Background of the Invention

Field of the Invention

The present invention relates to compounds which incorporate both an ultraviolet light stabilizer and a hydrazide heat stabilizer functional groups. The ultraviolet light absorber can be either a 2-(2-hydroxypheny1)-2H- benzotriazole derivative or an oxanilide derivative.

Description of the Prior Art

In addition .o activity as a stabilizer on a πolar basis (i.e., UV absorber, heat s-abilizer, etc.), a successful stabilizer additive

must have both excellent compatibility with and/or solubility in numerous polymer substrates, along with superior resistance to loss from the stabilized composition during procesing and end-use application. Many stabilizer additives exhibit limited compatibility in certain substrates, and excessive tendency to exude, sublime and/or volatilize during weathering or processing of stabilized compositions, particularly when use conditions require exposure to elevated temperatures. Because of this problem, several attempts have been made to increase the compatibility and reduce the volatility of such stabilizer additives by modifying their structure. While improvements have been noted over the years, experience has shown that state-of-the- art stabilizers do not exhibit the desired combination of properties in all resins and that new polymeric compositions continue to invoke additional structural modifications on any potential heat and/or light stabilizer intended for use. Two examples of this would be in "high solids" coatings which require greater solubility of the stabilizer due to the use of less solvent, and in engineering thermoplastics where processing

temperatures (in excess of 250 ^β C) require the use of stabilizers with high thermal stability and very low volatility. No one stabilizer to date provides the properties necessary for universal application and there is a constant commercial need for new stabilizers offering a range of property advantages.

Systems which incorporate UV absorbers and other functional groups are known. Multifunctional stabilizers have been prepared by reacting one type of stabilizer with another to obtain a higher molecular weight compound having dual functionality or by reacting two or more stabilizers with a multifunctional coupling agent in a stepwise fashion.

Japanese Patent 73/43568 (Chemical Abstracts 8JL:122589s) discloses the use of a 2-(2- hydroxypheny1)-2H-benzotriazole UV absorber and a hydrazide to give enhanced resistance to photodegradation of polyurethane copolymer fibers. U.S. Patent 4,785,063 discloses certain benzotriazole hydrazides and a copolymerizable acyl hydrazide derivative.

Summary of the Invention The novel compounds of this invention have the following general formulas:

or

or

where

R is alkyl of 1-4 carbons or phenyl.

R is hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted alkoxy of 1-8 carbons, substituted or unsubstituted alkoxycarbonyl of 2-8 carbons, alkylaminocarbonyl of 2-5 carbons, dialkylaminocarbonyl of 3-9 carbons, substituted or unsubstituted N-(alkyl)-N-(aryl)aminocarbonyl of

8-15 carbons, alkoxysulfonyl of 1-4 carbons,

-C(=0)-0H-, -C(=0)NH ₂ , or -S(=0) ₂ -OH. Preferably, R 1 i.s hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted alkoxy of 1-8 carbons, ethoxycarbonyl, ethoxycarbonyl, carboxy, chloro or

1 . S(=0) -OH. Most preferaoly, R is hydrogen, alkyl of 1-4 carbons, ethoxy, ethoxy, chloro, or carbox .

R2 is hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted aryl of 6-14 carbons, substituted or unsubstituted araliphatic of 7-22 carbons, substituted or unsubstituted alkoxy of 1-8 carbons, alkyla inocarbonyl of 2-5 carbons, dialkylaminocarbonyl of 3-9 carbons, or substituted or unsubstituted N-(alkyl) -N-(aryl) aminocarbonyl of

8-15 carbons. Preferably, R 2 i.s hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, or substituted or unsubstituted araliphatic of 7-9 carbons. Most preferably, R 2 is methyl, ethyl, t-butyl, t-octyl, or 1-methyl-l- phenylethyl. R 3 i.s hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons, substituted or unsubstituted araliphatic of 7-22 carbons, or substituted or unsubstituted alicyclic of 5-12 carbons. Preferably, R 3 i.s hydrogen. R , R , R and R are independently hydrogen, hydroxy, substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted aryl of 6-14 carbons, substituted or unsubstituted araliphatic of 7-22 carbons, substituted or unsubstituted alkoxy of 1-12 carbons

or substituted or unsubstituted alkylthio of 1-12 carbons, chloro, bro o, or substituted or unsubstituted alkoxycarbonyl of 2-8 carbons. Preferably, R 4, R5, R6 and R7 are independently hydrogen, hydroxy, alkyl of 1-8 carbons, alkoxy of

1-8 carbons, alkylthio of 1-8 carbons, chloro, bromo, or alkoxycarbonyl of 2-8 carbons. Most preferably, R , R , R and R are independently hydrogen, hydroxy, alkyl of 1-8 carbon, alkoxy of 1-4 carbons, alkylthio of 1-4 carbons, ethoxycarbonyl or ethoxycarbonyl.

X is X when attached to ring A, X, when attached to ring B and Xe when attached to either ring E. Xa is a direct bond.

X,b and Xe _Λ are divalent ^' radicals of formula -Z _χ -R ⁸ -{-N(R ⁹ )-[C(=0) ] _y -R ¹⁰ -) ₂ -.

Z is -0-, -NCR ¹¹ )-, -S- , or -S(=0) ₂ ~. x, y and z are independently 0 or 1. o R is a direct bond or substituted or unsubstituted alkylene diradical of 1-4 carbons. Preferably, R is a direct bond, methylene or

1,2-ethanediyl.

9 . R is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons.

substituted or unsubstituted alicyclic of 5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons, or substituted or unsubstituted

₉ . araliphatic of 7-22 carbons. Preferably, R is hydrogen, substituted or unsubstituted aliphatic of

1-12 carbons, substituted or unsubstituted alicyclic of 5-8 carbons, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-9 carbons. Most

₉ . preferably, R s selected from hydrogen, substituted or unsubstituted aliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-14 carbons. R 10 i.s a direct bond, substituted or unsubstituted aliphatic diradical of 1-20 carbons, substituted or unsubstituted aryl diradical of 6-12 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons. Preferably, R is a direct bond, aliphatic diradical of 1-8 carbons, 1,3-phenylene diradical or 1,4-phenylene diradical. Most preferably, R ^~ is a direct bond or alkylene diradical of 1-8 carbons.

R11 independently is any of the groups of

R ⁹ . n is 1 or 2

17 ϋ „19

R 12 i.s hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of 5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons, or substituted or unsubstituted araliphatic of 7-22 carbons. Preferably, R 12 is hydrogen, subs i~u ed or unsubstituted aliphatic oj

1-12 carbons, substituted or unsubsti~uted

alicyclic of 5-8 carbons, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-9 carbons. Most preferably, R 12 i.s hydrogen, substituted or unsubstituted aliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-14 carbons. R 13 i.s hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of 5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons, or substituted or unsubstituted araliphatic of 7-22 carbons, and when alicyclic,

13 R may optionally contain 1-6 heteroatoms -0-, -S- or -N(R 21)-, with the proviso that multiple heteroatoms must be separated from each other and the chain ends by at least one carbon atom.

Preferably, R 13 i.s hydrogen, substituted or unsubstituted aliphatic of 1-12 carbons, substituted or unsubstituted alicyclic of 5-8 carbons, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-9 carbons, and wnen alicyclic, R 13 may optionally contain 1 or 2 heteroatoms -O- and -N(R' ^ώ )-, with

- li ¬

the proviso that multiple heteroatoms are separated from each other and the chain ends by at least one carbon atom. Most preferably, R 13 i.s hydrogen, substituted or unsubstituted aliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, or substituted or unsubstituted araliphatic of 7-14 carbons, and when alicyclic, R 13 i.s substituted 2,2,6,6- tetraalkyl-4-piperidinyl. Q is -C(=0)- except when x and z are 0,

-S(=0) ₂ -, -C(=0)-0-, -[C(=0)] ₂ -0-, -C(=0)-N(R ²² )-,

~[C(=0)] ₂ -N(R ²² )-, -C(=S)-N(R ²² )-,

-C(=0)-R ¹⁷ -C(=0)-N(R ²² )-, or, when n is l, a direct bond between the nitrogen and R 13. Preferably, Q is -C(=0)- except when x and z are 0, -C(=0)-0-,

~[C(=0)] ₂ -0-, -C(=0)-N(R ²² )-, -[C(=0) ] ₂ -N(R ²² )-, or, when n is 1, a direct bond between the nitrogen R 14 and R15 are independently hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of 5-12 carbons, substituted or unsubstituted aryl of

6-14 carbons, or substituted or unsubstituted araliphatic of 7-22 carbons, or R 14 and R~5 may be linked together to form a substituted or

unsubstituted alicyclic ring of 5-12 carbons or may be linked together through a heteroatom -N(R 21)-,

-O- or -S- to form a heterocyclic ring of 5-12 atoms. Preferably, R 14 and R15 are independently substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted alicyclic of

5-8 carbons, substituted or unsubstituted aryl of

6-12 carbons, and substituted or unsubstituted araliphatic of 7-14 carbons, and may be linked together to form a substituted or unsubstituted cyclohexyl ring or a substituted or unsubstituted

2,2,6,6-tetraalkyl-4-piperidine ring. Most preferably, R 14 and R15 are independently ali.phati.c of 1-8 carbons, alicyclic of 5-8 carbons or may be linked together to form a substituted or unsubstituted cyclohexyl ring or a 2,2,6,6- tetramethyl-4-piperidinyl ring.

16

R is a substituted or unsubstituted aliphatic diradical of 2-200 carbons with the proviso that when x and z are 0 R 16 is not 1,2- ethenediyl, substituted or unsubstituted aryl diradical of 6-14 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted aralinhatic

diradical of 7-22 carbons, and the diradical may optionally contain 1-6 heteroatoms -0-, -S- or -N(R 21)-, with the provisos that (a) multiple heteroatoms must be separated from each other and the diradical ends by at least one carbon atom, and

(b) the cyclic group formed contains 5 or 6 atoms in the ring. Preferably, R 16 is a substituted or unsubstituted aliphatic diradical of 2-30 carbons, substituted or unsubstituted ortho-phenylene, substituted or unsubstituted alicyclic diradical of 6-8 carbons and the diradical may optionally contain 1 or 2 heteroatoms -0- or -N(R 21)-, with the provisos stated above. Most preferably, R 16 is a substituted or unsubstituted aliphatic diradical of 2-20 carbons. R 17 i.s a substituted or unsubstituted aliphatic diradical of 1-200 carbons, substituted or unsubstituted aryl diradical of 6-14 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons, and the diradical may optionally contain 1-6 heteroatoms -0-, -S-, or -N(R 21)-, with the proviso τhat multiple heteroatoms must be seDarated from each other and the diradical ends by at least one carbon

atom. Preferably, R17 i.s a substituted or unsubstituted aliphatic diradical of 2-18 carbons, substituted or unsubstituted phenylene, substituted or unsubstituted alicyclic diradical of 6-8 carbons, and the diradical may optionally contain 1 or 2 heteroatoms -O- or -N(R 21)-, with the proviso

17 . stated above. Most preferably, R is a substituted or unsubstituted aliphatic diradical of

2-8 carbons. R 18 is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons, substituted or unsubstituted araliphatic of 7-22 carbons, or substituted or unsubstituted alicyclic of 5-12 carbons. Preferably, R 18 is hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted araliphatic of 7-8 carbons, or substituted or unsubstituted alicyclic of 5-8 carbons. Most preferably, R 18 is hydrogen, substituted or unsubstituted aliphatic of 1-10 carbons, substituted or unsubstituted cyclohexyl or benzyl.

