U.S. patent application number 14/159719 was filed with the patent office on 2014-05-15 for liquid phosphite compositions having different alkyl groups.
This patent application is currently assigned to ADDIVANT USA LLC. The applicant listed for this patent is Michael Gelbin, Jonathan Hill, Maurice Power. Invention is credited to Michael Gelbin, Jonathan Hill, Maurice Power.
Application Number | 20140135435 14/159719 |
Document ID | / |
Family ID | 42651283 |
Filed Date | 2014-05-15 |
United States Patent
Application |
20140135435 |
Kind Code |
A1 |
Gelbin; Michael ; et
al. |
May 15, 2014 |
Liquid Phosphite Compositions Having Different Alkyl Groups
Abstract
A composition comprising a mixture of at least two different
alkylaryl phosphites, wherein some alkyl groups have a different
number of carbon atoms than other alkyl groups and wherein the
mixture is a liquid at ambient conditions.
Inventors: |
Gelbin; Michael;
(Middlebury, CT) ; Hill; Jonathan; (Flixton,
GB) ; Power; Maurice; (Trafford, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gelbin; Michael
Hill; Jonathan
Power; Maurice |
Middlebury
Flixton
Trafford |
CT |
US
GB
GB |
|
|
Assignee: |
ADDIVANT USA LLC
Middlebury
CT
|
Family ID: |
42651283 |
Appl. No.: |
14/159719 |
Filed: |
January 21, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12804680 |
Jul 26, 2010 |
8633267 |
|
|
14159719 |
|
|
|
|
61230652 |
Jul 31, 2009 |
|
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Current U.S.
Class: |
524/151 ;
252/400.2 |
Current CPC
Class: |
C08K 5/52 20130101; C08K
5/526 20130101; C08K 2201/014 20130101; C07F 9/145 20130101 |
Class at
Publication: |
524/151 ;
252/400.2 |
International
Class: |
C08K 5/52 20060101
C08K005/52 |
Claims
1. A phosphite composition of at least two different alkylaryl
phosphites, comprising at least a first alkylaryl phosphite and a
second alkylaryl phosphite of structure (XI) ##STR00023## wherein
m, n, o, p and q are integers independently selected from 0, 1, 2
and 3 provided that m+n+o+p+q=3 each Ar is an independently
selected aromatic moiety of 6 to 18 carbon atoms, each R.sub.8 is a
straight or branched C.sub.1-C.sub.18 alkyl group having the same
number of carbon atoms, each R.sub.9 is a straight or branched
C.sub.1-C.sub.18 alkyl group having the same number of carbon
atoms, provided that R.sub.8 has a different number of carbon atoms
than R.sub.9, said first aralkyl phosphite contains an aromatic
moiety substituted by at least one R.sub.8 and said second aralkyl
phosphite contains an aromatic moiety substituted by at least one
R.sub.9, the molar ratio of R.sub.8 groups to R.sub.9 groups in the
phosphites of the composition is from 1:10 to 10:1, and from 0 to
10% by weight of one or more free phenol having the structure:
##STR00024## based on the combined weight of all phosphites and
said free phenol in the composition, wherein the phosphite
composition comprises one or more tris(monoalkylaryl) phosphites of
structure (XI) wherein m, p and q are 0 and n+o=3, in an amount
from 20 to 80 weight percent based on the total weight of all
phosphites in the phosphite composition, wherein the composition is
a liquid at ambient conditions.
2. The composition of claim 1, wherein the composition comprises
one or more bis(monaoalkylaryl)dialkylaryl phosphites of structure
(XI) wherein m+p+q=1 and n+o=2, in an amount from 15 to 60 weight
percent.
3. The composition of claim 2, wherein the composition comprises
one or more bis(dialkylaryl)alkylaryl phosphites of structure (XI)
wherein m+p+q=2 and n+o=1, in an amount from 2 to 20 weight
percent.
4. The composition of claim 3, wherein the composition comprises
one or more tris(dialkylaryl) phosphites of structure (XI) wherein
m+p+q=3 and n and o are 0 in an amount from 0.1 to 20 weight
percent.
5. The composition of claim 1, wherein the composition comprises
from 0.01 to 5 weight percent of said phenols based on the total
weight of all phosphites and said free phenol in the
composition.
6. The phosphite composition of claim 1, wherein R.sub.8 and
R.sub.9 are selected from propyl, n-butyl, sec-butyl, t-butyl,
n-amyl, sec-amyl, neo-amyl and t-amyl.
7. The composition of claim 1, comprising a first alkylaryl
phosphite having the structure: ##STR00025## and a second alkylaryl
phosphite having the structure: ##STR00026## wherein a, b, c, and d
are independently integers selected from 0, 1, 2, and 3, provided
that a+b=3 and c+d=3, wherein each Ar is phenyl, and wherein each
R.sub.8 is an alkyl group having the same number of carbon atoms,
and each R.sub.9 is an alkyl group having the same number of carbon
atoms, provided that R.sub.9 has a different number of carbon atoms
than R.sub.8.
8. The composition of claim 7, wherein R.sub.8 is propyl or
t-butyl.
9. The composition of claim 7, wherein R.sub.9 is t-amyl.
10. The composition of claim 7, wherein R.sub.8 is t-butyl and
R.sub.8 is t-amyl.
11. A phosphite composition of claim 1, wherein at least one of the
first or second phosphites has the structure. ##STR00027## wherein
e, f, g and h are independently selected from 0, 1 and 2, provided
that e+f+g+h=3, e+f=1 or 2, and g+h=1 or 2, Ar is phenyl, R.sub.8
and R.sub.9 are independently selected from straight or branched
C.sub.1-C.sub.18 alkyl groups, provided that R.sub.8 has a
different number of carbon atoms than R.sub.9.
12. The composition of claim 11, wherein R.sub.8 is propyl or
t-butyl.
13. The composition of claim 11, wherein R.sub.9 is t-amyl.
14. The composition of claim 11, wherein R.sub.8 is t-butyl and
R.sub.9 is t-amyl.
15. The phosphite composition of claim 1, wherein least one of the
first or second alkylaryl phosphites is of the structure (XI)
wherein m is an integer selected from 1, 2 and 3; n, o, p and q are
integers independently selected from 0, 1 and 2, provided that
m+n+o+p+q=3, wherein each Ar is phenyl, and wherein each R.sub.8 is
an alkyl group having the same number of carbon atoms and each
R.sub.9 is an alkyl group having the same number of carbon atoms,
provided that R.sub.8 has a different number of carbon atoms than
R.sub.9.
16. The composition of claim 15, wherein R.sub.8 is propyl or
t-butyl.
17. The composition of claim 15, wherein R.sub.9 is t-amyl.
18. The composition of claim 15, wherein R.sub.8 is t-butyl and
R.sub.9 is t-amyl.
19. A stabilized polymer composition comprising a polymer and the
phosphite composition of claim 1.
Description
[0001] This application claims benefit under USC 119(e) of U.S.
provisional application No. 61/230,652, filed Jul. 31, 2009, the
disclosure of which is incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to novel phosphite
compositions suitable for use as antioxidants in polymer
compositions. It also relates to stabilized polymer compositions
and stabilizer concentrates comprising the novel liquid phosphite
compositions.
BACKGROUND OF THE INVENTION
[0003] Organic phosphites are well-known and are commonly used as
secondary antioxidants in polymer compositions including, for
example, polyolefins, polyvinyl chloride, and elastomers. Examples
of such phosphites are disclosed in H. Zweifel (Ed) Plastics
Additives Handbook, 5th edition, Hanser Publishers, Munich 2000.
Phosphite stabilizers, both liquid and solid, are known in the
art.
[0004] Solid organic phosphite stabilizers are widely used as
secondary antioxidants in polymer compositions. One commercially
available antioxidant is tris(2,4-di-t-butylphenyl) phosphite,
shown below, a solid antioxidant commonly known as Alkanox.TM. 240,
Irgafos.TM. 168 and Doverphos.TM. S-480. U.S. Pat. No. 5,254,709,
the entirety of which is incorporated herein by reference,
describes the synthesis of tris(2,4-di-t-butylphenyl) phosphite by
reacting 2,4-di-t-butyl phenol with phosphorus trichloride in the
presence of catalyst. The isolated phosphite is described as a
white crystalline solid having a melting between 180-185.degree.
C.
##STR00001##
[0005] Tris(2,4-di-t-butylphenyl) phosphite has been demonstrated
to effectively reduce peroxide induced oxidative degradation for
many polymers including polyolefins, polycarbonates, ABS and
polyesters. The trialkylaryl phosphite has low volatility that
allows for its use at high temperatures commonly required for
processing thermoplastic polymers. Owing to its solid form and
concomitant processing limitations, however,
tris(2,4-di-t-butylphenyl) phosphite is not well-suited for the
stabilization of all polymers and has been demonstrated to plate
out during processing of some plastics, in particular low melting
point plastics, and forming deposits on processing machinery
surfaces.
[0006] Liquid phosphite compositions are also well known and do not
possess the handling problems associated with solid phosphite
compounds. In addition, liquid phosphite compositions generally
exhibit better processability than solid phosphite compositions for
polymers that process at low temperatures. Tris(p-nonylphenyl)
phosphite (TNPP), for example, is one alkylaryl phosphite that is a
stable liquid at ambient conditions.
##STR00002##
TNPP is a versatile phosphite stabilizer that is useful in
stabilizing a large number of polymers such as HDPE, LLDPE, SBR,
ABS, PVC and others. There is, however, a need to replace TNPP due
to the alleged estrogenicity of nonylphenol, which is commonly used
in the synthesis of TNPP.
[0007] Many commercially available alkylaryl phosphites share a
common alkyl group. U.S. Pat. No. 5,254,709, for example, the
entirety of which is incorporated herein by reference, describes
the synthesis of tris(2,4-di-t-butylphenyl) phosphite by reacting a
2,4-di-t-butyl phenol with phosphorus trichloride in the presence
of catalyst according to the following reaction:
##STR00003##
[0008] U.S. Pat. No. 7,468,410 describes a mixture of phosphites
including a tri(4-sec-butylphenyl)phosphite and a
tri(2-sec-butylphenyl)phosphite. Each of these phosphites is a
liquid when isolated, and the combination is a liquid.
[0009] U.S. Pat. No. 5,254,709 describes various secondary
antioxidants including a solid phosphite made from 2:1 molar ratio
of 2,4-di-t-amyl phenol and 2,4-di-t-butyl phenol, and a liquid
phosphite made from 2-t-butyl-4-nonyl phenol.
[0010] The need remains for novel, safe and effective phosphite
stabilizers that can effectively stabilize polymer resins and
compositions against heat and light degradation and that are liquid
at ambient conditions.
SUMMARY OF THE INVENTION
[0011] The invention is directed to various compositions comprising
a mixture of at least two different alkylaryl phosphites, wherein
some alkyl groups have a different number of carbon atoms than
other alkyl groups and wherein the mixture is a liquid at ambient
conditions. The first and second phosphites broadly correspond to
the structure:
##STR00004##
wherein R.sub.1, R.sub.2, and R.sub.3 are independently selected
alkylated aryl groups, each aryl moiety being an independently
selected aromatic moiety of from 6 to 18 carbon atoms, and wherein
each aromatic moiety is substituted with at least one straight or
branched C.sub.1-C.sub.18 alkyl group. Typically R.sub.1, R.sub.2,
and R.sub.3 are independently selected alkylated aryl groups of the
structure:
##STR00005##
wherein R.sub.4, R.sub.5, and R.sub.6 are independently selected
from the group consisting of hydrogen and straight or branched
C.sub.1-C.sub.8 alkyl provided that at least one of R.sub.4,
R.sub.5, and R.sub.6 is not hydrogen.
[0012] Thus, at least the first and second alkylaryl phosphites of
the inventive composition, while different, each have the general
structure:
##STR00006##
wherein m, n, o, p and q are integers independently selected from
0, 1, 2 and 3 provided that m+n+o+p+q=3, each Ar is an
independently selected aromatic moiety of 6 to 18 carbon atoms,
typically phenyl, each R.sub.8 is a straight or branched
C.sub.1-C.sub.18 alkyl group having the same number of carbon atoms
and each R.sub.9 is a straight or branched C.sub.1-C.sub.18 alkyl
group having the same number of carbon atoms, provided that R.sub.8
has a different number of carbon atoms than R.sub.9 and the first
phosphite contains an aromatic moiety substituted by at least one
R.sub.8 and the second phosphite contains an aromatic moiety
substituted by at least one R.sub.9. R.sub.8 and R.sub.9 are
independently selected from straight or branched C.sub.1-C.sub.18
alkyl groups, for example, straight or branched C.sub.1-C.sub.12
alkyl groups, such as isomers of propyl, butyl and amyl, for
example, isopropyl, sec-butyl, t-butyl, sec-amyl and t-amyl. Where
the aromatic moiety is phenyl, each respective alkyl group is
typically in the ortho and/or para positions, although other
positions are possible.
[0013] In a first general embodiment, the phosphite composition
comprises a first alkylaryl phosphite having, the structure:
##STR00007##
and a second alkylaryl phosphite having the structure:
##STR00008##
wherein a, b, c, and d are independently integers selected from 0,
1, 2, and 3, provided that a+b=3 and c+d=3, and Ar, R.sub.8 and
R.sub.9 are as defined above.
