Title of Invention

PHENYL ETHER SUBSTITUTED HYDROXYPHENYL TRIAZINE ULTRAVIOLET LIGHT ABSO RBERS

Abstract This invention relates generally to phenyl ether substituted triazines compounds and compositions containing same and their use to protect against degradation by environmental forces. A method for stabilizing a material by incorporating such triazines is also disclosed.
Full Text PHENYL ETHER-SUBSTITUTED HYDROXYPHENYL TRIAZINE ULTRAVIOLET LIGHT
ABSORBERS
Field of the Invention
This invention relates generally to novel triazine ultraviolet (UV) light absorbers. More
particularly, this invention relates to a 1,3,5-hydroxyphenyl triazine UV light absorbers
substituted with phenyl ether and their use to protect against degradation by environmental
forces, including ultraviolet light, actinic radiation, oxygen, moisture, atmospheric pollutants
and combinations thereof.
BACKGROUND OF THE INVENTION
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 that 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. Disclosures of a
number of such trisaryl-1,3,5-thazines can be found in the patent literature such as disclosed
in United States Patent Nos. 3,843,371 and 3,896,125.
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. Patents No. 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" substituted triazines and the latter are referred to as
"bondable" substituted 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. Patent 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 cross-linking 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.
This invention discloses a novel class of triazine UV absorbers containing at least
one substituent on the triazine derived from phenyl ether or substituted phenyl ether, which
have been found to have better performance than some of the similar commercial triazine UV
absorbers.

SUMMARY OF THE INVENTION
The present invention provides a new class of hydroxyphenyl substituted triazines
depicted below, in which a substituent attached to the hydroxyphenyl triazine ring is based on
phenyl ether:

where R1,R2, R3 ,R4, R5 are the same or different and each is hydrogen, halogen, alkyl of 1
to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl
of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl
of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR, S02R, S03H, S03M, wherein
M is an alkali metal, R and R' are the same or different and each is hydrogen, alkyl of 1 to 24
carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to
24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl
of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,
and optionally with either of R1 and R2, R3 and R4, or R4 and R5, taken together being a part
of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in
the ring;
each of T and T' is independently a direct bond, oxygen, NR, sulfur or a functional group
containing these elements;
X is independently selected from hydrogen and a blocking group;
each of Y, R6 and R7 are independently a hydrogen, hydrocarbyl group, a functional
hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -0(functional

hydrocarbyl), -N(hydrocarbyl)2, -N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional
hydrocarbyl), -S(hydrocarbyl), -S(functional hydrocarbyl), -SO2(hydrocarbyl),
-SO2(hydrocarbyl), -SO3(hydrocarbyl), -SO3(functional hydrocarbyl), -C02
(hydrocarbyl), -C02 (functional hydrocarbyl), -CO(hydrocarbyl), -CO(functional
hydrocarbyl, -OCO(hydrocarbyl), -OCO(functional hydrocarbyl), -CONH2,
-CONH(hydrocarbyl), -CONH(functional hydrocarbyl), -CON(hydrocarbyl)2,
-CON(hydrocarbyl)(functional hydrocarbyl), -CON(functional hydrocarbyl) 2,
-S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional hydrocarbyl),
or a hydrocarbyl group substituted by any of the above groups;
Z is Y,

and where L is hydrogen, a hydrocarbyl of 1 to 24 carbon atoms, or a functional hydrocarbyl
of 1 to 24 atoms.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a new class of hydroxyphenyl substituted triazines
depicted below, which are suitable to be used as UV light stabilizers, in which a substituent
attached to the hydroxyphenyl triazine ring is based on phenyl ether:


where R1 R2, R3, R4, R5 are the same or different and each is hydrogen, halogen, alkyl of 1
to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl
of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl
of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR, SO2R, SO3H, SO3M, wherein
M is an alkali metal, R and R' are the same or different and each is hydrogen, alkyl of 1 to 24
carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to
24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl
of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,
and optionally with either of R1, and R2, R3 and R4, or R4 and R5, taken together being a part
of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in
the ring;
each of T and T' is independently a direct bond, oxygen, NR, sulfur or a functional group
containing these elements;
X is independently selected from hydrogen and a blocking group;
each of Y, R6 and R7 are independently a hydrogen, hydrocarbyl group, a functional
hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -0(functional hydrocarbyl),
-N(hydrocarbyl)2, -N(functional hydrocarbyl) 2, -N(hydrocarbyl)(functional hydrocarbyl),
-S(hydrocarbyl), -S(functional hydrocarbyl), -SO2(hydrocarbyl), -SO2(hydrocarbyl),
-SO3(hydrocarbyl), -SO3(functional hydrocarbyl), -C02 (hydrocarbyl), -CC)2 (functional
hydrocarbyl), -CO(hydrocarbyl), -CO(functional hydrocarbyl, -OCO(hydrocarbyl),
-OCO(functional hydrocarbyl), -CONH2, -CONH(hydrocarbyl), -CONH(functional hydrocarbyl),
-CON(hydrocarbyl)2, -CON(hydrocarbyl)(functional hydrocarbyl), -CON(functional
hydrocarbyl) 2, -S(functional hydrocarbyl), -SO2(functional hydrocarbyl), -SO3(functional
hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups.

Preferably, T is an oxygen atom and Y is a group L where L is defined below.
Also preferably, T is a direct bond and Z is Y, or TZ has the Formulas lla, llb and llc:

L is selected from the group consisting of : hydrogen; an alkyl of 1 to 24 carbon atoms
optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido,
carbamato, or epoxy groups, and which may contain one or more carbonyl groups, oxygen
atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atoms optionally
substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato,
or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
an aralkyl of 7 to 24 carbon atoms optionally substituted by one or more hydroxy,
alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or
epoxy groups, and which may contain one or more carbonyl groups, oxygen
atoms or nitrogen atoms in the chain;
a polyoxyalkylene radical of the Formula XII
—CH2— CH(OH)— CH2—O—(CH2(CH2)U—O—)mm—D1 (XII)
wherein D1 is hydrogen,

—CH2—CH(OH)—CH2—OH, —CH2—CH2—CH2 or R25

a polyoxyalkylene radical of the Formula XIII
—CO—(CH2)U—O—(CH2—(CH2)U—O—)mm—D2 (XIII)
wherein D2 is —(CH2)U—CO—R22 or R25;
a polyoxyalkylene radical of the Formula VIII
_YY—O—CO—(CH2)U—O—(CH2-(CH2)u—O—)mm—D3 (XIV)
wherein D3 is — (CH2)U—CO—R22 or R25;
a polyoxyalkylene radical of the Formula XV
—(CH2)kk—CH(R21)—CO—B1—(CnnH2nn—0—)mm—CnnH2nn—B1—D4 (XV)
wherein D4 is hydrogen or R25;
a polyoxyalkylene radical of the Formula XVI
—CO—CH2—CH2—NH—(CnnH2nn—O—)mm—CnnH2nn—D5 (XVI)
wherein D5 is —NH2, —NH—(CH2)2—COO—R23 or—O—R25;
a polyoxyalkylene radical of the Formula XVII
_YY—O—CO—CH2—CH2—NH—(CnnH2nn—O—)mm—CnnH2nn—D5 (XVII)
wherein D5 is as defined under Formula XVI;
a polyoxyalkylene radical of the Formula XVIII
—(CnnH2nn—O—)mm—CnnH2nn—D6 (XVIII)
wherein D6 is —NH—CO—R24, —OR25, OH or H;
a polyoxyalkylene radical of the Formula XIX
—CH(R17)—CH2—(OCH(R17)—CH2)m—D7 (XIX)
wherein D7 is —OR25, —NHCOR24 or —OCH2CH2OR25;
R21 is hydrogen or C1—C16 alkyl;
R22 is halogen or—O—R23;
R23 is hydrogen, C1—C6 alkyl, C3—C6 alkenyl, aryl, or
aryl—C1—C4—alkyl;
R24 is hydrogen, C1—C12 alkyl or aryl;
R25 is C1—C12 alkyl, C5—C12 cycloalkyl, C3—C6 alkenyl,
C1—C12 alkylaryl or aryl—C1—C4 alkyl;
R26 is hydrogen or C1—C4 alkyl;
R27 is hydrogen, C1—C18 alkyl, C3—C6 alkenyl, C1—C18 alkoxy, halogen or aryl—C1—
C4—alkyl;
R28 and R29 independently of one another are hydrogen,

C1—C18 alkyl, C3—C6 alkenyl, C1—C18 alkoxy, or halogen;
R30 is hydrogen, C1—C4 alkyl or CN;
YY is unsubstituted or substituted C2—C20 alkyl;
kk is zero or an integer from 1 -16;
B1 is O or NH;
mm is an integer from 2 to 60;
nn is an integer from 2 to 6;
u is an integer from 1 to 4.
A preferred embodiment of the present invention is Formula IV below where the
substituents are defined above:
Another preferred embodiment of the present invention is Formula V below where the
substituents are defined above:


More preferred Formulas IV and V are when R1 to R7 and X are hydrogen, T' is
oxygen and Y is L. More preferably L is a C1 to C12 alkyl or hydoxyalkyl.
The phenyl ether-substituted triazines of the present invention further comprise
oligomeric species of Formulas (VI) and (VII):

where R1 to R7, T, Z, X are defined above and where
r is an integer between 2 and 4;
when r is 2, D is selected from the group consisting of C2—C16 alkyl, C4—C12 alkenyl,
xylylene, C3—C20 alkyl which is interrupted by one or more oxygen atoms,
hydroxy-substituted C3—C20 alkyl which is interrupted by one or more oxygen

atoms, —CH2CH(OH)CH20—R15—OCH2CH(OH)CH2, —CO—R16—CO—, —
CO—NH—R17—NH—CO—, — (CH2)5—COO—R18—OCO—(CH2)5—
a polyoxyalkylene bridge member of the Formula XX
—CH2—CH(OH)—CH2—O—(CH2—(CH2)U—O—)mm—CH2—CH(OH)
—CH2— (XX),
a polyoxyalkylene bridge member of the Formula XXI
—CO—(CH2)u-0—(CH2—(CH2)U—O—)mm—(CH2)U—CO— (XXI),
a polyoxyalkylene bridge member of the Formula XXII
_YY—O—CO(CH2)u—6—(CH2-(CH2)U—O—)mm—(CH2)U—COO
—YY— (XXII),
a polyoxyalkylene bridge member of the Formula XXIII
—(CH2)kk—CH(R21)—CO—B1-(CnnH2nn—O—)mmCnnH2nn—B1—CO—
CH(R21)-(CH2)kk— (XXIII),
a polyoxyalkylene bridge member of the Formula XXIV
—COC(R21)HCH2NH(CnnH2nnO)mCnnH2nn-NHCH2-C(R21)HCO—
a polyoxyalkylene bridge member of the Formula XXV
_YY—O—CO—(CH2)2—NH—(CnnH2nn—O—)mm—CnnH2nn—NH—
(CH2)2COO—YY— (XXV),
a polyoxyalkylene bridge member of the Formula XXVI
—(CnnH2nn—O—)mm—CnnH2nn— (XXVI),
and a polyoxyalkylene bridge member of the Formula XXVII
—CH(CH3)—CH2—(O—CH(CH3)—CH2)a—(O—CH2—CH2)b—(O—CH2—
CH(CH3)C)— (XXVII),
wherein a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0,
R21 is hydrogen or C1—C16 alky!,
R22 is halogen or—O—R23,
R23 is hydrogen, C1—C6 alkyl, C3—C6 alkenyl, aryl, or aryl—C1—C4—alkyl,
R24 is hydrogen, C1—C12 alkyl or aryl,
R25 is C1—C16 alkyl, C5—C12 cycloalkyl, C3—C6 alkenyl,
C1—C12 alkylaryl or aryl—C1—C4 alkyl,
R26 is hydrogen or C1—C4 alkyl,
R27 is hydrogen, C1—C18 alkyl, C3—C6 alkenyl, C1—C18 alkoxy, halogen or
aryl—C1—C4 alkyl,
R28 and R29 independently of one another are hydrogen, C1—C18 alkyl, C3—C6
alkenyl, or
C1—C18 alkoxy, or halogen;

kk is zero or an integer from 1 -16,
B1 is O or NH,
mm is an integer from 2 to 60,
nn is an integer from 2 to 6,
u is an integer from 1 to 4;
when r is 3, D is — [-(CH2)s—COO-]3— R19
and when r is 4, D is — [-(CH2)S—COO-]4—R20
wherein R19 is C3—C10 alkanetriyl and R20 is C4—C10 alkanetetryl; and
S is 1-6;
R15 is C2—C10 alkyl, C2—C10 oxaalkyl or C2—C10 dithiaalkyl, phenyl, naphthyl,
diphenyl, or C2—C6 alkenyl, or phenylene-XX-phenylene wherein XX is
—O—, —S—, — SO2—, —CH2—, or —C(CH3)2—;
R16 is C2—C10 alkyl, C2—C10 oxaalkyl or C2—C10 dithiaalkyl, phenyl, naphthyl,
diphenyl, or C2—C6 alkenyl provided that when r is 3 the alkenyl has at
least 3 carbons;
R17 is C2—C10 alkyl, phenyl, naphthyl, diphenyl, or C2—C6 alkenyl,
methylenediphenylene, or C4—C15 alkylphenyl; and
R18 is C2—C10 aikyl, or C4—C20 alkyl interrupted by one or more oxygen atoms.