R 19 ^y i.s R13-NH- or OM.

20 .

R is a substituted or unsubstituted aliphatic diradical of 1-20 carbons, substituted or unsubstituted aryl diradical of 6-12 carbons,

substituted or unsubstituted alicyclic diradical of 5-14 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons. Preferably,

20 R is a substituted or unsubstituted aliphatic diradical of 2-12 carbons, substituted or unsubstituted aryl diradical of 6-12 carbons, substituted or unsubstituted alicyclic diradical of

5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-12 carbons. Most

20 . preferably, R is a substituted or unsubstituted aliphatic diradical of 2-10 carbons, substituted or unsubstituted phenylene, substituted or unsubstituted alicyclic diradical of 5-8 carbons, or substituted or unsubstituted araliphatic diradical of 7-12 carbons.

21 . R is hydrogen, aliphatic of 1 to 8 carbons, aliphatic acyl of 2-6 carbons, or substituted or unsubstituted benzoyl. Preferably,

21 . R is methyl or hydrogen. As used herein, the term "acyl" refers to a radical generated from a carboxylic acid by removal of the OH group to provide a free valence on the C(=0) group, for example DC(=0)-OH would become the DC(=0)- substituent, referred to generally as a D acyl group.

R22 is hydrogen or aliphatic of 1 to 4 carbons. Preferably, R 22 i.s methyl or hydrogen.

M is hydrogen, sodium ion, potassium ion or ammonium ion. Preferably, M is hydrogen or sodium ion. Most preferably, M is hydrogen.

Optional substituents for R , R2, R3, R8, 9 10 11 _R 12 -13 14 15 16 17 18

R 19, R20 and R21 are independently one or more of the following: chloro, bromo, alkyl of 1-4 carbons, alkoxy of 1-8 carbons, phenoxy, cyano, hydroxy, epoxy, carboxy, alkyoxycarbonyl of 2-6 carbons, acyloxy of 1-4 carbons, acryloyl, acryloyloxy, methacryloyl, methacryloyloxy, hydroxymethyl, hydroxyethyl, alkylthio of 1-4 carbons, or trialkoxysilyl of 3-12 carbons. Additional optional substituents for R 13

are aliphatic of 1-20 carbons, cycloaliphatic of

5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxy of 1-20 carbons, cycloalkoxy of 5- 12 carbons, aryloxy of 6-14 carbons, aralkoxy of

7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclic acyloxy of 6-13 carbons, aryl acyloxy of

7-15 carbons, or araliphatic acyloxy of 8-16 carbons.

Additional optional substituents for R17

and R .18 are independently alkyl of 5-180 carbons, alkylthio of 5-180 carbons, aralkylthio of 7-20 carbons, arylthio of 6-20 carbons, alkenyl of 2-180 carbons, cycloalkenyl of 5-12 carbons, aryl of 6-16 carbons, aralkyl of 7-17 carbons, aryloxy of 6-16 carbons, alkoxycarbonyl of 7-10 carbons, or (alkoxycarbonyl)alkylthio of 3-30 carbons.

Detailed Description of the Preferred Embodiments General Formula

The novel compounds of Formulas IE and l_l are UV absorber compounds.

The compounds of Formula III are ester precursors used as intermediates to make certain hydrazides of Formula 1 _^ having corresponding structures and substituents. The compounds of the present invention have the following general formulas:

or

or

1 2 3 4 5 6 7 8 9 where R, R ^* , R , R , R , R , R , R , R , R , X

Y, all substituenύs thereof, and n are as previously defined.

Generic Group Examples

As substituted or unsubstituted aliphatic of 1-8 carbons, R , R , R , R , R , R and R are, independently, for example, methyl, 2-hydroxyethyl, ethyl, 2-acetoxy thyl, isopropyl, 2-chloroethyl, allyl, methallyl, pentyl, 2-(methacryloyloxy)ethyl, 3-pentyl, t-butyl, hexyl, octyl, or t-octyl.

As substituted or unsubstituted aliphatic of 1-20 carbons, R 3, R9, R11, R12, R13, R1 ^x 4 , R15, R 18 and R19 are, independently, for example, methyl, ethyl, n-propyl, isopropyl, butyl, allyl, n-pentyl, 2-bromoethyl, hexyl, heptyl, octyl, nonyl, decyl, propargyl, octadecyl, dodecyl, isododecyl, 2-acetoxyethyl, tetradecyl, 2-methallyl, 2-hexenyl, 10-undecenyl, 2-dodecenyl, n-butyl, 2-hydroxyethyl, 2-butenyl, 2-hydroxy- hexadecyl, 2-hydroxypropyl, 2-hexenyl, 10- undeceny1, 2-hydroxydodecy1, 2-hydroxy-5-hexenyl, 2-hydroxyhexy1, 2-hydroxydecyl, 2-hydroxyoctadecyl, 2-hydroxy-3- (methacryloyloxy)propyl, 2-hydroxy-3- ( cryloylox )propyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-(4-methoxyphenoxy)propyl, 2-hydroxy-3- isopropoxypropyl, 2-hydroxy-3-ιτethoxypropyl, 2-hydrcxy-3-(2-ethylhexyloxy)propyl.

3-(trimethoxysilyl)propyl, 2-hydroxy-3- (cyclohexy1oxy)propyl, 2-hydroxy-3- (benzyloxy)propyl, 2-hydroxy-3-(benzoyloxy)propyl, 2-hydroxy-3-dodecyloxypropyl, 2-hydroxybutyl, 1- methyl-2-hydroxypropyl, cyanomethyl,

2,3-epoxypropyl, or 2-(dimethylamino)ethyl.

As substituted or unsubstituted alkoxy of 1-8 carbons, R 1 and R2 are, independently, for example, ethoxy, ethoxy, 2-ethylhexyloxy, isopropoxy, 2-hydroxypropoxy, 2-(acyloyloxy)ethoxy, or sec-butoxy.

As substituted or unsubstituted alkoxycarbonyl of 2-8 carbons, R 1, R4, R5 and R7

are, independently, for example, methoxycarbonyl, ethoxyσ.arbonyl, 2-hydroxyethylcarbonyl, allyloxycarbonyl, or butoxycarbonyl.

As alkylaminocarbonyl of 2-5 carbons, dialkylaminocarbonyl of 3-9 carbons and substituted or unsubstituted N-(aryl)-N-(alkyl)aminocarbonyl of 8-15 carbons, R 1 and R2 are, independently, for example, methylaminocarbonyl, ethylaminocarbonyl, butylaminocarbonyl, N-(4-methylpheny1)-N- methylaminocarbonyl, N-phenyl-N- ethyl minocarbonyl, N-(2-ethoxyphenyl)-N- ethylaminocarbonyl, N-(3-isopropenylpheny1)-N-

butyla inocarbonyl, dimethylaminocarbonyl, or dibutylaminocarbonyl.

As alkoxysulfonyl of 1-4 carbons, R is, for example, methoxysulfonyl, or butoxysulfonyl. As substituted or unsubstituted alkoxy of

1-12 carbons or substituted or unsubstituted alkylthio of 1-12 carbons, R , R , R and R are, independently, for example, methoxy, ethoxy, 2- ethylhexyloxy, isopropoxy, 2-hydroxypropoxy, 2- (acyloyloxy)ethoxy, sec-butoxy, dodecyloxy, methylthio, ethylthio, isopropylthio, butylthio, dodecylthio, octylthio, or hexylthio.

As substituted or unsubstituted alicyclic of 5-12 carbons, R ³ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R 18 and R19 are, independently, for example, cyclohexyl, trimethylcyclohexyl, cyciooctyl, cyclododecyl, 4-t-butylcyclohexyl, 2- hydroxycyclododecyl, 3-cyclohexenyl, 2- hydroxycyclohexyl, 2-hydroycyclopentyl, cyclododecyl, 4-octylcyclohexyl, or 2-methyl-4- octylcyclohexyl.

As substituted or unsubstituted aryl of

6-14 carbons, R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹² , R 13, R~ ■ -- ^* , R15 and R ¹ ~9 are, independently, for

example, phenyl, tolyϊ, 4-chlorophenyl, isopropylphenyl, isopropenylphenyl, anisyl, 3,5-di-t-butyl-4-hydroxyphenyl, 3,5-di-t-amyl-4- hydroxyphenyl, 4-vinylpheny1, 3-t-butyl-5-methyl- 4-hydroxyphenyl, naphthyl, 3-methyl-5-t-butyl-4- hydroxyphenyl, 3,4,5-trimethoxyphenyl, or 4- di(methylamino)phenyl.

As substituted or unsubstituted araliphatic of 7-22 carbons, R , R , R , R , R , R ⁷ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁸ and R ¹⁹ are, independently, for example, benzyl, 3-methylbenzyl, 4-t-butylbenzyl, cinnamyl, 3,5-di-t-butyl-4- hydroxybenzyl, 2-hydroxy-2-phenylethyl, 2-phenylethyl, cumyl, trimethylbenzyl, 4-octyloxybenzyl, naphthylmethyl, or

(4-dodecylphenyl)methyl, 2-(3,5-di-t-butyl-4- hydroxyphenyl)ethyl, 2-(3,5-di-t-amyl-4- hydroxyphenyl)ethyl, or 2-(3-t-butyl-5-methyl-4- hydroxyphenyl)ethyl. As substituted or unsubstituted alkylene g diradical of 1-4 carbons, R is, for example, methylene, 1,2-ethanediyl, 1,1-ethanediyl, 2- hydroxy-l,3-propanediyl, 1,2-propanediyl, 1,3- propanediyl, 2-methoxy-l,3-propanediyl, 1,2- butanediyl, 1,3-butanediyl, or 1,4-butanediyl.

As substituted or unsubstituted aliphatic diradical of 1-20 carbon, substituted or unsubstituted aryl diradical of 6-12 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons and substituted or unsubstituted araliphatic diradical of 7-22 carbons, R 10 i.s, for example, methylene, 1,2-ethanediyl, 1,2- propanediyl, 1,3-propanediyl, 1,4-butanediyl,

1,18-octadecanediyl, 2,2-dimethyl-l,3-propanediyl, 2-methylpentane-2,4-diyl, 1,10-decanediyl, 1,12- dodecanediyl, 3-oxapentane-l,5-diyl, 4-oxaheptane- 1,7-diyl, 3,6-dioxaoctane-l,8-diyl, 4,9- dioxadodecane-l,12-diyl, 4-methyl-4-azaheptane- 1,4-diyl, 3,6-diaza-3,6-dimethyl-l,8-octanediyl, 3-methyl-3-azapentane-l,5-diyl, 1,2- cyclohexanediyl, 1,4-cyclohexanediyl, 1,2- ethenediyl, 1,2-propenediyl, l-chloro-1,2- ethenediyl, l-phenyl-l,2-ethenediyl, 1,3- hexanediyl, 1,2-cyclohexanediyl, 1,2-phenylene, 4- methyl-4-cyclohexene-l,2-diyl, 4-cyclohexene-l,2- diyl, 4-methylcyclohexane-l,2-diyl, 4-carboxy-1,2- phenylene, 4-methoxycarbonyl-l,2-phenylene, propane-2,2-bis[4-cyclohexyl] , 3-oxapentane-l,5- diyl, methylenebis[4-cyclohexyl] , 1,2-, 1,3-, or 1,4-phenylene, 1,2-, 1,3-, or 1,4-

phenylenebis(methyl) , biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl- 3,4'-diyl, or methylenebis[phenylene] .