[0014] In a second general embodiment, the phosphite composition
comprises one or more phosphites having the structure:
##STR00009##
wherein e, f, g and h axe independently selected from 0, 1 and 2,
provided that e+f+g+h=3, e+f=1 or 2, and g+h=1 or 2, and Ar,
R.sub.8 and R.sub.9 are as defined above.
[0015] In a third general embodiment, the phosphite composition
comprises one or more phosphites of the structure XI wherein m is
an integer selected from 1, 2 and 3; n, o, p and q are integers
independently selected from 0, 1 and 2, provided that m+n+o+p+q=3,
and Ar, R.sub.8 and R.sub.9 are as defined above. In this
embodiment, the phosphite composition comprises at least two
different alkylaryl phosphites, wherein at least one of the
alkylaryl phosphites has at least one aryl moiety with two or more
alkyl groups having a different number of carbon atoms.
[0016] In another embodiment, the invention is to a composition
comprising a mixture of at least two different alkylaryl
phosphites, wherein at least one of the alkylaryl phosphites has
two or more alkyl groups having a different number of carbon atoms
which alkyl groups are substituents on different aryl moieties, and
wherein the mixture is a liquid at ambient conditions.
[0017] The phosphite composition is conveniently prepared by
reacting a phosphorous trihalide, for example, PCl.sub.3, with a
mixture of at least two different alkylaryl phosphites.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention provides phosphite compositions, which
are liquid at ambient conditions, comprising at least two different
alkylaryl phosphites provided that the phosphite composition
includes two or more alkyl groups, whether on the same or different
phosphite compounds, wherein the two or more alkyl groups having a
different number of carbon atoms. The incorporation of the two or
more alkyl groups having a different number of carbon atom are
leads to at least three different general embodiments of the
present invention as follows: [0019] (i) Mixed Phosphite
Embodiment. In the first general embodiment, the two or more alkyl
groups having a different number of carbon atoms are on different
phosphite compounds. That is, at least one phosphite bears aryl
groups substituted with alkyl groups having a first number of
carbon atoms and another phosphite bears aryl groups substituted
with alkyl groups having a second number of carbon atoms, where the
first and second numbers are different. The first embodiment is
referred to as the "mixed phosphites" embodiment as such
compositions are conveniently formed by mixing two separately
synthesized phosphites or phosphite mixtures. [0020] (ii) Mixed
Alkylate Embodiment. In the second general embodiment, the two or
more alkyl groups having a different number of carbon atoms can be
found on adjacent aryl moieties of a single phosphite compound.
That is, a phosphite of this embodiment comprises one or more aryl
moieties substituted with an alkyl group having the first number of
carbon atoms and also one or more aryl moieties substituted with an
alkyl group having a second number of carbon atoms, where the first
and second numbers are different. The second embodiment is referred
to as "mixed alkylates" embodiment because such phosphite
compositions are conveniently formed by reacting a phosphorous
halide with an alkylate composition comprising at least two
separately synthesized alkylates or alkylate mixtures. [0021] (iii)
Mixed Olefins Embodiment. In a third general embodiment, the two or
more alkyl groups having a different number of carbon atoms may
both be on the same aryl moiety of one or more phosphites. The
third embodiment is referred to as "mixed olefins" embodiment
because such compositions are conveniently formed by reacting a
mixture of olefins having a different number of carbon atoms with a
hydroxyaryl compound to form a complex alkylate composition, and
reacting this alkylate composition with a phosphorous halide.
[0022] It should be appreciated that two or more of the first,
second and third embodiments may be combined to form even more
diverse phosphite compositions.
[0023] While the various embodiments of the present invention lead
to different phosphite compositions, there are certain
characteristics shared by each phosphite composition. The phosphite
compositions are liquid at ambient conditions. By "ambient
conditions" it is meant room temperature, e.g., 25.degree. C., and
1 atmosphere pressure. As discussed herein, the fact that the
phosphite compositions axe liquid at ambient conditions is
surprising and unexpected because in most eases it would be
expected that each of the individual phosphites contained in the
phosphite composition, when isolated, would be a solid at ambient
conditions. This is particularly surprising given that the prior
art teaches several examples of solid phosphite compositions, the
components of which are separately solids at ambient condition,
(See JP 59030842; WO 9303092; CA 2,464,551; U.S. Pat. No.
5,254,709). In contrast, phosphite compositions of the invention
are liquid even though the individual components would he expected
to be solid.
[0024] Table 1 provides the melting points, each of which is above
room temperature, for several pure phosphite compounds.
TABLE-US-00001 TABLE 1 Phosphite Melting Point
tris(4-t-butylphenyl) phosphite 75-76.degree. C.
tris(2,4-di-tertbutylphenyl) phosphite 181-184.degree. C.
bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite 63-65.degree.
C. bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite
100-103.degree. C. tris(4-t-amylphenyl) phosphite 52-54.degree. C.
tris(2,4-di-t-amylphenyl) phosphite 103.degree. C.
[0025] As used herein, by "liquid," it is meant that the phosphite
composition remains liquid after at least three "freeze/thaw"
cycles as opposed to "meta-stable liquids," which do not remain
liquid after three or fewer cycles. A freeze/thaw cycle is defined
as follows: 1) An ambient temperature composition is stirred for
0.5 hours; 2) The stirred composition is then refrigerated at about
-5 to -10.degree. C. for three days; and 3) The refrigerated
composition is then brought to ambient temperature, and held at
ambient for 3 days. After step 3, the composition is checked for
solids content, e.g., crystallization. Completion of steps 1-3
defines one freeze/thaw cycle.
[0026] The viscosity of the phosphite composition will vary
depending on the relative amounts of the various phosphite
compounds contained therein. In some exemplary embodiments, the
phosphite composition has a viscosity less than 11,000 cSt, e.g.,
less than 7,300 cSt, less than 5,000 cSt, less than 3,000 cSt or
less than 2850 cSt, these viscosities being measured at 30.degree.
C. Thus, the viscosity of the composition may range from 1 cSt to
15,000 cSt, from 100 cSt to 12,000 cSt, from 500 cSt to 10,000 cSt,
from 500 cSt to 6,500 cSt, from 500 cSt to 5,000 cSt, front 500 cSt
to 3,000 cSt, from 1,000 cSt to 4,000 cSt, from 1,500 cSt to 3,500
cSt, from 2,000 cSt to 3,000 cSt, or from 2,000 to 2,800 cSt, these
viscosities being measured at 30.degree. C.
[0027] It has now been discovered that by increasing the diversity
of the alkylaryl phosphites in the phosphite composition, handling
characteristics (e.g., liquid physical state and viscosity) as well
as solubility/compatibility with various polymers can be
advantageously improved. The invention provides various ways to
increase phosphite diversity by incorporating alkyl groups having
different numbers of carbon atoms. In various embodiments, for
example, the liquid composition may comprise at least 2, e.g., at
least 4 or at least 10, different alkylaryl phosphites, and
optionally from 2 to 100 different alkylaryl phosphites, e.g., from
3 to 20 different alkylaryl phosphites or from 4 to 10 different
alkylaryl phosphites.
[0028] Another advantage of the present invention is that alkylaryl
phosphites derived from mixed alkylates helps to mitigate
processing costs and eliminates the conventional need for
substantially pure starting materials (e.g., olefins and/or
alkylated phenotics).
[0029] Generally, each phosphite in the composition has the
structure:
##STR00010##
wherein R.sub.1, R.sub.2, and R.sub.3 are independently selected
alkylaryl groups and wherein the composition is a liquid at ambient
conditions.
[0030] The aryl moiety (Ar) present in the compounds of the present
invention is an aromatic moiety of from 6 to 18 carbon atoms, e.g.,
phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl,
o-cresyl, m-cresyl, p-cresyl, xylenols and the like, preferably
phenyl.
[0031] Generally, each aromatic moiety is substituted with at least
one branched or straight chain C.sub.1-C.sub.18 alkyl group, e.g.,
C.sub.1-C.sub.12 alkyl group, C.sub.2-C.sub.6 alkyl group or
C.sub.3-C.sub.5 alkyl group, but in certain embodiments a minor
amount of phosphites bearing an unsubstituted aromatic moiety is
present. In one embodiment, the two or more alkyl groups having a
different number of carbon atoms are selected from branched or
straight chain C.sub.1-C.sub.12 alkyl group, e.g., a C.sub.3C.sub.5
alkyl group, or C.sub.4-C.sub.5 alkyl group. The alkyl groups are
selected, for example, from the group consisting of methyl, ethyl,
propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
and isomers thereof; the alkyl group maybe nonyl, but this is
generally avoided. In particular embodiments the alkyl groups are
selected from propyl, butyl and amyl groups, for example,
isopropyl, see-butyl, t-butyl, sec-amyl, t-amyl and neo-amyl. In
many embodiments, neither of the alkyl groups is C.sub.8-C.sub.10
alkyl, e.g., C.sub.9 alkyl. Thus, in a preferred embodiment, the
alkyl moieties do not include nonyl, meaning the phosphite
composition preferably comprises less than 50 wppm, e.g., less than
10 wppm or less than 5 wppm nonyl substituted aryl phosphite
compounds, and most preferably no detectable nonyl substituted aryl
phosphite compounds. In addition, the phosphite composition
preferably comprises less than 50 wppm, e.g., less than 10 wppm or
less than 5 wppm nonylphenol, and most preferably no detectable
nonylphenol.
[0032] The aromatic moieties are mono, di and to a lesser extent,
tri substituted, generally in the ortho and/or para positions, but
each phosphite of the composition does not contain exclusively mono
substituted aryls or exclusively disubstituted aryls or exclusively
trisubstituted aryls. Typically, the phosphite compositions of the
invention generally include some phosphite compounds having aryl
moieties that are monoalkylated and dialkylated. The combination of
mono and di-substituted aryl moieties in combination with employing
different alkyl groups allows for very diverse phosphite
compositions. A small amount, if any of the aryl moieties are
trisubstituted, for example either 0 to 5 wt % or 0.1 to 5 wt % of
the aryl moieties are trisubstituted, for example, 1-3 wt %, e.g.
2-3 wt % are trisubstituted. Often fewer than 3 wt % of the aryl
moieties are trisubstituted, e.g., fewer than 2 wt %, or fewer than
1 wt %.
[0033] Typically, few if any of the aryl moieties are
monosubstituted in the ortho position, for example 0 to 5 wt % and
often less than 3 wt %, e.g., less than 2 wt % or less than 1 wt %
of the aryl moieties are monosubstituted in the ortho position. In
some embodiments, for example 0.1 to 5 wt %, 1-3 wt %, or 2-3 wt %
of the aryl moieties are monosubstituted in the ortho position.
There may also be a similarly small amount of unsubstituted aryl
groups.
[0034] The phosphite composition may contain phosphite compounds
having aryl groups that are substituted with alkyl groups having
hydrogen atoms in the .alpha. position, for example, n-propyl,
iso-propyl, n-butyl, iso-butyl, sec-butyl, n-amyl, sec-amyl,
iso-amyl and the like. In other embodiments, the phosphite
composition is substantially free of phosphite compounds having
aryl groups that are substituted with alkyl groups having hydrogen
atoms in the .alpha. position, for example, in some embodiments, at
least 95%, at least 98% or at least 99% of the aryl moieties are
substituted with alkyl groups having tertiary .alpha.-carbons, for
example, t-butyl and/or t-amyl.
[0035] R.sub.1, R.sub.2, and R.sub.3 are, for example,
independently selected alkylated aryl groups of the structure:
##STR00011##
wherein R.sub.4, R.sub.5, and R.sub.6 are independently selected
from the group consisting of hydrogen and straight or branched
C.sub.1-C.sub.8 alkyl, e.g., methyl, ethyl, propyl, butyl, amyl,
hexyl, heptyl, octyl, and isomers thereof, e.g., isopropyl,
sec-butyl, t-butyl, sec-amyl, t-amyl, neo-amyl, provided that at
least one of R.sub.4, R.sub.5, and R.sub.6 is not hydrogen. In one
embodiment R.sub.4 and R.sub.6 are hydrogen, and R.sub.5 is not
hydrogen. In one embodiment, the ortho alkyl groups, i.e., R.sub.4
and R.sub.6, have no .alpha.-hydrogen atoms. In one embodiment, the
ortho alkyl groups, i.e., R.sub.4 and R.sub.6, have tertiary
.alpha.-carbon atoms selected from the group consisting of t-butyl
and t-amyl.
[0036] In one embodiment, R.sub.4 and R.sub.5 are independently
selected from the group consisting of methyl, ethyl, propyl, butyl,
amyl, hexyl, and isomers thereof, and R.sub.6 is hydrogen. In
another embodiment, R.sub.4 and R.sub.6 are hydrogen and R.sub.5 is
independently selected from the group consisting of methyl, ethyl,
propyl, butyl, amyl, hexyl, and isomers thereof. In one aspect of
these embodiments, at least one of R.sub.4, R.sub.5, and R.sub.6 is
C.sub.4 or C.sub.5 alkyl, often t-butyl or t-amyl.
