. However,
by controlling the molar ratio of reactants, the amount of hydroxyl
groups at a chain end is preferably limited to no more than 1-2
chains within the molecule, depending on the amount of excess chain
stopper.
[0185] By employing the methods and techniques described
hereinabove, it is possible to control the molecular weight and
hydroxyl termination of an alkylphenol-free liquid polymeric
polyphosphite of formula (IV)
##STR00010##
wherein each R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be the same
or different and independently selected from the group consisting
of C.sub.1-20 alkyl, C.sub.2-22 alkenyl, C.sub.3-40 cycloalkyl,
C.sub.3-40 cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers,
C.sub.3-20 alkyl glycol ethers and Y--OH as an end-capping group;
each Y is independently selected from the group consisting of
C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene,
C.sub.3-20 methoxy alkyl glycol ethers, C.sub.3-20 alkyl glycol
ethers, C.sub.2-40 alkylene, C.sub.3-40 alkyl lactone, and
--R.sup.7--N(R.sup.8)--R.sup.9--; R.sup.7, R.sup.8 and R.sup.9 are
independently selected from the group consisting of C.sub.1-20
alkyl, C.sub.2-22 alkenyl, C.sub.6-40 cycloalkyl, C.sub.7-40
cycloalkylene and H; m is an integral value ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are terminated with an hydroxyl group comprising the steps
of:
[0186] reacting a triphosphite with a limiting molar amount of a
dihydroxy-terminated reactant with a molar excess of a
monofunctional chain stopper;
[0187] adding a base;
[0188] heating said triphosphite, dihydroxy-terminated reactant and
monofunctional chain stopper and base; and
[0189] isolating said alkylphenol-free liquid polymeric
polyphosphite.
[0190] The invention further comprises a process to control the
molecular weight and hydroxyl termination of an alkylphenol-free
liquid polymeric polyphosphite of formula
##STR00011##
wherein each R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 can be
the same or different and independently selected from the group
consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl, C.sub.3-40
cycloalkyl, C.sub.3-40 cycloalkylene, C.sub.3-20 methoxy alkyl
glycol ethers, C.sub.3-20 alkyl glycol ethers and A-OH and B--OH as
an end-capping group; each A and B is independently selected from
the group consisting of C.sub.2-40 alkylene, C.sub.1-20 alkyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy
alkyl glycol ethers, C.sub.3-20 alkyl glycol ethers, C.sub.3-40
alkyl lactone, and --R.sup.7--N(R.sup.8)--R.sup.9-- wherein
R.sup.7, R.sup.8 and R.sup.9 are independently selected from the
group previously defined for R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5; m and n are integral values ranging from 2 to 100
inclusive; x is an integral value ranging from 1 to 1,000; and
further wherein no more than two of R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 are terminated with an hydroxyl group
comprising the steps of:
[0191] reacting a triphosphite with a limiting molar amount of at
least two dihydroxy-terminated reactants with a molar excess of a
monofunctional chain stopper;
[0192] adding a base;
[0193] heating said triphosphite, at least two dihydroxy-terminated
reactants and monofunctional chain stopper and base; and
[0194] isolating said alkylphenol-free liquid polymeric
polyphosphite.
[0195] The above illustrates that it is within the scope of the
invention to have more than one alkylene glycol reactant. In that
scenario, the polyphosphite backbone will have at least two
different moieties. It is equally envisioned to be within the scope
of the invention to have more than one monohydroxy terminated chain
stopper as a reactant. In that scenario, the polyphosphite will
have at least two different chain stoppers in the molecule.