When alicyclic and optionally containing 1-6 heteroatoms -0-, -S- and -N(R 21)-, with the proviso that multiple heteroatoms must be separated from each other and the chain ends by at least one carbon atom, R 13 i.s, for example, 2,2,6,6- tetramethyl-4-piperidinyl, 2,6-diethyl-l,2,3,6- tetramethyl-4-piperidinyl, l-acetyl-2,2,6,6- tetramethyl-4-piperidinyl and 1-(4-methylbenzoyl)- 2,6-dimethyl-2,6-dipropyl-3-ethyl-4-piperidinyl.

When linked together to form a substituted or unsubstituted alicyclic ring of 5-12 atoms or when linked together through a heteroatom -N(R ²¹ )-, -0- or -S-, R ¹⁴ and R ¹⁵ are, for example, cyclopentyl, cyclohexyl, cycloheptyl, 4-t-butyl- cyclohexyl, 2-methylcyclohexyl, cyclooctyl, 2,2,6,6-tetramethyl-4-piperidinyl, 2,6-diethyl- 2,3,6-trimethyl-4-piperidinyl, 1,2,2,6,6- pentamethyl-4-piperidinyl, l-ethyl-2,2,6,6- tetramethyl-4-piperidinyl, 4-oxacyclohexyl, and 4- thiacyclohexyl.

As substituted or unsubstituted aliphatic diradical of 2-200 carbons, substituted or

unsubstituted aryl diradical of 6-14 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons, any of which may optionally contain 1-6 heteroatoms -0-, -S-, or -N(R 21)-, with the provisos that (a) multiple heteroatoms must be separated from each other by at least one carbon atom and (b) the cyclic group formed contains 5 or 6 atoms in the ring, R 16 is, for example, 1,2-ethanediyl, 1,2-ethenediyl except when x and z are 0, 1,3-propanediyl, 1,2- propenediyl, 2-thiapropane-l,3-diyl, 2-oxapropane- 1,3-diyl, l-chloro-l,2-ethenediyl, 1-phenyl-l,2- ethenediyl, 1,3-hexanediyl, 2-azapropane-l,3-diyl, 2-methyl-2-azapropane-l,3-diyl, 1,2- cyclohexanediyl, 1,2-phenylene, 4-methyl-4- cyclohexene-l,2-diyl, 4-cyclohexene-l,2-diyl, 4- methylcyclohexane-l,2-diyl, norbornane-2,3-diyl, 5-norbornene-2,3-diyl, bicyclo[2.2.2]octane-2,3- diyl, bicyclo[2.2.2]oct-5-ene-2,3-diyl, bicyclo[2.2.1]heptane-1,2-diyl, bicyclo[2.2.l]heptane-l,2-diyl, 4-carboxy-l,2- phenylene, 4-methoxycarbonyl-l,2-phenylene; 1- (substituted)ethane-1,2-diyl, wherein the substituent is hydrogen, chloro, phenyl, methyl,

ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, hexenyl, isohexenyl, diisobutenyl, decenyl, dodecenyl, isododecenyl, octenyl, nonenyl, tetradecenyl, hexadecenyl, octadecenyl, isooctadecenyl, triacontenyl, or polyisobutenyl; 1-(substituted)ethane-1,2-diyl, 5- (substituted)norbornane-2,3-diyl, 5- (substituted)bicyclo[2.2.2]octane-2,3-diyl, or 4- (substituted)cyclohexane-1,2-diyl, wherein the substituent is methylthio, ethylthio, butylthio, hexylthio, octylthio, hexadecylthio, octadecylthio, 2-hydroxyethylthio, phenylthio, benzylthio, (3,5- di-t-butyl-4-hydroxyJphenylthio, or (3-t-butyl-5- methyl-4-hydroxyphenyl)benzylthio. As substituted or unsubstituted aliphatic diradical of 1-200 carbons, substituted or unsubstituted aryl diradical of 6-14 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons, any of which may optionally contain 1-6 heteroatoms -0-, -S-, or -N(R 21)-, with the proviso that multiple heteroatoms must be separated from each other by at least one carbon atom, R is, for example, methylene, 1,2-ethanediyl, 1,2-ethenediyl, 1,3-

propanediyl, 1,2-propenediyl, 2-thiapropane-l,3- diyl, 3-thiapentane-l,2-diyl, 2-oxapropane-l,3- diyl, l-chloro-l,2-ethenediyl, 1-phenyl-l,2- ethenediyl, 1,3-hexanediyl, 2-azapropane-l,3-diyl, 2-methyl-2-azapropane-l,3-diyl, 1,2- cyclohexanediyl, 1,2-phenylene, 4-methyl-4- cyclohexene-1,2-diyl, 4-cyclohexene-l,2-diyl, 4- methylcyclohexane-1,2-diyl, norbornane-2,3-diyl, 5-norbornene-2,3-diyl, bicyclo[2.2.2]octane-2,3- diyl, bicyclo[2.2.2]oct-5-ene-2,3-diyl, bicyclo[2.2.ljheptane-1,2-diyl, bicyclo[2.2.1]heptane-1,2-diyl, 4-carboxy-1,2- phenylene, 4-methoxycarbonyl-l,2-phenylene, propane-2,2-biε[4-cyclohexyl] , 3-oxapentane-l,5- diyl, methylenebis[4-cyclohexyl] , 1,2-, 1,3-, or 1,4-phenylene, 1,2-, 1,3-, or 1,4- phenylenebis(methyl) , or 2,5-diazahexane-l,6-diyl, biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl- 3,4'-diyl, methylenebis[phenylene] ; 1- (substituted)ethane-1,2-diyl, wherein the substituent is hydrogen, chloro, phenyl, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, hexenyl, isohexenyl, iisobu-enyl, decenyl, dodecenyl, isododecεnyl, ocrenyl, nonenyl, terradecenyl, hexadecenyl,

octadecenyl, isooctadecenyl, triacontenyl, or polyisobutenyl; 1-(substituted)ethane-1,2-diyl, 5- (substituted)norbornane-2,3-diyl, 5- (substituted)bicyclo[2.2.2]octane-2,3-diyl, or 4- (substituted)cyclohexane-1,2-diyl, wherein the substituent is methylthio, ethylthio, butylthio, hexylthio, octylthio, hexadecylthio, octadecylthio, 2-hydroxyethylthio, phenylthio, benzylthio, (3,5- di-t-butyl-4-hydroxy)phenylthio, or (3-t-butyl-5- methyl-4-hydroxyphenyl)benzylthio.

As substituted or unsubstituted aliphatic diradical of 1-20 carbons, substituted or unsubstituted aryl diradical of 6-12 carbons, substituted or unsubstituted alicyclic diradical of 5-12 carbons, or substituted or unsubstituted araliphatic diradical of 7-22 carbons, R 20 is, for example, methylene, ethane-1,2-diyl, ethene-1,2- diyl, propane-1,3-diyl, propene-1,2-diyl, 2- thiapropane-1,3-diyl, 2-oxapropane-l,3-diyl, hexane-1,3-diyl, 2-azapropane-l,3-diyl, 2-methyl- 2-aza-propane-l,3-diyl, cyclohexane-1,2-diyl, 1,2- phenylene, 1,3-phenylene, 1,4-phenylene, hexane- 1,6-diyl, octane-l,8-diyl, decanε-1,10-diyl, dodecane-l,12-diyl, 3-hexene-l,6-diyl, 4-methyl- 1,2-phenylene, 4-chloro-l,2-phenylene, 4-

methylcyclohexane-1,2-diyl, cyclohexane-1,2-diyl, 4-methyl-4-cyclohexene-l,2-diyl, toluene-alpha, - diyl, toluene-alpha,3-diyl, toluene-alpha,4-diyl, or isophoronediyl. As aliphatic acyl of 2-6 carbons and substituted or unsubstituted benzoyl, R 21 i.s, for example, acetyl, propionyl, pivaloyl, isobutanoyl, hexanoyl, benzoyl, 4-hydroxybenzoyl, 4- methylbenzoyl, 2,4-dichlorobenzoyl, 3,5-di-t- butyl-4-hydroxybenzoyl, or 3-isopropenylbenzoyl.

List of Example Compounds

Examples of stabilizer compounds of the present invention include the following, non- limiting list of compounds: 1. 10-[2-hydroxy-3-(2H-benzotriazol-2- yl)-5-methylpheny1]-5,6,9-triaza-4,7,8- trioxodecanoic acid, sodium salt

2. l,20-di[3-(2H-benzotriazol-2-yl)-4- hydroxy-5-t-butylpheny1]-4,5,7,14,16,17-hexaaza- 3,6,15,18-tetraoxoecosane

3. l,18-di[2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphenyl]-2,5,6,13,1 ,17- hexaaza-3 , 4 , 1 , 12 , 15 ,16-hexaoxooctadecane

4. l,16-di[3-hydroxy-4-(2H- benzotriazol-2-yl)phenoxy]-3,4,13,14-tetraaza- 2,5,12,15-tetraoxo-6 ,11-dioxahexadecane

5. l,4-phenylenebis{N'-[4-( [ (2-hydroxy- 3-(2H-benzotriazol-2-yl)-5- ethylphenyl)methyl]amino)-4-oxobutanoyl]sulfonyl hydrazide}

6. l,28-di[2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methyl]- 2,9,10,12,17,19,20,27-octaaza-3,8,21,26-tetraoxo- ll,18-di(thioxo) octacosane

7. N-[ (2-hydroxy-3-(2H-benzotriazol-2- yl) -5-methylphenyl)methyl]hydrazinecarboxamide

8. 2-{ [2-hydroxy-3-(2H-benzotriazol-2- yl)-5-methylphenyl]methylamino)-2-oxoacetyl hydrazide

9. 3-{N-[2-hydroxy-3-(2H-benzotriazol- 2-yl)-5-t-butylphenyl]methyl-N-methylamino}-3-oxo- N'-methylpropionyl hydrazide 10. 4-{N-[2-hydroxy-3-(5-chloro-2H- benzotriazol-2-yl)-5-ethylphenyl]methyl-N- butylamino}-4-oxo-N'-(benzoyl)butanoyl hydrazide

11. 4-{N-[2-hydroxy-3-(5- (ethoxycarbonyl) -2H-benzotriazol-2-yl) -5-t-

amylphenyl]methyl-N-ethylamino}-4-oxo- N'- (ethylaminocarbonyl)butanoyl hydrazide

12. 9-{ [2-hydroxy-3-(5-[aminocarbonyl]- 2H-benzotriazol-2-yl)-5-(1-methyl-l- phenylethyl)phenyl]methyla ino}-9-oxo-N'- (diethylaminocarbonyl)nσnanoyl hydrazide