[0037] In one embodiment, R.sub.1, R.sub.2, and R.sub.3 are
independently selected groups of the structure:
##STR00012##
wherein R.sub.4, R.sub.5, and R.sub.6 are defined above and R.sub.7
is hydrogen or methyl, provided that one of R.sub.4, R.sub.5,
R.sub.6, and R.sub.7 is methyl and that at least two of R.sub.4,
R.sub.5, R.sub.6 and R.sub.7 are not hydrogen. Such phosphites are
formed, for example, by the reaction of one or more alkylated
cresol compounds, e.g., alkylated ortho-, meta- and/or para-cresol,
with a phosphorous halide such as PCl.sub.3.
[0038] The phosphite compositions typically have an overall
phosphorus content that is equal to or greater than TNPP, e.g., at
least 4.5 mole %, e.g., at least 4.8 mole %, or at least 5.1 mole
%. In terms of ranges, the overall phosphorus content of the
phosphite composition may range from 4.5 to 10.0 mole %, e.g., from
4.8 to 8.0 mole %, or 5.1 to 6.0 mole %, of all phosphorous
containing compounds in the phosphite composition.
[0039] In general, the liquid phosphite composition has a low level
or is substantially free of phenolics (e.g., phenols, cresols or
xylenols), whether alkylated or unalkylated, referred to herein as
"free phenolics" when contained in the phosphite composition. In
many embodiments, a minor amount of free phenolics may be
beneficial, for example, as a viscosity reducing agent. These free
phenols of the invention are generally unreacted phenolics from the
reaction with phosphorous trihalide and reflect the structures of
the alkylated aryl groups of the phosphites, for example, the free
phenols have the structures:
##STR00013##
wherein R.sub.8 and R.sub.9 are as described above. The phosphite
composition preferably comprises 0 to 10 wt % free phenols, for
example, 0.01 to 5 wt %, 0.01 to 4 wt %, 0.5 to 3 wt % or 0.1 to 3
wt %, based on the combined weight of phosphites and the free shown
phenols above. In one embodiment, the phosphite composition
comprises a minor amount of free phenolics, e.g., from 0.1 to 5
weight percent or 1 to 5 weight percent, e.g., 0.1 to 4 weight
percent, e.g., from 2 to 3 weight percent, for example, there is
less than 5 wt %, e.g., less than 3 wt %, less than 1 wt %, of free
phenolics, and in some embodiments less than less than 0.5 wt %,
e.g., less than 0.2 wt % or less than 0.1 wt %. Phosphites are
often used in combination with certain hindered phenol primary
antioxidants, and the present phosphite compositions may also be
used in combination with such primary antioxidants. However, the
composition of the present invention is specifically a mixed
phosphite composition, which is liquid at room temperature when it
consists essentially of the phosphites described above and the free
phenolics of the preceding structures, which composition may be
blended with other materials.
[0040] In addition, the phosphite composition is often
substantially free of phosphite compounds having unsubstituted aryl
moieties, e.g., triphenylphosphites, bis(phenyl)alkylphenyl
phosphites or bis(alkylphenyl)phenyl phosphites. That is, the
phosphite composition typically comprises less than 2 wt %, e.g.,
less than 1 wt % or less than 0.5 wt %, phosphite compounds having
an unsubstituted aryl moiety, based on the total weight of the
phosphite composition. Alternatively, the alkylate used to prepare
the phosphite composition may contain a minor amount of phenol,
i.e., 10% or less, typically less than 5%, e.g., from 0.01 to 10
weight percent, 0.01 to 5 weight % phenol, and generally 3% or
less, which may react during the phosphite synthesis process to
form phenyl phosphites.
[0041] Thus, the composition of the present invention is generally
a phosphite composition of at least two different alkylaryl
phosphites, comprising at least a first alkylaryl phosphite and a
second alkylaryl phosphite of structure (XI)
##STR00014##
wherein m, n, o, p and q are integers independently selected from
0, 1, 2 and 3 provided that m+n+o+p+q=3, each Ar is an
independently selected aromatic moiety of 6 to 18 carbon atoms,
preferably phenyl, each R.sub.8 is a straight or branched
C.sub.1-C.sub.18 alkyl group having the same number of carbon
atoms, and each R.sub.9 is a straight or branched C.sub.1-C.sub.18
alkyl group having the same number of carbon atoms, provided that
R.sub.8 has a different number of carbon atoms than R.sub.9, said
first aralkyl phosphite contains an aromatic moiety substituted by
at least one R.sub.8 and said second aralkyl phosphite contains an
aromatic moiety substituted by at least one R.sub.9, wherein the
molar ratio of R.sub.8 groups to R.sub.9 groups in the phosphites
of the composition is from 1:10 to 10:1, and from 0 to 10% by
weight of one or more free phenol having the structure:
##STR00015##
based on the combined weight of all phosphites and said free phenol
in the composition, wherein the phosphite composition comprises one
or more tris(monoalkylaryl) phosphites of structure (XI) wherein m,
p and q are 0 and n+o=3, such as a
tris(4-tert-alkylphenyl)phosphite, in an amount from 20 to 80
weight percent and one or more bis(monoalkylaryl)dialkylaryl
phosphites of structure (XI) wherein m+p+q=1 and n+o=2, such as a
bis(4-tert-alkylphenyl)-2,4-di-tert-alkylphenylphosphite, in an
amount from 15 to 60 weight percent, based on the total weight of
all phosphites in the phosphite composition, wherein the
composition is a liquid at ambient conditions.
[0042] The phosphite composition also typically comprises one or
more bis(dialkylaryl) monoalkylaryl phosphites of structure (XI)
wherein m+p+q=2 and n+o=1 in an amount of from 2 to 20 weight
percent, e.g., from 4 to 20 weight percent or from 5 to 10 weight
percent, based on the total weight of all phosphites in the
phosphite composition. Typically tris(dialkylaryl) phosphites of
structure (XI) wherein m+p+q=3 and n and o are 0 are also present
in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5
weight percent or from 0.5 to 1 weight percent, based on the total
weight of all phosphites in the phosphite composition.
[0043] The relative amounts of the phosphites in the phosphite
composition may vary so long as the phosphite composition is a
liquid at ambient conditions. In one embodiment, the molar ratio of
the first phosphite(s) to the second phosphite(s), is from 1:10 to
10:1, e.g., from 1:4 to 4:1 or from 2:1 to 1:1. For example, by
including a greater amount of phosphites with smaller alkyl groups,
the overall phosphorus content may be advantageously maximized or
one of the phosphites is chosen to improve, e.g., lower, the
viscosity and processing characteristics for the overall phosphite
composition.
[0044] In some embodiments, the phosphite composition includes one
or more hydrolytic stabilizers. Preferred stabilizers include
amines of the structure:
##STR00016##
wherein x is 1, 2 or 3; R.sub.10 is selected from the group
consisting of hydrogen, and straight or branched C.sub.1-C.sub.6
alkyl, preferably straight or branched C.sub.1-C.sub.4alkyl, e.g.,
methyl or ethyl and R.sub.11 is a straight or branched
C.sub.1-C.sub.30 alkyl, preferably C.sub.5-C.sub.20 alkyl, e.g.,
straight or branched C.sub.10-C.sub.20 alkyl or straight or
branched C.sub.12-C.sub.18 alkyl. In one embodiment, x is 1 and
R.sub.11 is straight or branched C.sub.5-C.sub.20 alkyl, e.g.,
C.sub.12-C.sub.18 alkyl. In one embodiment, x is 2 and R.sub.11 is
straight or branched C.sub.10-C.sub.20 alkyl, e.g.,
C.sub.12-C.sub.18 alkyl.
[0045] In one aspect the amine is selected from the group
consisting of triethanolamine, triisopropanolamine, diethanolamine,
diisopropanolamine, and tetraisopropanolethylenediamine.
[0046] In another aspect the amine is selected from the group
consisting of octyl-bis(2-ethanol)amine, nonyl-bis(2-ethanol)amine,
decyl-bis(2-ethanol)amine, undecyl-bis(2-ethanol)amine,
dodecyl-bis(2-ethanol)amine, tridecyl-bis(2-ethanol)amine,
tetradecyl-bis(2-ethanol)amine, pentadecyl-bis(2-ethanol)amine,
hexadecyl-bis(2-ethanol)amine, heptadecyl-bis(2-ethanol)amine,
octadecyl-bis(2-ethanol)amine, octyl-bis(2-propanol)amine,
nonyl-bis(2-propanol)amine, decyl-bis(2-propanol)amine,
undecyl-bis(2-propanol)amine, dodecyl-bis(2-propanol)amine,
tridecyl-bis(2-propanol)amine, tetradecyl-bis(2-propanol)amine,
pentadecyl-bis(2-propanol)amine, hexadecyl-bis(2-propanol)amine,
heptadecyl-bis(2-propanol)amine, octadecyl-bis(2-propanol)amine,
and isomers thereof.
[0047] Additional hydrolytic stabilizers include epoxies such as
epoxidized soybean oil (ESBO) commercially available as Drapex.TM.
39, Drapex 392, Drapex 4.4, and Drapex 6.8 (Chemtura Corp.).
[0048] The amine may be present in an amount of from 0.01 to 5 wt
%, e.g., from 0.1 to 1.5 wt % or from 0.2 to 0.8 wt %, based on the
total weight of the phosphite composition.
[0049] The general embodiments of the present invention are
described in more detail below.
Mixed Phosphites Embodiment
[0050] In one general embodiment the phosphite compositions
comprise one or more first phosphites having exclusively first
alkyl groups and one or more second phosphites having exclusively
second alkyl groups, wherein the first alkyl groups have a
different number of carbon atoms than the second alkyl groups. The
phosphite compositions comprise phosphites having at least the
following two structures:
##STR00017##
wherein a, b, c, and d are independently integers selected from 0,
1, 2, and 3, provided that a+b=3 and c+d=3, Ar, R.sub.8 and R.sub.9
are as described above.
[0051] For example, the first phosphite comprises aryl moieties
with Alkyl-A groups, i.e., alkyl groups having A carbon atoms, and
the second phosphite comprises aryl moieties with Alkyl-B groups,
i.e., alkyl groups having B carbon atoms. It should be noted that
each of Alkyl-A and Alkyl-B may include multiple isomers of alkyl
groups having the same number of carbon atoms. For example, Alkyl-A
groups may include sec-butyl and t-butyl, and Alkyl-B groups may
include sec-amyl and t-amyl.
[0052] The first phosphite is therefore selected from the group
consisting of tris(Alkyl-A-aryl) phosphite,
tris(di-Alkyl-A-aryl)phosphite, bis(Alkyl-A-aryl)di-Alkyl-A-aryl
phosphite, and bis(di-Alkyl-A-aryl)Alkyl-A-aryl phosphite; and the
second phosphite is selected from the group consisting of
tris(Alkyl-B-aryl) phosphite, tris(di-Alkyl-B-aryl) phosphite,
bis(Alkyl-B-aryl)di-Alkyl-B-aryl phosphite, and
bis(di-Alkyl-B-aryl)Alkyl-B-aryl phosphite. Other phosphites may
also be present.
[0053] To elaborate, when Alkyl-A is isopropyl and Alkyl-B is
t-butyl the first phosphite is selected from the group consisting
of tris(4-isopropyl phenyl) phosphite, tris(2,4-dipropylphenyl)
phosphite, bis(4-propylphenyl)-2,4-dipropylphenyl phosphite, and
bis(2,4-di-isopropylphenyl)-4-isopropylphenyl phosphite and the
second phosphite is selected from the group consisting of
tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl)
phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and
bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite.
[0054] In another example, Alkyl-A is isopropyl and Alkyl-B is
t-amyl and thus the first phosphite is selected from the group
consisting of tris(4-isopropyl phenyl) phosphite,
tris(2,4-di-isopropyl phenyl) phosphite, bis(4-isopropyl
phenyl)-2,4-di-isopropyl phenyl phosphite, and bis(2,4-di-isopropyl
phenyl)-4-isopropyl phenyl phosphite, and the second phosphite is
selected from the group consisting of tris(4-t-amylphenyl)
phosphite, tris(2,4-di-t-amylphenyl) phosphite,
bis(4-t-amylphenyl)-2,4-di-t-amylphenyl phosphite, and
bis(2,4-di-t-amylphenyl)-4-t-amylphenyl phosphite.
[0055] In a third example, Alkyl-A is t-butyl and Alkyl-B is
t-amyl, so that a first phosphite is selected from the group
consisting of tris(4-t-butylphenyl) phosphite,
tris(2,4-di-t-butylphenyl) phosphite,
bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and
bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite and a second
phosphite is selected from the group consisting of
tris(4-t-amylphenyl) phosphite, tris(2,4-di-t-amylphenyl)
phosphite, bis(4-t-amylphenyl)-2,4-di-t-amylphenyl phosphite, and
bis(2,4-di-t-amylphenyl)-4-t-amylphenyl phosphite.
[0056] In some embodiments, the phosphite composition comprises at
least three, e.g., at least four or at least five, of the generic
or specific phosphites identified above.