wherein T, T', Y, Z, R, - R7, are as defined above; r is 2 or 3; when r is 2, X' is —CO—R16—
CO—, —C02—R16—CO2—, —SO2-R16—SO2—, — CO—NH—R17—NH—CO—, a

polyoxyalkylene bridge member of Formula — CO—(CH2)U—O—(CH2—(CH2)U—O—)mm—
(CH2)U—CO—, or
—COC(R21)HCH2NH(CnnH2nnO)mCnr,H2nn-NHCH2-C(R21)HCO—
when r = 3, X' is:
—(—CO2—R16)R19, — (-CONH—R16)R19, —(—SO2— R16)R19
wherein R16, R17, R18, and R19 are as defined above.
The triazines of the present invention also comprise oligomeric species of the
Formulas (VIII) and (IX):

wherein T, T', Y, Z, R1 to R7 ,and X, are as defined above;
R6 is selected from the group consisting of straight chain alkyl of 1 to 12 carbon
atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12
carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl,
alkyl substituted by phenylene, alkyl interrupted by phenylene, benzylidene, —
S—, —S—S—, —S—E—S—, —SO—, — SO2—, —SO—E—SO—, —S02—
E—S02—, —CH2—NH—E—NH—CH2—, and


wherein E is selected from the group consisting of alkyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8
to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms;
and
r is an integer between 2 and 4.

wherein Y, X, and R1 to R7 are defined above;
each of T and T is independently a direct bond, oxygen, NR, sulfur or a functional
group containing these elements;
r is an integer between 2 and 4;
when r is 2, D is selected from the group consisting of C2—C16alkylene, C4—
C12alkenylene, xylylene, C3—C2oalkylene which is interrupted by one or more
oxygen atoms, hydroxy-substituted C3—C20alkylene which is interrupted by
one or more oxygen atoms, —CH2CH(OH)CH20—R15—OCH2CH(OH)CH2, —
CO—R16—CO—, —CO—NH—R17—NH—CO—, and —(CH2)S—COO—R18—
OCO—(CH2)S—; and
when r is 3, D is — [-(CH2)S—COO-]3— R19
and when r is 4, D is — [-(CH2)S— COO-]4— R20
wherein R19 is C3—C10alkanetriyl and R20 is C4—C10alkanetetryl;
s is 1-6;

R15 is C2—C10 alkylene phenylene or a phenylene-x-phenylene- group, wherein X is
—O—, —S—, — SO2—, —CH2—, or —C(CH3)2—;
R16 is C2—C10 alkylene, C2—C10 oxaalkylene or C2—C10 dithiaalkylene, phenylene,
naphthylene, diphenylene or C2—C6 alkenylene;
R17 is C2—C10 alkylene, phenylene, naphthylene, methylenediphenylene or C7—C15
alkylphenylene, and
R18 is C2—C10 alkylene or C4—C2o alkylene which is interrupted by one or more
oxygen atoms.
The triazines of the present invention may optionally have the added benefit of being
capable of being chemically bonded to appropriate polymer systems via functionality
attached to the triazine groups (e.g., by a hydroxyl, ethylenic unsaturated and/or activated
unsaturated group in one or more of Y or Z).
The triazines of the present invention may in general be prepared via a number of
procedures well known in the art, for example, those described in Brunetti, H; Luethi, C;
Helv. Chemica Acta, 55 (1972) pp. 1566-1595; Tanimoto, S.; Yamagata, M. Senryo to
Yakahin, 40 (1995) pp 339ff; U. S. Patent Nos. 5,106,972; 5,288,868; 5,438,138 and
5,478,935; EP 395,938; EP 577,559; EP 649,841; EP 779,280; WO 9,628,431; GB 884,802;
WO 00/29392 and Japanese Patent Kokai Tokkyo Koho 9,059,263 all of which are
incorporated herein by reference for all purposes as if fully set forth. The preferred method is
the procedure in WO/29392.
The novel triazines of the present invention are particularly useful as ultraviolet light
absorber agents for stabilizing a wide variety of materials including, for example, organic
compounds, oils, fats, waxes, cosmetics, dyes and biocides, and particularly various organic
polymers (both cross-linked and non-cross-linked) used in applications such as photographic
materials, plastics, fibers or dyed fibers, rubbers, paints and other coatings, and adhesives.
The present invention, consequently, also relates to (1) a method of stabilizing a material
which is subject to degradation by actinic radiation (e.g., an organic material such as an
organic polymer in the form of a film, fiber, shaped article or coating) by incorporating into
said material an amount of an actinic radiation stabilizer composition effective to stabilize the
material against the effects of actinic radiation, wherein the actinic radiation stabilizer
composition comprises the inventive triazines; and (2) the material so stabilized.
The novel triazines of the present invention are also effective as ultraviolet light
screening agents in applications such as sunscreens and other cosmetic preparations,
capstock layers for extruded polymers, dyed fibers and laminated UV-screening window
films, among others. The present invention, consequently, also relates (1) to a method of
protecting a substrate against degradation by actinic radiation by applying to the substrate an

actinic radiation screening layer (e.g., a coating film or capstock layer) containing an actinic
radiation screening composition in an amount effective to reduce the amount of actinic
radiation impinging on the substrate, wherein the actinic radiation screening composition
comprises the inventive triazines; and (2) the substrate so protected.
The novel triazines of the present invention may also be employed to form light
stabilizing compositions. Such light stabilizing compositions may include a variety of other
components known in the art including other ultraviolet light absorbers of the triazine class,
other ultraviolet light absorbers of different classes (e.g. benzotriazoles, benzophenones),
hindered amine light stabilizers, radical scavengers, antioxidants and the like.
The term "hydrocarbyl" in the context of the present invention, and in the above
formulas, broadly refers to a monovalent hydrocarbon group in which the valency is derived
by abstraction of hydrogen from a carbon atom. Hydrocarbyl includes, for example, aliphatics
(straight and branched chain), cycloaliphatics, aromatics and mixed character groups (e.g.,
aralkyl and alkaryl). Hydrocarbyl also includes such groups with internal unsaturation and
activated unsaturation. More specifically, hydrocarbyl includes (but is not limited to) such
groups as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl, preferably
having up to 24 carbon atoms. A hydrocarbyl may optionally contain a carbonyl group or
groups (which is/are included in the carbon count) and/or a heteroatom or heteroatoms (such
as at least one oxygen, sulfur, nitrogen or silicon), in the chain or ring.
The term "functional hydrocarbyl" in the context of the present invention, and in the
above formulas, broadly refers to a hydrocarbyl possessing pendant and/or terminal reactive
and/or latent reactive functionality and/or leaving groups. "Reactive" functionality refers to
functionality which is reactive with common monomer/polymer functionality under normal
conditions well understood by those persons of ordinary skill in the relevant art. As non-
limiting examples of reactive functionality may be mentioned active hydrogen-containing
groups such as hydroxyl, amino, carboxyl, thio, amido, carbamoyl and activated methylene;
isocyanato; cyano; epoxy; ethylenically unsaturated groups such as allyl and methallyl; and
activated unsaturated groups such acryloyl and methacryloyl, and maleate and maleimido
(including the Diels-Alder adducts thereof with dienes such as butadiene). "Latent reactive"
functionality within the meaning of the present invention and, as would clearly be understood
by those persons of ordinary skill in the art, refers to reactive functionality which is blocked or
masked to prevent premature reaction. As examples of latent reactive functionality may be
mentioned ketimines and aldimines (amines blocked, respectively, with ketones and
aldehydes); amine-carboxylate salts; and blocked isocyanates such as alcohol (carbamates),
oxime and caprolactam blocked variations. A "leaving" group within the meaning of the
present invention, as would clearly be understood by those persons of ordinary skill in the

relevant art, is a substituent attached to the hydrocarbyl chain or ring which during reaction is
dislodged or displaced to create a valency on a carbon or heteroatom in the hydrocarbyl
chain or ring, said valency being filled by a nucleophile. As examples of leaving groups may
be mentioned halogen atoms such as chlorine, bromine and iodine; hydroxyl groups
(protonated and unprotonated); quaternary ammonium salts (NT4+); sulfonium salts (ST3+);
and sulfonates (—OSO3T); where T is, e.g., methyl or para-tolyl. Of all these classes of
reactive functionality, the preferred functionality includes hydroxyl, —COOR50, —CR51=CH2,
—CO—CR51=CH2, CI, an isocyanate group, a blocked isocyanate group and —NHR50, where
R50 is selected from hydrogen and a hydrocarbyl (preferably of up to 24 carbon
atoms); and
R51 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms (preferably
hydrogen and methyl).
The term "hydrocarbylene" in the context of the present invention is a divalent
hydrocarbon group in which both valencies derive by abstraction of hydrogens from carbon
atoms. Included within the definition of hydrocarbylene are the same groups as indicated
above for hydrocarbyl and functional hydrocarbyl with, of course, the extra valency (for
example, alkylene, alkenylene, arylene, etc.).
The term "functional hydrocarbylene" in the context of the present invention refers to
a species of hydrocarbylene possessing pendant reactive functionality, latent reactive
functionality and/or leaving groups. The term "non-functional hydrocarbylene" in the context
of the present invention refers generally to a hydrocarbylene other than a functional
hydrocarbylene.
The triazines in accordance with the present invention also relate to latent stabilizing
compounds against actinic radiation where at least one of the hydroxyl groups on an aryl ring
ortho to the point of attachment to the triazine is blocked, that is, wherein at least one X is
other than hydrogen. Such latent stabilizing compounds liberate the effective stabilizers by
cleavage of the O—X bond, e.g., by heating or by exposure to UV radiation. Latent
stabilizing compounds are desirable because they have many favorable properties, i.e., good
substrate compatibility, good color properties, a high cleavage rate of the O—X bond and a
long shelf life. The use of latent stabilizing compounds is further described in U. S. Patent
Nos. 4,775,707; 5,030,731; 5,563,224 and 5,597,854, which are incorporated herein for all
purposes as if fully set forth.
Latent stabilizing compounds comprising the triazines of the present invention can be
prepared from compounds when at least one X is hydrogen, by subjecting said compounds to
a further reaction to form latent stabilizing compounds, as described in the immediately
preceding incorporated references.

As preferred examples of blocking groups X may be mentioned one or more of the
following groups: allyl, — CORa, —S02Rb, —SiRcRdRe, —PRfR9 or—PORfR9, —CONHRh,
wherein
each Ra is independently selected from C1—C8 alkyl, halogen-substituted d—C8
alkyl, C5—C12 cycloalkyl, C2—C8 alkenyl, — CH2—CO—CH3, C1—C12 alkoxy,
and phenyl or phenoxy which is unsubstituted or substituted by C1—C12 alkyl,
C1—C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1—C12 alkyl, C6—C10 aryl and C7—C18
alkylaryl;
each Rc, Rd and Re is independently selected from C1—C18 alkyl, cyclohexyl, phenyl
and C1—C18 alkoxy;
each Rf and R9 is independently selected from C1—C12 alkoxy, C1—C12 alkyl, C5—C12
cycloalkyl, and phenyl or phenoxy which is unsubstituted or substituted by
C1—C12 alkyl, C1—C4 alkoxy, halogen and/or benzyl; and
each Rh is independently selected from C1—C8 alkyl, C5—C12 cycloalkyl, C2—C8
alkenyl, —CH2—CO—CH3, and phenyl which is unsubstituted or substituted
by C1—C12 alkyl, C2—C8 alkenyl, C1—C4 alkoxy, halogen and/or benzyl.
The reaction to give the latent stabilizing compounds of the present invention in which
X is allyl, —CORa, —S02Rb, —SiRcRdRe, —PRfR9 or—PORfR9, can be carried out, for
example, by reaction of the compounds of the present invention when at least one X is
hydrogen with the corresponding halides such as allyl chloride, CI—CORa, CI—S02Rb, CI—
SiRcRdRe, CI—PRfR9, or CI—PORfR9. The reaction to give the latent stabilizing compounds
of the present invention in which X is —CONHRh can be carried out, for example, by reaction
of the compounds when at least one X is hydrogen with the corresponding isocyanates.
Furthermore, acylated compounds can be obtained by reaction with anhydrides, ketenes or
esters, such as lower alkyl esters, as is well known to one skilled in the art. The above-
described reagents may be used in approximately equimolar amounts or in excess, for
example, from 2 to 20 mol with respect to the hydroxyl groups desired to be made latent in
the starting compound.
Catalysts customarily used for acylation, sulfonylation, phosphonylation, silylation or
urethanation reactions may be used in forming the latent stabilizing triazines of the present
invention. For example, acylation and sulfonylation reaction catalysts such as tertiary or
quaternary amines, such as triethylamine, dimethylaminopyridine or tetrabutylammonium
salts, may be used for forming these latent stabilizing compounds.
The reaction may be carried out in the presence of a solvent, such as relatively inert
organics, e.g., hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as

carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or dibutyl ether, or
without a solvent. Alternatively, the reagent(s) may be employed as the solvent. The
reaction temperature is usually between room temperature and about 150°C, for example, up
to the boiling point of the solvent when a solvent is used.
In preferred embodiments, each X is hydrogen.
In preferred embodiments, L is selected from the group consisting of hydrogen, d—
C24 alkyl or mixtures thereof; C1—C24 branched alkyl or mixtures thereof; C3—
C6 alkenyl; —COR12; — COOR12; —CONHR12; —S02R13; C1—C18 alkyl which
is substituted with one or more of the groups: hydroxy, C1—C18 alkoxy, C3—
C18 alkenoxy, halogen, phenoxy, C1—C18 alkyl—substituted phenoxy, C1—C18
alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH, —
COOR8, —CONH2, —CONHR9, —CON(R9)(R10), —NH2, —NHR9, —
N(R9)(R10), —NHCOR11, —N(R9)COR11, —NHCOOR11, —N(R9)COOR11, —
CN, — OCOR11, —OC(O)NHR9, —OC(O)NHR9, —OC(O)N(R9)(R10); C2—C50
alkyl which is interrupted by one or more oxygen atoms or carbonyl groups
and optionally substituted by one or more substituents selected from the group
consisting of hydroxy, C1—C12 alkoxy, and glycidyloxy; glycidyl; and cyclohexyl
optionally substituted with hydroxyl or—OCOR11.
R9 and R10 independently of one another are C1—C12 alkyl, C3—C12 aikoxyaikyl, C4—
C16 dialkylaminoalkyl, or C5—C12 cycloalkyl, or R9 and R10 taken together are
C3—C9 alkylene or C3—C9 oxoaalkylene or C3—C9 azaalkylene.
R11 is a hydrogen or a hydrocarbyl of 1 to 18 carbon atoms which may optionally be
substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms and/or contain one or more oxygen
and/or nitrogen atoms in the chain.
R12 is hydrogen or an alkyl of 1 to 4 carbon atoms.
R13 is hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms phenyl.
Some of these groups as well as others are described in U.S. Patent Nos. 5,106,891;
5,189,084; 5,356,995; 5,637,706; 5,726,309, EP 434,608; EP 704,437; WO 96/28431 and
GB 2,293,823 which are incorporated herein by reference for all purposes as if fully set forth.
L may also be an alkyl of 1-24 carbon atoms substituted by a hindered amine light
stabilizer (HALS) group of the general Formula XI. Triazines containing tetramethylpiperidine
groups are described in U.S. Patent Nos. 4,161,592 and 5,376,710, which are hereby
incorporated by reference herein as if fully set forth.


