U.S. patent application number 15/312752 was filed with the patent office on 2017-07-06 for stabilizer compounds.
This patent application is currently assigned to SOLVAY SPECIALTY POLYMERS USA, LLC. The applicant listed for this patent is SOLVAY SPECIALTY POLYMERS USA, LLC. Invention is credited to Gregory GOSCHY, Joel POLLINO, Satchit SRINIVASAN.
Application Number | 20170190874 15/312752 |
Document ID | / |
Family ID | 53276090 |
Filed Date | 2017-07-06 |
United States Patent
Application |
20170190874 |
Kind Code |
A1 |
POLLINO; Joel ; et
al. |
July 6, 2017 |
Stabilizer Compounds
Abstract
A piperidine-based stabilizer compound of formula (I) or (II)
that imparts UV, thermal, and/or thermo-oxidative stability to
polymer compositions and more specifically to aromatic polymers and
polymer compositions thereof.
Inventors: |
POLLINO; Joel; (John Creeks,
GA) ; GOSCHY; Gregory; (Atlanta, GA) ;
SRINIVASAN; Satchit; (Dallas, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SOLVAY SPECIALTY POLYMERS USA, LLC |
Alpharetta |
GA |
US |
|
|
Assignee: |
SOLVAY SPECIALTY POLYMERS USA,
LLC
Alpharetta
GA
|
Family ID: |
53276090 |
Appl. No.: |
15/312752 |
Filed: |
May 20, 2015 |
PCT Filed: |
May 20, 2015 |
PCT NO: |
PCT/EP2015/061080 |
371 Date: |
November 21, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62001336 |
May 21, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D 211/46 20130101;
C08K 5/43 20130101; C08K 5/3435 20130101 |
International
Class: |
C08K 5/3435 20060101
C08K005/3435; C07D 211/46 20060101 C07D211/46; C08K 5/43 20060101
C08K005/43 |
Claims
1-16: (canceled)
17. A stabilizer compound (SC) of formula (I) or formula (II):
##STR00040## wherein R.sub.J is selected from the group consisting
of --H, aliphatic groups and alkoxy groups, and wherein each of
R.sub.K, equal or different from each other and from R.sub.J, is
selected from aliphatic groups, and wherein R.sub.L is a monovalent
substituent selected from the group consisting of: a group of
formula (Y-I): ##STR00041## and a group of formula (Y-II):
##STR00042## wherein Ri and Rm are the same or different from each
other and are independently selected from the group consisting of
--H, --CF.sub.3, --CN, --C(.dbd.O)NH.sub.2, --NO.sub.2, alkyl
groups, perfluorinated groups, aryl groups, aryl amine groups, aryl
ether groups, aryl sulfone groups, aryl thioether groups, fused
aryl ring systems, sulfonic acids, carboxylic acids, phosphonic
acids, sulfonic acid salts, carboxylic acid salts, and phosphonic
acid salts, and wherein Ri is either in an ortho, meta or para
position, and wherein Rm is either in an ortho or meta position,
and wherein Q is selected from the group consisting of a bond, and
--SO.sub.2--, and wherein G is --C(.dbd.O)NH.sub.2, wherein R.sub.N
is a divalent substituent of formula (Z-I): ##STR00043## wherein Ri
and Rm are the same or different from each other and are
independently selected from the group consisting of --H,
--CF.sub.3, --C(.dbd.O)NH.sub.2, --NO.sub.2, alkyl groups,
perfluorinated groups, aryl groups, aryl amine groups, aryl ether
groups, aryl sulfone groups, aryl thioether groups, fused aryl ring
systems, sulfonic acids, carboxylic acids, phosphonic acids,
sulfonic acid salts, carboxylic acid salts, and phosphonic acid
salts, wherein Ri and Rm are independently either in an ortho or
meta position, and wherein Q is selected from the group consisting
of a bond, and --SO.sub.2--.
18. The stabilizer compound (SC) of formula (I) of claim 17,
wherein the stabilizer compound (SC) is selected from the group
consisting of: ##STR00044##
19. The stabilizer compound (SC) of formula (II) of claim 17,
wherein the stabilizer compound (SC) is selected from the group
consisting of: ##STR00045##
20. The stabilizer compound (SC) according to claim 17, wherein Rm
is --H.
21. A method for making the stabilizer compound of formula (I) of
claim 17, comprising the step of reacting compounds of formulae
(III) and (IV) together in the presence of a base; ##STR00046##
wherein Xi is a halogen selected from the group consisting of
chlorine, fluorine, bromine, and iodine, and wherein R.sub.J,
R.sub.K, R.sub.L are as defined in claim 17 for formula (I).
22. A method for making the stabilizer compound of formula (II) of
claim 17, comprising the step of reacting compounds of formulae
(III) and (IV) together in the presence of a base; ##STR00047##
wherein Xi or Xj are the same or independently selected halogens
from the group consisting of chlorine, fluorine, bromine, and
iodine, and wherein R.sub.J, R.sub.K, R.sub.N are as defined in
claim 17 for formula (II).
23. The method of claim 21, wherein the reaction is carried out in
a polar aprotic solvent.
24. The method of claim 23, wherein the polar aprotic solvent is
tetrahydrofuran and the reaction is carried out at a temperature of
between 25.degree. C. and 66.degree. C.
25. The method of claim 23, wherein the polar aprotic solvent is
N-methylpyrrolidone and the reaction is carried out at a
temperature of between 25.degree. C. and 204.degree. C.
26. A polymer composition (P), comprising at least one stabilizer
compound (SC) of claim 17, and at least one polymer selected from
the group consisting of polyketones, poly(etherketone)s,
poly(ethersulfone)s, and mixtures thereof.
27. The polymer composition (P) of claim 26, wherein the polymer
composition (P) further comprises at least another ingredient
selected from the group consisting of dyes, pigments, fillers, UV
stabilizers, light stabilizers, optical brighteners, and mixtures
thereof.
28. A method for stabilizing a polymer comprising adding at least
one stabilizing compound (SC) of claim 17 to at least one
polymer.
29. The method of claim 28, where the at least one stabilizing
compound (SC) acts as an acid scavenger for the at least one
polymer.
30. An article comprising the polymer composition (P) of claim
26.
31. The method of claim 22, wherein the reaction is carried out in
a polar aprotic solvent.
32. The method of claim 31, wherein the polar aprotic solvent is
tetrahydrofuran and the reaction is carried out at a temperature of
between 25.degree. C. and 66.degree. C.
33. The method of claim 31, wherein the polar aprotic solvent is
N-methylpyrrolidone and the reaction is carried out at a
temperature of between 25.degree. C. and 204.degree. C.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. provisional patent
application No. 62/001,336, filed on May 21, 2014 and incorporated
herein by reference.
TECHNICAL FIELD
[0002] The present invention describes the use and synthesis of new
piperidine-based stabilizer compounds (SC), which provide UV,
thermal, and thermo-oxidative stability to polymers.
BACKGROUND
[0003] High performance aromatic polymers feature, because of their
very high glass transition temperatures and/or melting
temperatures, excellent properties including outstanding heat
resistance. Aromatic polysulfones and polyetherketones are, for
example, widely used in applications where their strength,
resistance to harsh chemicals and to high temperatures is
necessary.