13. 7-{ [2-hydroxy-3-(5-[carboxy]-2H- benzotriazol-2-yl)-5-(1-ethylpentyl)- phenyl] ethylamino}-7-oxo-4-thia-N'- (phenylsulfonyl)heptanoyl hydrazide

14. 3-[3-(2H-benzotriazol-2-yl)-4- hydroxy-5-t-octylphenyl]-N'-(propyl)propionyl hydrazide

15. 2-[3-(5-chloro-2H-benzotriazol-2- yl)-4-hydroxy-5-t-butylphenyl]-N'-

(ethoxycarbonyl)acetyl hydrazide

16. 5-[3-(5-[ethoxycarbonyl]-2H- benzotriazol-2-yl)-4-hydroxy-5-methylphenyl]- pentanoyl hydrazide, 2,2,6,6-tetramethyl-4- piperidone hydrazone

17. 2-[3-hydroxy-4-(2H-benzotriazol-2- yl)phenoxy]-N'-methylacetyl hydrazide

18. 3-[3-hydroxy-4-(5-chloro-2H- benzotriazol-2-yl)phenylamino]-3-oxo-N'- (acetyl)propionyl hydrazide

19. 2-[3-iiydroxy-4-(5-[ethoxycarbonyl]- 2H-benzotriazol-2-yl)phenylthio]-N'- (butylaminocarbonyl)acetyl hydrazide

20. 5-{N-[3-hydroxy-4-(5-ethyl-2H- benzotriazol-2-yl)phenyl]-N-methylamino}-N'-

(methoxycarbonyl)pentanoyl hydrazide

21. N-{ [3-hydroxy-4-(2H-benzotriazol-2- yl)phenylsulfinyl]butyl}-N- methyIhydrazinecarboxamide 22. N-{2-[3-hydroxy-4-(5-chloro-2H- benzotriazol-2-yl)phenylsulfonyl]ethyl}-2- phen Ihydrazinecarboxamide

23. 2-(2-hydroxy-5-methylphenyl)-2H- benzotriazol-5-carboxylic hydrazide 24. 2-(2-hydroxy-5-t-butylphenyl)-6- chloro-2K-benzotriazol-5-carboxylic hydrazide 25. 2-[2-hydroxy-5-(l-methyl-l- phen lethyl)phenyl]-6-methyl-2H-benzotriazol-5- carboxylic hydrazide 26. 2-(2-hydroxy-5-t-octylphenyl)-6- methoxy-2H-benzotriazol-5-carboxylic hydrazide 27. 2-(2-hydroxy-5-ethylphenyl)-6- butoxi ^τ -N'-acetyl-2H-benzotriazol-5-carboxylic hydrazide

- 33 -

28. 2-(2-hydroxy-5-propylphenyl) -6- (ethoxycarbonyl) -N'-benzoyl-2H-benzotriazol-5- carboxylic hydrazide

29. 2-(2-hydroxy-5-ethoxyphenyl) -6- (butylaminocarbonyl)-N'-methyl-2H-benzotriazol-5- carboxylic hydrazide

30. 2-(2-hydroxy-5- (dimethylaminocarbonyl)phenyl) -6- (diethyla inocarbonyl) -N'-phenyl-2H-benzotriazol- 5-carboxylic hydrazide

31. 2-(2-hydroxy-5-butylphenyl) -6- (methoxysulfonyl) -N'-(ethoxycarbony1) -2H- benzotriazol-5-carboxylic hydrazide

32. 2-(2-hydroxy-5- [octylaminocarbonyl]phenyl) -6-carboxy-N- (2- octylsuccinimido) -2H-benzotriazol-5-carbonamide

33. 2- (2-hydroxy-5-t-amylphenyl) -6- (aminocarbonyl) -2H-benzotriazol-5-carboxylic hydrazide, acetone hydrazone 34. 2-(2-hydroxy-5-[phenyl]phenyl) -6- sulfo-N'-lauroyl-2H-benzotriazol-5-carboxylic hydrazide.

35. 2-{2-[ (2 ^" -methoxi ^τ phenylamino) -2-oxo- acetamidojphenoxy}acetyl hydrazide

36. 2-{4-[ (2-methoxyphenylamino)-2-oxo- acetamido]phenoxy}-N'-(butylaminocarbonyl)acetyl hydrazide

37. 2-{4-[ (2-methoxyphenylamino)-2-oxo- acetamido]phenoxy}-N'-(butylaminocarbonyl)acetyl hydrazide

38. 2-{4-[ (2-ethoxyphenylamino)-2-oxo- acetamido]phenoxy}-N-(succinimido)acetamide

39. 2-{2-[ (2-ethylphenylamino)-2-oxo- acetamido]phenoxy)acetyl hydrazide, acetone hydrazone

40. 2-{2-[ (2,4-dimethoxyphenylamino)-2- oxoacetamido]phenox }-N'-(benzoyl)acetyl hydrazide

41. 2-{2-[ (4-butylpheny1amino)-2-oxo- acetamido]phenoxy}-N'-phenylacetyl hydrazide

42. 2-{2-[ (2,4-dimethylphenylamino)-2- oxoacetamido]phenoxy}-N'-(ethoxycarbonyl)acetyl hydrazide

43. 2-{2-[ (2-methoxyphenylamino)-2-oxo- acetamido]phenoxy}acetyl hydrazide

44. l,16-di{2-[ (2-methoxyphenylamino)- 2-oxoacetamido]phenyl}-2,3,5,12,14,15-hexaaza-

1,4,13,16-tetraoxohexadecane

45. 2-{4-[ ^' (2-methoxy-5- octylphenylamino)-2-oxoacetamido]- phenyla ino}acetyl hydrazide

46. 4-{3-[ (2-ethoxy-5-t- butylphenylammo)-2-oxoacetamido]phenylamino}-N'- (iεopropoxycarbonyl)butanoyl hydrazide

47. 4-[ (2-ethoxy-5-methylphenylamino)- 2-oxoacetamido]benzoyl hydrazide

48. 3-{3-[ (2-butoxyphen la ino)-2-oxo- acetamido]phenylamino}-N'-(benzyl)propionyl hydrazide

49. 2-{3-[ (2-hexoxyphenylamino)-2-oxo- aceta ido]phenylthio}-N'-ethylacetyl hydrazide

50. l,22-di{3-[ (2-ethoxyphenylamino)-2- oxoacetamido]-4-methylphenylamino}-7,8,15,16- tetraaza-1,6,9,14,17,22-hexaoxodocosane

51. 3-{4-[ (2-(ethylthio)phenylamino)-2- oxoaceta ido]phenoxy}-N'-(3- carbcxypropoxy)propionyl hydrazide 52. 2-{3-[ (2-hydroxyphenylamino)-2-oxo- acetamido]phenyl mino}-N'-(2-dodecyl-3- carboxypropionyl)acetyl hydrazide, sodium salt

53. 2-{2-[ (4-(phenyl)phenylamino)-2- oxoacetanido phenoxy}aceryl hydrazide

54 . 2- {4- [ (2-methoxy-4-

(benzy1)phenylamino) -2-oxoacetamido] henoxy}-N-(2- octylsuccini ido)acetyl hydrazide

55. 1,14-di{2-[ (2-chlorophenylamino)-2- oxoacetamido]phenoxy}-3,4,11,12-tetraaza-

2,5,10,13-tetraoxotetradecane

56. 2-{4-[(2- (methoxycarbonyl)phenylamino)-2-oxoacetamido]-3- methylphenoxy}acetyl hydrazide, cyclohexanone hydrazone.

utility

The novel stabilizers of this invention are very effective additives for the stabilization of polymeric compositions which are normally subject to thermal and actinic light degradation.

At times it may be beneficial to add extraneous additives generally referred to hereinafter which will act as synergists with the UV absorber groups of the compounds of this invention. As used herein, the terms "polymer" and

"polymeric composition(s) " include homopoly ers or any type of copolymers.

One way in which the 2-(2- hydroxyphenyl) -2K-benzotriazole or oxanilide

derivative stabilizers of the present invention can be used to stabilize polymeric compositions against degradative effects of light is by merely mixing or blending with the polymeric composition a compound of the present invention in an amount effective to stablize the polymer composition against the degradative effects of light. In this first process of stabilizing polymers, the polymeric compositions need not be, and typically are not, coreactive with the stabilizers. Thus, the stabilizers of the present invention are effective UV stabilizers even when mixed with inert polymers.

In addition to being useful in stabilizing inert polymeric compositions, the stabilizers of the present invention provide increased performance and more long-term stabilization when they are in the form of reactive additives which coreact with the polymeric compositions to be stabilized. The hydrazide functionalized UV absorbers of the present invention (where Y is NH_) are reactive additives that can be attached to coreactive polymers to form polymer bound additives containing photooxidative and thermaloxidative stabilizing groups. Once reacted with the coreactive polymers, the

stabilizer groups become chemically bound to the polymers and will not be lost via volatilization, migration or extraction. Non-limiting examples of coreactive polymers are those which include ester, epoxide or anhydride groups, regardless of whether such groups form part of the polymer backbone, are at the end of the polymers or are pendant from the polymer backbone.

Thus, this second aspect of the present invention relates to a polymeric compound comprising the reaction product of (a) a polymer containing at least one ester, epoxide or anhydride functional group, or combinations thereof, in the polymer backbone, on grafted side chains, as a pendant unit or combinations thereof and (b) a UV absorber compound of Formulas I or II where R 12 is hydrogen, R 13 i.s hydrogen, Q is a direct bond and x and z are not 0.

The novel compounds of Formula III are ester precursors used as intermediates to make certain hydrazides of Formula 1 _^ having corresponding structures and substituents.

The novel stabilizers of this invention can be blended with various polymeric compositions in high concentrations to form masterbatches which

can then be blended with additional polymer either of the same or different type.

The amount of stabilizer used to stabilize the polymeric composition will depend on the particular polymer system to be stabilized, the degree of stabilization desired and the presence of other stabilizers in the composition. Normally it is advisable to have about 0.01% to about 5% by weight of the UV absorber moiety of the compound of this invention present in the polymeric composition. An advantageous range is from about 0.05% to about 3% by weight of the UV absorber portion of the molecule in the final composition. In some cases about 0.5% to about 1% by weight is sufficient.

Non-limiting examples of polymeric compositions which may be stabilized by the stabilizer compounds of the present invention include: l. Polyolefins, such as high, low and linear low density polyethylenes, which may be optionally crosslinked, polypropylene, polyisobutylene, poly(methylbutene-1) , polyacetylene and, in general, polyolefins derived

from monomers having from 2 to about 10 carbon atoms, and mixtures thereof.

2. Polyolefins derived from diolefins, such as polybutadiene and polyisoprene. 3. Copolymers of monoolefins or diolefins, such as ethylene-propylene, propylene- butene-1, propylene-isobutylene and ethylene- butene-1 copolymer.

4. Terpolymers of ethylene and propylene with dienes (EPDM) , such as butadiene, hexadiene, dicyclopentadiene and ethylidene norbornene.

5. Copolymers of alpha-olefins with acrylic acid or methacrylic acids or their derivatives, such as ethylene-acrylic acid, ethylene-methacrylic acid and ethylene-ethyl acrylate copolymers.