[0057] The phosphite composition comprises
tris(monoalkylaryl)phosphites, e.g., tris(Alkyl-A-phenyl) phosphite
and tris(Alkyl-B-phenyl) phosphite, in an amount from 20 to 80
weight percent, in some embodiments from 55 to 80 weight percent,
20 to 55 weight percent, or from 37 to 54 weight percent, based on
the total weight of all phosphites in the phosphite composition.
The tris(monoalkylaryl)phosphite component may be
tris(Alkyl-A-aryl) phosphite or tris(Alkyl-B-aryl) phosphite, but
often, the tris(monoalkylaryl)phosphite component comprises both
the tris(Alkyl-A-aryl) phosphite and tris(Alkyl-B-aryl)
phosphite.
[0058] The phosphite composition also comprises
bis(monoalkylaryl)dialkylaryl phosphites, e.g.,
bis(Alkyl-A-phenyl)di-Alkyl-A-phenyl phosphite, and
bis(Alkyl-B-phenyl)di-Alkyl-B-phenyl phosphite, in an amount from
15 to 60 weight percent, e.g., from 31 to 50 weight percent, based
on the total weight of all phosphites in the phosphite composition.
As with the tris(monoalkylaryl)phosphite above, the
bis(monoalkylaryl) dialkylaryl phosphite component of this general
embodiment may be a combination of (Alkyl-A-aryl)di-Alkyl-A-aryl
phosphite and bis(Alkyl-B-aryl)di-Alkyl-B-aryl phosphite.
[0059] If present, the phosphite composition comprises
bis(dialkylaryl)monoalkylaryl phosphites, e.g.,
bis(di-Alkyl-A-phenyl)Alkyl-A-phenyl phosphite and
bis(di-Alkyl-B-phenyl)Alkyl-B-phenyl phosphite, in an amount of
from 2 to 20 weight percent, e.g., from 4 to 20 weight percent or
from 5 to 10 weight percent, based on the total weight of all
phosphites in the phosphite composition. If present, the phosphite
composition comprises tris(dialkylaryl) phosphites, e.g.,
tris(di-alkyl-A-phenyl) phosphite and/or tris(di-Alkyl-B-phenyl)
phosphite in an amount from 0.1 to 20 weight percent, e.g., from
0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on
the total weight of all phosphites in the phosphite
composition.
[0060] The phosphite compositions of the mixed phosphite embodiment
are typically prepared by separately making each phosphite and
blending the separate phosphites together. The phosphites can also
be conveniently prepared by reacting a phosphorous trihalide with a
first alkylate composition, which may be a mixture of mono, di and
optionally tri substituted aryls formed from the reaction between a
hydroxyaryl compound and a first olefin, similarly reacting a
phosphorous trihalide with a second alkylate composition formed
from the reaction between a hydroxyaryl compound and a second
olefin, wherein the second olefin has a different number of carbon
atoms than the first olefin as in the scheme below.
##STR00018##
[0061] The two reaction mixtures are then combined. A minor amount
of other alkylated phenols, e.g., ortho-substituted monoalkylated
phenols, may be included as an additional reactant in the above
reaction scheme and would form additional derivative phosphites,
but these additional reactants and products have been omitted from
this reaction for clarity.
[0062] As the invention comprises two different phosphites having
different alkyl groups, one or more of the products shown above in
scheme (VII), optionally may be separated or partially separated
(e.g., through distillation) from the other reaction products. In
this aspect, two relatively pure phosphites may be optionally
heated and blended to form a mixture of phosphite compounds, each
having a different alkyl groups.
Mixed Alkylates Embodiment
[0063] In the second general embodiment, the liquid alkylaryl
phosphite compositions comprise two or more phosphite compounds,
wherein at least some of the phosphite compounds are substituted
with multiple alkyl groups including at least a first alkyl group
and a second alkyl group having a different number of carbon atoms
than the first alkyl group, provided that no individual aryl moiety
is substituted with both the first alkyl group and the second alkyl
group. That is, each respective aryl moiety is substituted
exclusively with either the first alkyl group or the second alkyl
group, but not both.
[0064] At least one of the phosphites in this embodiment therefore
has the structure (VI):
##STR00019##
wherein e, f, g and h are independently selected from 0, 1 and 2,
provided that e+f+g+h=3, e+f=1 or 2, and g+h=1 or 2, Ar, R.sub.8
and R.sub.9 are as described above.
[0065] In this embodiment, the phosphite composition comprises
phosphites, selected from the group consisting of
bis(Alkyl-A-aryl)di-Alkyl-B-aryl phosphite,
bis(Alkyl-B-aryl)di-Alkyl-A-aryl phosphite,
bis(di-Alkyl-A-aryl)Alkyl-B-aryl phosphite,
bis(di-Alkyl-B-aryl)Alkyl-A-aryl phosphite,
(Alkyl-A-aryl)(Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite,
(Alkyl-A-aryl)(Alkyl-B-aryl)(di-Alkyl-B-aryl) phosphite,
(Alky-A-aryl)(di-Alkyl-B-aryl)(di-Alkyl-A-aryl)phosphite,
(Alkyl-B-aryl)(di-Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite,
bis(di-Alkyl-A-aryl)di-Alkyl-B-aryl phosphite, and
bis(di-Alkyl-B-aryl)di-Alkyl-A-aryl phosphite. Other phosphites,
possibly having an alkyl substituents other than Alkyl-A and
Alkyl-B, may also be included in the phosphite composition.
[0066] As before, the tris(monoalkylaryl)phosphite of the present
compositions can include either or both of tris(Alkyl-A-aryl)
phosphite and tris(Alkyl-B-aryl) phosphite, but in this embodiment,
as in the mixed alkylate embodiment, the
tris(monoalkylaryl)phosphites may also comprise
bis(Alkyl-A-phenyl)Alkyl-B-aryl phosphite and bis(Alkyl-B-phenyl)
Alkyl-A-aryl phosphite.
[0067] In particular aspects of this embodiment, Alkyl-A is propyl,
e.g., isopropyl, and Alkyl-B is butyl, e.g., t-butyl; in another
aspect, Alkyl-A is propyl, e.g., isopropyl, and Alkyl-B is amyl,
e.g., t-amyl; in another aspect, Alkyl-A is butyl, e.g., t-butyl,
and Alkyl-B is amyl, e.g., t-amyl.
[0068] In this embodiment, the phosphite compositions may be
particularly diverse containing many different phosphite compounds.
For example a tris(monoalkylaryl) phosphite and a tris(dialkylaryl)
phosphite may include tris compounds having exclusively the same
alkyl groups (either Alkyl-A or Alkyl-B), or may comprise a mixture
of alkyl groups (e.g., Alkyl-A and Alkyl-B). Similarly, the
bis(dialkylaryl)monoalkylaryl phosphites and
bis(monoalkylaryl)dialkylaryl phosphites may include exclusively
the same alkyl group or different alkyl groups.
[0069] Generally, the phosphites of the second embodiment are
reaction products of a phosphorous halide and an alkylate
composition that is a mixture of alkylated hydroxyaryl compounds,
some of which are alkylated with Alkyl-A and some of which are
alkylated with Alkyl-B. As opposed to the preparation of the mixed
phosphite embodiment, the alkylated hydroxyaryl compounds are
combined to form a mixed alkylate composition prior to reaction
with a phosphorous halide. For example, the alkylate composition
may comprise, (i) a first alkylate composition comprising mono
and/or di-Alkyl-A-phenols, and (ii) a second alkylate composition
comprising mono and/or di-Alkyl-B-phenols.
[0070] In one preferred embodiment, the alkylate composition
comprises two or more compounds selected from the group consisting
of a propylated hydroxyaryl compound, a butylated hydroxyaryl
compound and an amylated hydroxyaryl compound. The propylated
hydroxyaryl compound preferably is selected from the group
consisting of 4-isopropyl phenol and 2,4-di-isopropyl phenol; the
butylated hydroxyaryl compound preferably is selected from the
group consisting of 4-t-butyl phenol and 2,4-di-t-butyl phenol; and
the amylated hydroxyaryl compound preferably is selected from the
group consisting of 4-t-amyl phenol and 2,4-di-t-amyl phenol,
although in many embodiments other isomers and/or other alkyl
groups are present.
Mixed Olefins Embodiment
[0071] In the third general embodiment of the present invention,
the liquid phosphite composition comprises one or more, preferably
two or more, three or more, or four or more phosphites, having at
least one aryl moiety that includes two or more alkyl groups having
a different number of carbon atoms, for example, the phosphite
composition comprises at least one phosphite of the structure:
##STR00020##
wherein m is an integer selected from 1, 2 and 3; n, o, p and q are
integers independently selected from 0, 1 and 2, provided that
m+n+o+p+q=3, Ar, R.sub.8 and R.sub.9 are as described above.
Typically, R.sub.8 and R.sub.9 are selected from isomers of propyl,
butyl and amyl, as in the previously described general embodiments.
Other phosphites may also be present including phosphites not
having the general structure (XI).
[0072] In this embodiment, the phosphite compositions may be
particularly diverse containing many different phosphite compounds,
potentially more than in either the first or second general
embodiments because each individual aryl moiety has the option of
being substituted by both R.sub.8 and R.sub.9. That is a third
alkylaryl moiety, Alkyl-A-Alkyl-B-aryl is also available.
[0073] Generally, the liquid phosphite composition of the third
general embodiment is a reaction product of a phosphorous halide
and an alkylate composition, where the alkylate composition is the
reaction product of two or more olefins having different numbers of
carbon atoms and at least one hydroxyaryl compound. Thus, while the
mixed phosphites embodiment prepares Alkyl-A substituted aryl
phosphites and Alkyl-B substituted aryl phosphites separately and
the mixed alkylates embodiment prepares the alkylated hydroxyaryls
separately but mixes them prior to reaction with phosphorous
halide, the mixed olefins embodiment prepares a mixture of
alkylates by reaction of an hydroxyaryl moiety with different
olefins and then reaction this mixture with a phosphorous halide.
Using different olefins in the process allows the formation of
hydroxy aryl compounds, at least some of which are substituted with
two or more alkyl groups having different numbers of carbon atoms.
The composition of the alkylate composition may be modified by
varying types and ratios of the reactants (e.g., olefins to
hydroxyaryl compound as well as the ratio of first olefin to second
olefin) and/or by modifying processing conditions of the alkylation
process. The mixture of olefins independently includes two or more
straight or branched C.sub.2-C.sub.18 olefins, e.g.,
C.sub.3-C.sub.5 olefins, or C.sub.4-C.sub.5 olefins. In one
embodiment, the first olefin is a C.sub.2-C.sub.12 olefin and the
second olefin is a C.sub.3-C.sub.18 olefin. Preferably, at least
one of the first or second olefins is a branched olefin. Often the
olefins include propylene, isobotylene and isoamylene.
[0074] During the alkylation, the mixture of olefins may be reacted
in parallel with the hydroxyaryl compound, i.e., the first and
second olefins are reacted together. In another embodiment, the
mixture of olefins may be reacted with the hydroxyaryl compound in
a consecutive manner, e.g., the first olefin is reacted first
followed by the second olefin. Each of these embodiments is
described in detail below.
Alkylation of Hydroxyaryl Moieties
[0075] The hydroxyaryl compound in each embodiment is an aromatic
moiety having at least one hydroxyl and from 6 to 18 carbon atoms,
e.g., phenol, 1-naphthol 2-naphthol, 9-phenanthrol indanol,
catechol, resorcinol, anthracen-2-ol, 4-biphenol, 4,4'-biphenol,
xylenol, cresol, and derivatives thereof, preferably phenol.
[0076] In one aspect, as in the mixed phosphite and mixed alkylates
embodiments, each alkyl substituted hydroxyaryl, also referred to
herein as an alkylate, may be separately formed by the reaction
between an olefin, e.g., propylene, butylene or amylene, and a
hydroxyaryl compound, e.g., phenol. For example, the first alkylate
is derived from a first olefin, and the second alkylate is derived
from a second olefin having a different number of carbon atoms than
the first olefin. Alternatively, as in the mixed olefins
embodiment, the alkylate composition may be formed in a single
reaction between the first and second olefins and the hydroxyaryl
compound, for example, a mixture of alkenes such as lower alkenes
(e.g., two or more C.sub.3-C.sub.6 olefins, such as a mixture of
butylene and amylenes) may be reacted with a phenol either in
parallel (feed in olefin A and B at the same time) or consecutively
(i.e. olefin A is reacted first followed by olefin B).
[0077] Thus, the alkylates may be formed by contacting one or more
phenolics with two or more olefins (in separate reactions or in a
single reaction process) in the presence of a catalyst and under
conditions effective to form the alkylate composition. Each of the
two or more olefins contains from 2 to 18 carbons, e.g., from 2 to
8 carbons, or from 3 to 5 carbons, provided that the first olefin
has a different number of carbon atoms than the second olefin. As
an alternative to using an olefin alkylating agent, one or more
C.sub.1-C.sub.18 alkyl halides, alcohols, MTBE or TAME may be
employed. The alkylating agents may comprise or be derived from a
hydrocarbon stream comprising alkanes and alkenes, such as a
petrochemical raffinate stream from a C.sub.4 or C.sub.5 fraction,
or a dehydrogenation reaction product of an alkane, e.g., isobutane
or isopentane. In this aspect, the alkanes pass through the
alkylating process unaltered and may be easily separated from the
product alkylate composition.