wherein
J is —0—, —NR30—, —T—(CH2)2—NR30— wherein T is —O— or —S—, and R30 is
C1—C12 alkyl or hydrogen;
R31 is hydrogen or C1—C8 alkyl;
R32 is hydrogen, oxygen, C1—C21 alkoxyalkyl, C7—C8 aralkyl, 2,3-epoxypropyl, and
aliphatic acyl group with 1-4 C atoms or one of the groups —CH2COOR33, —
CH2—CH(R34)—OR35, —COOR36 or—CONHR36, wherein R33 is C1—C12 alkyl,
C3—C6 alkenyl, phenyl, C7—C8 aralkyl or cyclohexyl, R34 is a hydrogen, methyl
or phenyl, R35 is hydrogen, an aliphatic, aromatic, araliphatic or alicyclic acyl
group with 1-8 C atoms, wherein the aromatic part is unsubstituted or is
substituted by chlorine, C1—C4 alkyl, C1—C8 alkoxy or by hydroxyl, and R36 is
C1—C12 alkyl, cyclohexyl, phenyl or benzyl;
R37 is hydrogen, —OH or one of the groups — O—CO—R38 or —NR36—CO—R38,
wherein R38 is C1—C12 alkyl or phenyl; and
K is —O—(CmmH2mm)— wherein mm is 1 to 6,
Preferred among the sterically hindered amines are members of the group consisting
of: bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-
yl)sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-
dichloro-1,3,5-triazine; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-
yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; 3-dodecyl-1-(2,2,6,6-
tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-1-(1-acetyl-2,2,6,6-
tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; a mixture of 4-hexadecyloxy- and 4-stearyloxy-
2,2,6,6-tetramethylpiperidine, and mixtures thereof.
Most preferably, each L group is independently selected from hydrogen, an alkyl of 1
to 24 carbon atoms, or mixtures thereof; an alkyl of 4 to 20 carbon atoms containing one or
more oxygen atoms in the chain and optionally substituted with one or more hydroxyl groups,
or mixtures thereof.

Each of R6 and R7 is independently selected from hydrogen, a hydrocarbyl group of 1
to 24 carbon atoms, a hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl group of 2 to 24
carbon atoms and an acyloxy group of 2 to 24 carbon atoms.
In preferred embodiments, each of R6 and R7 is independently selected from
hydrogen, halogen, an acyl of 2 to 24 carbon atoms, benzoyl, alkyl of 1 to 24 carbon atoms,
an alkenyl of 2 to 24 carbon atoms, a cycloalkyl of 5 to 24 carbon atoms; and an aralkyl of 7
to 24 carbon atoms.
Another preferred embodiment is when R, to R7 and X is hydrogen, T' is oxygen and
Y is hydrogen or a C1 to C8 alkyl.
In yet another embodiment, R6 and R7 are independently methylene, alkylidene, or
benzylidene substituted by a benzophenone UV absorber or a benzotriazole UV absorber.
Related triazine-benzotriazole and triazine-benzophenone hybrid UV absorbers are disclosed
in U.S. Patent No. 5,585,422 which is incorporated by reference herein for all purposes fully
set forth. In a related preferred embodiment, R6 and R7 are independently methylene,
alkylidene, or benzylidene substituted by a second triazine UV absorber. Related triazine
dimers (and oligomers) are disclosed in U.S. Patent No. 5,726,309 and EP 704,437, which
are incorporated by reference herein for all purposes fully set forth.
Preferred benzotriazoles comprise at least one member of the group consisting of: 2-
(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(3\5'-di-tert-butyl-2'-
hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)benzothazole; 2-(2'-hydroxy-5'-
(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-
chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole; 2-(3'-
sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-4'-
octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole; 2-(3',5'-
bis(,-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole; a mixture of 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5,-[2-(2-
ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-
5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-
methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-
6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2-
methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R—
CH2CH—COO(CH2)3]2 - where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl; and

derivatives thereof. Most preferred benzotriazoles are members of the group consisting of: 2-
(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3',5'-di-tert-amyl-2'-
hydroxphenyl)benzotriazole;2-(3',5'-bis(,-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, the
transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-
hydroxyphenyl]benzotriazole with polyethylene glycol 300 and mixtures thereof.
In preferred embodiments, R11 is a hydrogen or a hydrocarbyl of 1 to 18 carbon atoms
which may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms and/or
contain one or more oxygen and/or nitrogen atoms in the chain. More preferably, R11 is
selected from hydrogen and hydrocarbyl of 1 to 18 carbon atoms, which may optionally be
substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms.
In preferred embodiments, R12 is selected from hydrogen and an alkyl of 1 to 4 carbon
atoms. More preferably, R12 is selected from hydrogen and a methyl group.
In preferred embodiments, R13 is selected from hydrogen, a hydrocarbyl group of 1 to
8 carbon atoms, or phenyl. More preferably, R13 is hydrogen or methyl.
Further preferred embodiments may include any combination of the parameters
mentioned above.
Methods of Preparation
The method of preparing the novel triazines of the present invention can be
preformed by any suitable method as mentioned above. Preferably, the method of producing
the novel triazine compound is from the method described in WO 00/29392 herein
incorporated by reference in its entirety.
The term "Lewis acid" is intended to include aluminum halides, alkylaluminum halides,
boron halides, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium
halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides,
and the like. Preferred Lewis acids include aluminum trichloride, aluminum tribromide,
trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride,
tin dichloride, tin tetrachloride, or a mixture thereof.
As used herein the term "reaction promoter" is understood to comprise a compound,
which is used in combination with the Lewis acid to facilitate the reaction. Suitable reaction
promoters include acids, bases, water, alcohols, aliphatic halides, halide salts, acid halides,
halogens, alkenes, alkynes, ester, anhydride, carbonate, urethane, carbonyl, epoxy, ether,
acetal compounds, or mixtures thereof. For a more detailed list of reaction promoters, refer
to WO 00/29392.

The novel triazines of the present invention can be prepared through the modified
Friedel-Crafts reaction of a cyanuric halide with a phenyl ether in the presence of a reaction
promoter and a Lewis acid, (see Scheme 1), followed by or reacted concurrently with a
resorcinol-based phenolic compound.

wherein Z' is fluorine, bromine, chlorine, or iodine and the other substituents are defined
above.
The relative amounts of the reactants are as follows. The amount of phenyl ether
compound should be in sufficient amounts to react with the cyanuric halide to produce the
desired intermediate compound. If a mono-phenyl ether triazine compound is desired, then
about 1 molar equivalents should be reacted with the cyanuric halide. If a bis(phenyl ether)
triazine compound is desired, then about 2 molar equivalents of phenyl ether should be
reacted with the cyanuric halide. It should be noted that other embodiments of the present
invention are the mono-phenyl ether and bis(phenyl ether) triazine intermediate compounds.
The amount of Lewis acid, such as AICI3, used in the reaction should be in sufficient
amounts to transform the cyanuric halide to the desired intermediate and/or end product.
The amount of Lewis acid should be between about 0.5 to about 500 mol equivalents to the
cyanuric halide. Preferably, the amount of Lewis acid should be between about 1 to about 5

mol equivalents to the cyanuric halide or about 2 to about 4 mol equivalents to cyanuric
halide. The preferred Lewis acid is aluminum trichloride.
Advantageously, a reaction promoter can be used in conjunction with a Lewis acid
when synthesizing the desired compounds. Preferably, the amount of reaction promoter
should be between about 0.01 mol to about 5 mol equivalents, or about 0.1 mol to about 2
mol equivalents.
The reaction should run for a sufficient amount of time, at a sufficient temperature
and pressure to synthesize the desired triazine. The preferred reaction time for the synthesis
of the intermediate compound, i.e., the first step, is between about 5 minutes and about 48
hours, more preferred between about 15 minutes and about 24 hours. The preferred
reaction time for the synthesis of end product compound, i.e., the second step, is between
about 10 minutes and about 24 hours, more preferably time is between about 30 minutes and
about 12 hours. The preferred reaction temperature for the first step is between about -50°C
and about 150°C, more preferred reaction temperature between about-30°C and about
50°C. The reaction pressure is not critical and can be about 1 atmosphere or higher if
desired. Preferably, the reaction is carried out under an inert gas such as nitrogen or argon.
The preferred reaction temperature for the second step is between about 0°C and about
120°C, a more preferred reaction temperature is between about 20°C and about 100°C.
The step-wise process comprises mixing at least one Lewis acid, at least one reaction
promoter, cyanuric halide and phenyl ether, preferably until the reaction is between about
70% to about 100% completed. Thereafter, the product is isolated and purified. The
intermediate product is then added to the subsequent reactant along with Lewis acid and
optionally a reaction promoter to synthesize the desired end product. The step-wise
sequence allows for the isolation, purification, and storage of compounds of the intermediate
prior to subsequent reaction with phenol-based compounds, such as resorcinol.
The continuous reaction comprises allowing the cyanuric halide to react with one or
more phenyl ethers in the presence of at least one Lewis acid and at least one a reaction
promoter preferably until the reaction is between about 70% to about 100% complete.
Thereafter, without isolating the intermediate product, the resorcinol-based phenolic
compound is allowed to react with the intermediate product in the presence of optionally at
least one second Lewis acid and optionally at least one second reaction promoter preferably
until the reaction is between about 70% to about 100% complete. The continuous reaction
eliminates the need to purify the intermediate product or use of additional reagents such as
solvents, and optionally Lewis acids and acids. Moreover, the one-step process simplifies
the synthetic reaction pathway such that no unnecessary handling or processing of the
reaction mixture is required until the reaction is completed.

In an another process as disclosed in United States Patent No. 6,225,468 B1
cyanuric chloride can be simultaneously reacted with phenyl ether and resorcinol in the
presence of Lewis acid, such as aluminum chloride, to obtain the desired product.
Uses of the triazines
As indicated earlier, the novel triazines of the present invention are particularly
useful as ultraviolet light absorber agents for stabilizing a wide variety of materials including,
for example, various polymers (both cross-linked and thermoplastic), photographic materials
and dye solutions for textile materials, as well as in ultraviolet light screening agents (such as
sunscreens). The novel triazines of the present invention can be incorporated into such
material in any one of a variety of conventional manners, including for example, physical
mixing or blending, optionally, with chemical bonding to the material (typically to a polymer),
as a component in a light stabilizing composition such as a coating or solution, or as a
component in a UV screening composition such as a sunscreen composition.
In one embodiment of the present invention, the triazines of the present
invention can be employed to stabilize materials which are subject to degradation by
ultraviolet radiation by incorporating the presently claimed compounds into a composition
comprising polymeric materials, either chemically or physically. Non-limiting examples of
polymeric materials that may be so stabilized are polyolefins, polyesters, polyethers,
polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes,
high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles,
polybutadienes, polystyrenes, ABS, SAN (styrene acrylonitrile), ASA (acrylate styrene
acrylonitrile), cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides,
polyetherimides, polyphenylsulfides, PPO, polysulfones, polyethersulfones,
polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic TPO's,
aminoresin cross-linked polyacrylates and polyesters, polyisocyanate cross-linked polyesters
and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde
resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins
cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and
epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic
and aromatic glycidyl compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated
and methylene compounds, ketimines with activated unsaturated and methylene compounds,
polyketimines in combination with unsaturated acrylic polyacetoacetate resins, polyketimines
in combination with unsaturated acrylic resins, radiation curable compositions,