6. Styrenic polymers, such as polystyrene (PS) and poly(p_-methylstyrene) . 7. Styrenic copolymers and terpolymers such as styrene-butadiene (SBR) , styrene-allyl alcohol and styrene-acrylonitrile (SAN) , styrene- acrylonitrile- ethacrylate terpolymer, styrene- butadiene-styrene block copolymers (SBS) , rubber modified styrenics such as styrene-acrylonitrile

copolymers modified with acrylic ester polymer (ASA) , graft copolymers of styrene on rubbers, such as polybutadiene (HIPS) , polyisoprene or styrene- butadiene-εtyrene block copolymers (Stereon™products available from Firestone

Synthetic Rubber and Latex Co.), graft copolymers of styrene-acrylonitrile on rubbers, such as butadiene (ABS) , polyisoprene or εtyrene- butadiene-styrene block copolymers, graft copolymers of styrene-methyl methacrylate on rubbers, such as polybutadiene (MBS) , butadiene- εtyrene radial block copolymers (e.g. KRO 3™ of Phillips Petroleum Co.), selectively hydrogenated butadiene-styrene block copolymers (e.g. Kraton G™ from Shell Chemical Co.), and mixtures thereof.

8. Polymers and copolymers derived from halogen-containing vinyl monomers, such as poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride) , poly(vinylidene fluoride), poly(tetrafluoroethylene) (PTFE), vinyl chloride-vinyl acetate copolymers, vinylidene chloride-vinyl acetate copolymers and ethylene- tetrafluoroethylene copolymers.

9. Halogenated rubbers, such as chlorinated and/or brominated butyl rubbers or polyolefins and fluoroelastomers.

10. Polymerε and copolymerε derived from alpha, beta-unsaturated acids, anhydrides, esters, amides and nitriles or combinations thereof, such as polymerε or copolymers of acrylic and methacrylic acids, alkyl and/or glycidyl acrylates and methacrylates, acrylamide and methacrylamide, acrylonitrile, maleic anhydride, maleimide, the various anhydride containing polymersand copolymers described in this disclosure, copolymers of the polymers set forth in this paragraph and various blends and mixtures thereof, as well as rubber modified versions of the polymers and copolymers set forth in this paragraph.

11. Polymers and copolymers derived from unsaturated alcohols or their acylated derivatives, such as poly(vinyl alcohol), pol (vinyl acetate), poly(vinyl stearate) , poly(vinyl benzoate) , poly(vinyl maleate) , poly(vinyl butyral) , poly(allyl phthalate), poly(allyl diethylene glycol carbonate) (ADC) , ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymers.

12. Polymerε and copolymers derived from unsaturated amines, such as poly(allyl melamine) .

13. Polymers and copolymers derived from epoxides, such aε polyethylene oxide, polypropylene oxide and copolymers thereof, as well as polymers „ derived from bis-glycidyl etherε.

14. Poly(phenylene oxides), poly(phenylene etherε) and modifications thereof containing grafted polystyrene or rubbers, as well as their various blends with polystyrene, rubber modified polystyrenes or nylon.

15. Polycarbonates and especially the aromatic polycarbonates, such aε those derived from phosgene and bisphenols such as bisphenol-A, tetrabromobiεphenol-A and tetramethylbiεphenol-A.

16. Polyeεter derived from dicarboxylic acidε and diols and/or hydroxycarboxylic acids or their corresponding lactones, such aε polyalkylene phthalates (e.g. polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , and poly(l,4- dimethylcyclohexane terephthalate) or copolymers thereof) and polylactones εuch as polycaprolactone.

17. Polyarylates derived from bisphenols (e.g. bisphenol-A) and various aromatic acidε, εuch

as isophthalic and terephthalic acids or mixtures thereof.

18. Aromatic copolyestercarbonates having carbonate aε well aε eεter linkageε preεent in the backbone of the polymerε, such as those derived from bisphenolε, iεo- and terephthaloyl chlorides and phosgene.

19. Polyurethanes and polyureas.

20. Polyacetals, such as polyoxy ethylenes and polyoxy ethylenes which contain ethylene oxide aε a comonomer.

21. Polysulfones, polyetherεulfoneε and polyimidesulfones.

22. Polya ides and copolyamideε which are derived from diamineε and dicarboxylic acids and/or from aminocarboxylic acidε or the corresponding lactones, such as the following nylons: 6, 6/6, 6/10, 11 and 12.

23. Polyimideε, polyetherimideε, polyamideimides and copolyetheresters.

24. Cross-linked polymers which are derived from aldehydes on the one hand and from phenols, ureaε and melamine on the other hand, such aε phenol-formaldehyde, urea-formaldehyde and melamine-formaldehvde resins.

25. Alkyl resinε, such as glycerol- phthalic acid reεinε and mixtures thereof with melamine-formaldehyde resinε.

26. Blends of vinyl monomers and unεaturated polyester resins which are derived from copolyesterε of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as from vinyl compounds (croεslinking agents) and alεo halogen-containing, flame reεistant modifications thereof.

27. Natural polymerε, εuch as cellulose and natural rubber, aε well as the chemically modified homologous derivatives thereof, such as cellulose acetateε, cellulose propionate, cellulose butyrate and the cellulose ethers, such as methyl and ethyl cellulose.

In addition, the novel stabilizerε of thiε invention may be uεed to εtabilize various combinationε or blends of the above polymers or copoly erε. They are particularly uεeful in the εtabilization of polyolefins, acrylic coatings, εtyrenicε, rubber modified styrenics, poly(phenylene oxides) and their various blends with styrenics, rubber-modified styrenics or nylon. The novel ultraviolet light absorbers of

this invention can be ^" used together with other additives to further enhance the properties of the finished polymer. Examples of other additives that can be used in conjunction with the stabilizers of this invention include antioxidants, such as alkylated monophenols, alkylated hydroquinoneε, hydroxylated thiodiphenyl etherε, alkylidene-bis- phenolε, hindered phenolic benzyl compoundε, acylaminophenolε, eεterε of 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionic acid, esters of 3-(5-t- butyl-4-hydroxy-3-methylphenyl)propionic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl)propionic acid amides; other UV absorbers and light stabilizers such as 2-hydroxybenzophenones, benzylidene malonate eεterε, eεterε of εubεtituted or unεubεtituted benzoic acidε, diphenyl acrylateε, nickel chelates, oxalic acid diamides, and hindered amine light stabilizers; other additives such as metal deactivatorε, phoεphiteε and phosphonites, peroxide decompoεerε, fillerε and reinforcing agentε, plasticizers, lubricantε, corroεion and ruεt inhibitorε, emulsifierε, mold releaεe agentε, carbon black, pigments, fluorescent brighteners, both organic and inorganic flame retardantε and nondripping agents, melt flow improvers and

antistatic agents. Numerous examples of suitable additives of the above type are given in Canadian Patent 1,190,038.

Preparative Methods The novel UV absorber hydrazides are prepared by reacting UV absorber-substituted carboxylic acid eεterε and halides, sulfonic acid esters and εulfonyl halideε with hydrazine or hydrazine hydrate. Typically the eεter iε diεεolved in a polar εolvent and converted to the desired hydrazide by stirring with an equivalent amount or slight excess of hydrazine or hydrazine hydrate. The reaction may proceed at room temperature or may require heating. Preferably, the hydrazinolysis reaction is carried out in methanol or ethanol at about 10°C to about 30°C, but other solvents, such as isopropanol or ethylene glycol, are also acceptable. In most cases the resulting hydrazides can be purified by recryεtallization from the lower alcohols.

Substituted hydrazides can be prepared by reacting the esters with substituted hydrazines.

Suitable benzotriazole-subεtituted carboxylic acid esterε and oxaniiide-substituted

carboxylic acid eεterέ are deεcribed in U.S. Patents 3,218,332 and 3,906,966, British Patent Application Publication Nos. 2,197,318 A, 2,188,631 A and 2,196,966 A, and French Patent 1,506,632. Other benzotriazole-substituted carboxylic acid esters and oxanilide-substituted carboxylic acid esterε may be prepared according to the following exampleε.

A. Reacting hydroxy, amino or thio εubεtituted benzotriazoleε with chloro-substituted or bromo-subεtituted acid eεterε in the presence of an acid acceptor (e.g. potassium carbonate, tertiary amine) and optionally in the presence of alkylation catalysts (e.g. aminopyridineε, potassium iodide) :

C HO

C HO

and

HO

\

C-C 00 C-C o

H 4

RO-C-R -0

\

where Z' is -0-, -N(R 7)- or -S-, R lε lower alkyl of 1-4 carbonε or phenyl and R 1 and R4 are aε previouεly defined.

B. Esterifying benzotriazole-substituted acidε and oxanilide-substituted acidε. The preparation of such acids and esters are described in U.S. Patents 3,399,173, 3,766,205, 3,629,191, 3,862,087, 3,214,436 and European Patent Application Publication No. 57,160.

where R' is lower alkyl of 1-4 carbonε or allyl, and R 1, R2 and R4 are as previously defined.

C. Reacting aminoalkyl-substituted benzotriazoles with mono ester acid chlorideε of dicarboxylic acidε.

\

R ² 0 0

C HO CH.-NH-C U-R 10 - IC-OR'

\ ₂ R^ where R' , R 1 , R 2 and R 10 are as previously defined.

Esters of this type, where R is 1,2-ethanediyl are disclosed in U.S. Patent 3,629,192. When R is a direct bond, εuch esters may also be prepared by reaction with lower dialkyl oxalate or diphenyl oxalate.

\

R ² 0 0

\ 2 R

1 2 . . where R, R and R are as previously defined. The preparation of the aminoalkyl-substituted benzotriazoles are described in U.S. Patents

3,862,087 and 3,629,192. D. Reacting amino-substituted- benzotriazoleε and oxanilides with mono ester acid chlorides of dicarboxylic acids.

0 0 tertiary II ₁₀ 0 amine + Cl-C-R -C-OR' s>

The amino-εubεtituted benzotriazoleε are deεcribed in U.S. Patentε 3,272,891 and 3,159,646.

Non-limiting exampleε of εu table hydrazines include hydrazine, hydrazine hydrate, 35-85% hydrazine hydrate, methylhydrazine, ethylhydrazine, propylhydrazine, isopropylhydrazine, n-butyIhydrazine, sec- butylhydrazine, n-amylhydrazine, εec-amylhydrazine, n-hexylhydrazine and n-octylhydrazine, t- butyIhydrazine, phenyIhydrazine, benzylhydrazine and sec-octyIhydrazine. Hydrazone derivativeε of this invention are prepared by reacting the hydrazides with ketones, aldehydeε or formaldehyde in inert solvents, preferably in hydrocarbon solvents under azeotropic conditions. They may also be prepared by reacting hydrazoneε of ketoneε or aldehydεε with UV absorber-containing esters.

The novel carbamoyl and thiocarbamoyl derivatives are preparεd by reacting the hydrazides

with isocyanates, diε cyanateε, iεothiocyanates or diisothiocyanates in aprotic polar solvents, such as tetrahydrofuran or dimethylformamide.

The reactions of hydrazides with ketoneε, aldehydeε, isocyanates, diisocyanateε, iεothiocyanates, and diisothiocyanateε are well known in the art and can occur under a wide variety of tempεratureε, times, solvents and concentrations. Generally a mole ratio of 0.9:1.0 to 1.1:1.0 of the hydrazide to the monofunctinal corεactant is εmployed. If the coreactant is difunctional, then a mole ratio of 1.8:2.0 to 1.1:1.0 of the hydrazide to the difunctional coreactant is employed. If the coreactant is a compound that can eaεily bε rεmovεd from the product, e.g. acetone or methyl ethyl ketone, lower mole ratios may be desirable. The coreactant may be used as the solvent.