[0078] The ratio of olefins to phenolic is such that the resulting
alkylate composition is suitable for conversion to the desired
phosphite composition when reacted with a phosphorous halide,
keeping in mind that the resulting alkylate, e.g., first alkylate,
may be blended with another alkylate, e.g., second alkylate, to
form the alkylate composition that will be used in synthesizing the
phosphite composition. In some exemplary embodiments, the total
olefins to phenolic compound mole ratio ranges from 1:1 to 6:1,
e.g., from 1.1:1 to 2:1 or from 1.25:1 to 1.4:1. The ratios may
vary depending, for example, on the catalyst used in the alkylation
process and the desired composition and viscosity for the
ultimately formed phosphite composition.
[0079] In certain embodiments, the reaction of the phenol and the
two or more olefins (whether forming the first and second alkylates
separately or together) occurs in an inert atmosphere (e.g., under
nitrogen) at a temperature of from 60 to 160.degree.C., e.g., from
70 to 145.degree. C. or from 80 to 140.degree. C., generally at a
pressure of from 0.2 to 10 atm, e.g., from 0.2 to 5 atm or from 0.2
to 4 atm. In a batch reaction, the reaction time may last from 1 to
12 hours, e.g., from 2 to 10 hours, or from 3 to 5 hours. In a
continuous reaction, the residence time may be from 0.1 to 5 hours,
e.g., from 0.2 to 4 hours or from 0.5 to 1 hour. The alkylation is
typically performed in the presence of a catalyst. The catalyst
may, for example, be selected from the group consisting of acid
clay catalyst, cationic ion exchange resins, Bronsted acids, e.g.,
sulfuric acid, trifiuoromethanesulfonic acid (triflic acid) and
phosphotungstic acid, and Lewis acids, e.g., BF.sub.3. Suitable
commercial acid clay catalysts include Fulcat.TM. 22B. In one
embodiment, the sulfonic acid-type cation-exchange resin catalyst
useful in the present invention can be, for example, a sulfonated
styrene-divinyl benzene copolymer, a sulfonated crosslinked styrene
polymer, a phenol formaldehyde-sulfonic acid resin, or a benzene
formaldehyde-sulfonic acid resin. Many common commercial cation
exchange resins are useful in the present invention and include for
example styrene-divinylbenzene types of strong acid ion exchange
resins such as Dowex.TM. 50WX4, Dowex 50WX2, Dowex M-31, Dowex
Monosphere M-31, Dowex DR-2030 and Dowex Monosphere DR-2030
catalysts. Other appropriate resins include: Amberlyst.TM. 15,
Amberlyst 131, Amberlyst 35, Amberlyst 36, and A21; Diaion.TM.
WA30, Diaion SK104, Diaion SK1B, Diaion PK208, Diaion PK212 and
Diaion PK216; Tulsion.TM. T-38, Tulsion T-62, Tulsion T-66, Tulsion
T-3825 and Tulsion T-3830; Lewatit.TM. K1131, Lewatit K1221,
Lewatit K1261 and Lewatit SC 104; Indion.TM. 180 and Indion 225;
and Purolite.TM. CT-175, Purolite.TM. CT-169, and Purolite.TM.
CT-275.
[0080] In one embodiment, a batch alkylate synthesis takes place in
a pot-type reactor. In another embodiment, the alkylate synthesis
is conducted on a continuous basis in a continuous type reactor. In
one aspect of the process, any free phenolic compounds that are not
reacted with the olefins may be removed from the mixture of
reaction products through distillation at a temperature, for
example, of from 70 to 160.degree. C. and at a pressure of from 1
to 10 mbar.
[0081] The components and component concentrations in the alkylate
composition will vary depending on the desired composition and
target viscosity tor the alkylate composition as well as the
ultimately formed phosphite composition. For example, in one
embodiment the alkylate composition comprises 4-butyl phenol, e.g.,
4-t-butyl phenol, and 2,4-diamyl phenol, e.g., 2,4-di-t-amyl
phenol, in combination, in an amount greater than 80 wt %, 90 wt %
or greater than 95 wt %. In other specific examples, the alkylate
composition comprises 4-amyl phenol, e.g., 4-t-amyl phenol, and
2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol; 4-isopropyl phenol
and 2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol; 4-butyl
phenol, e.g., 4-t-butyl phenol, and 2,4-di-isopropyl phenol;
4-isopropyl phenol and 2,4-diamyl phenol, e.g., 2,4-di-t-amyl
phenol; or 4-amyl phenol, e.g., 4-t-amyl phenol, and
2,4-di-isopropyl phenol; each in combination in an amount greater
than 80 wt %, 90 wt % or greater than 95 wt %. In other
embodiments, the alkylate composition comprises a complex mixture
of phenolics, for example, comprising three or four of the
following: a 4-butyl phenol (e.g., 4-t-butyl phenol), a 2,4-dibutyl
phenol (e.g., 2,4-di-t-butyl phenol), 4-amyl phenol (e.g., 4-t-amyl
phenol), and a 2,4-diamyl phenol (e.g., 2,4-di-t-amyl phenol),
preferably in combination in an amount greater than 80 wt %, 90 wt
% or greater than 95 wt %. Similar complex alkylate compositions
are also possible with propyl/amyl and propyl/butyl, as well as
other combinations of C.sub.1-18 is alkyl groups.
[0082] In terms of component concentrations, the alkylate
composition may comprise, for example, from 5 to 95 wt %, e.g.,
from 10 to 80 wt % or from 30 to 65 wt %, of one or more
p-alkylated, phenol and from 10 to 70 wt % or from 30 to 65 wt %,
of one or more o,p-dialkylated phenol.
[0083] Typically, the alkylate composition comprises a monoalkyl
phenol, e.g., one or more 4-alkyl phenols, and a dialkyl phenol,
e.g., one or more 2,4-di-alkyl phenols. The 4-alkyl phenol is
typically present in an amount greater than 40 wt %, greater than
50 wt %, greater than 60 wt %, greater than 70 wt % or greater than
75 wt % and in an amount less than 95 wt %, e.g., less than 85 wt
%, less than 80 wt %, less than 75 wt % or less than 65 wt %. In
terms of ranges, in some embodiments, the 4-alkyl phenol, is
present in an amount ranging from 25 wt % to 99 wt %, e.g., from 45
wt % to 80 wt %, from 60 wt % to 75 wt %, or from 65 wt % to 75 wt
%. In this aspect, the dialkyl phenols, typically are present in an
amount ranging from 1 wt % to 60 wt %, e.g., from 10 wt % to 50 wt
%, from 25 wt % to 40 wt %, or from 25 wt % to 35 wt %. Optionally,
the dialkyl phenol is present in an amount less than 60 wt %, e.g.,
less than 55 wt %, less than 45 wt % or less than 35 wt %. In terms
of lower range limitations, the dialkyl phenol, e.g., 2,4-di-t-amyl
phenol and/or 2,4-di-t-butyl phenol, optionally is present in an
amount greater than 10 wt %, greater than 20 wt %, greater than 30
wt %, or greater than 40 wt %.
[0084] The weight ratio of monoalkyl phenols to dialkyl phenols, is
selected or adjusted so as to produce the desired alkylate
composition that is suitable for being used as a reactant for
forming an alkylaryl phosphite composition that is a liquid at
ambient conditions. For example, the weight ratio of monoalkyl
phenols to dialkyl phenols in the alkylate compositions ranges from
9:1 to 1:1, e.g., from 8:1 to 1:1, from 8:1 to 1.5:1, or from 7:1
to 2:1.
[0085] As stated above, the mixed olefins embodiment is typically
formed from a mixture of alkylates prepared by reaction of an
hydroxyaryl moiety with different olefins, often using either the
parallel alkylation process or the consecutive alkylation
process.
[0086] When fed in parallel, i.e., parallel alkylation, the
alkylate composition may be formed by contacting one or more
hydroxyaryl compounds with a mixture of two or more olefins,
typically in the presence of a catalyst, and under conditions
effective to form the alkylate composition as described in
preceding embodiments. As an alternative to using an olefin
alkylating agent, two or more alkyl halides or alcohols may be
employed where the two or more alkyl halides or alcohols have
different numbers of carbon atoms. The alkylating agent that is
employed may comprise or be derived from a petrochemical raffinate
stream, e.g., a C.sub.4 or C.sub.5 raffinate stream, comprising a
combination of both alkanes and alkenes.
[0087] In one embodiment, the mixture of olefins is pre-mixed prior
to the alkylation of the hydroxyaryl compound.
[0088] A schematic of one reaction method using parallel alkylation
to form an alkylate composition is shown below, where Olefin.sub.1
and Olefin.sub.2 are independently straight or branched
C.sub.2-C.sub.8, e.g., C.sub.3-C.sub.5 or C.sub.4-C.sub.5, olefins
having a different number of carbon atoms and R is the alkyl group
formed from Olefin.sub.1, and R' is the alkyl group formed from
Olefin.sub.2.
##STR00021##
[0089] As before, the molar ratio of hydroxyaryl compound to the
olefin mixture is such that the resulting alkylate composition is
suitable for conversion to the desired phosphite composition when
reacted with a phosphorous halide. For example, the hydroxyaryl
compound to olefin mixture mole ratio ranges from 1:6 to 1:1, e.g.,
from 1:4 to 1:1.2 or from 1.5:1 to 1:1.5.
[0090] In consecutive alkylation, one or more hydroxyaryl compounds
are reacted with one olefin, typically in the presence of a
catalyst, and under conditions effective to form a partial alkylate
composition. The molar ratio of hydroxyaryl compounds to the first
olefin is from 6:1 to 1:2, e.g. from 5:1 to 2:3, or form 2:1 to
3:4. The partial alkylate composition is then reacted with the
second olefin (having a different number of carbon atoms than the
first olefin) under similar conditions to form the alkylate
composition. Optionally, an additional amount of hydroxyaryl
compounds may also be charged to the partial alkylate composition.
The molar ratio of the partial alkylate to the second olefin is
from 15:1 to 2:1, e.g., from 8:1 to 3:1 or from 6:1 to 4:1. When
consecutively added, it is preferred that the olefin having a fewer
number of carbon atoms is initially added followed by the other
olefin. Alternatives to olefin alkylating agents described in
context of parallel reactions may also be used in consecutive
alkylation.
[0091] A schematic of one reaction method using consecutive
alkylation to form an alkylate composition is as follows where
Olefin.sub.1, Olefin.sub.2, R and R' are defined above. The
conditions effective to form the desired alkylate composition are
typically as described in preceding embodiments.
##STR00022##
[0092] The alkylate composition thus comprises at least some
dialkylated hydroxyaryl compounds, e.g., o,p-dialkylated phenols,
that are substituted with both Alkyl-A and Alkyl-B. In addition,
the alkylate composition may comprise a p-alkylated phenol such as
p-Alkyl-A phenol, p-Alkyl-B phenol or both p-Alkyl-A phenol and
p-Alkyl-B phenol. Additional o,p-dialkylated phenols in the
alkylate composition may include o,p-di-Alkyl-A phenol,
o,p-di-Alkyl-B phenol, or both o,p-di-Alkyl-A phenol and
o,p-di-Alkyl-B phenol.
[0093] The phosphite compositions of the invention may then be
conveniently prepared by reacting a phosphorous trihalide,
preferably is selected from phosphorus trichloride and phosphorus
tribromide with one of the above described alkylate compositions.
When a catalyst is used, the catalyst may be selected from the
group consisting of pyridine, N,N-dimethyldodecylamine, and
dilauryl methyl amine or their hydrochloride salts. The molar ratio
of alkylate composition (i.e., alkylated phenol compounds) to
phosphorus trihalide preferably is from 3:1 to 5:1, e.g., from 3:1
to 4:1 or from 3.1 to 3.7:1.
[0094] The reaction of the alkylated phenols with a phosphorus
trihalide may be conducted under an inert atmosphere (e.g.,
nitrogen) at a temperature of from 5 to 70.degree. C., e.g., from
40 to 70.degree. C. or from 50 to 70.degree. C. Preferably, the
temperature is held at or below 70.degree. C. during the addition
of the alkylate composition to prevent refluxing the phosphorus
trihalide. Optionally, the alkylate composition is charged to the
reactor and the phosphorus trihalide is added thereto. After the
addition of alkylate composition, the temperature is optionally
held for 10 minutes to 12 hours, e.g., from 30 minutes to 10 hours,
or from 1 hour to 3 hours, typically at a pressure of 0.8 to 4 atm,
e.g., from 0.9 to 3 atm or from 1 to 2 atm. Next, the temperature
may be ramped to a ramped temperature ranging from 70.degree. C. to
250.degree. C., e.g., from 80.degree. C. to 225.degree. C. or from
90.degree. C. to 200.degree. C. Preferably, the reaction is held at
the ramped temperature for from 10 minutes to 12 hours, e.g., from
30 minutes to 10 hours, or from 1 hour to 3 hours optionally at a
reduced pressure of 0.01 to 0.5 atm, e.g. from 0.03 to 0.4 atm or
from 0.04 to 0.1 atm. During the reaction time, hydrochloric or
hydrobromic gas will be evolved, and may be removed by reducing the
pressure to about 0.05 atm or sweeping an inert gas such as
nitrogen over the reaction mixture. In one aspect the removal of
such gases may be performed until the total chloride content in the
reaction mixture is less than 50 wppm, e.g., less than 25 wppm or
less than 10 wppm.