epoxymelamine resins, organic dyes, cosmetic products, cellulose-based paper formulations,
photographic film paper, ink, and blends thereof.
The preferred polymeric material is selected from the group consisting of polyolefms;
copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with
other vinyl monomers; hydrocarbon resins (such as C5—C9) including hydrogenated
modifications thereof and mixtures of polyalkylenes and starch; polyesters; copolyethers
esters; polyethers; polyketones; polyamides and copolyamides derived from diamines,
dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams; natural and
synthetic rubbers and elastomers; polyurethanes; polystyrenes, poly--methylstyrenes and
copolymers with other vinyl monomers; graft copolymers of styrene; high impact polystyrenes;
polyacrylic acids, polymethacrylics acids, polyacrylates, polymethacrylates, polyacrylamides,
polyacrylonitriles; homo- and copolymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof such as polyvinyl alcohol, polyvinyl acetate,
polyacetals, and polybutyrals; homo- and copolymers of cyclic ethers such as alkylene
glycols and alkylene oxides, as well as copolymers with bisglycidyl ethers; polybutadienes;
polystyrenes; ABS (acrylonitrile butadiene styrene); SAN (styrene acrylonitrile); ASA (acrylate
styrene acrylonitrile); cellulosic acetate butyrate; cellulosic polymers; polyureas; polyimides;
polyamides-imides; polyester-imides; polyether-imides; polyhydantoins; polybenzimidazoles;
polyphenylsulfide; PPO (polypropylene oxide); polysuifones; polyether sulfones; polyether
ketones; halogen-containing polymers; polyvinylchlorides; polycarbonates; polyester
carbonates; thermoplastic TPO's; amino resin cross-linked polyacrylates and polyesters;
polyisocyante cross-linked polyesters and polyacrylates; phenol/formaldehyde,
urea/formaldehyde and melamine/formaldehyde resins; saturated and unsaturated polyester
resins; cross-linkable acrylic resins derived from substituted acrylates such as epoxy
acrylates, hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester acrylates;
alkyd resins, polyester resins, and acrylate resins cross-linked with melamine resins, urea
resins, isocyanates, isocyanurates, carbamates, or epoxy resins; cross-linked epoxy resins
derived from aliphatic cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds which
are cross-linked with anhydrides or amines; polysiloxanes; Michael addition polymers of
amines or blocked amines (e.g., ketimines) with activated unsaturated and/or methylene
compounds; of ketimines with activated unsaturated and/or methylene compounds such as
acrylates and methacrylates, maleates, and acetoacetates; polyketimines in combination with
unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins; radiation
curable compositions; epoxymelamine resins; natural polymers such as cellulose, rubber,
gelatin, and chemically modified derivatives thereof; organic dyes and pigments; any mixture

or blends of the above; cosmetic products; celluiose-based paper formulations; photographic
film; paper; ink; and intraocular lenses.
Depending upon their ultimate end use, the triazines of the present invention may be
combined with a variety of additives conventionally employed in the UV stabilizing art such as
anti-oxidants, UV absorbers and stabilizers, metal deactivators, phosphites and
phosphonites, hydroxylamines, nitrones, thiosynergists, co-stabilizers, nucleating agents,
fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological
additives, catalysts, level agents, optical brighteners, flameproofing agents, anti-static agents
and blowing agents. Examples of these additives may be found, for example, in U.S. patent
No. 6,096,886, herein incorporated by reference in its entirety. Further examples are those
described in many of the previously incorporated references as well as Ullmann's
Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim
1991; and Calbo, Leonard J., ed., Handbook of Coatings Additives, New York:Marcel Dekker
(1987).
Especially preferred are other UV stabilizers and anti-oxidants including, but not
limited to 2-(2'-hydroxyphenyl)benzotriazoles, oxamides, 2-(2-hydroxphenyl)-1,3,5-triazines,
2-hydroxybenzophenones, sterically hindered amines and hindered phenol antioxidants.
Examples of such anti-oxidants and UV stabilizers are: 2-(2'-hydroxy-5'-
methylpheny!)-benzotriazoie; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(5'-tert-
butyl-2'-hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-
chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole; 2-(3'-
sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-4'-
octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole; 2-(3',5'-
bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole; a mixture of 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chIoro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyIoxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-
methylphenyl)benzotriazole and 2-(3'-tert-buty!-2'-hydroxy-5'-(2-
isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-
6-benzotriazol-2-ylphenoI], the transesterification product of 2-[3'-tert-butyl-5'-(2-
methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R—
CH2CH—COO(CH2)3]2 B where R = 3'-tert-buty|-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;

bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4-
yl)succinate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(1-octyloxy-2,2,6,6-
tetramethylpiperidin-4-yl)sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-
butyI-4-hydroxybenzyimaionate; the condensate of 1-(2-hydroxyethy!)-2,2,6,6-tetramethy!-4-
hydroxypiperidine and succinic acid; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-
4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6,6-
tetramethyipiperidin-4-yi) nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-
butanetetracarboxylate; 1,1 '-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-
2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-
pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)maionate; 3-n-octyl-
7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione; bis(1 -octyloxy-2,2,6,6-
tetramethylpiperidyl)sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-
morpholino-2,6-dichloro-1,3l5-triazine; the condensate of 2-chloro-4,6-bis(4-n-butylamino-
2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; the
condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethyipiperidyt)-1,3,5-triazine
and 1,2-bis-(3- aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-
triazaspiro[4.5]decane-2,4-dione; 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-
dione; 3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrroiidin-2,5-dione; 3-
dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; a mixture of 4-
hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate of N,N'-
bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyciohexyiamino-2,6-
dichloro-1,3,5-triazine; the condensate of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-
1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-
1-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperanziny!-triazines and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and
epichlorohydrin;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-
bis(2,4-dimethy!phenyl)-1,3,5-triazine;2-(2-hydroxy-4-(mixed iso-octyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-
hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-
dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-
tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-
butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-[2-hydroxy-4-(2-
hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyi)-1,3,5-triazine; 2-[4-

dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine; 2-
(2-hydroxy-4-methoxyphenyl)-4,6-diphenyI-1,3,5-triazine;2,4,6-tris[2-hydroxy-4-(3-butoxy-2-
hydroxypropoxy)phenyl]-1,3,5-triazine;2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-
1,3,5-triazine, 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-
4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone; 2-hydroxy-4-
dodecyloxybenzophenone; 2-hydroxy-4-benzyloxybenzophenone, 4,2',4-
trishydroxybenzophenone; 2'-hydroxy-4,4'-dimethoxybenzophenone;
1,3,5-tris( 2,6-dimethyl-4-tert-butyl-3hydroxybenzyl)isocyanurate; 1,3,5-tris(3,5-di-tert-buty)-4-
hydroxybenzy!)isocyanurate; 1,3,5- tris(3,5- di-tert-butyl-4-hydroxybenzyl) -2,4,6-
trimethylbenzene; 2,6-di-tert-butyl-4-methy]phenol; 2,2,-ethylidene-bis(4,6-di-tert-butylphenol);
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of 0>-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionic acid with mono- or polyhydric alcohols;
esters of -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric
alcohols; dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; diethyl-3,5-di-tert-butyl-4-
hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and the calcium salt of the
monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid; amides of fi-(3,5-di-tert-
butyl-4-hydroxyphenyl)propionic acid such as N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)trimethylenediamine; and N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hydrazine.
The weight ratio of the triazine compounds of the present invention to the other
additives, such as the preferred additives may be, for example from about 500:1 to about
1:500, or about 100:1 to about 1:100, or about 10:1 to about 1:10. The novel triazines of the
present invention can also be employed in multilayer systems. In such systems, a polymer
composition having from about 0.1 to about 20% by weight and preferably a relatively high
content of novel triazine stabilizer, for example, about 5-15% by weight, is applied in a thin
film (e.g., about 5 - 500 m thick and, preferably, about 10 -100 m thick) to a shaped article
made from a polymer containing little or no ultraviolet stabilizers. Such composition may be
applied at the same time as the shaping of the base structure, for example by co-extrus,on in
a manner analogous to that described in U. S. Patent No. 4,948,666 (incorporated by
reference herein for all purposes as if fully set forth). Alternatively, application can also be
made to the ready-formed base structure, for example by lamination with a film or by coating
with a solution. The outer layer or layers of the finished article have the function of a UV

filter, which protects the interior of the article from UV light. The outer layer preferably
contains about 0.1 to about 20%, preferably about 1 to about 15%, and most preferably about
2 to about 10% by weight of the outer layer composition, of at least one of the triazine
compounds of the present invention.
The polymers stabilized in this way are notable for high weathering resistance,
especially for high resistance to UV light. This enables them to retain their mechanical
properties, and their color surface properties such as gloss and distinctness of image, for a
long time even when used outside. Moreover, due to the bondable nature of the presently
claimed triazine compounds, migration of these UV absorbers between the layers of the
multi-layer coatings can, under the appropriate circumstances, be minimized.
In another embodiment of the present invention, the novel triazine compounds can be
used as stabilizers for coatings, for example for paints such as disclosed in numerous
references (see, e.g., U. S. Patent Nos. 4,619,956; 4,740,542; 4,826,978; 4,962,142;
5,106,891; 5,198,498; 5,298,067; 5,322,868; 5,354,794; 5,369,140; 5,420,204; 5,461,151;
5,476,937; EP-0434608 and EP-A-0444323). Of particular interest are coatings and paints
for the automobile industry. The invention therefore also relates to those compositions which
are film-forming binders for coatings.
Such novel coating compositions comprise about 0.01 to about 20%, preferably about
0.01 to about 10%, and more preferably about 0.02 to about 5% by weight of the binder of
the coating composition of the presently claimed triazines of the present invention.
To achieve maximum light stability, it is of particular interest to add sterically hindered
amines, examples of which are set out in the above-mentioned section b(vi). The invention
therefore also relates to a coating composition which, in addition to the binder, the novel
triazines and, optionally, additional UV absorbers, comprises a light stabilizer of the sterically
hindered amine type. The sterically hindered amine is employed in an amount of about 0.01
to 5% by weight based on the weight of the solid binder, preferably about 0.02 to 2% by
weight.
One specific example of such a sterically hindered amine is a 2,2,6,6-tetramethyi
piperazinone containing at least one group of the formula:

in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy (such as
methoxy) or acyl.


More preferably the stabilizer is a 2,2,6,6-tetraalkylpiperidine derivative containing at
least one group of the formula:
in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy (such as
methoxy) or acyl.
Examples of tetraalkylpiperidine derivatives which can be used in combination with
the present trisaryl-1,3,5-triazine compounds are given in U. S. Patent Nos. 4,314,933;
4,344,876; 4,426,471; 4,426,472; 4,619,956; 5,004,770; 5,006,577; 5,064,883; 5,112,890;
5,124,378; 5,106,891; 5,204,473 and 5,461,151, which are incorporated by reference herein
for all purposes as if fully set forth. It is particularly expedient to employ the following
tetraalkylpiperidine derivatives, as well as their N-alkyl, N-acyl, N-hydroxyl and N-alkoxy
analogs (where not already included in the following list):
bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,
di(1,2,2,6,6-pentamethylpiperid-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis(1-
octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, tetra(2,2,6,6-tetramethylpiperid-4-yl)
butane-1,2,3,4-tetracarboxylate, tetra(1,2,2,6,6-pentamethylpiperid-4-yl) butane-1,2,3,4-
tetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,
and 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione.
Commercially available examples of these and other tetraalkylpipieridine derivatives include
SANDUVOR® 3050, 3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.); TINUVIN®
079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals); CHIMASORB® 119 and
944 (Ciba Specialty Chemicals); and CYASORB® UV-3346, UV 3529, UV-3853, UV-500 and
UV-516 (Cytec Industries Inc.).
The novel coating compositions according to the invention can be applied to any
desired substrates, for example to metal, wood, plastic, fiberglass or ceramic materials. The
coating compositions can be pigmented mono-coats or multi-layer
(primer/basecoat/clearcoat) systems typical of automotive finishes. In the latter case, the
novel coating composition can be used for either the base coat, or clear coat, or for both
layers. If the topcoat of an automotive finish comprises two layers, of which the lower layer is
pigmented and the upper layer is not pigmented, the novel coating composition can be used

for either the upper or the lower layer or for both layers, but preferably for the upper topcoat
layer.
For more detailed examples of these and other uses for UV stabilizers, such
as the triazines of the present invention, see U.S. Serial No. 09/335,886, filed on June 18,
1999, (WO 99/67226, pages 33 to 81), herein incorporated by reference.
The invention will now be illustrated by the following examples. The examples are not
intended to be limiting of the scope of the present invention. In conjunction with the general
and detailed descriptions above, the examples provide further understanding of the present
invention.
EXAMPLES
Examples and reaction schemes for producing specific examples of phenyl ether
substituted triazines in accordance with the invention are provided below. While the following
examples illustrate preparations with one or more phenyl ethers, one of ordinary skill will
understand that these reactions may also be carried out with any of a variety of other
substituted phenyl ethers.
PREPARATIVE EXAMPLES
Example 1: Reaction of cyanuric chloride with phenyl ether: Preparation of 2-chloro-4,6-
bis(4-phenoxyphenyl)-1,3,5-triazine

To a stirring mixture of 18.4 gm of cyanuric chloride, 40 gm of aluminum chloride in 250
ml of chlorobenzene cooled in an ice-bath was added 2 ml of cone. HCI. To it was then
added 32.3 gm of phenyl ether and the reaction mixture stirred around 0°C for 6 hr. It was
then stirred at room temperature for 18 hr and then quenched with water. The mixture was
extracted with methylene chloride, and the organic layer washed with water, and concentrated

chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine.
Almost pure 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine was isolated by
column chromatography which was further reacted with resorcinol as discussed in Example 2.
Example 2: Reaction of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine with resorcinol:
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine

A mixture of 5.9 gm of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 2.6 gm
aluminum chloride and 1.6 gm of resorcinol in 25 ml chlorobenzene was heated under nitrogen
at 85°C for 3 hr. An additional 0.17 gm resorcinol was added, and the heating continued for
another 1 hr. The reaction mixture was cooled to room temperature, and quenched with water.
The precipitated product was filtered, washed with water, and dried to give 5.1 gm of crude 2-
(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine.
Example 3: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-
triazine
To a stirring mixture of 3.7g of cyanuric chloride, 8 gm of aluminum chloride in 50 ml of
chlorobenzene cooled in an ice-bath was added 0.4 ml of cone. HCI. To it was then added 6
ml of phenyl ether, and the reaction mixture stirred around 00C for 1 hr. The cooling bath was
then removed, and the mixture stirred at room temperature for about 20 hr. At this stage, 2.42
gm of resorcinol was added to the reaction flask, and the contents heated to 80°C for 3 hr.
The heating was discontinued, and the mixture cooled to room temperature. To it was then
added 150 ml of cold HCI. The resulting mixture was concentrated under reduced pressure to
dryness. The residue was then stirred with 200 ml water for 4 hr at room temperature, the
precipitated material filtered, washed with additional water, and dried to give 8.2 gm of crude
2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine.