The hydrazides also react with unsubstituted or N-subεtituted amic acid esters in lower alcohol solutions to form 1,2-amoyl hydrazines. Thε rεactions arε normally carried out in refluxing alcohol (i.e. methanol) but may be carried out in higher boiling aprotic εolventε or without εolvent by heating a mixture of the two

components above their melting points. The methyl and ethyl esters of N-εubstituted oxamates and succinamates are the prefεrrεd corεactants. Thε novel acyl derivatives of the hydrazide may be prepared by reacting the esters with acid hydrazides in refluxing alcohol (i.ε. methanol) .

The novel alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl and . aralkoxycarbonyl derivatives of the hdyrazideε may be prepared by reacting the ester (as described above) with the corresponding alkyl, cycloalkyl, aryl or aralkyl carbazates in refluxing alcohol (i.e. methanol). Alternately, thesε derivatives may be prepared by reacting the hydrazide with a disubstituted carbonate or εubεtituted haloformate. When a haloformate iε used, an additional base (inorganic or amine) may be used to react with the halogen acid formed. The novel sulfonyl derivatives of the hydrazides may be prepared by reacting the esterε with the corresponding sulfonyl hydrazide.

The novel alkyl derivatives of the hydrazidεs may be prepared by reacting the hydrazides with epoxideε. The reactions are

generally carried out neat or in a minimum amount of a high boiling solvent. Reaction generally occurs quite readily at about 140°C to about 150 C. The hydrazide group reacts with two equivalents of epoxide. The ratio of the unεubstituted hydrazidε to thε monoalkylated and dialkylated products is dependεnt upon the mole ratio of epoxidε to hydrazidε, thε temperature and the concentration, if the reaction is run in a solvent.

Non-limiting examplεs of suitable ketones include acetone, methyl ethyl ketonε, 2-pεntanonε, 2-hexanone, 3-hεxanonε, 2-decanone, 3-methyl-2- pentanone, 4-methyl-2-pentanone, 4-methoxy-4- mεthyl-2-pentanone, cyclopentanone, cyclohexanone, 2,4-dimethyl-4-heptanonε, 3,5-dimethyl-4-heptanone, 2,4-dimethyl-3-pεntanonε, 1,3-diphenylacetonε, 2- octanonε, 3-octanonε, dihydroiεophoronε, 4-t- butylcyclohεxanonε, mεthyl cyclohεxyl ketone, acεtophenone, 2,2,6,6-tetramethyl-4-piperidone and 2,6-diεthyl-2,3,6-trimεthyl-4-pipεridone.

Non-limiting examplεε of εuitablε aldεhydεε includε formaldehyde, acetaldεhydε, butyraldehyde, dodεcyl aldεhyde, 2- ethylbutyraldehyde, heptaldεhyde, isobutyraldehyde,

iεovaleraldehyde, octyl aldεhyde, propionaldehyde, benzaldehyde, 3,5-di-t-butyl-4-hydroxybenzaldehyde, 2,3-dimethyl-p_-aniεaldehyde, 3-hydroxybenzaldehyde, 1-naphthaldehydε, εalicylaldεhyde, p-tolualdehydε and 2,3,4-trimethoxybεnzaldεhyde.

Non-limiting exampleε of εuitable iεocyanatεs includε allyl isocyanatε, bεnzyl isocyanate, n-butyl isocyanatε, sεc-butyl iεocyanate, isobutyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate, isopropyl isocyanate, 4-methoxyphenyl isocyanate, methyl isocyanate, octadecyl isocyanatε, 1-naphthyl isocyanate, phenyl isocyanate, o_-tolyl isocyanate, m-tolylisocyanate and p_-tolyl isocyanate, dimethyl-m- iεopropεnylbεnzyl iεocyanate and 2-isocyanatoethyl mεthacrylat .

Non-limiting εxamplεs of suitablε isothiocyanatεs includε allyl isothiocyanatε, bεnzyl isothiocyanate, 4-bromophenyl iεothiocyanate, n-butyl iεothiocyanatε, sεc-butyl isothiocyanatε, isobutyl isothiocyanatε, t-butyl isothiocyanatε, 3-chlorophεnyl iεothiocyanatε, cyclohεxyl isothiocyanate, ethyl isothiocyanate, methyl isothiocyanate, propyl iεothiocyanatε,

isopropyl isothiocyanatε, 1-naphthyl isothiocyanate, t-octyl isothiocyanate, phenethyl isothiocyanatε, phenyl isothiocyanate, propyl isothiocyanate, £-tolyl iεothiocyanate, m-tolyl isthiocyanate and p_-tolyl isothiocyanateε.

Non-limiting exampleε of suitable amic acid esterε include mεthyl oxamate, εthyl oxamatε, propyl oxamate, iεopropyl oxamate, n-butyl oxamate, phenyl oxamate, methyl εuccinamatεε, εthyl succinamate, propyl εuccinamate, iεopropyl εuccinamatε, n-butyl εuccinamatε, phεnyl εuccinamatε, εthyl N-(2,2,6,6-tεtramεthyl-4- piperidinyl)oxamate, methyl N-(2,2,6,6- tεtramethyl-4-piperidinyl)oxamatε, ethyl N- (2,2,6,6-tetramethyl-4-pipεridinyl)εuccinamatε, mεthyl N-(2,2,6,6-tetramethyl-4- pipεridinyl)succinamatε, εthyl N-(3,5-di-t-butyl- 4-hydroxyphεnyl)oxamatε, mεthyl N-(3,5-di-t-butyl- 4-hydroxyphenyl)oxamate, ethyl N-(3,5-di-t-butyl- 4-hydroxyphεnyl)succinamatε and mεthyl N-(3,5-di- t-butyl-4-hydroxyphεnyl)succinamatε.

Non-limiting εxamplεs of suitablε acid hydrazidεs includε acεtyl hydrazide, propionic hydrazide, butyric hydrazide, isobutyrichydrazide, valεric hydrazidε, isovalεric hydrazidε, caproic

hydrazidε, dεcanoic hydrazidε, lauric hydrazide, stearic hydrazide, benzhydrazide, 3,5-di-t-butyl- 4-hydroxybεnzhydrazidε, 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionic acid hydrazide, 3-(n- hexylthio)propionic acid hydrazide, (4-benzoyl-3- hydroxyphenoxy)acetyl hydrazide and 3- (dimethylaminoethylthio)propionic acid hydrazide.

Non-limiting examplεs of suitablε carbazatεε include ethyl carbazate, methyl carbazate, propyl carbazate, isopropyl carbazate, butyl carbazate, cyclohexyl carbazate, cyclopentyl carbazatε, cyclododεcyl carbazate, phenyl carbazate, bεnzyl carbazate, 4-t-butylcyclohexyl carbazatε, 2-εthylhεxyl carbazatε, 4-mεthylphεnyl carbazatε and 3-methoxypheny1 carbazate.

Non-limiting examples of suitable diaryl carbonates include diphenyl carbonate, di-(4- methylphenyl) carbonate, di-(3-methylphεnyl) carbonate, di-(3-methoxypheny1) carbonate, di- (2,6-dimethylphεnyl) carbonate and di-(2,5-di-t- butylphεnyl) carbonate.

Non-limiting examples of suitable sulfonyl halidεs include benzenesulfonyl hydrazide, 4-bromobenzεnεεulfonyl hydrazidε, 1-butanεεulfonyl hydrazide, 4-t-butylbenzenesulfonyl hydrazide, t>-

tolueneεulfonyl hydrazide, ethaneεulfonyl hydrazide, εthanεsulfonyl hydrazidε, 4- fluorobenzεneεulfonyl hydrazide, 1- hεxadεcanesulfonyl hydrazidε, isopropanεsulfonyl hydrazidε and 1-naphthalεnεεulfonyl hydrazidε. Non-limiting εxamplεs of suitable epoxidεs includε 1,2-εpoxybutane, 2,3-epoxybutanε, 1,2-εpoxycyclododεcanε, 1,2-εpoxycyclohεxanε,1,2- εpoxyoctanε, 1,2-εpoxydεcanε, 1,2-εpoxydodecane, 1,2-epoxyoctadecanε, l,2-εpoxy-3-phεnoxypropane, 2,3-epoxypropyl acrylatε, 2,3-epoxypropyl methacrylatε, 2,3-εpoxypropyl 4-mεthoxyphεnyl εthεr, glycidyl isopropyl εthεr, glycidyl n-hεxyl εthεr, glycidyl dodεcyl εthεr and glycidyl octadεcyl εthεr.

Thε following εxamples are preεentεd to provide a more detailed explanation of the preεεnt invεntion and arε intεndεd aε illuεtrationε and not limitations of thε invεntion. Unless otherwisε stated herein, the tεmpεraturεs arε in dεgrεεε Cεntigrade and all parts are by weight.

EXAMPLE I

Preparation of 2-(2-[ (phenylamino)-2- oxoacetamido]phenoxy) cetyl hydrazide

Into a 125 ml flaεk were placed N- phεny1-N'-(2-[ethoxycarbonyl ethoxy] phenyl)oxamidε (2.0g, 0.006 mole), 35 ml methanol,

35 ml tetrahydrofuran (THF) and 10 ml 54% aquεous hydrazinε. The mixture was stirred at room tempεraturε for 2 hrs. during which timε a solid prεcipitatεd. Thε solid waε iεolatεd by filtration, εlurriεd with 150 ml watεr and filtered, then εlurried with 75 ml methanol and filtered again and air dried on the filter giving l.Og of white solid (m.p. 183-186°C) . The THF/methanol filtrate waε stripped using aspirator vacuum to give a tan solid residue. This reεidue waε slurried with 10 ml THF and filtered again. The solid was dried on the filter giving 0.5g of slightly tan solid (m.p. 179-182°C) . The samples werε shown to bε thε samε by infrarεd spεctra and wεrε combinεd. Thε infrared εpectrum εhowεd an NH band at 3300 cm ^" and carbonyl bandε at 1670 and

1600 cm . The eεter carbonyl of the starting

-η material (1750 cm ) was not present.