[0095] In one aspect of the process, any free phenol that is not
reacted with the phosphorus trihalide may be liberated by raising
the reaction temperature to up to 275.degree. C., e.g., up to
250.degree. C. or up to 225.degree. C., or up to 200.degree. C.,
and in a vacuum at a pressure of 0.0001 to 0.1 atm. In one
embodiment, a wiped-film molecular (Short-Path) still, wiped film
evaporator (WFE), thin film evaporator, or similar equipment may be
used to further remove the free cresol or phenol to the very low
levels indicated above.
[0096] In one embodiment, the step of forming the phosphite
composition occurs in one or more neutral solvents, which solvents
include toluene, xylene, methylene chloride, heptane, chloroform,
and benzene.
Stabilizers
[0097] A stabilizing amount or effective amount of the phosphite
composition of the invention may be used as a secondary antioxidant
for various types of polymers. As used herein, by "stabilizing
amount" and an "effective amount" it is meant when the polymer
composition containing the phosphite compositions of the invention
shows improved stability in any of its physical or color properties
in comparison to an analogous polymer composition which does not
include a phosphite composition of the invention. Examples of
improved stability include improved stabilization against, for
example, molecular weight degradation, color degradation, and the
like from, for example, melt processing, weathering, and/or long
term field exposure to heat, light, and/or other elements. In one
example, improved stability is obtained in the form of one or both
of lower initial color or additional resistance to weathering, as
measured, for example, by initial yellowness index (YI), or by
resistance to yellowing and change in color, when compared to a
composition without the stabilizer additive.
[0098] The additives and stabilizers described herein are present
in an amount effective to improve composition stability. For
example, the phosphite composition is generally present in an
amount from about 0.001 to about 5 wt %, e.g., from about 0.0025 to
about 2 wt % or from about 0.005 to about 1 wt %, based on the
total weight of the polymer including the weight of the phosphite
composition and any other stabilizers or additives. The phosphite
compositions of this invention stabilize resins especially during
high temperature processing with relatively little change in melt
index and/or color, even after multiple extrusions.
[0099] The invention further relates to a stabilized
thermoplastics, comprising a base polymer the phosphite
compositions of the invention. The polymer resin may be a polymer
such as a polyolefin, and the liquid phosphite composition may be
used with a costabilizer, for example, hindered phenolics, aromatic
amines, hydroxylamines, lactones, and thioethers. The thermoplastic
is stabilized by the phosphite compositions of the present
invention optionally contains one or more additional stabilizers or
mixtures of stabilizers selected from the group consisting of
phenolic antioxidants, hindered amine light stabilizers (HALS),
ultraviolet light absorbers, phosphites, phosphorites, alkaline
metal salts of fatty acids, hydrotalcites, metal oxides, epoxydized
soybean oils, hydroxylamines, tertiary amine oxides, lactones,
thermal reaction products of tertiary amino oxides, and
thiosynergists.
[0100] In one embodiment, the amount of each component in the
stabilizing mixture, based on the total weight percent of the
polymer or polymeric resin, is shown in Table 4.
TABLE-US-00002 TABLE 4 Component Range Preferred Range Liquid
phosphite compositions 0.001-5.0 wt % 0.005-1.0 wt % Primary
antioxidant 0-5.0 wt % 0.005-2.0 wt % UV or light stabilizers 0-3.0
wt % 0.001-2.0 wt % Metal deactivators 0-3.0 wt % 0.001-2.0 wt %
Other secondary antioxidants 0-3.0 wt % 0.001-2.0 wt % Peroxide
scavengers 0-3.0 wt % 0.001-2.0 wt % Polyamide stabilizers 0-3.0 wt
% 0.001-2.0 wt % Basic co-stabilizers 0-3.0 wt % 0.001-2.0 wt %
Nucleating or clarifying agents 0-3.0 wt % 0.001-2.0 wt % Aminoxy
propanoate 0-3.0 wt % 0.001-2.0 wt %
[0101] Primary antioxidants include the following: [0102] (i)
Alkylated monophenols, for example:
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,
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,
2,6-bis(.alpha.-methylbenzyl)-4-methylphenol
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6,-tricyclohexyphenol, and
2,6-di-tert-butyl-4-methoxymethylphenol [0103] (ii) Alkylated
hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, and
2,6-diphenyl-4octadecyloxyphenol. [0104] (iii) Hydroxylated
thiodiphenyl ethers, for example,
2,2'-thio-bis-(6-tert-butyl-4-methylphenol),
2,2'-thio-bis-(4-octylphenol),
4,4'-thio-bis-(6-tert-butyl-3-methylphenol), and
4,4'-thio-bis(6-tert-butyl-2-methyphenol). [0105] (iv)
Alkylidene-bisphenols, for example,
2,2'-methylene-bis-(6-tert-butyl-4-methylphenol),
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol),
2,2'-methylene-bis-(4-methyl-6-(.alpha.-methylcyclohexyl)phenol),
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol),
2,2'-methylene-bis-(6-nonyl-4-methylphenol),
2,2'-methylene-bis-(6-nonyl-4-methylphenol),
2,2'-methylene-bis-(6-(.alpha.methylbenzyl)-4-nonylphenol,
2,2'-methylene-bis-(6-(alpha,alpha-dimethylbenzyl)-4-nonyl-phenol),
2,2'-methylene-bis-(4,6-di-tert-butylphenol),
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol),
4,4'-methylene-bis-(2,6-di-tert-butylphenol),
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane,
1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,6-di-(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-dodecyl-mercaptobutane,
Ethyleneglycol-bis-(3,3,-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-d-
i-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, and
di-(2-(3'tert-butyl-2'hydroxy-5'methyl-benzyl)-6-tert-butyl-4-methylpheny-
l)terephthalate [0106] (v) Benzyl compounds, for example,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate,
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate,
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,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-Triazine-2,4,6-(-
1H,3H,5H)-trione,
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, calcium
salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. [0107]
(vi) Acylaminophenols, for example, 4-hydroxylauric acid anilide,
4-hydroxy-stearic acid amilide,
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine,
and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbanate. [0108]
(vii) Esters of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic
acid with monohydric or polyhydric alcohols, for example, methanol,
diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol,
pentaerythritol, neopentylglycol, tris-hydroxyethylisocyanurate,
thiodiethyleneglycol, di-hydroxyethyl oxalic acid diamide. Such
phenols also include tetrakis [methylene
{3,5-di-tert-butyl-4-hydroxycinnamate}]methane. [0109] (viii) Thio
esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic
acid with monohydric or polyhydric alcohols, for example, methanol,
diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol,
pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate,
thiodiethyleneglycol, dihydroxyethyl oxalic acid diamide. [0110]
(ix) Amides of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic
acid for example,
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexammethyl-
en-diamine,
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,
N,N'-di-(3,5-di-tert-butyl-4-hydroxypropionyl)hydrazine,
N,N'-Hexamethylene
bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide, and
1,2-Bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine. [0111]
(x) Other phenolic antioxidants include polymeric phenols such as
the reaction product of 4-methylphenol with dicyclopentadiene and
isobutylene, alkylidene-poly-phenols, such as 1,3
tris(3-methyl-4-hydroxyl-5-t-butyl-phenyl)-butane; thio phenols
such as
2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)
phenol, 4,6-bis (octylthiomethyl)-o-cresol;
4,6-bis(dodecylthiomethyl)-o-cresol, ester phenols include
bis[3,3-bis(4-hydroxy-3-tert-butyl phenyl)butanoic acid]glycol
ester and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)
ethyl]-4,6-di-tert-pentylphenyl acrylate. [0112] (xi) Other primary
antioxidants include hydroxyl amines, and n-oxides such as
bis(octadecyl)hydroxylamine.
[0113] In one embodiment, the stabilizing composition comprises one
primary antioxidant selected from the group consisting of
tetrakismethylene (3,5-di-t-butyl-4-hydroxylhydrocinnamate)
methane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)1,3,5-triazine-2,4,-
6-(1H,3H,5H)trione, octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate, bis(octadecyl)hydroxylamine, 1,3,5-trimethyl-2,4,6-tris
(3,5-di-tert-4-hydroxybenzyl) benzene,
2,6-bis(.alpha.-methylbenzyl)-4-methylphenol,
3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid,
2,6-di-t-butyl-4-ethyl-phenol, and mixtures thereof, and the liquid
phosphite composition defined herein.
[0114] The phosphite compositions and/or the resulting stabilized
polymeric compositions optionally also comprise one or more UV
absorbers and/or light stabilizers, such as the following: [0115]
(i) 2-(2'-hydroxyphenyl)-benzotriazoles, for example, the
5'-methyl-, 3'5'-di-tert-butyl-, 3'5'-di-tert-amyl-,
5'-tert-butyl-, 5'-tert-amyl-, 5'(1,1,3,3-tetramethylbutyl)-,
5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'methyl-,
3'-sec-butyl-5'tert-butyl-,4'-octoxy,
3',5'-ditert-amyl-3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-derivatives.
[0116] (ii) 2-Hydroxy-benzophenones, for example, the 4-hydroxy,
4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-,
2,4-dihydroxy-, 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy-
derivative. Exemplary 2-hydroxy-benzophenones include
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone,
2,4-dihydroxybenzophenone, and 2-hydroxy-4-propoxybenzophenone.
[0117] (iii) Esters of substituted and unsubstituted benzoic acids
for example, phenyl salicylate, 4-tert-butylphenyl-salicilate,
octylphenyl salicylate, dibenzoylresorcinol,
bis-(4-tert-butylbenzoyl)-resorcinol, Benzoylresorcinol,
2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate and
hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate. [0118] (iv) UV
absorbers and light stabilizers may also comprise acrylates, for
example, alpha-cyano-beta, beta-diphenylacrylic acid-ethyl ester or
isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester,
alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or
butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl
ester, N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline.
[0119] (v) Nickel compounds are also suitable UV absorbers and
light stabilizers. Exemplary nickel compounds include nickel
complexes of 2,2'-thio-bis(4-(1,1,1,3-tetramethylbutyl)-phenol),
such as the 1:1 or 1:2 complex, optionally with additional ligands
such as n-butylamine, triethanolamine or
N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel
salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl
esters, such as of the methyl, ethyl, or butyl ester, nickel
complexes of ketoximes such as of 2-hydroxy-4-methyl-penyl undecyl
ketoxime, nickel complexes of
1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional
ligands. [0120] (vi) Sterically hindered amines may be used as
light stabilizers, for example
bis(2,2,6,6-tetramethylpiperidyl)-sebacate,
bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate,
n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid
bis(1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and
succinic acid, condensation product of
N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and
4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-carbonic
acid, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).
Such amines include hydroxylamines derived from hindered amines,
such as di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate:
1-hydroxy 2,2,6,6-tetramethyl-4-benzoxypiperidine;
1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxy
Hydrocinnamoyloxy)-piperdine; and
N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-epsiloncaprolactam.
[0121] (vii) Oxalic acid diamides, for examples,
4,4'-dioctyloxy-oxanilide,
2,2'-di-octyloxy-5',5'-di-tert-butyloxanilide,
2,2'-di-dodecyloxy-5',5'di-tert-butyl-oxanilide,
2-ethoxy-2'-ethyl-oxanilide,
N,N'bis(3-dimethylaminopropyl)-oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with
2-ethoxy-2'ethyl-5,4-di-tert-butyloxanilide and mixtures of o- and
p-methoxy- as well as of o- and p-ethoxy-disubstituted
oxanilides.
[0122] The polymer resins and phosphite compositions of the
invention may also include one or more additional additives,
including, for example, one or more of the following: [0123] (i)
Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,
N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,
N,N'-bis-(3,5-di-tert-butyl-4-hydrophenylpropionyl)-hydrazine,
salicyloylamino-1,2,4-triazole, bis-benzyliden-oxalic acid
dihydrazide. [0124] (ii) Peroxide scavengers, for example, esters
of betathiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc-dibutyldithiocaramate,
dioctadecyldisulfide,
pentaerythritoltetrakis-(beta-dodecylmercapto)-propionate. [0125]
(iii) Polyamide stabilizers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese may also be included in the polymer resin and/or
phosphite composition. [0126] (iv) Basic co-stabilizers, for
example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines,
polyamides, polyurethanes, hydrotalcites, alkali metal salts and
alkaline earth metal salts of higher fatty acids, for example, Ca
stearate, calcium stearoyl lactate, calcium lactate, Zn stearate,
Zn octoate, Mg stearate, Na ricinoleate and K palmirate, antimony
pyrocatecholate or zinc pyrocatecholate. [0127] (v) Nucleating and
clarifying agents, for example, metal salts of 4-tert butylbenzoic
acid, adipic acid, diphenylacetic acid, sorbitol and derivatives
thereof, sodium benzoate, and benzoic acid. [0128] (vi) Aminoxy
propanoate derivatives such as
methyl-3-(N,N-dibenzylaminoxy)propanoate;
ethyl-3-(N,N-dibenzylaminoxy)propanonoate;
1,6-hexamethylene-bis(3-N,N-dibenzylaminoxy)proponoate);
methyl-(2-(methyl)-3(N,N-dibenzylaminoxy)propanoate);
octadecyl-3-(N,N-dibenzylaminoxy)propanoic acid; tetrakis
(N,N-dibenzylaminoxy)ethyl carbonyl oxymethy)methane;
octadecyl-3-(N,N-diethylaminoxy)-propanoate;
3-(N,N-dibenzylaminoxy)propanoic acid potassium salt; and
1,6-hexamethylene Bis(3-(N-allyl-N-dodecyl aminoxy)propanoate).