[0004] Unfortunately, many natural and synthetic polymers such as
the above mentioned high performance aromatic polymers are prone to
light absorption and are attacked by UV radiation. As a result,
they undergo oxidation, chain scission, uncontrolled radical
recombination and cross-linking reactions. This phenomenon, known
as UV degradation, is usually catalyzed in high heat environments
in the presence of oxygen. The UV degradation of polymers can
affect a material's mechanical properties, produce discoloration
and fading, roughen the surface, decrease tensile strength, and
reduce their overall life time performance.
[0005] A wide range of light and heat stabilizers for polymers are
known and have been used alone or in various combinations to
prevent or retard the kinetics of polymer degradation that is
initiated by exposure to light and heat. The effectiveness of
stabilizers to defend a material against UV radiation and heat
depends on several factors including; the intrinsic efficacy of the
stabilizer, its concentration, and its solubility in a particular
polymer matrix, as well as how well it is distributed in the
matrix. Intrinsic volatility of the stabilizer is also an important
factor to consider when working with materials which are processed
at high temperatures as it may lower the concentration of the
stabilizer in a particular polymer matrix as a result of
evaporation during processing and subsequent use.
[0006] Heat stabilizers have been used for many years in various
polymer matrixes. Common types of heat stabilization packages
include organophosphites, used as a short-term antioxidant to
protect the polymer from the high temperature and high shear,
and/or phenolic antioxidants used for long-term protection.
[0007] Over the past century, a number of light stabilizer
compounds have also been developed and commercialized as additives
tailored to retard or eliminate photo-initiated oxidative
processes. These additives are generally categorized into one of 4
classes: UV absorbers, excited state quenchers, radical scavengers,
and peroxide decomposers. Certain derivatives of
2,2,6,6-tetramethyl piperidine, also known as hindered amine light
stabilizers (HALS), have been known for a long time to improve the
light stability, aging properties, and extended field life of
polymeric compositions. For example, U.S. Pat. No. 4,049,647
discloses their use in low melting temperature polymeric materials
such as polyolefins, aliphatic polyamides and polystyrene.
[0008] Nearly all commercially available heat and light stabilizers
are indeed well suited for blending with low melting temperature
commodity polymers requiring low process temperatures (i.e. below
250.degree. C.).
[0009] However, such commercial heat and light stabilizers are
generally poorly suited for high performance aromatic polymers
where process temperatures are substantially more intense (i.e.
above 250.degree. C.), owing to the highly aliphatic character of
most commercial stabilizing compounds, which is prone to
thermo-oxidative decomposition upon exposure temperatures above
200.degree. C.
[0010] Additionally, the Applicant has found that, upon blending
many commercial heat and light stabilizers with high performance
aromatic polymers, a disastrous reduction in the thermal properties
of such systems occurs, especially with respect to a detrimental
lowering of the glass transition temperature, which in turn
diminishes the high temperature mechanical performance of such
polymeric engineering materials.
[0011] There exists a need, therefore, to identify and develop
stabilizer compounds that are well suited for high performance
aromatic polymers in that they possess good inherent
thermal-oxidative stability and impart good light stability, while
also maintaining the glass transition temperature of the polymer(s)
they are blended with so to preserve the high temperature
mechanical performance of such materials.
SUMMARY
[0012] The present invention relates to stabilizer compounds (SC)
of formula (I) or formula (II):
##STR00001##
wherein R.sub.J is selected from the group consisting of --H,
aliphatic groups and alkoxy groups, and wherein each of R.sub.K,
equal to or different from each other and from R.sub.J, is selected
from aliphatic groups, and wherein R.sub.L is a monovalent
substituent selected from the group consisting of: [0013] a group
of general formula (Y-I):
[0013] ##STR00002## [0014] a group of general formula (Y-II):
##STR00003##
[0014] wherein Ri and Rm are the same or different from each other
and are independently selected from the group consisting of --H,
--CF.sub.3, --CN, --C(.dbd.O)NH.sub.2, --NO.sub.2, alkyl groups,
perfluorinated groups, aryl groups, aryl amine groups, aryl ether
groups, aryl sulfone groups, aryl thioether groups, fused aryl ring
systems, sulfonic acids, carboxylic acids, phosphonic acids,
sulfonic acid salts, carboxylic acid salts, and phosphonic acid
salts, and wherein Ri is either in an ortho, meta or para position,
and wherein Rm is either in an ortho or meta position, and wherein
Q is selected from the group consisting of a bond, --O--,
--CH.sub.2--, --C(CH.sub.3).sub.2--, --NH--, --S--,
--C(CF.sub.3).sub.2--, --C(.dbd.CCl.sub.2)--, and --SO.sub.2--, and
wherein G is a group selected from the group consisting of
--C(.dbd.O)NH.sub.2, --NO.sub.2, alkyl groups, perfluorinated
groups, aryl groups, aryl amine groups, aryl ether groups, aryl
sulfone groups, aryl thioether groups, fused aryl ring systems,
sulfonic acids, carboxylic acids, phosphonic acids, sulfonic acid
salts, carboxylic acid salts, and phosphonic acid salts, wherein
R.sub.N is a divalent substituent selected from the group
consisting of: [0015] a group of general formula (Z-I):
[0015] ##STR00004## [0016] a group of general formula (Z-II):
##STR00005##
[0016] wherein Ri and Rm are the same or different from each other
and are independently selected from the group consisting of --H,
--CF.sub.3, --C(.dbd.O)NH.sub.2, --NO.sub.2, alkyl groups,
perfluorinated groups, aryl groups, aryl amine groups, aryl ether
groups, aryl sulfone groups, aryl thioether groups, fused aryl ring
systems, sulfonic acids, carboxylic acids, phosphonic acids,
sulfonic acid salts, carboxylic acid salts, and phosphonic acid
salts, wherein Ri and Rm are independently either in an ortho or
meta position, and wherein Q is as above described and wherein G*
is a divalent group selected from the group consisting of alkyl
groups, perfluorinated groups, aryl groups, aryl amine groups, aryl
ether groups, aryl sulfone groups, aryl thioether groups, and fused
aryl ring systems.
[0017] Another aspect of the present invention relates to two
distinct methods for the manufacture of said stabilizer compounds
(SC).
[0018] Still another aspect of the present invention relates to a
polymer composition (P) comprising said at least one stabilizer
compound (SC) and at least one polymer and to a method for
stabilizing a polymer comprising the addition of at least one
stabilizing compound (SC) to at least one polymer.
[0019] Yet another aspect of the present invention is directed to
an article comprising said polymer composition (P).
DETAILED DESCRIPTION OF THE INVENTION
[0020] The Applicant has discovered that stabilizer compounds (SC)
of formula (I) or formula (II):
##STR00006##
wherein R.sub.J, R.sub.K, R.sub.L and R.sub.N are as above
described, imparts high performance aromatic polymers compositions
with good heat and light resistance, while surprisingly maintaining
their glass transition temperatures to a very high level.
[0021] In the formulas (I) and (II), R.sub.J can be a --H, or a
branched, linear or cyclic aliphatic groups or alkoxy groups.
Non-limitive Examples of R.sub.J are notably --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --(CH.sub.2).sub.5CH.sub.3,
--(CH.sub.2).sub.7CH.sub.3, --(CH.sub.2).sub.2OCH.sub.3,
--OCH.sub.3, --O(CH.sub.2).sub.5CH.sub.3,
--O(CH.sub.2).sub.7CH.sub.3,
##STR00007##
[0022] R.sub.J is preferably selected from the group consisting of
--H, --CH.sub.3, --CH.sub.2CH.sub.3, --OCH.sub.3, and
--OCH.sub.2CH.sub.3. Most preferably, R.sub.J is --CH.sub.3.