EXAMPLE II

Preparation of N-[(3-[2H-benzotriazol-

2-yl]-2-hydroxy-4-methyl)benzyl]-3- piperidinecarboxylic hydrazide A. Preparation of ethyl N-[ (3-[2H-benzotriazol-2- yl]-2-hydroxy-4-methyl)benzyl]-3-piperidine carboxylate

2-(2-hydroxy-4-mεthylphεnyl)-2H- benzotriazole (42.8g, 0.19 mole) and n-butanol (50 ml) werε slurriεd in a reaction flaεk under a nitrogen atmoεpherε at room tεmpεraturε. Ethyl nipεcotatε (44.8g, 0.28 molε) and paraformaldehyde (9.7g, 0.32 equiv.) werε added, the paraformaldehyde addition cauεing aε 4"C rise in the tempεraturε. Thε reaction was heated to 101°C over 40 min. dissolving the solidε. The reaction was maintained at this tempεraturε for 24 hrε. The reaction mixture waε εtirred with 250 ml water and 250 ml methylenε chloridε. Thε phasεs wεrε separated and the organic phasε washεd twicε with 200 ml portions of water. The organic solution was dried with anhydrous εodium εulfate and magneεium εulfate and stripped using aεpirator vacuum. The reεidual yεllow oil wεighεd 104g. Liquid chromatographic assay εhowεd about 60% of thε title compound, about 30% n-butanol and about 4% starting benzotriazolε. Upon prolongεd cold storage, a

εolid precipitatεd. Some of thiε εolid was isolatεd by filtration, slurriεd in mεthanol and filtered, then washed with methyl t-butyl ethεr. Thε resulting slightly yellow solid had a m.p. of 87-90°C. The infrared spectra of both the original oil and the isolated solid εhowεd a carbonyl peak

- ₁ at 1720 cm

B. Preparation of N-[ (3-(2H-benzotriazol-2-yl)-2- hydroxy-4-methyl)benzyl]-3-pipεridine- carboxylic hydrazide

The crude eεtεr prεparεd in Stεp A of thiε Example (84g) waε slurried with 100 ml mεthanol in a flask undεr nitrogεn atmoεphεrε at room tεmpεrature. Hydrazine hydrate (85% aqueouε, 50 ml, 0.85 molε) was added over 10 min. at 26- 29°C. The rεaction was hεated to rεflux (77°C) over 50 min. , dissolving the eεter. After refluxing 2.5 hrε., εolidε began precipitating, thickening the reaction mixture. Additional methanol, 100 ml, waε added and the mixture refluxed for a total of 11 hrε. The mixture waε εtirrεd with 500-600 ml watεr and thε εolid iεolatεd by filtration. Thε solid was εlurriεd with 350 ml mεthyl t-butyl εthεr and filtεrε , thεn waεhεd with 250 ml watεr and filtered. The

rεsidual moisture was evaporatεd under reduced presεure. Thε off-white εolid weighed 45.5g and had a m.p. of 189-192°C.

EXAMPLE III Preparation of 2-([2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphenyl]- methylamino)-2-oxoacetyl hydrazide

A. Preparation of ethyl 2-([2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphεnyl]- methylamino)-2-oxoacεtatε

(1) From ethyl oxalyl chloride

2-(2-hydroxy-3-aminomethyl-5-methyl)-2H- benzotriazole (50.8g, 0.2 mole) was slurried with

600 ml methylenε chloridε. Triεthyla ine (22.2g, 0.2 molε) waε added. Ethyl oxalyl chloride (27.4g, 0.2 mole) diluted with 120 ml methylεnε chloridε was addεd slowly over 20 min., causing the temperature to rise from 23°C to 38°C. Thε slurry was present throughout this addition, most solids dissolving shortly after completε addition. The reaction waε continued 18 hrs. at room temperature. The reaction mixture was filterεd of insolublεs and transfεrrεd to a εeparatory funnel and waεhed with 400 ml water, then 400 ml 5% aq. HCl (εmulεion at interface) , then 400 ml water (εmulεion at interface) . The εmulεified interfaceε werε isolated, diluted with water and the organic

εolution which εeparatεd waε returned to the main organic εolution. The εolvent was stripped under rεducεd prεssurε yielding a εolid which was washed with 600 ml mεthanol and driεd on thε filtεr. Thε product wεighεd 55.5g and had a melting point of 148-152°C.

(2) From diethyl oxalate Diethyl oxalate (8.8g, 0.06 mole) was placed in a flask and diluted with 150 ml methanol. 2-(2-Hydroxy-3-aminomethyl-5-mεthyl)-2H- benzotriazole (13.5g, 0.05 mole) was added and the solution stirred for 2 hrs. at room temperature, during which time the benzotriazolε slowly dissolvεd and waε rεplaced by the precipitating product. Thε εolid waε filtεrεd, rinsed with methanol and air dried. The product weighεd 14.6g and had a m.p. of 160-166°C.

B. Prεparation of 2-{ [2-hydroxy-3-(2H- bεnzotriazol-2-yl)-5-mεthylphenyl]- methyl}amino-2-oxoacetyl hydrazide

Thε εstεr prεparεd by εithεr procεdure

(1) or (2) of Step A of thiε Example (82.6g, 0.23 mole) waε εlurriεd with 1200 ml methanol. To this was added 54% aq. hydrazine (27.3g, 0.46 mole) and another 400 ml methanol to facilitate stirring of

thε slurry. Thε rεaction waε allowed to εtir for 2 hrε. The εolid waε filtεred and the εolid was air dried. The product weighεd 94.9g and had a m.p. of

256-262°C. An infrared spectrum of the product εhowed two carbonyl peakε at 1625 and 1645 cm

EXAMPLE IV

Preparation of 3-[3-(2H-benzotriazol-2-yl)-4- hydroxy-5-t-butylphenyl]propionyl hydrazide

Polyethylεne glycol eεter with 3-[3-(2H- benzotriazol-2-yl)-4-hydroxy-5-t-butylphenyl]- propionic acid (Tinuvin 1130, a product of Ciba- Geigy) (332g, about 0.51 mole) was mixεd with 335 ml mεthanol (two liquid phasεε) . To thiε waε addεd 54% aq. hydrazinε (60g, 0.1 molε). Thε reaction waε heated to 40 C, forming a homogeneouε solution. This temperature was maintained for 1 hr. and the progresε followed by infrared εpectroεcopy (eεtεr carbonyl convεrting to hydrazidε carbonyl) . The mixture waε then refluxed for 3.5 hrε. The εolid which had formed waε filtεrεd and washεd with 400 ml fresh methanol, giving 155.3g product having a m.p. of 171-175°C. The filtrate was checkεd by IR εpεctrum, showing unrεactεd εstεr. Thε filtrate waε mixed with additional 54% hydrazine (lOg, 1.18 mole total) and refluxed for 1.5 hrε. The methanol waεh from the above rinse was concentratεd to about

- 67 -

100 ml and added to the refluxing filtrate. The reaction waε refluxed for 1 hr. more, then allowed to cool and εtand while the product precipitated. The product waε filterεd and air driεd giving another 36.Og product having a m.p. of 172-180 C.

EXAMPLE V

Preparation of 4-{[2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphenyl]- methylamino}-4-oxobutanoyl hydrazide A. Preparation of Ethyl 4-{ [2-hydroxy-3-(2H- benzotriazol-2-yl)-5-mεthylphεnyl]- methylamino}-4-oxobutanoate

Into a 250 ml flask were placed 2-(2- hydroxy-3-aminomethyl-5-methylphenyl)-2H- bεnzotriazolε (14.lg, 0.05 molε), 125 ml methylεnε chloride and triethylamine (6.0g, 0.06 mole). Ethyl succinyl chloride (8.6g, 0.052 mole) diluted with 25 ml methylenε chloridε was addεd slowly ovεr 5 min. causing thε temperaturε to risε from 24°C to 42°C (refluxed) . The reaction mixturε was εtirrεd 30 min. at room tεmperature, hεatεd to rεflux and rεfluxεd 30 min. The reaction insolubles wεre filterεd hot and thε filtratε was transfεrrεd to a 500 ml sεparatory funnεl. It waε waεhεd with 100 ml water, then 100 ml 5% aq. HC1 (emulεion at interfacε) , thεn 100 ml watεr (3 timεε until rεaching a pH of 6) . The εolvent waε stripped

under reducεd preεεure, yielding a εolid which was air dried. Thε product wεighεd 13.3g, and had a mεlting point of 147-150°C. The infrared spectrum showed a εtrong εharp OH band at 3310 cm , a

-1 εtrong sharp carbonyl band at 1640 cm , and a

-1 medium broad carbonyl band at 1545 cm

B. Preparation of 4-{ [2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphεnyl]- mεthylamino}-4-oxobutanoyl hydrazidε Thε ester preparεd in Stεp A of this

Example (13.95g, 0.038 mole) was slurriεd in 150 ml of mεthanol in a 500 ml flaεk. Added to the eεtεr was 54% hydrazine (5g, 0.084 mole). Shortly after addition thε reaction gelled. Methanol (50 ml) was added to dilute the reaction. The rεaction was heated to reflux, and refluxed for 1.5 hrs., then cooled and allowed to stand 16 hrs. The rεaction was again hεated to reflux and refluxεd for 2 hrs. Thε insolublεs wεrε filtεrεd from thε hot (60°C) εolution. Thε filtratε waε rεducεd in volume by distillation (144 ml removεd) . Thε solution was coolεd to 60 C, and solids filtεrεd. A prεcipitate formed in the filtrate and this was isolated by another filtration. The combined solids were air dried and weighεd 1.5g and had a m.p. of 212-216°C. Thε infrarεd spectrum εhowed a εtrong OH band at

3295 cm , a εtrong εharp carbonyl band at 1635 cm , and a mεdiu εharp carbonyl band at 1550 cm , with a wεak εhoulder at 1510 cm

EXAMPLE VI Reaction of the Hydrazide of Example IV with 2-Ethylhexyl Glycidyl Ether

The hydrazide of Example IV (8.83g, 0.025 mole) and 2-ethylhεxyl glycidyl εther (4.65g, 0.025 mole) werε combinεd in a flask without solvεnt. Thε mixturε was heatεd to 160°C, with the mixture liquifying at 145°C. The mixturε was hεatεd for 1 hr. betwεεn 160-170 C. Thε rεaction was cooled and slurried with 400 ml methanol. The solid that was formed (1.6g) was removed by filtration. The methanol filtrate was stripped under reduced preεεurε, lεaving 8.6g of a yεllow, viεcouε liquid. Liquid chromatographic analysis of the product indicaεted it waε a mixture of the εtarting hydrazide and the monoalkylated and dialkylatεd productε.

EXAMPLE VII

Reaction of the Hydrazide of Example

IV with Kraton FG 1910 X ¹ "

Kraton FG 1901 X™ (a sytrenε/butadiene block copolymer grafted with 2% maleic anhydride, a product of Shell Chemical Company) (30.Og, 0.006 maleic anhydride eguiv.) was addεd to 300 ml of hot xylene (122°C) . After the polymεr dissolvεd, the hydrazide of Example IV (2.2g, 0.006 mole) was added. The mixture was heatεd to reflux, and azeotropically distilled for 3 hrs. (no water formation noted) . The xylene (125 ml) was distilled from thε rεaction. Thε mixturε was cooled and stirred with 700 ml methanol for 1 hr. Thε solids which formed werε filtεrεd. Thε solids werε procεssed for 2 min. in 500 ml methanol using a Waring blender. The solidε wεrε filtεred, giving a weight of 22.6g. The infrarεd spectrum (nujol mull) showεd an imide band at 1730 cm . EXAMPLE VIII

Reaction of the Hydrazide of Example IV with Epolene E43™

Epolenε E43™ (polypropylεne grafted with

6-7% maleic anhydride, a product of Eastman Chemical Company) (50g, 0.03-0.05 maleic anhydridε εquiv.) was added to 300 ml hot stirrεd xylenε

(110°C) in a flask. Aftεr the Epolene dissolved,

thε hydrazidε of Exa plε IV was slowly added at 120 C. The mixture was heated to reflux, azeotropically distilling off all the water (collected 0.7 ml) over 1.5 hrs. The reaction mixture was clear yellow. The reaction was coolεd and thε solvεnt εtrippεd undεr prεssure yielding a εolid wεighing 55.53g and having a m.p. of 130- 136°C. Thε infrarεd spεctrum (xylene solution) showed a εtrong εharp imide band at 1730 cm , and a vεry wεak amic acid band at 1755 cm -1

EXAMPLE IX

Preparation of 3-[3-(2H-benzotriazol-

2-yl)-4-hydroxy-5-t-butylphenyl]-N'-

(butylaminocarbonyl) ropionyl hydrazide The hydrazide of Example IV (17.05g, 0.05 mole) was diluted with 200 ml THF in a 500 ml flask. Butyl isocyanate (5.0g, 0.05 mole) diluted with 25 ml THF was added to the hydrazide over 5 min. causing the tεmpεrature to rise from 23"C to 28°C. The mixture waε heatεd to reflux, clearing the initally milky white εolution. The reaction waε refluxεd for 1 hr, thεn cooled to room temperature and εtripped of εolvent under reduced pressurε to yiεld a εolid wεighing 20.4g and having a m.p. of 166-170°C. Thε infrarεd εpεctrum εhowεd

a strong carbonyl band at 1670 cm-1 with a weak shoulder at 1655 cm ^" .