Example 4: Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with n-butyl iodide: Preparation of 2-(2-hydroxy-4-butoxyphenyl)-4,6-bis(4-
phenoxyphenyl)-1,3,5-triazine

A mixture of 4.5 gm 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine,
2.02 gm 1-iodobutane, 4.83 gm anhydrous potassium carbonate, 0.25 gm Aliquat 336 and 50
ml acetone was heated to reflux for 7 hr. The reaction mixture was cooled to room
temperature, diluted with water and extracted with methylene chloride. The organic layer was
washed with water, and concentrated under reduced pressure. The residue thus obtained
was analyzed by HPLC and mass spectroscopy to contain the desired 2-(2-hydroxy-4-
butyloxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine.
Example 5: Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with n-octyl iodide: Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-
phenoxyphenyl)-1,3,5-triazine

A mixture of 5 gm 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 2.5
gm 1-iodooctane, 6.6 gm anhydrous potassium carbonate, 0.5 gm Aliquat 336 and 25 ml MIBK
was heated to reflux for 3 hr. The reaction mixture was cooled to room temperature, diluted

with methylene chloride, filtered through Celite. The filtrate was concentrated under reduced
pressure. The residue thus obtained was passed through a silica gel column. The material
thus obtained was crystallized with acetone to give 3.5 gm of pure 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine.

Example 6: Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with ethyl chloroacetate

To a stirring mixture of 4.5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine, 4.83 gm of potassium carbonate, 0.25 gm of Aliquat 336 and 50 ml acetone was
added 1.35 gm of ethyl chloroacetate. The reaction mixture was heated to reflux under
nitrogen for 7 hr. It was cooled to room temperature, diluted with water, and extracted with
methylene chloride. The methylene chloride extract was washed with water, dried, and
concentrated under reduced pressure to give 3 gm of crude derivative analyzed based on
HPLC and mass spectroscopy.

Example 7:Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with 2,4-dimethyl-3-chloromethyl-6-terf.butylphenol

To a stirring mixture of 5.3 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine, 4.1 gm of potassium carbonate, 0.25 gm of Aliquat 336 and 25 ml MIBK was
added 2.3 gm of 2,4-dimethyl-3-chloromethyl-6-tert.butylphenol. The reaction mixture was
heated to reflux under nitrogen for 2 hr. It was cooled to room temperature, diluted with water,
and extracted with methylene chloride. The methylene chloride extract was washed with
water, dried, and concentrated under reduced pressure to give 4.5 gm of a crude product
analyzed based on HPLC and mass spectroscopy to contain the desired product.
Example 8: Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with benzoyl chloride

To a stirring mixture of 4.5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine, 4.83 gm of potassium carbonate, 0.5 gm of Aliquat 336 and 50 ml acetone was
added 1.41 gm of benzoyl chloride. The reaction mixture was heated to reflux under nitrogen

for 6 hr. It was cooled to room temperature, diluted with water, and extracted with methylene
chloride. The methylene chloride extract was washed with water, dried, and concentrated
under reduced pressure to give 1.8 gm of crude benzoate derivative, analyzed based on
HPLC and mass spectroscopy.
Example 9: Reaction of 2-(2,4-dihydroxyphenyI)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with benzenesulfonyl chloride

To a stirring mixture of 4.5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine, 4.8 gm of potassium carbonate, 0.5 gm of Aliquat 336 and 50 ml acetone was
added 1.8 gm of benzenesulfonyl chloride. The reaction mixture was heated to reflux under
nitrogen for 6 hr. It was cooled to room temperature, diluted with water, and extracted with
methylene chloride. The methylene chloride extract was washed with water, dried, and
concentrated under reduced pressure to give 3.4 gm of crude sulfonate derivative analyzed
based on HPLC and mass spectroscopy.
Example 10: Reaction of 2-chloro-4,6-bis{4-phenoxyphenyl)-1,3,5-triazine with
resorcinol: Preparation of 2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(4-phenoxyphenyl)-

1,3,5-triazine


A mixture of 0.9gm of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 0.24gm of m-
cresol and 0.4gm AICI3 in 5 ml chlorobenzene was heated to 70°C under nitrogen and efficient
stirring. After about 4 hr at 70°C, the reaction mixture was analyzed by HPLC, which showed
the formation of a new product, and almost disappearance of the starting triazine. The
reaction mixture was cooled to room temperature and quenched with water. It was then
extracted with methylene chloride, and the organic layer separated, washed with water, dried,
and concentrated to give a crude product. The crude product was crystallized from acetone to
give almost pure 2-(2-hydroxy-4-methylphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
identified by HPLC, NMR and mass spectroscopy.
Example 11: Reaction of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine with 3,4-
diemthylphenol: Preparation of 2-(2-hydroxy-4,5-dimethylphenyl)-4,6-bis(4-
phenoxyphenyl)-1,3,5-triazine

A mixture of 0.9gm of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 0.27gm of 3,4-
dimethylphenol and 0.4gm AICI3 in 5 ml chlorobenzene was heated to 70°C under nitrogen
and efficient stirring. After 8 hr at 70°C, the reaction mixture was cooled to room temperature
and quenched with water. The crude product obtained after distilling off chlorobenzene was
shown to contain the product 2-(2-hydroxy-4,5-dimethylphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine based on HPLC and Mass spectroscopy.

Example 12: Reaction of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine 4-
hexylresorcinol: Preparation of 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-
phenoxyphenyl)-1,3,5-triazine

A mixture of 0.9 gm of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 0.39 gm of 4-
hexylresorcinol and 0.2 gm AICI3 in 5 ml chlorobenzene was heated to 95°C under nitrogen
and efficient stirring. After about 7 hr at 95X, the reaction mixture was analyzed by HPLC,
which showed the formation of a new product, and almost disappearance of the starting
triazine. The reaction mixture was cooled to room temperature and quenched with water. It
was then extracted with methylene chloride, and the organic layer separated, washed with
water, dried, and concentrated to give a crude product. The crude product was analyzed to
contain 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine identified by
HPLC, NMR and mass spectroscopy.
Example 13: Reaction of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine with m-cresol:
Preparation of 2-(2-hydroxy-4-methylphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine


A mixture of 0.9gm of 2-chloro-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine, 0.24gm of m-
cresol and 0.4gm AICI3 in 5 ml chlorobenzene was heated to 70°C under nitrogen and efficient
stirring. After about 4 hr at 70°C, the reaction mixture was analyzed by HPLC, which showed
the formation of a new product, and almost disappearance of the starting triazine. The
reaction mixture was cooled to room temperature and quenched with water. It was then
extracted with methylene chloride, and the organic layer separated, washed with water, dried,
and concentrated to give a crude product. The crude product was crystallized from acetone to
give pure 2-(2-hydroxy-4-methylphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine identified by
HPLC, NMR and mass spectroscopy.
Example 14: Reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine
with 1,8-diiodooctane: Preparation of a triazine dimer


To a stirring mixture of 5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-phenoxyphenyl)-
1,3,5-triazine, 10 gm of potassium carbonate and 0.5 gm of Aliquat 336 in 25 ml of MIBK was
added 1,8-diiodooctane. The reaction mixture was heated to reflux for 10 hr. The reaction
mixture was then cooled to room temperature, diluted with methylene chloride, and filtered
through Celite. The filtrate was concentrated to give the crude product containing the desired
dimer product identified based on HPLC and mass spectroscopy.
Example 15: Preparation of 2,4-bis(2,4-dihydroxyphenyl)-6-(4-phenoxyphenyl)-1,3,5-
triazine
To a stirring mixture of 9 gm of cyanuric chloride, 20 gm of aluminum chloride in 50
mL of o-dichlorobenzene was added 8.5 gm of phenyl ether followed by 11 gm of resorcinol.
The reaction mixture was first stirred at room temperature and then gradually heated to 110-
115°C, and then held for 4 hr at this temperature. The heating was discontinued, and the
reaction mixture quenched with water. O-Dichlorobenzene was removed azeotropically from
the product mixture, the precipitated material filtered, and washed with water. The crude
product was purified by column chromatography to give 2.3 gm of pure 2,4-bis(2,4-
dihydroxyphenyl)-6-(4-phenoxyphenyl)-1,3,5-triazine, identified by HPLC, NMR, LC-UV and
mass spectroscopy.

Example 16: Reaction of 2,4-bis(2,4-dihydroxyphenyl)-6-(4-phenoxyphenyl)-1,3,5-
triazine with n-octyl iodide: Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4-(2,4-
dihydroxyphenyl)-6- (4-phenoxyphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-4-
octyloxyphenyl)-6- (4-phenoxyphenyl)-1,3,5-triazine

A mixture of 1 gm 2,4-bis(2,4-dihydroxyphenyl)-6-(4-phenoxyphenyl)-1,3,5-triazine,
0.36 gm 1-iodooctane, 1.4 gm anhydrous potassium carbonate, 0.2 gm Aliquat 336 and 10
mL MIBK was heated to reflux for 8 hr. The reaction mixture was cooled to room
temperature, diluted with methylene chloride, and filtered through Celite. The filtrate was
concentrated under reduced pressure. The residue thus obtained was analyzed by HPLC,
LCUV and LCMS to contain a mixture of 2-(2-hydroxy-4-octyloxyphenyl)-4-(2,4-
dihydroxyphenyl)-6- (4-phenoxyphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-4-

octyloxyphenyl)-6- (4-phenoxyphenyl)-1,3,5-triazine and some unreacted 2,4-bis(2,4-
dihydroxyphenyl)-6-(4-phenoxyphenyl)-1,3,5-triazine.
PERFORMANCE OF THE TRIAZINE LIGHT STABILIZER OF THE
INVENTION COMPARED TO CONVENTIONAL TRIAZINE LIGHT STABILIZERS
Examples 17 to 19: Preparation of performance samples containing 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine (Compound A) and other
commercial UV absorbers in Polycarbonate Plaques.
Compound A, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-phenoxyphenyl)-1,3,5-triazine,
at a loading level of 0.35% by weight and 0.05% phosphite (Ultranox 641, commercially
available from General Electric Specialty Chemicals of Morgantown, WV) was dry blended
into a Lexan101-1111 polycarbonate pellets (containing 0.5% phosphite) or Lexan 100 virgin
polycarbonate flakes (both commercially available from General Electric Specialty Chemicals
of Morgantown, WV). The blended material was melt mixed and then extruded in a
Brabender PL-2000 torque rheometer (commercially available from Pasedena Hydraulics of
The City of Industry, CA) equipped with a single mixing screw extruder at 300°C. The
extrudate was cooled dried and pellitized. The pellets were injection molded into sample
plaques (2 inches x 2.5 inches x 125 mils) using an Arburg Allrounder 320-210-750 injection
molding machine (commercially available from Arbury GmbH & Co. of Lossburg, Germany) at
300°C. Plaques with a commercially available triazine light stabilizer, TINUVIN® 1577, a
product of Ciba Specialty Chemicals, [2-(2-hydroxy-4-hexyloxyphenyl)-4,6-bis(phenyl)-1,3,5-
triazine] and control plaques without any UV absorber were prepared in an identical manner.
Examples 20 to 22: Effects of Weathering on UV Stabilized Plaques
Sample plaques were subjected to xenon-arc accelerated weathering. Xenon-arc
accelerated weathering was carried out by exposing the sample plaques in a xenon-arc
weatherometer as determined by the ASTM G-155 Standard using Test Method B.
Discoloration as measured by yellowing index (Yl) as a function of weathering time. Color
development was determined with a Macbeth Color Eye Colorimeter under laboratory
conditions with illuminate C, 2° observer, specular component excluded, and UV component
included.
Table 1 below shows the effect of xenon-arc accelerated weathering, as measured by
Yl (yellow index) values, for polycarbonate plaques containing 0.35% by weight of Compound
A, TINUVIN1577 (Tin-1577), and blank polycarbonate plaques for control. An increase in Yl
indicates an unfavorable discoloration of the polycarbonate.

Table 1: Xenon-Arc Accelerated Weathering Of A Polycarbonate UV Stabilized Plague

The results in Table 1 show that the initial Yl for compound A compared to the
commercially available product is significantly better resulting in less initial discoloration of
the polycarbonate plaques. The results also demonstrate that the polycarbonate plaque
stabilized with Compound A showed equal or improved performance compared to the
polycarbonate plaques containing TINUVIN 1577 and no stabilizer when the plaques were
subjected to xenon-arc accelerated weathering.
Examples 23 to 24: Effect on Severe Molding Conditions on UV Stabilizer
Polycarbonate Plaques
Table 2 shows the effect on Yl values of exposing the polycarbonate pellets to severe
conditions during the injection molding process used to manufacture the plaques. The
plaques contained 0.35% by weight of the UV stabilizers compounds and 0.05% of a
phosphite. As noted above, plaques are typically processed with temperatures up to 300°C.
Under the severe conditions the plaques are processed at a temperature of 340°C with the
compound filling the length of the injection molder barrel for either 40 seconds (refer to as
severe 40 seconds) or for 5 minutes (refer to as severe 5 minutes).
Table 2: Effect of Severe Injection Molding Conditions on Yl Values


The results in Table 2 demonstrate that the stability of polycarbonate plaques
containing Compound A was marginally superior to the stability of polycarbonate plaques
containing 0.35% of TINUVIN 1577 as measured by Yl values, when the plaques were
subjected to severe processing conditions.
Overall the results show that Compound A is effective at stabilizing polymeric
compounds, such as polycarbonates, against discoloration. Moreover, the results
demonstrate that Compound A is superior to a similar commercially available conventional
triazine light stabilizer in initial discoloration, and equal or marginally better when subject to
accelerated weathering and severe molding conditions.
The invention described and claimed herein is not to be limited in scope by the
specific embodiments herein disclosed, since these embodiments are intended as
illustrations of several aspects of the invention. Any equivalent embodiments are intended to
be within the scope of this invention. Indeed, various modifications of the invention in
addition to those shown and described herein will become apparent to those skilled in the art
from the foregoing description. Such modifications are also intended to fall within the scope
of the appended claims.