[0023] In the formulaes (I) and (II), each of R.sub.K, equal to or
different from each other and from R.sub.J, can be any branched,
linear or cyclic aliphatic groups. Non-limiting examples of R.sub.K
are notably:
##STR00008##
[0024] R.sub.K is preferably selected from the group consisting of
--CH.sub.3, and --CH.sub.2CH.sub.3.
[0025] In the same formula (I), R.sub.L is a monovalent substituent
selected from the group consisting of a group of general formula
(Y-I) and (Y-II), as above defined.
[0026] In formulae (Y-I) and (Y-II), Ri may be in an ortho, meta or
para position, and Rm may be in an ortho or meta position. Ri is
preferably in a para position. Ri and Rm are preferably --H.
[0027] In formula (Y-I), Q is preferably --SO.sub.2--.
[0028] In formula (Y-II), G is preferably --C(.dbd.O)NH.sub.2.
[0029] In the formula (II), R.sub.N is a divalent substituent
selected from the group consisting of a group of general formula
(Z-I) and (Z-II), as above defined.
[0030] Non-Limiting examples of Ri and Rm are notably:
Alkyl Groups: --CH.sub.3--CH.sub.2--O--CH.sub.3,
##STR00009##
Perfluorinated Groups: --CF.sub.3,
--CH.sub.2--(CF.sub.2).sub.5CF.sub.3,
Aryl Groups:
##STR00010##
[0031] Aryl Amine Groups:
##STR00011##
[0032] Aryl Ether Groups:
##STR00012##
[0033] Aryl Sulfone Groups:
##STR00013##
[0034] Aryl Thioether Groups:
##STR00014##
[0035] Fused aryl ring systems:
##STR00015##
[0036] In formula (Z-I), Q is as above described for formula (Y-I).
It is preferably a bond or --SO.sub.2--.
[0037] In formula (Z-II), G* may be selected from the group
consisting of alkyl groups, perfluorinated groups, aryl groups,
aryl amine groups, aryl ether groups, aryl sulfone groups, aryl
thioether groups, fused aryl ring systems.
[0038] In a first embodiment, the stabilizer compounds (SC) of
formula (I) are preferably selected from the group consisting of
structures (A-A) to (A-C) herein below:
##STR00016##
[0039] In a second embodiment, the stabilizer compounds (SC) of
formula (II) are preferably selected from the group consisting of
structures (B-A) to (B-B) herein below:
##STR00017##
[0040] Various stabilizer compounds (SC) of the two formulae (I)
and (II) were synthesized in the laboratory with high yields
(65-85%).
[0041] Therefore, another aspect of the present invention is
directed to a method for the manufacture of the stabilizer compound
of formula (I), comprising the step of reacting compounds of
formulae (III) and (IV) together in the presence of a base,
##STR00018##
wherein X.sub.i is a halogen selected from the group consisting of
chlorine, fluorine, bromine, and iodine, and wherein R.sub.J,
R.sub.K, R.sub.L are as defined above for formula (I). X.sub.i is
preferably selected from the group consisting of chlorine and
fluorine.
[0042] Here, the compounds of formula (IV) possess preferably an
electron withdrawing group para to the halogen Xi.
[0043] Still another aspect of the present invention is directed to
a method for the manufacture of the stabilizer compound of formula
(II), comprising the step of reacting compounds of formulae (III)
and (IV) together in the presence of a base,
##STR00019##
wherein X.sub.i or X.sub.j are the same or independently selected
halogens from the group consisting of chlorine, fluorine, bromine,
and iodine, and wherein R.sub.J, R.sub.K, R.sub.N are as defined
above for formula (II). Xi is preferably selected from the group
consisting of chlorine and fluorine.
[0044] In the methods for the manufacture of the stabilizer
compounds of formula (I) or (II), the reaction is preferably
carried out in a polar aprotic solvent. Any polar aprotic solvent
that is capable of dissolving the two starting materials (i.e.
compounds of formulae (III) and (IV) or (III) and (V)) can be used
in the disclosed methods. The polar aprotic solvent is preferably
selected from tetrahydrofuran (THF) or N-methylpyrrolidone
(NMP).
[0045] The reaction temperature can be any temperature up to the
boiling point of the solvent, while the lower temperatures usually
lead to slower kinetic rates of the reaction(s). If the solvent
used is THF, then the reaction is preferably carried out at a
temperature of between 25.degree. C. and 66.degree. C. at
atmospheric pressure, more preferably between 40 and 66.degree. C.
and most preferably between 55 and 66.degree. C. If the solvent
used is N-methylpyrrolidone, then the reaction is preferably
carried out at a temperature of between 25.degree. C. and
204.degree. C. at atmospheric pressure, more preferably between 50
and 150.degree. C. and most preferably between 80 and 120.degree.
C. Excellent results were obtained when the reaction was carried
out at a temperature of 66.degree. C. at atmospheric pressure when
the solvent used was THF, and 100.degree. C. at atmospheric
pressure when the solvent used was NMP.
[0046] The steps of reacting compounds of formulae (III) and (IV)
or compounds of formulae (III) and (V) in the above dislcosed
methods for the manufacture of the stabilizer compounds of formula
(I) or (II), are preferably carried out in the presence of a base
capable of deprotonating a secondary alcohol, and preferably having
a pKa of at least 16. The base can be added to compound of formula
(III) alone or to a mixture of compounds of formulae (III) and
(IV). The base is most preferably the potassium tert-butoxide.
[0047] To prepare the desired stabilizer compounds (SC) of the
general formula (I) shown above, one of two general synthesis
procedures were carried out. Specifically, in a first embodiment,
the first general procedure was utilized when para-substitution
with an electron withdrawing group, R.sub.L, as given above (i.e.
SO.sub.2, CF.sub.3, CN, etc) allowed for the reaction to proceed
toward completion and produce high yields aided by utilizing reflux
with THF as the polar aprotic solvent.
[0048] In a second embodiment, the second general procedure was
preferably used when there was an absence of an electron
withdrawing group, where the use of a higher boiling and more polar
aprotic solvent lead to higher yields and/or lower reaction
times.
[0049] The synthesis of both stabilizer compounds (SC) of formulae
(I) and (II) respectively--resulted in the formation of the desired
products. Relative yields depended strongly upon the activity of
the reactants and to a lesser extent the degree of substitution.
Inactivated halogenated reactants, such as fluorobenzene,
4-fluorobiphenyl, and the 4,4'-difluoro-biphenyl were substantially
less reactive than activated halogenated reactants such as
4,4'-dichloro diphenyl sulfone, 4-chloro diphenyl sulfone,
4,4'-difluoro benzophenone, and 4-fluoro benzophenone. Such
inactive halogenated reactants necessitated use of the more polar
solvent (NMP) and higher reaction temperatures (100.degree. C.).
These stabilizer compounds (SC) were then blended to several
polymers to evaluate their light and thermal stabilizing
effect.
[0050] Thus, another aspect of the present invention relates to a
polymer composition (P), comprising at least one of the above
disclosed stabilizer compounds (SC) and at least one polymer. The
polymers of the polymer composition (P) are high performance
aromatic polymers comprising advantageously more than 35 mol %,
preferably more than 45 mol %, more preferably more than 55 mol %,
still more preferably more than 65 mol % and most preferably more
than 75 mol % of recurring units which are aromatic recurring
units. For the purpose of the present invention, the expression
"aromatic recurring unit" is intended to denote any recurring unit
that comprises at least one aromatic group in the main polymer
backbone.