[0196] Therefore, what has been described is an alkylphenol-free
liquid polymeric polyphosphite which comprises:
##STR00012##
[0197] wherein [0198] each R.sup.1, R.sup.2, R.sup.3 and R.sup.4
can be the same or different and independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.3-40 cycloalkyl, C.sub.3-40 cycloalkylene, C.sub.2-20 methoxy
alkyl glycol ethers, C.sub.2-20 alkyl glycol ethers and Y--OH as an
end-capping group; [0199] each Y is independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.6-40 cycloalkyl,
C.sub.7-40 cycloalkylene, C.sub.3-20 methoxy alkyl glycol ethers,
C.sub.3-20 alkyl glycol ethers, C.sub.2-40 alkylene, C.sub.3-40
alkyl lactone, and --R.sup.7--N(R.sup.8)--R.sup.9--; [0200]
R.sup.7, R.sup.8 and R.sup.9 are independently selected from the
group consisting of C.sub.1-20 alkyl, C.sub.2-22 alkenyl,
C.sub.6-40 cycloalkyl, C.sub.7-40 cycloalkylene and H; [0201] m is
an integral value ranging from 2 to 100 inclusive; [0202] x is an
integral value ranging from 1 to 1,000; and further wherein [0203]
no more than two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
terminated with an hydroxyl group.
[0204] In one aspect of the invention, no more than two of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are difunctional having two reactive
terminal groups and a remainder are monofunctional with one
reactive terminal group.
[0205] In a more preferred embodiment, the polymeric polyphosphite
will have no more than one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4
which are terminated with an hydroxyl group, most preferably,
essentially all of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
terminated by an alkyl group. The dihydroxy terminated reactant
will preferably be a polyalkylene glycol, more preferably a
polyethylene glycol or a polypropylene glycol. In one aspect of the
invention, each R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are aliphatic
and will further contain an alkanolamine.
[0206] What has been demonstrated is that it is possible to design
a phosphite that meets all of the required performance attributes
without the use of alkylphenols as a secondary antioxidant. The
high molecular weight reduces plate-out during process and
minimizes exudation/bloom during post-processing. The higher
molecular weight also results in reduced volatility and reduced
migration and exposure.
[0207] What has also been determined is that the percent phosphorus
correlates with performance of the phosphite in terms of melt index
("MI") control during melt processing. A comparison with some very
commonly employed secondary antioxidants reveals that Example #2
has approximately 4.9% phosphorus, while tris(nonylphenyl)
phosphite has approximately 4.5% phosphorus and
tris(2,4-di-t-butylphenyl) phosphite has approximately 4.8%
phosphorus.
[0208] Ancillary benefits of the use of a high molecular weight
polyphosphite include increased compatibility with many polymers
resulting in reduced plate-out during extrusion and exudation/bloom
during post-processing. Plate-out is a result of incompatibility
during melt processing and results in material leaving deposits on
the equipment such as calendaring mills or the cooling drum/roll
during cast film product. Exudation/bloom is a physical
characteristic where over time, incompatible phosphites can bloom
to the surface of a polymer film (e.g., LLDPE film) after it has
been compounded/processed. This results in either rdusting/powder
or a sticky surface. The higher molecular weight polyphosphite
decreases phosphite migration resulting in consumer packaging
benefits.
[0209] These benefits were determined using an FDA-type migration
study. The selected additives below were compounded into LLDPE
using a Brabender torque rheometer at a concentration of 1000 ppm.
Formulations were then compression molded into plaques which were
exposed to 95% ethanol at 70.degree. C. for 2 hours. 95% ethanol is
considered a fatty food stimulant. Solutions were then analyzed for
additive content as measured as micrograms of additive that
migrated per square inch of surface.
TABLE-US-00010 TABLE 10 (micrograms of additive that migrated per
square inch of surface) Formula MW (g/mole) ppm in Food DTBP
##STR00013## 206 15.2 SP-1 ##STR00014## 646 5.2 TNPP ##STR00015##
688 5.9 SP-2 ##STR00016## 852 2.2 Example #2 >1500 <0.5
[0210] The amount of migration decreases with increasing molecular
weight and is not linear. However, migration is directly
proportional to the concentration of the additive in the polymer
and therefore, 500 ppm of SP-2 performs similarly to 1000 ppm of
SP-1. Therefore, migration can be reduced significantly by using a
high performance/high molecular weight stabilizer at a lower
loading leve.
[0211] The invention has been described with reference to preferred
and alternate embodiments. Obviously, modifications and alterations
will occur to others upon the reading and understanding of the
specification. It is intended to include all such modifications and
alterations insofar as they come within the scope of the appended
claims or the equivalents thereof.
* * * * *