WE CLAIM:
1. A compound of Formula I

wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon
atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
aracyl of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR,
SO2 R, SO3H, SO3M, wherein M is an alkali metal, R and R' are the
same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms,
haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,

cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,
and optionally with either of R1 and R2, R3 and R4, or R4 and R5, taken
together being a part of a saturated or unsaturated fused carbocyclic
ring optionally containing O, N, or S atoms in the ring;
each of T and T is independently a direct bond, oxygen, NR, sulfur or
a functional group containing these elements; X is independently
selected from hydrogen and a blocking group selected from one or
more of the following groups: allyl,-CORa, -SO2Rb, -SiRcRdRe, -PRf Rg, -
PORfRg and -CONHRh,
wherein
each Ra is independently selected from C1-C8 alkyl, halogen-
substituted C1-C8 alkyl, C5 -C12 cycloalkyl, C2-C8 alkenyl, -CH2 -CO-
CH3, C1-C12 alkoxy, and phenyl or phenoxy which is unsubstituted or
substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1-C12 alkyl, C1-C10 aryl and
C7-C18 alkylaryl;
each Rc, Rd and Re is independently selected from C1-C18 alkyl,
cyclohexyl, phenyl and C1-C18 alkoxy;
each Rf and Rg is independently selected from C1-C12 alkoxy, C1-C12
alkyl, C5-C12 cycloalkyl, and phenyl or phenoxy which is
unsubstituted or substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen
and/or benzyl;

and
each Rh is independently selected from C1-C8 alkyl, C5-C12 cycloalkyl,
C2-C8 alkenyl, -CH2 -CO-CH3, and phenyl which is unsubstituted or
substituted by C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen
and/or benzyl;
each of Y, R6 and R7 are each independently hydrogen, hydrocarbyl
group, a functional hydrocarbyl group, halogen, hydroxy 1, cyano, -
O(hydrocarbyl), -0(functional hydrocarbyl), -N(hydrocarbyl)2,
N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional hydrocarbyl), -
S(hydrocarbyl), -S(functional hydrocarbyl), -SO2 (hydrocarbyl),-SO2
(functional hydrocarbyl), -SO3 (hydrocarbyl), -SO3 (functional
hydrocarbyl), -CO2 (hydrocarbyl), -CO2 (functional hydrocarbyl), -
CO (hydrocarbyl), -CO (functional hydrocarbyl), -OCO(hydrocarbyl), -
OCO (functional hydrocarbyl), -CONH2, -CONH(hydrocarbyl), -
CONH(functional hydrocarby 1), -CON(hydrocarbyl)2,
CON(hydrocarbyl)(functional hydrocarbyl), -CON(functional
hydrocarbyl)2, wherein the hydrocarbyl or functional hydrocarbyl may
be the same or different and has 1 to 24 carbon atoms;
Z is Y,


and wherein L is selected from the group consisting of: hydrogen; an
alkyl of 1 to 24 carbon atoms optionally substituted by one or more
hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamate, or
epoxy groups, and which may contain one or more carbonyl groups,
oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24
carbon atoms optionally substituted by one or more hydroxy, alkoxy,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms
optionally substituted by one or more hydroxy, alkoxy, chloro, cyano,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain.
2, A compound as claimed in claim 1 wherein T' is an oxygen atom.

3. A compound as claimed in claim 1 wherein TZ is

R6 and R7 are independently hydrogen, hydrocarbyl, functional
hydrocarbyl, halogen, hydroxyl, -0(hydrocarbyl),-0(functional
hydrocarbyl), -S(hydrocarbyl), -SO2 (hydrocarbyl), -SO3 (hydrocarbyl),
-COO(hydrocarbyl), -CO(hydrocarbyl), -OCO(hydrocarbyl),
N(hydrocarbyl) (hydrocarbyl), -S(functional hydrocarbyl), -SO2
(functional hydrocarbyl), -SO3 (functional hydrocarbyl),
COO(functional hydrocarbyl), -CO(functional hydrocarbyl),
OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional
hydrocarbyl) or cyano.
4. A compound as claimed in claim 2 wherein R1 to R7 and X are
hydrogen, and TZ is

5. A compound as claimed in claim 1 wherein TZ is:


6. A compound as claimed in claim 5 wherein T is oxygen.
7. A compound as claimed in claim 6 wherein R1 to R7 and X are
hydrogen.
8. A compound of Formula VI:


wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl, of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon
atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
aracyl of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR,
SO2 R, SO3 H, SO3 M, wherein M is an alkali metal, R and R' are the
same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms,
haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms,
and optionally with either of R1, and R2, R3 and R4, or R4 and R5,

taken together being a part of a saturated or unsaturated fused
carbocyclic ring optionally containing O, N, or S atoms in the ring;
T is a direct bond, oxygen, NR, sulfur or a functional group containing
these elements;
X is independently selected from hydrogen and a blocking group
selected from one or more of the following groups: allyl, -CORa, -SO2
Rb, -SiRc Rd Re, -PRf Rg, -PORf Rg and -CONHRh,
wherein
each Ra is independently selected from C1-C8 alkyl, halogen-
substituted C1-C8 alkyl, C5-C12 cycloalkyl, C2-C8 alkenyl, -CH2 -CO-
CH3, C1-C12 alkoxy, and phenyl or phenoxy which is unsubstituted or
substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1-C12 alkyl, C6-C10 aryl and
C7-C18 alkylaryl;
each Rc, Rd and Re is independently selected from C1-C18 alkyl,
cyclohexyl, phenyl and C1-C18 alkoxy;
each Rf and Rg is independently selected from C1-C12 alkoxy, C1-C12
alkyl, C1-C12 cycloalkyl, and phenyl or phenoxy which is
unsubstituted or substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen
and/or benzyl;
and
each Rh is independently selected from C1-C8 alkyl, C5-C12 cycloalkyl,
C2-C8 alkenyl, -CH2 -CO-CH3, and phenyl which is unsubstituted or

substituted by C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen
and/or benzyl; each of Y, R6 and R7 are each independently hydrogen,
hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl,
cyano, -O(hydrocarbyl), -0(functional hydrocarbyl), -N (hydrocarbyl) 2, -
N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional hydrocarbyl), -
S(hydrocarbyl),-S(functional hydrocarbyl),-SO2 (hydrocarbyl), -SO2
(functional hydrocarbyl), -SO3 (hydrocarbyl), -SO2 (functional
hydrocarbyl), -CO2 (hydrocarbyl), -CO2 (functional hydrocarbyl), -
CO (hydrocarbyl), -CO(functional hydrocarbyl), -OCO (hydrocarbyl), -
OCO (functional hydrocarbyl), -CONH2, -CONH(hydrocarbyl),-
CONH(functional hydrocarbyl), -CON(hydrocarbyl)2,
CON(hydrocarbyl) (functional hydrocarbyl), -CON (functional
hydrocarbyl)2, wherein the hydrocarbyl or functional hydrocarbyl may
be the same or different and has 1 to 24 carbon atoms;
Z is Y,


and wherein L is selected from the group consisting of: hydrogen; an
alkyl of 1 to 24 carbon atoms optionally substituted by one or more
hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamate, or
epoxy groups, and which may contain one or more carbonyl groups,
oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24
carbon atoms optionally substituted by one or more hydroxy, alkoxy,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms
optionally substituted by one or more hydroxy, alkoxy, chloro, cyano,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
and r is an integer between 2 and 4;
when r is 2, D is selected from the group consisting of C2-C16 alkyl,
C4-C12 alkenyl, xylylene, C3-C20 alkyl which is interrupted by one or
more oxygen atoms, hydroxy-substituted C3-C20 alkyl which is
interrupted by one or more oxygen atoms, -CH2 CH(OH)CH2 O-R15 -
OCH2 CH(OH)CH2, -CO-R16 -CO-, -CO-NH-R17 -NH-CO-, -(CH2)s -
COO-R18 -OCO-(CH2)s-

a polyoxyalkylene bridge member of the Formula XX
-CH2-CH(OH)-CH2-O-(CH2-(CH2)u-O-)mm-
CH2CH(OH)-CH2- (XX),
a polyoxyalkylene bridge member of the Formula XXI
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO- (XXI),
a polyoxyalkylene bridge member of the Formula XXII
-YY-O-CO(CH2)u-O-(CH2-(CH2)u-0-mm-(CH2)u-
COO-YY- (XXII),
a polyoxyalkylene bridge member of the Formula XXIII
-(CH2)kk-CH(R21)-CO-B1-(CnnH2mm-O-)mmCnmH2nm-
B1-CO-CH(R21)-(CH2)kk (XXIII),
a polyoxyalkylene bridge member of the Formula XXIV
-COC(R21)HCH2NH(CnmH2nmO)mCnnH2nm-NHCH2-
C(R21)HCO- (XXIV),
a polyoxyalkylene bridge member of the Formula XXV
-YY-O-CO-(CH2)2-NH-(CnnH2nm-O-)mm-CnnH2nm-
NH-(CH2)2COO-YY- (XXV),

a polyoxyalkylene bridge member of the Formula XXVI
-(CnnH2nm-O-)mm-CnnH2nm- (XXVI),
and a a polyoxyalkylene bridge member of the Formula XXVII
-CH(CH3)-CH2-(O-CH(CH3)-CH2)a-(0-CH2CH2)b-
(O-CH2-CH(CH3)c- (XXVII),
wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=O,
R21 is hydrogen or C1-C16 alkyl,
YY is unsubstituted or substituted C2-C20 alkyl,
kk is zero or an integer from 1-16,
Bi is O or NH,
mm is an integer from 2 to 60,
nn is an integer from 2 to 6,
u is an integer from 1 to 4;
when r is 3, D is -[-(CH2)S -COO-]3 -R19
and when r 4, D is -[-(CH2)S -COO-]4 --R20
wherein R19 is C3 -C10 alkanetriyl and R20 is C4 -C10 alkanetetryl;
s is 1-6;

R15 is C2 -C10 alkyl, C2-C10 oxaalkyl or C2-C10 dithiaalkylene, phenyl,
naphthyl, diphenyl or C2 -C6 alkenyl, or phenylene-XX-phenylene
wherein XX is -O-, -S-, -SO2 -, -CH2-, or -C(CH3)2-;
R16 is C2 -C10 alkyl, C2 -C10 oxaalkylene or C2 -C10 dithiaalkylene,
phenyl, naphthyl, diphenyl or C2 -C6 alkenyl provided that when r is 3
the alkenyl has at least 3 carbons;
R17 is C2 -C10 alkyl, phenyl, naphthyl, diphenyl, or C2 -C6 alkenyl,
methylenediphenylene or C4 -C15 alkylphenyl, and
R18 is C2 -C10 alkylene or C4 -C20 alkyl interrupted by one or more
oxygen atoms.
9. A compound of Formula (VII):

wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon

atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
aracyl of 6 to 24 carbon atoms, OR, NRR1, CONRR', OCOR, CN, SR,
SO2 R, SO3 H, SO3M, wherein M is an alkali metal, R and R' are the
same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms,
haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,
and optionally with either of R1 and R2, R3 and R4, or R4 and R5, taken
together being a part of a saturated or unsaturated fused carbocyclic
ring optionally containing O, N, or S atoms in the ring;
each of T and T' is independently a direct bond, oxygen, NR, sulfur or
a functional group containing these elements;
X is independently selected from hydrogen and a blocking group
selected from one or more of the following groups: allyl, -COR.a, -SO2
Rb, -SiRc Rd Re, -PRf Rg,-PORf Rg and -CONHRh, wherein each Ra is
independently selected from C1-C8 alkyl, halogen-substituted C1-C8
alkyl, C5 -C12 cycloalkyl, C2 -C8 alkenyl, -CH2 -COCH3, C1 -C12 alkoxy,
and phenyl or phenoxy which is unsubstituted or substituted by C1 -
C12 alkyl, C1-C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1-C12 alkyl, C6-C10 aryl and
C7-C18 alkylaryl;

each Rc, Rd and Re is independently selected from C1-C18 alkyl,
cyclohexyl, phenyl and C1-C18 alkoxy;
each Rf and Rg is independently selected from C1-C12 alkoxy, C1-C12
alkyl, C5 -C12 cycloalkyl, and phenyl or phenoxy which is
unsubstituted or substituted by C1 -C12 alkyl, C1-C4 alkoxy, halogen
and/or benzyl;
and
each Rh is independently selected from C1-C8 alkyl, C5 -C12 cycloalkyl,
C2-C8 alkenyl, -CH2 -CO-CH3, and phenyl which is unsubstituted or
substituted by C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen
and/or benzyl;
each of Y, R6 and R7 are each independently hydrogen, hydrocarbyl
group, a functional hydrocarbyl group, halogen, hydroxy 1, cyano, -
O(hydrocarbyl), -0(functional hydrocarbyl), -N(hydrocarbyl)2,
N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional hydrocarbyl), -
S(hydrocarbyl), -S(functional hydrocarbyl), -SO2 (hydrocarbyl), -SO2
(functional hydrocarbyl), -SO3 (hydrocarbyl), -SO3 (functional
hydrocarbyl), -CO2 (hydrocarbyl), -CO2 (functional hydrocarbyl), -
CO(hydrocarbyl), -CO(functional hydrocarbyl), -OCO(hydrocarbyl), -
OCO(functional hydrocarbyl), -CONH2) -CONH(hydrocarbyl), -
CONH(functional hydrocarbyl), -CON(hydrocarbyl)2)
CON (hydrocarbyl) (functional hydrocarbyl), -CON(functional

hydrocarbyl)2, wherein the hydrocarbyl or functional hydrocarbyl may
be the same or different and has 1 to 24 carbon atoms;
Z is Y,