[0051] The polymer of the polymer composition (P) may be a
semi-crystalline polymer or an amorphous polymer. Semi-crystalline
polymers may typically have glass transition temperatures of at
least 120.degree. C., preferably at least 140.degree. C. and
melting temperatures generally greater than 250.degree. C.,
preferably greater than 300.degree. C.
[0052] Amorphous polymers typically have a glass transition
temperature of at least 140.degree. C., more typically of at least
150.degree. C. and up to 200.degree. C. Glass transition
temperature (Tg) and melting temperature (Tm) are generally
determined by DSC, according to ASTM D3418.
[0053] The polymer of the polymer composition (P) may be selected
from the group consisting of polyolefins, polyesters, polyethers,
polyketones, poly(etherketone)s, poly(ethersulfone)s, polyamides,
polyurethanes, polystyrenes, polyacrylates, polymethacrylates,
polyacetals, polytetrafluoroethylene, polyvinylidene fluoride,
polyacrylonitriles, polybutadienes, acrylonitrile butadiene
styrene, styrene acrylonitrile, acrylate styrene acrylonitrile,
cellulosic acetate butyrate, cellulosic polymers, polyimides,
polyamideimides, polyetherimides, polyphenylsulfides, polyphenylene
oxides, polyvinylchlorides, polyvinylbutyrates, polycarbonates,
epoxy resins, polysiloxanes, and polyketimines.
[0054] Among the more preferred polymers, one may cite the aromatic
poly(sulfone)s, aromatic poly(ether ketone)s such as poly(ether
ether ketone)s (PEEK), aromatic poly(amide)s, aromatic
poly(imide)s, poly(phenylene)s, and aromatic liquid crystalline
polymers.
[0055] Aromatic poly(sulfone)s include notably polyphenylsulfone,
polysulfone, polyethersulfone, and polyetherethersulfone, the
structural repeat units of which are listed below:
##STR00020##
[0056] Aromatic poly(ether ketone)s include notably
poly(etherketone), poly(etheretherketone) and
poly(etherketoneketone), the structural repeat units of which are
listed below:
##STR00021##
[0057] The polymer composition (P) may also further comprises at
least another ingredient selected from the group consisting of
dyes, pigments, fillers, UV stabilizers, light stabilizers, optical
brighteners.
[0058] The polymer composition (P) comprises advantageously at
least 0.01 wt. %, preferably at least 1.0 wt. %, more preferably at
least 1.5 wt. %, still more preferably at least 2.0 wt. % and most
preferably at least 2.5 wt. % of the stabilizer compounds (SC).
Also, the polymer composition (P) comprises advantageously at most
10 wt. %, preferably at most 9 wt. %, more preferably at most 8 wt.
%, still more preferably at most 6 wt. % and most preferably at
most 5 wt. % of the stabilizer compounds (SC).
[0059] When no other ingredient than the stabilizer compounds (SC)
and the at least one polymer are present, the polymer composition
(P) comprises advantageously at least 20 wt. %, preferably at least
30 wt. %, more preferably at least 40 wt. %, still more preferably
at least 50 wt. % and most preferably at least 60 wt. % of the at
least one polymer. Also, the polymer composition (P) comprises
advantageously at most 99.99 wt. %, preferably at most 99.95 wt. %,
more preferably at most 99.90 wt. %, still more preferably at most
99.5 wt. % and most preferably at most 99 wt. % of the at least one
polymer.
[0060] The polymer composition (P) may further comprise at least
one additional stabilizer selected from the group consisting of
2-(2'-hydroxyphenyl) benzotriazoles, oxamides,
2-(2-hydroxyphenyl)1,3,5-triazines, 2-hydroxybenzophenones,
cyanoacrylates, benzo-oxazolines, and hindered phenolic
antioxidants.
[0061] It may be advantageous to further incorporate in the polymer
composition (P) additional hindered amine light stabilizers
("HALS"). Examples of such HALS are (2,2,6,6-tetramethylpiperidyl)
sebacate, (2,2,6,6-tetramethylpiperidyl-) succinate, condensate of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic
acid, condensate of
N,N'-bis(2,2,6,6-tetramethyl-1-4-piperidyl)hexamethylene diamine
and 4-tert-octylamino-2,6-dichloro-1,3,-5-s-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 butanetetraoate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethyl piperidine, to
(1,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2
(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazas-piro[4.5]decane-2,4-dione,
to (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,
(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, and
compounds with similar chemical structures. As with the stabilizer
compounds (SC) of the present disclosure, the HALS may be
incorporated in the polymer composition (C) in conventional
amounts, generally higher than 0.05 wt. % and preferably higher
than 0.1 wt. %; further, these amounts are generally lower than 5
wt. % and preferably lower than 1 wt. %.
[0062] Further in accordance with the present disclosure, the
polymer composition (P) may also contain a variety of other polymer
additives in addition to the stabilizer compounds of the present
disclosure. These additives may include fillers in spherical,
spheroidal or polyhedral form, collectively known as "ingredients"
herein. Among these other fillers, calcium carbonate, calcium
sulfate, barium sulfate, glass beads, ceramic beads, antimony
trioxide, zinc borate, and other metal salts and oxides, can be
utilized.
[0063] Other optional conventional ingredients of the complete
polymer composition (P) include nucleating agents such as silica,
adhesion promoters, compatibilizers, curing agents, lubricants,
mold release agents, dyes and colorants, smoke-suppressing agents,
heat stabilizers, antioxidants, UV absorbers, tougheners such as
rubbers, plasticizers, anti-static agents, melt viscosity
depressants such as liquid crystalline polymers, and compounds of
similar structures. The choice of fillers and other ingredients in
the final polymer composition (C) including the stabilizer
compounds of the present disclosure will depend primarily on the
intended use for the articles of manufacture.
[0064] The components of the polymer composition (P) along with the
optional additional ingredients may be incorporated into the
polymer compositions (P) by a variety of different methods and
procedural steps which aim to provide their collective improvement
in stability properties throughout the mixture. For example, it is
possible to incorporate the above mentioned components and optional
additional ingredients by mixing them into the polymer at an early
processing stage, or at the start or at the end of the synthesis
reaction, or in a subsequent compounding process. A certain method
comprises dry mixing the essential components and optional
ingredients in powder or granular form, in appropriate proportions,
using e.g. a mechanical blender, such as a drum blender and
compounds of similar structures. The mixture is then melted
batch-wise or in a continuous device, e.g. extruders and compounds
of similar structures, extruding the mixture into strands and
chopping the strands into pellets. The mixture to be melted may
also be prepared by well-known master-batch methods. The continuous
melting device may also be fed with the components and ingredients
of the polymer composition (P) added separately without dry
premixing. A certain other method comprises dissolving the
polymer(s) in one or more organic solvents then causing the
dissolved polymer(s) to precipitate by the addition of a
non-solvent, and finally molding the recovered dried cake.
[0065] Of particular use for the polymer compositions (P) developed
according to this disclosure is the manufacture of shaped articles
by either extrusion or molding techniques. Therefore, another
aspect of the present invention relates to an article comprising
the polymer composition (P).
[0066] Indeed, the outstanding balance of advantageous properties
featured by the polymer compositions (C) of the present invention
in connection with their high glass transition temperature, thermal
stability, flame resistance, chemical resistance and melt
processability, makes them particularly suitable for the
manufacture, by any known processing method, of various articles.
