Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
1999-06-18
2001-05-29
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C544S214000, C544S215000
Reexamination Certificate
active
06239275
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to novel hindered phenol substituted trisaryl-1,3,5-triazines and the use thereof to protect against degradation by environmental forces, inclusive of actinic radiation, high temperature, oxidation, moisture, atmospheric pollutants and combinations thereof.
2. Description of Related Art
Exposure to sunlight and other sources of ultraviolet radiation are known to cause degradation of a variety of materials, especially a polymeric materials. For example, polymeric materials such as plastics often discolor and/or become brittle as a result of prolonged exposure to ultraviolet light. Accordingly, a large body of art has been developed directed towards materials such as ultraviolet light absorbers and stabilizers which are capable of inhibiting such degradation.
A class of materials known to be ultraviolet light absorbers are trisaryl-1,3,5-triazines, in which at least one of the aryl rings has a hydroxyl group ortho to the point of attachment to the triazine ring. In general this class of materials is well known in the art. Disclosures of a number of such trisaryl-1,3,5-triazines can be found in the patent literature. For example, U.S. Pat. No. 3,843,371 discloses hydroxyphenyltrizines for use in photographic materials. The triazines in this patent, however, show poor solubilities and poor stabilities.
U.S. Pat. No. 3,896,125 discloses hydroxyphenyl triazines, but these, too are poorly soluble and discolor with time.
Typically, the aforementioned aryl ring with the hydroxyl group ortho to the point of attachment to the triazine ring is based on resorcinol and, consequently, this aryl ring also contains a second substituent (either a hydroxyl group or a derivative thereof) para- to the point of attachment to the triazine ring. For example, U.S. Pat. Nos. 3,118,837 and 3,244,708 disclose p-alkoxy-o-hydroxyphenyl triazines with improved UV protection, but such triazines also exhibit poor solubility and poor long-term stabilities.
However, there remains a need for triazine UV absorbers which impart yellowing resistance to polymers, both under high temperature conditions and upon exposure to actinic radiation. The novel hindered phenol substituted trisaryl-1,3,5-triazines of the present invention satisfy that need.
SUMMARY OF THE INVENTION
The present invention provides a new class of trisaryl-1,3,5-triazines in which an aryl ring attached to the triazine ring (and preferably an aryl ring containing a hydroxyl group ortho- to the point of attachment to the triazine ring) is further substituted with a group comprising a hindered phenol. More specifically, the new trisaryl-1,3,5-triazines of the present invention have the following general formulas (I), (II) and (III):
wherein
each X is independently selected from hydrogen, allyl, —COR
a
, —SO
2
R
b
, —SiR
c
R
d
R
e
, —PR
f
R
g
and —POR
f
R
g
;
each of Y and Z is independently selected from an aryl ring of the general formula (IV)
each B is independently selected from —R or —OR;
each R is independently selected from a hydrogen, a hindered phenol, a hydrocarbyl group, a hydrocarbyl group comprising a hindered phenol, a functional hydrocarbyl group and a functional hydrocarbyl group comprising a hindered phenol;
each R
a
is independently selected from C
1
-C
8
alkyl, halogen-substituted C
1
-C
8
alkyl, C
5
-C
12
cycloalkyl, C
2
-C
8
alkenyl, —CH
2
—CO—CH
3
, C
7
-C
12
aralkyl, C
1
-C
12
alkoxy, or phenyl which is unsubstituted or substituted by C
1
-C
12
alkyl, C
1
-C
4
alkoxy, halogen and benzyl;
each R
b
is independently selected from C
1
-C
12
alkyl, C
6
-C
10
aryl and C
7
-C
18
alkylaryl;
each R
c
, R
d
and R
e
is independently selected from C
1
-C
8
alkyl, cyclohexyl, phenyl and C
1
-C
18
alkoxy;
each R
f
and R
g
is independently selected from C
1
-C
12
alkoxy, phenoxy, C
1
-C
2
alkyl, C
5
-C
12
cycloalkyl, benzyl, tolyl and phenyl;
each R
1
, R
1′
, R
2
, R
4
, R
4′
and R
4″
is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —O(hydrocarbyl), —O(functional hydrocarbyl), —SR, halogen, —SO
2
R, —SO
3
R, —COOR, —COR, —OCOR, —NRR and cyano; and
each R
3
is independently selected from R, —OR, —SR, halogen, —SO
2
R, —SO
3
R, —COOR, —COR, —NRR and cyano.