[0129] (vii) Other additives, for example, plasticizers,
lubricants, emulsifiers, pigments, dyes, optical brighteners,
frameproofing agents, anti-static agents, blowing agents and
thiosynergists such as dilaurythiodipropionate or
distearylthiodipropionate.
[0130] Optionally the polymer or polymeric resins may include from
5-50 wt %, e.g., 10-40 Wt % or 15-30 wt % fillers and reinforcing
agents, for example, calcium carbonate, silicates, glass fibers,
asbestos, talc, kaolin, mica, barium sulfate, metal oxides and
hydroxides, carbon black and graphite.
[0131] The invention further pertains to a stabilized polymer,
wherein one component comprises a liquid phosphite composition of
the present invention and the other a polymer, such as a
polyolefin, polyvinyl chloride, etc., or polymeric resins.
[0132] The polymer stabilized by such liquid phosphite compositions
may be any polymer known in the art, such as polyolefin
homopolymers and copolymers, thermoplastics, rubbers, polyesters,
polyurethanes, polyalkylene terephthalates, polysulfones,
polylmides, polyphenylene ethers, styrenic polymers and copolymers,
polycarbonates, acrylic polymers, polyamides, polyacetals,
halide-containing polymers, and biodegradable polymers. Mixtures of
different polymers, such as polyphenylene ether/styrenic resin
blends, polyvinyl chloride/ABS or other impact modified polymers,
such as methacrylonitrile and .alpha.-methylstyrene containing ABS,
and polyester/ABS or polycarbonate/ABS and polyester plus some
other impact modifier may also be used. Such polymers are available
commercially or may be made by means well known in the art.
However, the stabilizer compositions of the invention are
particularly useful in thermoplastic polymers, such as polyolefins,
polycarbonates, polyesters, polyphenylene ethers and styrenic
polymers, due to the extreme temperatures at which thermoplastic
polymers are often processed and/or used.
[0133] The polymers used in combination with liquid phosphite
compositions of the present invention are produced using a variety
of polymerization processes including solution, high-pressure,
slurry and gas phase using various catalysts including
Ziegler-Natta, single-site, metallocene or Phillips-type catalysts.
Non-limiting polymers useful with the liquid phosphite compositions
include ethylene based polymers such as linear low density
polyethylene, elastomers, plastomers, high density polyethylene,
substantially linear long chain branched polymers, and low density
polyethylene; and propylene based polymers such as polypropylene
polymers including atactic, isotactic, and syndiotactic
polypropylene polymers, and propylene copolymers such as propylene
random, block or impact copolymers.
[0134] Polymers used with liquid phosphites compositions of the
invention are useful in such forming operations as film, sheet, and
fiber extrusion and co-extrusion as well as blow molding, injection
molding and rotary molding. Films include blown or cast films
formed by coextrusion or by lamination useful as shrink film, cling
film, stretch film, sealing films, oriented films, snack packaging,
heavy duty bags, grocery sacks, baked and frozen food packaging,
medical packaging, industrial liners, membranes, etc. in
food-contact and non-food contact applications. Fibers include melt
spinning, solution spinning and melt blown fiber operations for use
in woven or non-woven form to make filters, diaper fabrics, medical
garments, geotextiles, etc. Extruded articles include medical
tubing, wire and cable coatings, geomembranes, and pond liners.
Molded articles include single and multi-layered constructions in
the form of bottles, tanks, large hollow articles, rigid food
containers and toys, etc. In addition to the above, the liquid
phosphite compositions are used in various rubber based products
such as tires, barriers and the like.
[0135] In one embodiment, the liquid phosphite compositions are
used in polymers, such as polyolefins, that are used in contact
with beverages, foods and other human consumables.
[0136] Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1,
polyisoprene, or polybutadiene, as well as polymers of
cycloolefins, for instance of cyclopentene or norbornene,
polyethylene (which optionally can be crosslinked), for example
high density polyethylene (HDPE), low density polyethylene (LDPE)
and linear low density polyethylene (LLDPE) may be used. Mixtures
of these polymers, 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), may also be used. Also useful are
copolymers of monoolefins and diolefins with each other or with
other vinyl monomers, such as, for example, ethylene/propylene,
LLDPE and its mixtures with LDPE, propylene/butene-1,
ethylene/hexene, ethylene/ethylpentene, ethylene/heptene,
ethylene/octene, propylene/isobutylene, ethylene/butane-1,
propylene/butadiene, isobutylene, isoprene, ethylene/alkyl
acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate
(EVA) or ethylene/acrylic acid copolymers (EAA) and their salts
(ionomers) and terpolymers of ethylene with propylene and a diene,
such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as
well as mixtures of such copolymers and their mixtures with
polymers mentioned above, for example polypropylene/ethylene
propylene-copolymers, LDPE/EVA, LDPE/EAA, LLDPE/EVA, and
LLDPE/EAA.
[0137] The olefin polymers may be produced by, for example,
polymerization of olefins in the presence of Ziegler-Natta
catalysts optionally on supports such as, for example, MgCl.sub.2,
chromium 20 salts and complexes thereof, silica, silica-alumina and
the like. The olefin polymers may also be produced utilizing
chromium catalysts or single site catalysts, e.g., metallocene
catalysts such as, for example, cyclopentadiene complexes of metals
such as Ti and Zr. As one skilled in the art would readily
appreciate, the polyethylene polymers used herein, e.g., LLDPE, can
contain various comonomers such as, for example, 1-butene, 1-hexene
and 1-octene comonomers.
[0138] The polymer may also include styrenic polymers, such as
polystyrene, poly-(p-methylstyrene), 5
poly-(.alpha.-methylystyrene), copolymers of styrene or
.alpha.-methylstyrene with dienes or acrylic derivatives, such as,
for example, styrene/butadiene (SBR), styrene/acrylonitrile,
styrene/alkyl methacrylate, styreue/maleic anhydride,
styrene/maleimide, styrene/butadiene/ethyl acrylate,
styrene/acrylonitrile/methylacrylate, mixtures of high impact
strength from styrene copolymers and another polymer, such as, for
example, from a polyacrylate, a diene polymer or an
ethylene/propylene/diene terpolymer; and block copolymers of
styrene, such as, for example, styrene/butadiene/styrene (SBS),
styrene/isoprene/styrene (SIS), styrene/ethylene/butylene/styrene
or styrene/ethylene/propylene/styrene.
[0139] Styrenic polymers may additionally or alternatively include
graft copolymers of styrene or .alpha.-methylstyrene such as, for
example, styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile; styrene and acrylonitrile (or
methacrylonitrile) on polybutadiene and copolymers thereof; styrene
and maleic anhydride or maleimide on polybutadiene; styrene,
acrylonitrile and maleic anhydride or maleimide on polybutadiene;
styrene, acrylontrile and methyl methacrylate on polybutadiene,
styrene and alkyl acrylates or methacrylates on polybutadiene,
styrene and acrylonitrile on ethylene-propylene-diene terpolymers,
styrene and acrylonitrile on polyacrylates or polymethacrylates,
styrene and acrylonitrile on acrylate/butadiene copolymers, as well
as mixtures thereof with the styrenic copolymers indicated
above.
[0140] Suitable rubbers include both natural rubber and synthetic
rubbers, and combinations thereof. Synthetic rubbers include, but
are not limited to, for example, thermoplastic rubbers,
ethylene/alpha-olefin/non-conjugated polyene (EPDM) rubbers,
ethylene/alpha-olefin (EPR) rubbers, styrene/butadiene rubbers,
acrylic rubbers, nitrile rubbers, polyisoprene, polybutadiene,
polychloroprene, acrylonitrile/butadiene (NBR) rubbers,
polychloroprene rubbers, polybutadiene rubbers,
isobutylene-isoprene copolymers, etc. Thermoplastic rubbers include
SIS, solution and emulsion SBS, etc.
[0141] Nitrile polymers are also useful in the polymer composition
of the invention. These include homopolymers and copolymers of
acrylonitrile and its analogs, such as polymethacrylonitrile,
polyacrylonitrile, acrylonitrile/butadiene polymers,
acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl
methacrylate/butadiene polymers, and various ABS compositions as
referred to above in regard to styrenics.
[0142] Polymers based on acrylic acids, such as acrylic acid,
methacrylic acid, methyl Methacrylic acid and ethacrylic acid and
esters thereof may also be used. Such polymers include
polymethylmethacrylate, and ABS-type graft copolymers wherein all
or part of the acrylonitrile-type monomer has been replaced by an
acrylic acid ester or an acrylic acid amide. Polymers including
other acrylic-type monomers, such as acrolein, methacrolein,
acrylamide and methacrylamide may also be used.
[0143] Halogen-containing polymers may also be stabilized with the
phosphite compositions of the present invention. These include
polymers such as polychloroprene, epichlorohydrin homo-and
copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl
fluoride, polyvinylidene chloride, chlorinated polyethylene,
chlorinated polypropylene, fluorinated polyvinylidene, brominated
polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate
copolymers, vinyl chloride-ethylene copolymer, vinyl
chloride-propylene copolymer, vinyl chloridestyrene copolymer,
vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene
chloride copolymer, vinyl chloride-styrene-maleic anhydride
terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl
chloride-butadiene copolymer, vinyl chloride isoprene copolymer,
vinyl chloride-chlorinated propylene copolymer, vinyl
chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl
chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid
ester copolymers, vinyl chloride-methacrylic acid ester copolymers,
vinyl chloride-acrylonitrile copolymer and internally plasticized
polyvinyl chloride.
[0144] Other useful polymers include homopolymers and copolymers of
cyclic ethers, such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bisglycidyl ethers;
polyacetals, such as polyoxymethylene and those polyoxymethylene
which contain ethylene oxide as a comonomer; polyacetals modified
with thermoplastic polyurethanes, acrylates or methacrylonitrile
containing ABS; polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with polystyrene or polyamides; polycarbonates
and polyester-carbonates; polysulfones, polyethersulfones and
polyetherketones; and polyesters which are derived from
dicarboxylic acids and diols and/or from hydroxycarboxylic acids or
the corresponding lactones, such as polyethylene terephthalate,
polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane
terephthalate, poly-2-(2,2,4(4-hydroxyphenyl)-propane)
terephthalate and polyhydroxybenzoates as well as block
copolyetheresters derived from polyethers having hydroxyl end
groups.
[0145] Polyamides and copolyamides which are derived from bisamines
and dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, such as polyamide 4, polyamide 6, polyamide
6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic
polyamides obtained by condensation of m-xylene bisamine and adipic
acid; polyamides prepared from hexamethylene bisamine and
isophthalic or/and terephthalic acid and optionally an elastomer as
modifier, for example poly-2,4,4 trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide may be useful.
Further copolymers of the aforementioned polyamides with
polyolefins, olefin copolymers, ionomers or chemically bonded or
grafted elastomers; or with polyethers, such as for instance, with
polyethylene glycol, polypropylene glycol or polytetramethylene
glycols and polyamides or copolyamides modified with EPDM or ABS
may he used.
[0146] In another embodiment, the polymer comprises a biodegradable
polymer or compostable polymer. Biodegradable polymers are those in
which the degradation results from the action of naturally
occurring microorganisms, such as bacteria, fungi and algae.
Compostable polymers undergoes degradation by biological processes
during composting to yield CO.sub.2, water, inorganic compounds and
a biomass at a rate consistent with other compostable materials.
Typically the biodegradable or compostable polymers are derived
from plant sources and are synthetically produced. Examples of
biodegradable or compostable polymers include poly(glycolic acid)
(PGA), poly(lactic acid) (PLA), and co-polymers thereof.
Biodegradable or compostable polymers may also be derived from a
blend of starch of a plant and a conventional petroleum-based
polymer. For example, the biodegradable polymer may be blended with
a polyolefin.
[0147] Polyolefin, polyalkylene terephthalate, polyphenylene ether
and styrenic polymers, and mixtures thereof are more preferred,
with polyethylene, polypropylene, polyethylene terephthalate,
polyphenylene ether homopolymers and copolymers, polystyrene, high
impact polystyrene, polycarbonates and ABS-type-graft copolymers
and mixtures thereof being particularly preferred.
[0148] In one embodiment, the liquid phosphite compositions are
added to stabilize natural and synthetic waxes, such as n-paraffin
waxes, chloroparaffins, .alpha.-olefin waxes, microcrystalline
waxes, polyethylene waxes, amide waxes, and Fisher-Tropsch waxes.
These waxes may be suitable for making candles.