The article of the present invention may be produced by extrusion
or molding techniques.
[0067] Various molding techniques may be used to form shaped
articles or parts of shaped articles from the polymer composition
(P). Powders, pellets, beads, flakes, reground material or other
forms of the polymer composition (P) may be molded, with or without
liquid or other additives, pre mixed or fed separately. The polymer
composition (P) may notably be molded into a film, a sheet, or any
molded article suitable for indoor and outdoor applications.
[0068] A last aspect of the present invention relates to a method
for stabilizing a polymer comprising adding at least one
stabilizing compound (SC) to at least one polymer. In particular,
the at least one stabilizing compound (SC) may act as an acid
scavenger for the at least one polymer.
[0069] The disclosure will now be illustrated with examples, which
are intended to illustrate the working disclosure and not intended
to take respectively to imply any limitations on the scope of the
present disclosure. Modifications and variations of the present
invention, related to alternative stabilizer compounds and their
derivatives, will be obvious to those skilled in the art from the
foregoing detailed description of the invention.
EXAMPLES
[0070] Nine compounds were synthesized using one of the two above
described methods for the manufacture stabilizer compounds (SC).
The effect of these nine compounds on the UV stability were tested
on an aromatic polymer, namely polysulfone Udel.RTM. P-1800
(manufactured by Solvay Specialty Polymers USA, L.L.C.) by
preparing solution cast films, where the compounds were present in
an amount of 5 mol %.
[0071] The structural purity of all stabilizer compounds were found
to be >95% using GC-MS, .sup.1H NMR, .sup.13C NMR and/or TLC.
All mass spectral data was generated on a Waters Synapt G2 HDMS
quadrupole time of flight (Q-TOF) operated in high resolution mode.
This instrument was equipped with an atmospheric solids analysis
probe (ASAP) and an atmospheric pressure chemical ionization source
(APCI) that was operated in positive mode, generating ions of
either M.sup.+.degree., [M+H].sup.+, or [M+H.sub.3O].sup.+.
[0072] These films were formed according to the Stabilizer
performance assessment description provided immediately below this
section. The results obtained for these films were then compared to
similar films obtained using other synthesized stabilizer compounds
and commercially available stabilizer compounds widely used in the
industry.
Example 1 (E1): Stabilizer Compound (A-A)
##STR00022##
[0074] Stabilizer compound (A-A),
1,2,2,6,6-pentamethyl-4-(4-(phenylsulfonyl)phenoxy) piperidine was
prepared using general synthetic method 1, more specifically;
potassium tert-butoxide (50 mL of a 1M solution in THF, .about.0.05
mol) was combined with a stirred solution of
1,2,2,6,6-pentamethylpiperidin-4-ol (10 g, 0.0495 mol) in THF (40
mL) at 25.degree. C. and allowed to stir for 15 min. The resultant
mixture, now slightly turbid, was slowly added to a stirred
solution of 1-chloro-4-(phenylsulfonyl) benzene (10 g, 0.04 mol) in
THF (50 mL) at 25.degree. C. and was then immediately heated to
reflux for 72 hours. To isolate the final product, compound (A-A),
the crude mixture was evaporated to dryness, recrystallized from
EtOH/H.sub.2O, and dried in vacuo to yield pure compound (A-A),
(10.02 g, 65%) as fluffy white crystals which were >99% pure as
determined via thin layer chromatography (TLC), (eluent: 1:1
hexanes/ethyl acetate) and GC-MS analysis.
[0075] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound; .delta.=7.93 (m, 2H, SO2ArH), 7.85 (m, 2H,
SO2ArH), 7.62 (m, 3H, ArH), 7.09 (m, 2H, O--ArH), 4.73 (m, 1H,
OCH), 2.17 (s, 3H, NCH.sub.3), 1.91 (m, 2H, CH.sub.2), 1.39 (t,
J=10.94 Hz, 2H, CH2), 1.07 (d, J=6.56 Hz, 12H, C(CH.sub.3).sub.2).
.sup.13C NMR (DMSO-d6): .delta.=161.2 (1C, CArO), 141.9 (1C,
SO.sub.2CAr), 133.3 (1C, SO2CAr), 132.2 (1C, CHAr), 129.7 (2C,
CHAr), 129.6 (2C, CHAr), 126.9 (2C, CHAr), 116.1 (2C, CHAr), 70.1
(1C, CHO), 54.6 (2C, CH(CH.sub.3).sub.2), 45.5 (2C, CH.sub.2), 32.6
(1C, NCH.sub.3), 27.7 (2C, CH.sub.3), 20.4 (2C, CH.sub.3). HRMS
(ASAP with APCI): m/z 388.1947 (M+H, calcd 388.1946). Anal. Calcd
for C.sub.22H.sub.30NO.sub.3S.
Example 2 (E2): Stabilizer Compound (A-B)
##STR00023##
[0077] Stabilizer compound (A-B),
4-(1,1'-biphenyl]-4-yloxy)-1,2,2,6,6-pentamethylpiperidine was
prepared instead by general procedure 2. The
1,2,2,6,6-pentamethylpiperidin-4-ol (15.91 g, 0.0929 mol) was added
to a solution of potassium tert-butoxide (10.4 g, 0.0929 mol)
dissolved in NMP (100 mL) at 25.degree. C. (the resultant solution
was red in color). Subsequently, 4-fluorobiphenyl (8.0 g, 0.0465
mol) was also dissolved in NMP (200 mL), added to the stirred
reaction mixture at 25.degree. C., heated to 100.degree. C. for 15
h, cooled, and the crude product mixture was rotary-evaporated to
dryness. The resultant solid was then suspended in H.sub.2O (500
mL), extracted repeatedly with EtOAc (3.times.300 mL) and the
organic layers were combined, dried over MgSO.sub.4, filtered, and
the solvent removed in vacuo to afford a white solid that was
subsequently recrystalized multiple times from EtOH. Successive
recrystallization fractions were collected and each was analyzed
for purity by thin layer chromatography (R.sub.f=0.3, streak from
baseline, in pure EtOAc). The presence of
1,2,2,6,6-pentamethylpiperidin-4-ol was visualized by using a
KMnO.sub.4 stain prior to combining pure fractions and drying
overnight in a vacuum oven to yield compound (A-C) (11.2 g, 74.46%)
as a fluffy, pearlescent white powder that was >99% pure by
GC-MS.
[0078] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound; .delta.=7.55 (m, 4H, ArH), 7.38 (m, 2H, ArH),
7.26 (m, 1H, ArH), 6.99 (m, 2H, OArH), 4.59 (m, 1H, OCH), 2.18 (s,
3H, NCH.sub.3), 1.97 (m, 2H, CH.sub.2), 1.42 (t, J=10.94 Hz, 2H,
CH.sub.2), 1.10 (d, J=11.67 Hz, 12H, C(CH.sub.3).sub.2). .sup.13C
NMR (DMSO-d6): .delta.=157.5 (1C, CArO), 140.4 (1C, CAr), 133.2
(1C, CAr), 129.1 (2C, CHAr), 128.2 (2C, CHAr), 127.0 (2C, CHAr),
126.5 (1C, CHAr), 116.7 (2C, CHAr), 70.3 (1C, CHO), 55.1 (2C,
CH(CH.sub.3).sub.2), 46.1 (2C, CH.sub.2), 33.0 (1C, NCH.sub.3),
28.2 (2C, CH.sub.3), 21.4 (2C, CH.sub.3). HRMS (ASAP with APCI):
m/z 324.2356 (M+H, calcd 324.2327). Anal. Calcd for
C.sub.22H.sub.30NO.
