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
2001-10-02
Raymond, Richard L. (Department: 1611)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C544S216000, C544S219000, C544S214000, C544S181000, C544S271000, C544S295000, C544S309000, C544S333000, C524S100000, C252S405000
Reexamination Certificate
active
06297377
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to novel benzocycle-substituted pyrimidines and triazines and their use as protectants against degradation by environmental forces, including ultraviolet light, actinic radiation, oxygen, moisture, atmospheric pollutants and combinations thereof.
2. Description of Related Art
Exposure to sunlight and other sources of ultraviolet radiation is known to cause degradation of a variety of materials, especially polymeric materials. For example, polymeric materials such as plastics often discolor and may become brittle as a result of 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 o-hydroxyphenyltriazines, in which at least one substituent on the 1, 3 or 5 carbon on the triazine ring is a phenyl group with 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.
For example, U.S. Pat. No. 3,843,371 discloses hydroxyphenyltriazines 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.
The use of hydroxyphenyltriazines alone or in combination with other light stabilizers such as hydroxyphenylbenzotriazoles, benzophenones, oxanilides, cyanoacrylates, salicylates, and hindered amine light stabilizers (HALS), for the stabilization of polymers is also well known. For example, U.S. Pat. Nos. 4,853,471, 4,921,966, and 4,973,701, 4,973,702 disclose such combinations.
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 many embodiments of such triazines exhibit poor compatibility and solubility, and poor yellowing performance.
This para-substituent can be “non-reactive,” as in the case of an alkyloxy group, or “reactive” as in the case of a hydroxyalkyloxy (active hydrogen reactive site) or (meth)acryloyl (ethylenic unsaturation reactive site) group. For the purposes of the present invention, the former are referred to as “non-bondable” benzocycle-substituted pyrimidines and triazines and the latter are referred to as “bondable” benzocycle-substituted pyrimidines and triazines.
Low volatility is an important characteristic of stabilizers used in any applications where high temperatures are encountered. High temperatures are used in the processing of thermoplastics and in the curing of thermoset resins and coatings. High temperatures are also often present in the end-use applications for the stabilized material. Low volatility will prevent loss of the stabilizer during processing, curing, and high temperature end-uses. Besides reducing losses of stabilizer during processing or curing, low volatility will minimize processing problems such as die lip build-up and plate-out.
Many polymer additives (such as ultraviolet light stabilizers) migrate out of the polymer substrate to be protected, or are adsorbed (chemically or physically) by one or more systems components (such as pigments), thereby diminishing their effectiveness. Such migration and adsorption problems are examples of the general problems of lack of solubility and compatibility found for many commercial polymer additives.
Bondable triazines are well known in the art. For example, U.S. Pat. Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondable and the incorporation of these compounds into polymers by chemical bonding. Bondable stabilizers have a potential advantage in this respect in that, depending on the bondable functionality and the particular polymer system to be stabilized, they can be chemically incorporated into a polymer structure via reaction of the bondable functionality either during polymer formation (such as in the case of polymerizing monomers or a crosslinking polymer system) or subsequently with a preformed polymer having appropriate reactive functionality. Accordingly, due to such bonding, migration of these UV absorbers between layers of multi-layer coatings and into polymer substrates is greatly reduced.
SUMMARY OF THE INVENTION
The present invention provides a new class of benzocycle-substituted pyrimidines and triazines depicted below, in which a substituent attached to the triazine or pyrimidine ring is a fused benzocyclic group:
wherein X signifies hydrogen or a blocking group, A can be a nitrogen or optionally substituted methine, and the fused ring designated by S is a non-aromatic 4 to 12 membered ring, optionally containing one or more heteroatoms; any of the three rings may bear one or more additional substituents. These fused benzocyclic-substituted triazines and pyrimidines have the advantage of being highly soluble in and compatible; of having extremely low volatility, and therefore low losses during high temperature processing or curing; of being highly effective in inhibiting yellowing; and of being highly effective in preventing degradation of polymers and coatings due to the action of actinic radiation, heat, oxygen, and moisture.
The benzocyclic substituted triazine and pyrimidine UV absorbers of the present invention possess exceptionally low volatility, lower than most current art UV absorbers. Furthermore these benzocyclic triazine UV absorbers, impart improved weatherability and yellowing resistance to polymers compared to current art UV absorbers. None of the previously available triazine UV stabilizers and absorbers combine the unexpected low volatility along with the weatherability, yellowing resistance, solubility, and compatibility of the benzocyclic substituted triazine and pyrimidine absorbers and stabilizers of the present invention.
More specifically, the new benzocycle-substituted pyrimidines and triazines of the present invention have general formula (I):
wherein
each A is independently nitrogen or methine optionally substituted with R
2
, and at least two A are nitrogen;
each of T and T′ is independently a direct bond, carbon, oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or functional groups containing these elements;
X is independently selected from hydrogen and a blocking group;
each of R
1
and R
2
is independently a hydrocarbyl group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano;
each of Y, Z, R
3
and R
4
are independently a hydrogen, hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, —O(hydrocarbyl), —O(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functional hydrocarbyl), —N(hydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl), —S(functional hydrocarbyl), —SO
2
(hydrocarbyl), —SO
2
(hydrocarbyl), —SO
3
(hydrocarbyl), —SO
3
(functional hydrocarbyl), —COO(hydrocarbyl), —COO(functional hydrocarbyl), —CO(hydrocarbyl), —CO(functional hydrocarbyl, —OCO(hydrocarbyl), —OCO(functional hydrocarbyl), —N(hydrocarbyl)(hydrocarbyl), —CONH
2
, —CONH(hyrdocarbyl), —CONH(functional hyrdocarbyl), —CON(hydrocarbyl)(hyrdocarbyl), —CON(hydrocarbyl)(functional hyrdocarbyl), —CON(functional hydrocarbyl)(functional hyrdocarbyl), —S(functional hydrocarbyl), —SO
2
(functional hydrocarbyl), —SO
3
(functional hydrocarbyl), —COO(functional hydrocarbyl), —CO(functional hydrocarbyl), —OCO(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups;
each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous, boron, silicon, selenium, tellurium, or functional groups containing these e
Fischer Robert G.
Gupta Ram B.
Jakiela Dennis J.
Balasubramanian Venkataraman
Cytec Technology Corporation
Pennie & Edmonds LLP
Raymond Richard L.
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