and wherein L is selected from the group consisting of: hydrogen; an
alkyl of 1 to 24 carbon atoms optionally substituted by one or more
hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or
epoxy groups, and which may contain one or more carbonyl groups,
oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24
carbon atoms optionally substituted by one or more hydroxy, alkoxy,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms

optionally substituted by one or more hydroxy, alkoxy, chloro, cyano,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
r is 2 or 3;
when r is 2, X' is -CO-R16-CO-; -C02 -R16 -C02 -, -SO2 -R16 -SO2 -, -
CO-NH-R17 -NH-CO-, a polyoxyalkylene bridge member of Formula
-CO-(CH2)u-O-(CH2-(CH2)u-O-)mm-(CH2)u-CO-,
or
-COC(R21)HCH2NH(CnmH2nmO)mCnnH2nm-NHCH2-
C(R21)HCO-
when r=3, X' is
-(-C02-R16)R19,-(CONH-R16)R19,-(-SO2-R16)R19
wherein R19 is C3-C10 alkanetriyl and
R16 is C2 -C10 alkyl, C2 -C10 oxaalkylene or C2 -C10 dithiaalkylene,
phenyl, naphthyl, diphenyl or C2 -C6 alkenyl provided that when r is 3
the alkenyl has at least 3 carbons;
R17 is C2 -C10 alkyl, phenyl, naphthyl, diphenyl, or C2-C6 alkenyl,
methylenediphenylene or C4 -C15 alkylphenyl,
R21 is hydrogen or C1-C16 alkyl; and
mm is an integer from 2 to 60,
nn is an integer from 2 to 6,

u is aninteger from 1 to 4.
10. A compound of Formula (VIII):

wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon
atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
aracyl of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR,
SO2 R, SO3 H, SO3 M, wherein M is an alkali metal, R and R' are the

same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms,
haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbon atoms,
and optionally with either R1 and R2, R3 and R4, or R4 and R5, taken
together being a part of a saturated or unsaturated fused carbocyclic
ring optionally containing O, N, or S atoms in the ring;
each of T and T' is independently a direct bond, oxygen, NR, sulfur or
a functional group containing these elements;
X is independently selected from hydrogen and a blocking group
selected from one or more of the following groups: allyl, -CORa, -SO2
Rb, -SiRc Rd Re, -PRf Rg, -PORf Rg and -CONHRh,
wherein
each Ra is independently selected from C1-C8 alkyl, halogen-
substituted C1-C8 alkyl, C5 -C12 cycloalkyl, C2 -C8 alkenyl, -CH2 -CO-
CH3, C1 -C12 alkoxy, and phenyl or phenoxy which is unsubstituted or
substituted by C1 -C12 alkyl, C1-C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1-C12 alkyl, C6-C10 aryl and
C2-C18 alkylaryl;
each Rc, Rd and Re is independently selected from C1-C818 alkyl,
cyclohexyl, phenyl and C1-C18 alkoxy;

each Rf and Rg is independently selected from C1-C12 alkoxy, C1-C12
alkyl, C5-C12 cycloalkyl, and phenyl or phenoxy which is
unsubstituted or substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen
and/or benzyl;
and
each Rh is independently selected from C1-C8 alkyl, C5-C12 cycloalkyl,
C2-C8 alkenyl,-CH2 -CO-CH3, and phenyl which is unsubstituted or
substituted by C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen
and/or benzyl;
each of Y and R7 are each independently hydrogen, hydrocarbyl
group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, -
O (hydrocarbyl), -O(functional hydrocarbyl), -N(hydrocarbyl)2,
N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional hydrocarbyl), -
S(hydrocarbyl), -S(functional hydrocarbyl), -SO2 (hydrocarbyl),-SO2
(functional hydrocarbyl), -SO3 (hydrocarbyl), -SO3 (functional
hydrocarbyl), -CO2 (hydrocarbyl),-CO2 (functional hydrocarbyl), -
CO (hydrocarbyl), -CO (functional hydrocarbyl), -OCO(hydrocarbyl), -
OCO(functional hydrocarbyl), -CONH2, -CONH(hydrocarbyl), -
CONH (functional hydrocarbyl), -CON(hydrocarbyl)2,
CON(hydrocarbyl)(functional hydrocarbyl), -CON(functional
hydrocarbyl)2, wherein the hydrocarbyl or functional hydrocarbyl may
be the same or different and has 1 to 24 carbon atoms;
Z is Y,


and wherein L is selected from the group consisting of: hydrogen; an
alkyl of 1 to 24 carbon atoms optionally substituted by one or more
hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or
epoxy groups, and which may contain one or more carbonyl groups,
oxygen atoms or nitrogen atoms in the chain; an alkenyl of 2 to 24
carbon atoms optionally substituted by one or more hydroxy, alkoxy,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain; an aralkyl of 7 to 24 carbon atoms
optionally substituted by one or more hydroxy, alkoxy, chloro, cyano,
carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups, and
which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
Re is selected from the group consisting of straight chain alkyl of 1 to
12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms,
cycloalkyl 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl
interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl

interrupted by phenylene, benzylidene, -S-, -S-S-, -S-E-S-, -SO-, -SO2
-, -SO-E-SO-, -SO2 -E-SO2 -, -CH2 -NH-E-NH-CH2 -, and

wherein E is selected from the group consisting of alkyl of 2 to 12
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by
cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of
8 to 12 carbon atoms; and r is an integer between 2 and 4.
11. A compound of Formula IX


wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon
atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
wherein M is an alkali metal, R and R' are the same or different and
each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon
atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon
atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon
atoms, or aracyl of 6 to 24 carbon atoms, and optionally with either of
R1 and R2, R3 and R4, or R4 and R5, taken together being a part of a
saturated or unsaturated fused carbocyclic ring optionally containing
O, N, or S atoms in the ring;
each of T and T is independently a direct bond, oxygen, NR, sulfur or
a functional group containing these elements;
X is independently selected from hydrogen and a blocking group
selected from one or more of the following groups: allyl, -CORa, -SO2
Rb, -SiRc Rd Re, -PRf Rg, -PORf Rg and -CONHRh,
wherein
each Ra is independently selected from C1-C8 alkyl, halogen-
substituted C1-C8 alkyl, C5-C512 cycloalkyl, C2-C8 alkenyl, -CH2 -CO-

CH3, C1-C12 alkoxy, and phenyl or phenoxy which is unsubstituted or
substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen and/or benzyl;
each Rb is independently selected from C1-C12 alkyl, C6-C10 aryl and
C7-C18 alkylaryl;
each Rc, Rd and Re is independently selected from C1-C18 alkyl,
cyclohexyl, phenyl and C1-C18 alkoxy;
each Rf and Rg is independently selected from C1-C12 alkoxy, C1-C12
alkyl, C5-C12 cycloalkyl, and phenyl or phenoxy which is
unsubstituted or substituted by C1-C12 alkyl, C1-C4 alkoxy, halogen
and/or benzyl; and
each Rh is independently selected from C1-C8 alkyl, C5-C12 cycloalkyl,
C2 -C8 alkenyl, -CH2 -CO-CH3, and phenyl which is unsubstituted or
substituted by C1-C12 alkyl, C2-C8 alkenyl, C1-C4 alkoxy, halogen
and/or benzyl;
each of Y, R6 and R7 are each independently hydrogen, hydrocarbyl
group, a functional hydrocarbyl group, halogen, hydroxy 1, cyano, -
O (hydrocarbyl), -O(functional hydrocarbyl), -N(hydrocarbyl)2,
N(functional hydrocarbyl)2, -N(hydrocarbyl)(functional hydrocarbyl), -
S(hydrocarbyl), -S(functional hydrocarbyl), -SO2 (hydrocarbyl), -SO2
(functional hydrocarbyl), -SO3 (hydrocarbyl), -SO3 (functional
hydrocarbyl), -CO2 (hydrocarbyl), -CO2 (functional hydrocarbyl), -
CO (hydrocarbyl), -CO(functional hydrocarbyl), -OCO(hydrocarbyl), -
OCO(functional hydrocarbyl), -CONH2, -CO NH (hydrocarbyl), -

CONH(functional hydrocarbyl), -CON(hydrocarbyl)2,
CON(hydrocarbyl) (functional hydrocarbyl), -CON (functional
hydrocarbyl)2, wherein the hydrocarbyl or functional hydrocarbyl may
be the same or different and has 1 to 24 carbon atoms;
r is an integer between 2 and 4;
when r is 2, D is selected from the group consisting of C2-C16
alkylene, C4-C12 alkenylene, xylylene, C3-C20 alkylene which is
interrupted by one or more oxygen atoms, hydroxy-substituted C3 -
C20 alkylene which is interrupted by one or more oxygen atoms, -CH2
CH(OH)CH2 O-R15 -OCH2 CH(OH)CH2, -CO-R16 -CO-, -CO-NH-17 -NH-
CO-, and -(CH2)S -COO-R18 -OCO-(CH2)s-; and
when r is 3, D is -[-(CH2)s -COO-]3 -R19 and
when r 4, D is -[-(CH2)s -COO-]4 -R20
wherein R19 is C3 -C10 alkanetriyl and R20 is C4 -C10 alkanetetryl;
s is 1-6;
R15 is C2 -C10 alkylene phenylene or a phenylene-x-phenylene- group,
wherein X is -0-, -S-, -SO2 -, -CH2 -, or -C(CH3)2 -;
R16 is C2 -C10 alkylene, C2 -C10 oxaalkylene or C2 -C10 dithiaalkylene,
phenylene, naphthylene, diphenylene or C2 -C6 alkenylene;
R17 is C2 -C10 alkylene, phenylene, naphthylene,
methylenediphenylene or C7 -C15 alkylphenylene, and
Ris is C2 -C10 alkylene or C4 -C20 alkylene which is interrupted by one
or more oxygen atoms.

12. A method of stabilizing a material which is subject to degradation
by actinic radiation by incorporating said material with the compound
of claim
13. The method as claimed in claim 12, wherein the amount of the
said compound is from about 0.01 to about 20% by weight based on
the weight of the material to bestabilized.
14. The method as claimed in claim 12, wherein the material to be
stabilized is selected from the group consisting of polyolefins,
polyesters, polyethers, polyketones, polyamides, natural and synthetic
rubbers, polyurethanes, polystyrenes, high-impact polystyrenes,
polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles,
polybutadienes, polystyrenes, acrylonitrile-butadiene-styrene, styrene
acrylonitrileacrylate styrene acrylonitrile, cellulosic acetate butyrate,
cellulosic polymers, polyimides, polyamideimides, polyetherimides,
polypheny lsulfide, polyphenylene oxide, polysulfones,
polyethersulfones, polyvinylchlorides, polycarbonates, polyketones,
aliphatic polyketones, thermoplastic olefin, aminoresin cross-linked
polyacrylates and polyesters, or polyisocyanate cross-linked polyesters
and polyacrylates, phenol/ formaldehyde, urea/ formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,

alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, and epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines
with activated unsaturated and methylene compounds, polyketimines
in combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,
cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, fibers and combinations thereof.
15. The method as claimed in claim 14, wherein the material is a
polyolefin, polyamide, polyurethane, polyester or a polycarbonate.
16. The method as claimed in claim 12 further comprising
incorporation of one or more hindered amine light stabilizers.
17. The method as claimed in claim 16, wherein said hindered amine
comprises at least one member of the group consisting of: bis(2,2,6,6-
tetramethylpiperidin-4-yl)sebacate; bis(2,2,6,6-tetramethylpiperidin-4-

yl)succinate; bis(l ,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(l-
octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis( 1,2,2,6,6-
pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-
hydroxybenzylmalonate; the condensate of l-(2-hydroxyethyl)-2,2,6,6-
tetramethyl-4hydroxypiperidine and succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6,6-
tetramethylpiperidin-4-yl)nitrilo triacetate; tetrakis(2,2,6,6-
tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate ; 1,1 '-(1,2-
ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-
tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(l,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-
tert-but ylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-l,3,8-
triazaspiro[4.5]decan-2,4-dione; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)succinate; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-
2,6-dichloro-l,3,5-triazine; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-2,2,6,6-tetramethylpiperidyl)-l,3,5-triazi ne and l,2-bis(3-
aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-tria zine and 1,2-
bis-(3-aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9-
tetramethyl-1,3,8-triazaspiro[4. 5]decane-2,4-dione; 3-dodecyl-1-

(2,2,6,6-tetrarnethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l-
(l-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-d ione; 3-
dodecy 1-1 - (1,2,2,6,6-pentamethylpiperidin-4 -yl) pyrrolidine-2,5-dione;
a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-
tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-
cyclohexylamino-2,6-dichloro-l,3,5-triazine; the condensate of 1,2-
bis(3-aminopropylamino)ethane, 2,4,6-trichloro-l,3,5-triazine and 4-
butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-
tetramethyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperanzinyl-
triazines; and the reaction product of 7,7,9,9-tetramethyl-2-
cycloundecyl- l-oxa-3,8-diaza-4-oxospiro[4.5]decane and
epichlorohydrin.
18. The method as claimed in claim 12 further comprising
incorporation of one or more additional UV absorbers wherein the
additional UV absorber is a benzotriazole derivative, a triazine
derivative, a benzophenone derivative, or a combination thereof.
19. A method of stabilizing a material which is subject to degradation
by actinic radiation by incorporating said material with the compound
of claims 8, 9, 10 or 11.