Example 3 (E3): Stabilizer Compound (A-C)
##STR00024##
[0080] Stabilizer compound (A-C),
4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy) benzamide was prepared
according to general procedure 2. A solution of
1,2,2,6,6-pentamethylpiperidin-4-ol (37.33 g, 0.217 mol) in NMP
(200 mL) was slowly added to a the stirred solution of KOtBu (24.35
g, 0.260 mol) in NMP (200 mL) resulting in a reaction that caused a
color change to purple and the resultant mixture was allowed to
stir at room temperature for 15 minutes to generate the potassium
salt nucleophile. Subsequently, 4-fluorobenzonitrile (12 g, 0.099
mol) was added in one step and the reaction was then heated to
100.degree. C. under nitrogen for 48 hours. Extraction was
performed as detailed above, but in this case, combined organic
layers were dried over anhydrous MgSO.sub.4, filtered, and the
solvent was removed under reduced pressure resulting in providing a
dark brown oil which solidified overnight. To isolate the desired
product a fractional distillation on a high vacuum line was
performed (vacuum distillation). The first fraction, comprised
primarily of 1,2,2,6,6-pentamethylpiperidin-4-ol, crystallized in
the distillation apparatus as fine needles. This fraction distilled
at 75.degree. C. and 1 torr (oil bath set to 140.degree. C.). The
second fraction, distilled at 85.degree. C. and 0.8 torr (oil bath
set to 160.degree. C.) resulting in a colorless oil. A third, very
high boiling fraction (temperature set=220.degree. C.) was isolated
as a yellow, transparent solid. This third fraction was dissolved
in acetone and all insoluble solids were subsequently filtered off.
The acetone soluble fractions were rotovapped to dryness and
subsequently recrystallized from tolune to afford compound VI (5.0
g, 18.5%) as a white powder that is >97% pure by GC-MS.
[0081] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound: .delta.=7.77 (m, 3H, C.dbd.ONH.sub.2ArH,
C.dbd.ONH.sub.2), 7.14 (bs, 1H, C.dbd.ONH.sub.2), 6.90 (m, 2H,
OArH), 4.67 (m, 1H, OCH), 2.14 (s, 3H, NCH.sub.3), 1.89 (m, 2H,
CH.sub.2), 1.36 (t, J=X Hz, 2H, CH.sub.2), 1.06 (d, J=X Hz, 12H,
C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=167.8 (1C,
C.dbd.ONH.sub.2), 160.0 (1C, OC.sub.Ar), 129.8 (2C, CH.sub.Ar),
126.7 (2C, CH.sub.Ar), 115.2 (2C, CH.sub.Ar), 69.7 (1C, CHO), 55.1
(2C, CH(CH.sub.3).sub.2), 46.2 (2C, CH.sub.2), 33.1 (1C,
NCH.sub.3), 28.1 (2C, CH.sub.3), 20.8 (2C, CH.sub.3). HRMS (ASAP
with APCI): m/z 291.2096 (M+H, calcd. 291.2073). Anal. Calcd for
C.sub.17H.sub.27N.sub.2O.sub.2.
Example 4 (E4): Stabilizer Compound (B-A)
##STR00025##
[0083] Stabilizer compound (B-A);
4,4'-((sulfonylbis(4,1-phenylene))bis(oxy))bis(1,2,2,6,6-pentamethylpiper-
idine) was prepared according to general procedure 1. As before,
the stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (26.24
g, 0.153 mol) in THF (200 mL) was prepared and within fifteen
minutes a solution of 4,4'-dichloro diphenyl sulfone (20 g, 0.0696
mol) was added to the stirred reaction vessel, which was heated,
refluxed under N.sub.2 for 72 hours, and followed by
recrystallization from a mixture of EtOH/H.sub.2O 90:10 yielding
compound VII (31.71 g, 81.8%) as a white fluffy solid.
[0084] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound: .delta.=7.76 (m, 4H, SO.sub.2ArH), 7.04 (m, 4H,
SO.sub.2ArH), 4.65 (m, 2H, OCH), 2.17 (s, 6H, NCH.sub.3), 1.91 (m,
4H, CH.sub.2), 1.41 (t, J=11.67 Hz, 4H, CH.sub.2), 1.05 (d, J=10.2
Hz, 24H, C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=161.5
(2C, CArO), 134.0 (2C, SO.sub.2CAr), 129.7 (4C, SO.sub.2CAr), 116.5
(4C, OCHAr), 70.9 (2C, CHO), 55.1 (4C, CH(CH.sub.3).sub.2), 46.2
(4C, CH.sub.2), 32.8 (2C, NCH.sub.3), 28.1 (4C, CH.sub.3), 21.4
(4C, CH.sub.3). HRMS (ASAP with APCI): m/z 557.3464 (M+H, calcd.
557.3413). Anal. Calcd for C.sub.32H.sub.49N.sub.2O.sub.4S.
Example 5 (E5): Stabilizer Compound (B-B)
##STR00026##
[0086] Stabilizer compound (B-C),
4,4'-bis((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)-1,1'-biphenyl,
was prepared according to general procedure 2. The
1,2,2,6,6-pentamethylpiperidin-4-ol (19.81 g, 0.1157 mol) solution
was followed by addition of the 4-4'-difluorobiphenyl (10.0 g,
0.0526 mol) solution as before and heated to 100.degree. C. for 72
hours, cooled, and the resultant solid isolated. The solid was
purified according to the same procedure used for examples 3,4, and
6, ultimately providing compound (B-C) (9.80 g, 37%) which appeared
as a fluffy, pearlescent white powder that was >95% pure as
determined by GC-MS
[0087] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound: .delta.=7.49 (m, 4H, ArH), 6.99 (m, 4H, ArH),
4.60 (m, 2H, OCH), 2.23 (s, 6H, NCH.sub.3), 1.96 (m, 4H, CH.sub.2),
1.46 (t, J=11.67 Hz, 4H, CH.sub.2), 1.15-1.11 (d, J=13.85 Hz, 24H,
C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=156.9 (2C,
CArO), 133.0 (2C, CAr), 127.6 (4C, CAr), 116.7 (4C, CHAr), 70.2
(2C, CHO), 55.1 (4C, CH.sub.2), 46.7 (4C, CH.sub.2), 33.0 (2C,
NCH.sub.3), 28.2 (4C, CH.sub.3), 21.4 (4C, CH.sub.3). HRMS (ASAP
with APCI): m/z 493.3844 (M+H, calcd. 493.3794). Anal. Calcd for
C.sub.32H.sub.49N.sub.2O.sub.2.
Comparative Example 1 (CE1): Stabilizer Compound (C-A)
##STR00027##
[0089] Stabilizer compound
(C-A),(4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)phenyl)(phenyl)
methanonealso was prepared according to general procedure 1, with
the exception that the potassium tert-butoxide stirred solution of
1,2,2,6,6-pentamethylpiperidin-4-ol was slowly added to a stirred
solution of 4-fluorobenzophenone and refluxed as above. The crude
mixture was isolated in the same manner as well, and the pure
compound A-B (12.53 g, 72% yield) also appeared as pure (>99%)
white crystals.