[0149] The instant stabilizers may readily be incorporated into the
polymer by conventional techniques at any convenient stage prior to
the manufacture of shaped articles therefrom. For example, the
stabilizer may be mixed with the polymer in dry powder form, or a
suspension or emulsion of the stabiliser may be mixed with a
solution, suspension, or emulsion of the polymer. The stabilized
compositions of the invention may optionally also contain from
about 0.001 to about 5 wt. %, e.g., from about 0.0025 to about 2
wt. % or from about 0.05 to about 0.25 wt. %, of various
conventional additives, such as those described previously, or
mixtures thereof.
[0150] The compositions of the present invention can be prepared by
a variety of methods, such as those involving intimate admixing of
the ingredients with any additional materials desired in the
formulation. Suitable procedures include solution blending and melt
blending. Because of the availability of melt blending equipment in
commercial polymer processing facilities, melt processing
procedures are generally preferred. Examples of equipment used in
such melt compounding methods include: co-rotating and
counter-rotating extruders, single screw extruders, disc-pack
processors and various other types of extrusion equipment. In some
instances, the compounded material exits the extruder through small
exit holes in a die and the resulting strands of molten resin are
cooled by passing the strands through a water bath. The cooled
strands can be chopped into small pellets for packaging and further
handling.
[0151] All of the ingredients may be added initially to the
processing system, or else certain additives may be pre-compounded
with each other or with a portion of the polymer or polymeric resin
to make a stabiliser concentrate. Moreover, it is also sometimes
advantageous to employ at least one vent port to allow venting
(either atmospheric or vacuum) of the melt. Those of ordinary skill
in the art will be able to adjust blending times and temperatures,
as well as component addition location and sequence, without undue
additional experimentation.
[0152] While the stabilizers of this invention may be conveniently
incorporated by conventional techniques into polymers before the
fabrication thereof into shaped articles, it is also possible to
apply the instant stabilizers by a topical application to the
finished articles. Articles may comprise the instant stabilizer
compounds and polymers and may be made into, for example, head lamp
covers, roofing sheets, telephone covers, aircraft interiors,
building interiors, computer and business machine housings,
automotive parts, and home appliances. The articles may be made by
extrusion, injection molding, roto-molding, compaction, and other
methods. This may be particularly useful with fiber applications
where the instant stabilizers are applied topically to the fibers,
for example, by way of a spin finish during the melt spinning
process.
[0153] The phosphite compositions of the invention may have uses in
addition to polymer stabilization. For example, it may be desirable
to react the phosphite composition to form a new derivative
product, that may of additional uses. Transesterification
processes, for example, such as those disclosed in Hechenbleikner
et al., U.S. Pat. No. 3,056,823, which is incorporated herein by
reference, may also be employed. Specifically, the process
described by Hechenbleikner et al. involves transesterifying a
triaryl phosphite with a monohydroxy hydrocarbon in the presence of
a small but catalylically effective amount of a metal alcoholate or
metal phenolate. To avoid contamination, the alcoholate of the
particular alcohol to be transesterified is employed. Instead of
employing a preformed alcoholate, the alcoholate can be formed in
situ by adding the metal, e.g., sodium, potassium or lithium to the
alcohol prior to adding the triaryl phosphite. The mono alcohol and
triaryl phosphite are reacted in the mol ratio of three mols of the
alcohol to one mol of the triaryl phosphite.
[0154] The present invention is further described by way of the
following non-limiting examples.
EXAMPLES
Example 1
Synthesis of Mixed Amyl/Butyl Phenols
[0155] Phenol (105 grams, 1.12 moles) and Fulcat 22B catalyst (2.25
grams) were charged to an oil jacketed flask and heated to
130.degree. C. under nitrogen. Isobutylene (64.6 grams, 1.15 moles)
was added via a sintered glass frit below the surface of the phenol
at a uniform rate over 30 minutes. During addition, the internal
temperature rose to 140.degree. C. Once the addition was completed,
the reaction mass was held at a jacket temperature of 130.degree.
C. for one hour. Amylene (39.2 grains, 0.56 mole) was then added
below the surface of the phenolics at a uniform rate over 1.25
hours. After the addition, the reaction mass was held at a jacket
temperature of 130.degree. C. for two hours. The reaction was then
filtered and the phenolic filtrate collected. The mixed
butylated/amylated phenol alkylate was subjected to vacuum
distillation to reduce the phenol content to less than 0.25% and
the water content to less than 50 ppm. Yield=161.8 grams.
[0156] GC analysis identified the following major components: 50.8%
4-t-butyl-phenol, 17.6% 2,4-di-t-butyl-phenol, 15.3%
4-t-amyl-phenol, 10.7% 2-t-amyl-4-t-butyl-phenol and
2-t-butyl-4-t-amyl-phenol, 1.3% 2,4-di-t-amyl-phenol, 1.4%
2-t-butyl-phenol, and 0.3% 2,4,6-tri-t-butyl-phenol.
Example 2
Conversion to a Phosphite of the Alkylate Obtained as per Example
1
[0157] Mixed butylated/amylated phenolic alkylate (148.7 grams,
0.86 mole) was charged to an oil jacketed flask and heated to
80.degree. C. under nitrogen. PCl.sub.3 (35.8 grams, 0.26 mole) was
added, below the surface of the phenolics, at a uniform rate over
three hours. During the addition, the temperature was ramped to
150.degree. C. The reaction mass was held at 150.degree. C. until
HCl evolution ceased, and then was heated to 200.degree. C. over
one hour while the pressure was reduced from 1000 to 50 mbar. The
reaction was held at 200.degree. C./50 mbar until the total Cl
content was less than 50 ppm. The phenolic excess was then removed
by distillation under one mbar pressure and an internal temperature
of 240.degree. C. (vapor temperature 140.degree. C.). Yield=123.1
grams.
[0158] The phosphite composition had kinematic viscosity of
@30.degree. C. of 8,541 cSt, @40.degree. C. of 3,198 cSt, and
@50.degree. C. of 812 cSt.
Example 3
[0159] 73.4 g (0.53 moles) of phosphorous trichloride and 1.74 ml
(6.41 mmols) of N,N-dimethyldodecylamine are charged to a jacketed
vessel under nitrogen. The contents of the vessel are agitated and
heated to 70.degree. C. Separately, a powdered blend of 193.1 g
(1.18 moles) of 4-tert-amylphenol and 121.3 g (0.56 moles) of
2,4-di-tert-butylphenol is prepared. The powdered blend is added in
uniform shots of 26.2 g, every 15 minutes over 3 hours. During the
addition the reaction is held at 70.degree. C. and evolved HCl is
absorbed by a scrubber unit.
[0160] Once all the phenols are added, the reaction temperature is
uniformly ramped from 70.degree. C. to 150.degree. C. over 1 hour.
The reaction mass is held at 150.degree. C. for 1 hour or until the
HCl evolution has stopped. Next, the reaction mass is further
heated from 150.degree. C. to 200.degree. C. and held for 1
additional hour. Once the reaction mass has reached 200.degree. C.,
the reaction is degassed by applying a vacuum at a pressure from
60-80 mbar until the total chlorine content is less than 50 ppm.
Excess phenols may be removed by distillation under a pressure of 7
mbar up to an internal temperature of 200.degree. C. (maximum vapor
temperature 127.degree. C.)
[0161] 1.89 g (9.9 mmoles) of triisopropanolamine is added to the
phosphite composition.
[0162] The resulting composition of phosphites had a kinematic
viscosity at 70.degree. C. of 97 cSt. The total phosphorous content
is 5.6%.
Example 4
[0163] A 1:1 molar ratio of 2-t-butyl-p-cresol and 4-t-amylphenol
were charged to an oil jacketed flask and heated to 80.degree. C.
under nitrogen. PCl.sub.3 (73.4 grams, 0.53 mole) was added, below
the surface of the phenolics, at a uniform rate over 2 hours.
During the addition the temperature was ramped to 150.degree. C.
and the reaction mass was held at 150.degree. C. until HCl
evolution ceased. Next the reaction mass was heated to over
200.degree. C. over 1 hour while the pressure was reduced from 1000
to 70 mbar, and held at these conditions until the total Cl content
was less than 50 ppm. The phenolic excess was then removed by
distillation under 8 mbar pressure and an internal temperature of
200.degree. C. The resulting composition of phosphites had a
kinematic viscosity at 70.degree. C. of 160 cSt. The total
phosphorous content is 5.9%.
Example 5
[0164] The composition of phosphites from Examples 3 and 4 were
tested and compared against a tris(nonylphenyl)phosphite, Weston
399, and showed the following results in Table 3. The phosphite
were added at the same phosphorous content for comparison (@17
ppm).
TABLE-US-00003 TABLE 3 Composition Example 3 Example 4 Weston 399
LLDPE 99.93 wt % 99.901 wt % 99.89 wt % ZnSt 0.05 wt % 0.05 wt %
0.05 wt % Anox PP18 0.02 wt % 0.02 wt % 0.02 wt % Phosphite Amount
0.0305 wt% 0.029 wt % 0.04 wt % YI (ASTM E313) during multipass @
230.degree. C. Initial -1.284 -1.07 -1.249 Pass 1 0.441 0.573 0.06
Pass 3 0.705 0.952 0.718 Pass 5 0.937 1.689 1.203 MFI @2.16 kg
during multipass @ 230.degree. C. Initial 0.975 0.958 0.967 Pass 1
0.939 0.909 0.904 Pass 3 0.782 0.781 0.778 Pass 5 0.591 0.629 0.637
MFI @ 2.16 kg during multipass @ 230.degree. C. Initial 23.635
22.817 23.027 Pass 1 23.203 22.986 23.066 Pass 3 22.022 21.656
21.614 Pass 5 21.344 20.694 20.973 MFI ratio during multipass @
230.degree. C. Initial 24.229 23.814 23.819 Pass 1 24.698 25.298
25.519 Pass 3 28.149 27.741 27.765 Pass 5 36.113 32.894 32.940 YI,
after NOx exposure 2 hours 2.37 2.84 3.26 25 hours 5.48 8.33 6.27
94 hours 8.63 9.14 9.34 120 hours 9.41 9.94 10.11 140 hours 10.19
-- 10.52
Examples 6
[0165] Using the method of Example 3, a phosphite composition was
prepared from a 1:1 (molar) mixture of 4-t-amylphenol (4-TAP) and
2,4-di-t-butylphenol (2,4-DTBP). Viscosities are provided in Table
4, below.
Comparative Example A
[0166] Reaction of phosphorus trichloride (1/3 mole) with
2,4-di-tertiary amyl phenol (2/3 mole) then with 2,4-ditertiary
butyl phenol (1/3 mole) from U.S. Pat. No. 5,254,709 produces a
solid phosphite composition.
[0167] One-third of a mole of phosphorus trichloride (46 g) was
charged into a 500 ml 3-neck flask. One hundred cubic centimeters
of toluene and 0.2 g mercaptobenzothiazole were added. Then 156 g
(2/3 mole) of melted 2,4-di-tertiary amyl phenol was dropped in
over a period of two hours, the temperature being maintained
between 55.degree. and 65.degree. C. The temperature was then
increased to 120.degree.-123.degree. C. for two hours. Nitrogen gas
was passed through the hot mix to remove residual hydrogen
chloride. The mix stood over the weekend at room temperature. An
infrared analysis showed no hydroxyl. The mixture was warmed to
60.degree. C. and 68.3 g (1/3 mole) of solid 2,4-di-tertiary butyl
phenol was added. The mix was gradually heated to 127.degree. C.
(over two hours) and then heated near that temperature for three
hours longer. Nitrogen gas was bubbled through the hot mix to
remove residual hydrogen chloride. The toluene was removed by
heating under diminished pressure. The residual product was a clear
liquid that hardened to a clear glassy product on cooling. Three
hundred cc of methanol was added and the mixture was stirred and
heated to 60.degree. C. The product gradually crystallized to a
white powder. After standing in the methanol at room temperature
overnight the solid product was filtered off and washed with 100 cc
of methanol. The dried produce weighed 197.6 g (90% of theory). The
material melted at 89.degree.-93.degree. C.
Comparative Examples B and C
[0168] Comparative Examples B and C were prepared in a similar
amount with different molar ratios of phenols and different phenols
as shown in Table 4 below. Comparative Examples B and C use
4-t-butylphenol (4-TBP).
TABLE-US-00004 TABLE 4 Viscosities (cSt) Ex. Phenol 1 Mol Phenol 2
Mol Ratio @ 40.degree. C. @ 50.degree. C. @ 60.degree. C. 3
2,4-DTBP 0.293 4-TAP 0.588 1:2 1189 420 175 6 2,4-DTBP 0.288 4-TAP
0.288 1:1 32,228 7351 1810 B 2,4-DTBP 0.661 4-TBP 0.661 1:1 --
10,265 1678 C 2,4-DTBP 2.938 4-TBP 5.878 1:2 10,486 1853 --
[0169] As shown in Table 4, replacing 4-TBP with 4-TAP reduces the
viscosity at lower temperatures, 30-50.degree. C. In addition,
providing a molar ratio of 2,4-DTBP to 4-TAP of 1:2 further reduces
the viscosity.
[0170] In view of the many changes and modifications that can be
made without departing from principles underlylng the invention,
reference should be made to the appended claims for an
understanding of the scope of the protection to be afforded the
invention.
* * * * *