The structures of formulas (I), (II) and (III) are further characterized in that at least one 4-position B group is a hindered phenol or comprises a hindered phenol, i.e., with the proviso that at least one R group of the 4-position B group comprises a hindered phenol, a hydrocarbyl group comprising a hindered phenol, or a functional hydrocarbyl group comprising a hindered phenol.
Hindered phenols are well known to those in the polymer and coatings stabilization arts. Typically, a hindered phenol comprises phenol which has both positions ortho to the phenol hydroxy group substituted by alkyl groups, at least one of which is sterically bulky. Sterically bulky groups are well known and include but are not limited to tertiary butyl, benzyl and substituted benzyl, for example. In the following example structure of a hindered phenol:
at least one of the ortho position R
i
and R
v
moieties typically are, independently, selected to comprise a sterically bulky group, such as those exemplified above and as described in detail throughout the specification, and R
ii
, R
iii
and R
iv
are typically independently selected from, e.g., hydrogen, alkyl or aralkyl, and from those groups described in detail throughout the specification. Hindered phenols as antioxidants are described in U.S. Pat. Nos. 3,723,427, 3,862,053, 3,923,869, 4,226,999, 4,284,790, 4,439,615, 4,613,642, 4,683,982 and 4,721,792 which are incorporated by reference herein in their entirety.
Preferred hindered phenols include but are not limited to:
wherein at least one of the ortho position R
i
and R
v
moieties are, independently, selected to comprise a sterically bulky group such as an alkyl of 4 to 12 carbon atoms or aralkyl of 7 to 24 carbon atoms and wherein R
ii
, R
iii
and R
iv
are independently selected from hydrogen, alkyl of 1 to 12 carbon atoms or aralkyl of 7 to 24 carbon atoms.
The trisaryl-1,3,5-triazines of the invention, comprising a hindered phenol, are particularly effective in protecting against actinic radiation, high temperature, oxidation, moisture, atmospheric pollutants and combinations thereof because the triazine and hindered phenol are bound together in a single compound. Such compounds, being of much higher molecular weight than either a typical trisaryl-1,3,5-triazine or a typical hindered phenol, do not tend to diffuse readily. Moreover, such compounds are not as easily extracted, for example, by solvents or by fluids, than are trisaryl-1,3,5-triazines or hindered phenols used alone or in physical combination, but not bound together.
These trisaryl-1,3,5-triazines may in general be prepared via a number of procedures described in the previously incorporated references, but preferably by reacting a trisaryl-1,3,5-triazine precursor, having at least one aryl ring with a hydroxyl group para- to the point of attachment to the triazine ring (and preferably hydroxyl groups both ortho- and para- to the point of attachment to the triazine ring), with an appropriate compound or compounds to functionalize the para- position hydroxyl with a hindered phenol group or with a group substituted by a hindered phenol, such as a hydrocarbyl group comprising a hindered phenol or a functional hydrocarbyl group comprising a hindered phenol.
In addition to providing UV protection, the triazine UV absorbers of the present invention have anti-oxidant activity. For example, they are effective in reducing thermal yellowing in coatings, particularly in coatings with high temperature cure schedules, for example coil coatings, powder coatings, or in coatings that are over-baked. These triazine UV absorbers are also effective in reducing yellowing and thermal degradation in plastics during high-temperature processing, as well as in imparting long-term light stability.
The n
Gupta Ram Baboo
Jakiela Dennis John
Balasubramanian Venkataraman
Ciba Specialty Chemicals Corporation
Raymond Richard L.
Stevenson Tyler A.
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