[0090] To confirm the (C-A) compound was isolated, again .sup.1H
NMR (DMSO-d6) analysis was performed as above with the following
results; .delta.=7.70 (m, 2H, C.dbd.OArH), 7.66 (m, 2H,
C.dbd.OArH), 7.59 (m, 1H, ArH), 7.52 (m, 2H, ArH), 7.03 (m, 2H,
OArH), 4.71 (m, 1H, OCH), 2.18 (s, 3H, NCH.sub.3), 1.97 (m, 2H,
CH.sub.2), 1.44 (t, J=11.67 Hz, 2H, CH2), 1.10 (d, J=9.48 Hz, 12H,
C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=194.6 (1C,
C.dbd.O), 161.6 (1C, CArO), 138.4 (1C, C.dbd.OCAr), 132.5 (1C,
C.dbd.OCAr), 132.2 (1C, CHAr), 129.8 (2C, CHAr), 129.4 (2C, CHAr),
128.7 (2C, CHAr), 115.6 (2C, CHAr), 70.5 (1C, CHO), 55.1 (2C,
CH(CH.sub.3).sub.2), 46.3 (2C, CH2), 33.0 (1C, NCH.sub.3), 28.1
(2C, CH.sub.3), 21.2 (2C, CH.sub.3). HRMS (ASAP with APCIEI): m/z)
352.2269 (M+H, calcd 352.2277). Anal. Calcd for
C.sub.23H.sub.29NO.sub.2.
Comparative Example 2 (CE2): Stabilizer Compound (C-B)
##STR00028##
[0092] Stabilizer compound (C-B),
1,2,2,6,6-pentamethyl-4-phenoxypiperidine was identically prepared
according to general procedure 2 with the exception that in this
case, 4-fluorobenzene (12.49 g, 0.130 mol) was added dropwise to
the stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (44.56
g, 0.260 mol) and upon complete addition, the reaction mixture was
heated to 85.degree. C. for 72 hours. The resultant product was
isolated, and further purified via fractional distillation
(85.degree. C., 0.8 torr) to yield compound A-D (17.47 g, 54%), as
a colorless oil that was >98% pure as determined by TLC (eluent:
EtOAc, Rf=0.4) and GC-MS.
[0093] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound; .delta.=7.23 (m, 2H, OArH), 6.86 (m, 3H, ArH),
4.55 (m, 1H, OCH), 2.15 (s, 3H, NCH3), 1.90 (m, 2H, CH2), 1.35 (t,
J=11.67 Hz, 2H, CH2), 1.04 (d, J=10.94 Hz, 12H, C(CH.sub.3).sub.2).
.sup.13C NMR (DMSO-d6): .delta.=157.6 (1C, CArO), 129.9 (2C, CHAr),
120.7 (1C, CHAr), 115.9 (2C, CHAr), 69.3 (1C, CHO), 55.0 (2C,
CH(CH.sub.3).sub.2), 46.4 (2C, CH2), 33.2 (1C, NCH.sub.3), 28.1
(2C, CH.sub.3), 20.8 (2C, CH3). HRMS (ASAP with APCI): m/z 248.2034
(M+H, calcd 248.2014). Anal. Calcd for C.sub.16H.sub.26NO).
Comparative Example 5 (CE5): Stabilizer Compound (C-C)
##STR00029##
[0095] Stabilizer compound (C-C),
bis(4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)phenyl)methanone,
was also prepared according to general procedure 1 using a stirred
solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (34.55 g, 0.20 mol)
in THF (200 mL). Fifteen minutes later, a solution of
difluorobenzophenone (20 g, 0.0917 mol) was added during stirring,
refluxed, and recrystallized from a mixture of EtOH/H.sub.2O 90:10
resulting in compound B-B (41.64 g, 87.1%) appearing as a white
fluffy solid.
[0096] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound: .delta.=7.69 (m, 4H, C.dbd.OArH), 7.05 (m, 4H,
C.dbd.OArH), 4.72 (m, 2H, OCH), 2.23 (s, 6H, NCH.sub.3), 1.99 (m,
4H, CH.sub.2), 1.50 (t, J=11.67 Hz, 4H, CH.sub.2), 1.15 (d, J=10.21
Hz, 24H, C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=193.3
(1C, C.dbd.O), 161.2 (2C, CArO), 132.1 (4C, CHAr), 130.6 (2C, CAr),
115.6 (4C, OCHAr), 70.6 (2C, CHO), 55.1 (4C, CH(CH.sub.3).sub.2),
46.4 (4C, CH.sub.2), 32.9 (2C, NCH.sub.3), 28.2 (4C, CH.sub.3),
21.4 (4C, CH.sub.3). HRMS (ASAP with APCI): m/z 521.3794 (M+H,
calcd. 521.3743). Anal. Calcd for
C.sub.33H.sub.49N.sub.2O.sub.3.
Comparative Example 6 (CE6): Stabilizer Compound (C-D)
##STR00030##
[0098] Stabilizer compound (C-D),
1,2,2,6,6-pentamethyl-4-((4trifluoromethyl)phenoxy)piperidine, was
synthesized according to general procedure 1 using
2,2,6,6-pentamethylpiperidin-4-ol (12.52 g, 0.073 mol) and
Potassium tert-butoxide (73 mL of a 1M solution in THF, 0.073 mol)
in THF (40 mL) and 4-fluorobenzotrifluoride (10 g, 0.061 mol) in
THF (50 mL). The final product was purified via multiple vacuum
distillations (100-110.degree. C. at 1 torr) to yield the desired
compound (A-E) (11.2 g, 58% yield) as a colorless oil that was 97%
pure as determined by GC-MS. For this compound, TLC analysis showed
a high degree of conversion to the desired product (eluent:
EtOAc/Hex 1:1, Rf=0.7).
[0099] The .sup.1H NMR (DMSO-d6) analysis provided the following
significant signals to assist in verifying the synthesis of the
desired compound: .delta.=7.62 (m, 2H, CF.sub.3ArH), 7.12 (m, 2H,
OArH), 4.75 (m, 1H, OCH), 2.19 (s, 3H, NCH.sub.3), 1.95 (m, 2H,
CH.sub.2), 1.41 (t, J=10.95 Hz, 2H, CH.sub.2), 1.09 (d, J=6.57 Hz,
12H, C(CH.sub.3).sub.2). .sup.13C NMR (DMSO-d6): .delta.=160.5 (1C,
CArO), 127.4 (4C, CF.sub.3, CF.sub.3CAr, CHAr), 116.2 (2C, CHAr),
70.1 (1C, CHO), 55.1 (2C, CH(CH.sub.3).sub.2), 46.0 (2C, CH2), 33.1
(1C, NCH.sub.3), 28.1 (2C, CH.sub.3), 20.8 (2C, CH.sub.3). HRMS
(ASAP with APCI): m/z 316.1918 (M+H, calcd. 316.1888). Anal. Calcd
for C.sub.17H.sub.25F.sub.3NO.
[0100] Table 1 below provides a summary of the nine stabilizer
compounds prepared including a listing of the general synthesis
methods utilized in making them.