20. A composition comprising (a) the compound of claim 1; and (b) at
least one other additive selected from group consisting of: UV
stabilizers and antioxidants.
21. The composition as claimed in claim 20 wherein said at least one
other additive is selected from the group consisting of 2-(2'-
hydroxyphenyl)benzotriazoles, oxamides, 2-(2-hydroxphenyl)-1,3,5-
triazines, 2-hydroxybenzophenones, sterically hindered amines and
hindered phenol antioxidants.
22. The composition as claimed in claim 21 wherein said at least
other additive is selected from the group consisting of: 2-(2'-hydroxy -
5'-methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'-
hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-( 1,3,3-
te trame thy lbutyl) phenyl) benzotriazole; 2-(3',5'-di-tert-butyl-2'-
hydroxyphenyl)-5-chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-
methylphenyl)-5-chloro-benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-4'-
octoxyphenyl) benzotriazole; 2-(3',5'-di-tert-amyl-2'-
hydroxphenyl) benzotriazole; 2-(3',5'-bis(. alpha.,, alpha. -
dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazo le; a mixture of 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-b

enzotriazole, 2-(3,-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-
hydroxyphenyl)- 5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-
(2-methoxycarbonylethyl)phenyl)-5-chloro-be nzotriazole, 2-(3'-tert-
buty 1- 2' - hydroxy- 5' - (2 - methoxy carbony lethy 1) phenyl) benzo triazol e, 2 -
(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl) phenyl) benzotriazo le, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy) carbonyle thy 1] - 2' -hydroxy phenyl) be nzotriazole, 2- (3' -
dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotria zole; 2,2-
methylenebis[4-(l,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol],
the transesterification product of 2-[3'-tert-butyl-5'-(2-
methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazol e with
polyethylene glycol 300; bis(2,2,6,6-tetramethylpiperidin-4-
yl)sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(l,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(l-octyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis( 1,2,2,6,6-
pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-
hydroxybenzylmalonate; the condensate of l-(2-hydroxyethyl)-2,2,6,6-
tetramethyl-4-hydroxypiperidine and succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6,6-
tetramethylpiperidin-4-yl)nitrilotriacetate; tetrakis(2,2,6,6-
tetramethylpiperidin-4yl)-1,2,3,4-butanetetracarboxylate; 1,1'-(1,2-

ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-
tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(l,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-
tert-but ylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-l,3,8-
triazaspiro[4.5]decan-2,4-dione; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)succinate; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-
2,6-dichloro-l,3,5-triazine; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-2,2,6,6-tetramethylpiperidyl)-l,3,5-triazi ne and l,2-bis(3-
aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-tria zine and 1,2-
bis-(3-aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9-
tetramethyl-1,3,8-triazaspiro[4. 5]decane-2,4-dione; 3-dodecyl-1 -
(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-1-
(l-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-d ione; 3-
dodecyl-l-(l,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-
tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-
cyclohexylamino-2,6-dichloro-l,3,5-triazine; the condensate of 1,2-
bis(3-aminopropylamino)ethane, 2,4,6-trichloro-l,3,5-triazine and 4-
butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-

tetramethyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperanzinyl-
triazines and the reaction product of 7,7,9,9-tetramethyl-2-
cycloundecyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane and
epichlorohydrin; 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazin e; 2-(2-hydroxy-4-(mixed iso-octyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-l,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-
6-(2,4-dimethylphenyl)-l,3,5-triazine ; 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine; 2-(2-hydroxy-
4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin e; 2-(2-
hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazi
ne; 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-
bis(2,4-dimethyl phenyl)-1 3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3-
actyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethy lphenyl)-l,3,5-
triazine; 2-[4-dodecyloxy/ tridecyloxy-2-hydroxypropoxy)-2-
hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine; 2-[2-
hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-
dimethyl phenyl)-1,3,5-triazine; 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-
diphenyl-1,3,5-triazine; 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-
1,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-
hydroxypropoxy) phenyl]-1,3,5-triazine; 2-(2-hydroxyphenyl)-4-(4-
methoxyphenyl)-6-phenyl-1,3,5-triazine, 2,4-dihydroxybenzophenone;

2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-
octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone; 2-
hydroxy-4-dodecyloxybenzophenone; 2-hydroxy-4-
benzyloxybenzophenone, 4,2',4-trishydroxybenzophenone; 2'-hydroxy-
4,4'-dimethoxybenzophenone; l,3,5-tris(2,6-dimethyl-4-tert-butyl-
3hydroxybenzyl)isocyanurate; 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)isocyanurate; 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)-2,4,6-trimethylbenzene; 2,6-di-tert-butyl-4-
methylphenol; 2,2'-ethylidene-bis(4,6-di-tert-butylphenol); 1,1,3-
tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of .beta.-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or
polyhydric alcohols; esters of .beta.-(5-tert-butyl-4-hydroxy-3-
methylphenyl)propionic acid with mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; diethyl-3,5-
di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-
butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-tert-butyl-4-
hydroxy-3-methylbenzylphosphonate; and the calcium salt of the
monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid
such as N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-
bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

23. The composition as claimed in claim 22 wherein TZ is

and T' is oxygen, and R1 to R7 and X are hydrogen.
24. The composition as claimed in claim 22 wherein TZ is:

and T' is oxygen, and R1 to R7 and X are hydrogen.
25. The composition as claimed in claim 20 comprising a material to
be stabilized selected from the group consisting of: polyolefins,

polyesters, polyethers, polyketones, polyamides, natural and synthetic
rubbers, polyurethanes, polystyrenes, high-impact polystyrenes,
polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles,
polybutadienes, polystyrenes, acrylonitrile-butadiene-styrene, styrene
acrylonitrile, acrylate styrene acrylonitrile, cellulosic acetate butyrate,
cellulosic polymers, polyimides, polyamideimides, polyetherimides,
polyphenylsulfides, polyphenylene oxide, polysulfones,
polyethersulfones, polyvinylchlorides, polycarbonates, polyketonee,
aliphatic polyketones, thermoplastic olefin, aminoresin cross-linked
polyacrylates and polyesters, polyisocyanate cross-linked polyesters
and polyacrylates, phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,
alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines
with activated unsaturated and methylene compounds, polyketimines
in combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,

cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, and mixtures thereof.
26. The composition as claimed in claim 20 wherein the amount of
said compound to said at least one other additive is from about 500:1
to about 1:500 by weight.
27. A composition comprising (a) the compound of claims 9, 10, 11 or
12; and (b) at least one other additive selected from group consisting
of: 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-
2-hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-( 1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-
hydroxyphenyl)-5-chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-
methylphenyl)-5-chloro-benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-4'-
octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'-
hydroxphenyl)benzotriazole; 2-(3',5'-bis(.alpha.,.alpha. -
dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazo le; a mixture of 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-b
enzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-
hydroxyphenyl)- 5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-
(2-methoxycarbonylethyl)phenyl)-5-chloro-be nzotriazole, 2-(3'-tert-

butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol e, 2-
(3,-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl) phenyl) benzotriazo le, 2 - (3 '-tert-butyl- 5' - [2 - (2 -
ethylhexyloxy) carbonylethyl] -2' -hydroxyphenyl) be nzotriazole, 2 - (3' -
dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotria zole; 2,2-
methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol],
the transesterification product of 2-[3'-tert-butyl-5'-(2-
methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazol e with
polyethylene glycol 300; bis(2,2,6,6-tetramethylpiperidin-4-
yl)sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate;
bis(l,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(l-octyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis( 1,2,2,6,6-
pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-
hydroxybenzylmalonate; the condensate of l-(2-hydroxyethyl)-2,2,6,6-
tetramethyl-4-hydroxypiperidine and succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6,6-
tetramethylpiperidin-4-yl)nitrilotriacetate; tetrakis(2,2,6,6-
tetramethylpiperidin-4-yl)-l,2,3,4-butanetetracarboxylate ; 1,1'-(1,2-
ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-
tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(l,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-

tert-but ylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-l,3,8-
triazaspiro[4.5]decan-2,4-dione; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6-
tetramethylpiperidyl)succinate; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-
2,6-dichloro-l,3,5-triazine; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-2,2,6,6-tetramethylpiperidyl)-l,3,5-triazi ne and l,2-bis(3-
aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-
butylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-tria zine and 1,2-
bis-(3-aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9-
tetramethyl-l,3,8-triazaspiro[4. 5]decane-2,4-dione; 3-dodecyl-l-
(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l-
(l-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-d ione; 3-
dodecyl-l-(l,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-
tetramethylpiperidine; the condensate of N, N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-
cyclohexylamino-2,6-dichloro-l,3,5-triazine; the condensate of 1,2-
bis(3-aminopropylamino)ethane, 2,4,6-trichloro-l,3,5-triazine and 4-
butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-
tetramethyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperanzinyl-
triazines and the reaction product of 7,7,9,9-tetramethyl-2-
cycloundecyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane and

epichlorohydrin; 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazin e; 2-(2-hydroxy-4-(mixed iso-octyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-
6-(2,4-dimethylphenyl)-l,3,5-triazine ; 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine; 2-(2-hydroxy-
4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin e; 2-(2-
hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazi
ne; 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-
bis(2,4-dimethyl phenyl)-1,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3-
octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethy lphenyl)-1,3,5-
triazine; 2-[4-dodecyloxy/ tridecyloxy-2-hydroxypropoxy)-2-
hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine; 2-[2-
hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-
dimethyl phenyl)-1,3,5-triazine; 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-
diphenyl-1,3,5-triazine; 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-
1,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-
hydroxypropoxy) phenyl]-1,3,5-triazine; 2-(2-hydroxyphenyl)-4-(4-
methoxyphenyl)-6-phenyl-1,3,5-triazine, 2,4-dihydroxybenzophenone;
2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-
octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone; 2-
hydroxy-4-dodecyloxybenzophenone; 2-hydroxy-4-

benzyloxybenzophenone, 4,2',4-trishydroxybenzophenone; 2'-
hydroxy4,4'-dimethoxybenzophenone; l,3,5-tris(2,6-dimethyl-4-tert-
butyl-3hydroxybenzyl)isocyanurate; l,3,5-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)isocyanurate; 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)-2,4,6-trimethylbenzene; 2,6-di-tert-butyl-4-
methylphenol; 2,2'-ethylidene-bis(4,6-di-tert-butylphenol); 1,1,3-
tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of .beta.-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or
polyhydric alcohols; esters of .beta.-(5-tert-butyl-4-hydroxy-3-
methylphenyl)propionic acid with mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; diethyl-3,5-
di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-
butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-tert-butyl-4-
hydroxy-3-methylbenzylphosphonate; and the calcium salt of the
monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid
such as N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-
bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
28. The composition as claimed, in claim 27 wherein the amount of
said compound to said at least one other additive is from about 500:1

to about 1:500 by weight.
29. The composition as claimed in claim 27 further comprising a
material to be stabilized selected from the group consisting of
polyolefins, polyesters, polyethers, polyketones, polyamides, natural
and synthetic rubbers, polyurethanes, polystyrenes, high-impact
polystyrenes, polyacrylates, polymethacrylates, polyacetals,
polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-
butadiene-styrene, styrene acrylonitrile, acrylate styrene acrylonitrile,
cellulosic acetate butyrate, cellulosic polymers, polyimides,
polyamideimides, polyetherimides, poly phenyl sulfide, polyphenylene
oxide, polysulfones, polyethersulfones, polyvinylchlorides,
polycarbonates, polyketones, aliphatic polyketones, thermoplastic
olefin, aminoresin cross-linked polyacrylates and polyesters, or
polyisocyanate cross-linked polyesters and polyacrylates,
phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,
alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, and epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,

polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines
with activated unsaturated and methylene compounds, polyketimines
in combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,
cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, fibers and combinations thereof.
30. A compound having the Formula

wherein R1, R2, R3, R4, R5 are the same or different and each is
hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24
carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon

Dated this 17th DAY OF OCTOBER, 2002

atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,
aracyl of 6 to 24 carbon atoms, OR, NRR', CONRR', OCOR, CN, SR,
SO2 R, SO3 H, SO3 M, wherein M is an alkali metal, R and R' are the
same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms,
haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,
alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,
cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,
aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,
and optionally with either of R1 and R2, R3 and R4, or R4 and R5, taken
together being a part of a saturated or unsaturated fused carbocyclic
ring optionally containing O, N, or S atoms in the ring: Z' is a halogen,
and W is

This invention relates generally to phenyl ether substituted triazines compounds and
compositions containing same and their use to protect against degradation by environmental
forces. A method for stabilizing a material by incorporating such triazines is also disclosed.

Documents:

590-CAL-2002-FORM 27.pdf

590-CAL-2002-FORM-27.pdf

590-cal-2002-granted-abstract.pdf

590-cal-2002-granted-claims.pdf

590-cal-2002-granted-correspondence.pdf

590-cal-2002-granted-description (complete).pdf

590-cal-2002-granted-examination report.pdf

590-cal-2002-granted-form 1.pdf

590-cal-2002-granted-form 18.pdf

590-cal-2002-granted-form 2.pdf

590-cal-2002-granted-form 3.pdf

590-cal-2002-granted-form 5.pdf

590-cal-2002-granted-gpa.pdf

590-cal-2002-granted-reply to examination report.pdf

590-cal-2002-granted-specification.pdf

590-cal-2002-granted-translated copy of priority document.pdf


Patent Number 226886
Indian Patent Application Number 590/CAL/2002
PG Journal Number 01/2009
Publication Date 02-Jan-2009
Grant Date 30-Dec-2008
Date of Filing 17-Oct-2002
Name of Patentee CYTEC TECHNOLOGY CORP.
Applicant Address 300 DELAWARE AVENUE, WILMINGTON, STATE OF DELEWARE 19801
Inventors:
# Inventor's Name Inventor's Address
1 GUPTA RAM BABOO 511 WEST MAIN STREET, UNIT 19, STAMFORD STATE OF CONNECTICUT 06902
2 SINGH HARGURPREET 2 BEHRLE DRIVE, ANSONIA, STATE OF CONNECTICUT 06401
3 CAPPADONA RUSSELL 64 VALLEY VIEW COURT, NORWALK, STATE OF CONNECTICUT 06851
PCT International Classification Number C 07 D 251/22
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/039,933 2001-11-09 U.S.A.