TABLE-US-00001 TABLE 1 Stabilizer compounds prepared by general
procedures 1 and 2 GENERAL EXAMPLE STABILIZER STRUCTURE
PROCEDURE.sup.1,2 YIELD.sup.3 E1 (A-A) ##STR00031## 1 65% E2 (A-B)
##STR00032## 2 74.4% E3 (A-C) ##STR00033## 2 18.5% E4 (B-A)
##STR00034## 1 81.8% E5 (B-B) ##STR00035## 2 37% CE1 (C-A)
##STR00036## 1 72% CE2 (C-B) ##STR00037## 2 54% CE5 (C-C)
##STR00038## 1 87.1% CE6 (C-D) ##STR00039## 1 58% .sup.1General
Procedure 1: Base: Potassium tert-butoxide, Solvent: THF, Reaction
Temperature: 66.degree. C., Reaction Time 16 h .sup.2General
Procedure 2: Base: Potassium tert-butoxide, Solvent: NMP, Reaction
Temperature: 100.degree. C., Reaction Time 16 h .sup.3All
Stabilizer Compounds (SC) were reacted with the yields provided and
obtained at >95% purity
Stabilizer Performance Assessment
[0101] To examine the efficacy of the stabilizer compounds in
retarding the rate of UV degradation in aromatic polymers, the
aromatic polymer polysulfone manufactured by Solvay Specialty
Polymers USA, L.L.C. under the tradename UDEL.RTM. polysulfone
P1800 was solution blended with stabilizer compounds E1, E2 and E4
(as summarized in Table 2) at 5 mol % loading. This was
accomplished by first dissolving the stabilizer compound and
polymer in dimethyl formamide (DMF) to prepare a 23 wt. % solution
(percent total solids) followed by film casting onto a glass plate
pre-heated to 70 C using a 15 mil side of a square applicator (BYK
Gardener). The resulting 4''.times.4''.times.50 micron thick film
was dried (on a glass plate) using a vacuum oven (120 C, <-25
mmHg) for 48 h, at which point the film was removed from the glass
substrate using a razor blade. The free-standing film was then cut
into 10 mm.times.100 mm.times.50 micron strips using a precision
trammel cutter and mounted onto an aluminum frame designed for use
in an Atlas ci4000 Xenon weather-o-meter. All films were checked
for removal of residual solvent using FT-IR (the carbonyl band for
DMF at 1680 cm-1 prior to UV exposure).
[0102] The same procedure was followed for the comparative
stabilizer compounds CE1, CE3 and CE4 allowing the comparison
between the stabilizers synthesized and two commercially available
light stabilizers (i.e. Chiguard 770 and Chiguard 353, commercially
available from Chitec.RTM. Technology, respectively called CE3 and
CE4).
[0103] All weathering experiments were carried out in 24 hour
increments for up to 5 days using the same weather-o-meter which
was also further equipped with a Type "S" borosilicate inner filter
and a soda lime outer filter. The cut-off filters eliminated all
wavelengths >340 nm. All weathering cycles were set for an
irradiance of 0.30 w/m.sup.2, with a panel temperature of
55.degree. C. a chamber temperature of 38.degree. C., and a
relative humidity of 55%. All other variables were controlled in
accordance with ASTM G155-4. Following exposure to UV, each film
was subsequently placed in a UV Vis spectrophotometer set to
transmission mode and the UV-Vis spectra was collected at a, =350
nm.
[0104] Table 2 summarizes the changes in transmission after UV
ageing (exposure) in the same weather-o-meter for the
mono-substituted piperidin-ol stabilizer compounds (A-A), (A-B),
and (A-C) as well as for the comparative examples CE1 (C-A), and
piperidine-based commercial compounds CE3 and CE4 (HALS).
[0105] Table 3 summarizes the change in glass transition
temperatures (Tg), which were measured by Differential scanning
calorimetry (DSC) performed under nitrogen using a TA instruments
DSC Q10 differential scanning calorimeter. The temperature program
provided two sequential heating and cooling cycles that were
carried out between 25.degree. C. and 225.degree. C. at a rate of
20.degree. C./min. All glass transition temperatures were
determined using TA Thermal Advantage and Universal Analysis
software and were made using the second heat cycle.
[0106] Table 4 summarizes the change in transmission after UV
ageing (exposure) in the same weather-o-meter for the
bis-substituted stabilizer compounds (B-A) (E4), and (B-B) (E5) as
well as for the comparative examples CE5 (compound (C-C)).
TABLE-US-00002 TABLE 2 Transmission (%) vs UV exposure time (days)
of Udel .RTM. PSU and its blends with 5 mol % monosubstituted
stabilizers UV Ageing Control - Time No UDEL .RTM. + UDEL .RTM. +
UDEL .RTM. + UDEL .RTM. + UDEL .RTM. + UDEL .RTM. + (days)
Stabilizer E1 E2 E3 CE1 CE3 CE4 0 80.70 80.70 80.70 80.70 80.70
80.70 80.70 1 36.55 48.96 51.88 49.88 37.06 60.78 51.38 2 30.21
40.76 42.02 40.32 29.24 42.16 43.94 3 24.00 34.59 36.23 35.37 24.27
38.49 37.61 4 23.26 30.20 31.69 30.68 17.96 35.01 35.05 5 16.33
27.48 29.59 29.43 17.69 28.67 27.75
TABLE-US-00003 TABLE 3 Glass transition temperatures Udel .RTM. PSU
and its blends with 5 mol % stabilizers UDEL .RTM. UDEL .RTM. +
UDEL .RTM. + UDEL .RTM. + UDEL .RTM. + UDEL .RTM. + UDEL .RTM. +
UDEL .RTM. + UDEL .RTM. + Control E1 E2 E4 E5 CE1 CE3 CE4 CE5 Tg
(.degree. C.) 185 172 167 176 165 168 152 156 176 .DELTA. Tg
(.degree. C.) N/A -13 -18 -9 -20 -17 -35.5 -31.83 -9
TABLE-US-00004 TABLE 4 Transmission (%) vs UV exposure time (days)
of Udel .RTM. PSU and its blends with 5 mol % disubstituted
stabilizers UV Ageing Control - UDEL .RTM. + UDEL .RTM. + UDEL
.RTM. + Time (days) No Stabilizer E4 E5 CE5 0 80.70 80.70 80.70
80.70 1 36.55 46.47 48.23 38.80 2 30.21 38.02 39.18 29.99 3 24.00
32.90 33.48 27.16 4 23.26 27.13 28.57 21.40 5 16.33 25.78 27.19
19.88
[0107] Compound (C-D) of CE6 presented a very low thermal
stability. The temperature at which 10% wt. loss was observed by
thermal gravimetric analysis (TGA) for compound (A-C) was
132.degree. C. and would therefore not be suitable to be used at
the processing temperatures of commodity polymers, let alone the
high processing temperatures of high performance aromatic
polymers.
[0108] Now, when analyzing the transmission data of tables 2 and 4,
it appears that the presence of stabilizer compounds E1, E2, E3,
CE3, CE4, E4 and E5 greatly improves the behavior ofUDEL.RTM. PSU
after 5 days exposure to UV, bringing the transmission values to at
least 25%, compared to the 16% obtained for the unstabilized
UDEL.RTM. PSU control.
[0109] However, these results are further evaluated with the data
provided on table 3 on the Tg of the films. It is important that
the incorporation of additives/stabilizers do not reduce too much
the Tg of the polymer. It is interesting to note that the Tg
obtained on the films containing the commercially available
stabilizers CE3 and CE4 dropped to very low and unacceptable Tg
values with a ATg compared to the Tg of the UDEL.RTM. polysulfone
alone of at least 31.degree. .degree. C. Surprisingly, the ketone
structures of CE1 and CE5, which contain benzophenone moieties, did
not impart increased UV stability.
[0110] Should the disclosure of any patents, patent applications,
and publications which are incorporated herein by reference
conflict with the description of the present application to the
extent that it may render a term unclear, the present description
shall take precedence.
* * * * *