EXAMPLE X Preparation of the 2-Butanone Hydrazone of the Hydrazide of Example IV

The hydrazide of Example IV (17.05g, 0.05 mole) and 250 ml xylene were combined in a flask.

2-Butanone (5.4g, 0.075 mole) was added to the stirring solution. The mixture was hεatεd to rεflux over 1 hr, cooled, then heated to azeotropically distill for 2 hrε., until watεr stoppεd coming over (collectεd 0.5 ml) . Thε solution was initially milky white, but turned clear at 105 C. The solution was cooled, and the solid filtered. The filtεr cakε was washεd with hexane and dried, leaving a powder weighing 16.8g, with a m.p. of 168-173°C. Thε infrarεd spectrum (nujol mull) εhowed a strong carbonyl band at 1660 cm ^" .

EXAMPLE XI

Reaction of the Hydrazide of Example IV with PA-18"

PA-18™ (an octadecene-maleic anhydride copolymer product of Chevron Chεmical Company) (21.9g, 0.0625 molε) was added to hot xylene

(100°C) in a 500 ml flask. The polymer solution

waε heated to 120°C and the hydrazidε of Examplε IV (17.05g, 0.05 molε) waε added over 1 min. The mixture was azeotropically distilled for 1.5 hrs. (collected 0.8g water). The reaction was stripped undεr rεduced prεεεure, yielding a solid weighing 35.3g, and having a m.p. of 120-124°C. The infrared spectrum (nujol mull) showed two strong sharp carbonyl bands at 1725 cm -l and 1610 cm-1

EXAMPLE XII Reaction of the Hydrazide of

Example IV with SMA 3000™

SMA 3000™ (a styrenε/malεic anhydridε copolymεr product of ARCO Chεmical Company) (26.8g,

0.0654 molε) was addεd to 250 ml hot xylεnε (100°C) in a 500 ml flask. Thε polymεr was heated to 120°C for the slow addition of thε hydrazide of Example IV (20.5g, 0.06 mole). Thε mixturε was azεotropically diεtillεd for 1.5 hrε. (collεctεd 0.9 ml watεr). Thε solution was coolεd to 100°C, thεn εtripped of εolvent undεr rεduced prεssurε, yiεlding a solid that weighed 45.9g, and had a m.p. of 195-199°C. The infrared spectrum (xylene εolution) εhowed a εtrong εharp carbonyl band at 1725 cm (i ide) and a wεak carbonyl band at 1780 cm (rεεidual anhydridε) .

EXAMPLE XIII

Preparation of 3-[3-(2H-benzotriazol-

2-yl)-4-hydroxy-5-t-butylphenyl]-N-(2- octadecylsuccinimido)propanamide Octadecyl succinic anhydride (17.6g, 0.05 mole) was placed in a 500 ml flask and diluted with

75 ml xylene. The solution was heatεd to azeotropically diεtill for 1 hr then cooled to

120°C. Additional xylene (175 ml) was added. At 130°C, the hydrazide of Examplε IV (17.05g, 0.05 molε) was slowly addεd. The mixture was azeotropically distilled for 2 hrs. The reaction was cooled and the εolvent stripped off under reduced pressure, leaving a viscous liquid. The liquid was placed on dry ice, causing solidification. The solid weighed 29.7g, and had a m.p. of 117-121°C. The infrared spεctrum (nujol mull) εhowed a strong sharp imide carbonyl band at

1730 cm -l, wi.th a shouldεr at 1675 cm-l.

EXAMPLE XIV

Reaction of the Hydrazide of Example III with Epolene E43™

Epolene E-43™ (50g, 0.018 mole) was added to 500 ml hot xylenε (100°C) . Thε hydrazidε of Examplε III (6.2g, 0.018 mole) waε added at 110°C.

The reaction was azeotropically distilled for 1.5 hrs. (collected 0.6g water). Thε reaction mixturε

waε cooled and thε precipitate filtered. The product wεighed 27.4g and had a m.p. of 139-144 C.

The infrared εpεctrum (xylene εolution) εhowed a weak anhydride band at 1775 cm —1, also a weak imide band at 1735 cm ^" , with an amide shoulder at 1700

_™ cm ^_1

EXAMPLE XVI Preparation of 2-( [2-hydroxy-3-(2H-benzo- triazol-2-yl)-5-methylphenyl]methylamino)- 2-oxo-N'-(3-carboxypropenoyl) cetyl hydrazide

Maleic anhydride (2.45g, 0.025 mole) and

250 ml THF were combined in a 500 ml flask equipped with a Dean Stark water separation assεmbly. The hydrazide of Example III (8.5g, 0.025 mole) was added accompanied by a riεe in temperature from

24°C to 29 ^β C. The mixture was heatεd to rεflux and rεfluxεd for 1 hr. , thεn coolεd. Thε solid was filtεred and rinsed with 250 ml THF. The filtrate and the rinsing solvent werε placed in a flask and heatεd. As the THF diεtilled, it waε rεplaced with xylene (200 ml) . When the solution temperature reachεd 135 ^β C the reaction was allowed to reflux 1 hour. The reaction mixture was cooled to 80 ^β C and the solid waε filtered and dried in air. The product weighεd 7.5g and had a m.p. of 198-210°C.

Thε infrarεd εpecturm ^* showed a εtrong carbonyl band at 1635 cm ^" .

EXAMPLE XVI Preparation of 2-([2-hydroxy-3-(2H-benzo- triazol-2-yl)-5-methylphenyl] ethylamino)- 2-oxo-N-(2-octadecysuccinimido)acetamide

Octadecylsuccinic anhydride (17.6g, 0.05 mole) and 250 ml xylene were combined in a 500 ml flask equipped with a Dean Stark water separation asεmbly. The mixture was warmed to 100"C for the incremental addition of the hydrazide of Example III (17.0g, 0.05 mole). Each portion gelled the reaction mixture and the temperature was raised to 130°C bεtwεεn additions to thin thε mixture. After completion, the reaction was refluxεd for 1 hr.

(collectεd 1.1 ml watεr). Thε rεaction mixturε was coolεd to 80"C and thε insolubleε removεd by filtration. Upon cooling to room tεmpεraturε, some of the product precipitatεd and waε isolatεd by filtration, giving 6.9g of solid with a m.p. of

104-108°C. Thε filtrate was stripped under reducεd prεssurε, leaving a viscous liquid. The liquid was εolidifiεd by cooling on dry ice for 30 min. The fine light yellow εolid weighεd 19.Og and had a m.p. of 106-110"C. Thε co binεd product weighed 25.9g. The infrared spectrum (xylene solution)

showed two sharp carbonyl bands at 1735 and 1685 cm

EXAMPLE XVII Preparation of 2-([2-hydroxy-3-(2H- benzotriazol-2-yl)-5-methylphenyl]methylamino)- 2-oxo-N'-(butylaminocarbonyl)acetyl hydrazide

The hydrazide of Example III (8.6g, 0.025 mol) was slurried with 200 ml THF in a 500 ml flask. Butyl isocyanatε (2.5g, 0.025 mole) in 25 ml THF was added and the mixture heated to reflux for 3 hrs. The mixture was coolεd and the solid filterεd. The solid was allowed to air dry yiεlding 8.Og of product having a m.p. of 201- 203"C. Thε infrared spectrum showed a weak carbonyl band at 1725 cm ^" and two strong carbonyl bands at 1690 and 1645 cm ^" .

EXAMPLE XVIII Preparation of 2-([2-hydroxy-3-(2H-benzo- triazol-2-yl)-5-methylphenyl]methylamino)- 2-oxo-N ⁷ -(octadecylaminocarbonyl)acetyl hydrazide

The hydrazide of Example III (8.6g, 0.025 mol) was slurried with 250 ml THF in a 500 ml flask. Octadecyl isocyanatε (7.4g, 0.025 mole) in

25 ml THF was added and the mixture stirrεd at room tεmpεraturε for 30 min., thεn hεated to reflux for

2 hrs. The mixture was filtered hot (100"C). The solid weighed S.lg and had a m.p. of 185-190 ^C C.

Upon standing, additional solid precipitated from the filtrate. Thiε, too, waε iεolated by filtration, giving 2.1g morε product with a m.p. of 185-190"C (total product 10.2g). Thε infrarεd εpectra of the two samples agreed, each having two strong sharp carbonyl bands at 1635 and 1685 cm with a shoulder at 1720 cm ^" .

EXAMPLE XIX Reaction of the Hydrazide of Example III with PA-18™

Xylenε (300 ml) waε hεatεd to 100-110°C in a 500 ml flaεk εquippεd with a Dean Stark water εeparation aεsεmbly. PA-18™ (21.9g, 0.0625 malεic anhydridε equiv.) was added. The mixture was cooled to 80°C for the addition of the hydrazide of Example III (17.Og, 0.05 mole) incremεntally over 90 minutes, allowing the hydrazide to disεolvε betweεn portionε. Aftεr half thε hydrazide waε added, the reaction waε heatεd to rεflux to rεmovε thε water that formed. The reaction waε cooled to 120 ^β C for thε addition of thε rεmaining hydrazide. The reaction waε rεfluxεd with azεotropic rεmoval of watεr for 2 hrε. Thε rεaction waε coolεd to 120 ^C C and thε insolublεε filtεrεd, then cooled to room tempεraturε and filtered again. The filtratε

waε stripped of solvent under reduced pressure to give 35.2g of product having a m.p. of 156-160°C. The infrarεd εpεctrum εhowεd a weak carbonyl band

— 1 at 1780 cm (anhydride) and strong carbonyl bands at 1730 and 1685 cm ^"1 .

EXAMPLE XX

Reaction of the Hydrazide of

Example II with PA-18™

PA-18™ (11.0g, 0.031 maleic anhydride eq.) was dissolved in 250 ml hot xylene in a 500 ml flask equipped with a Dean Stark water separation assembly. The polymer solution was hεatεd to reflux for thε addition of thε hydrazide of Examplε II (9.5g, 0.025 mole) in 3 portions over 30 min. After the addition, thε rεaction was azeotropically distilled to removε water for 90 min. (0.4-0.45 ml water collected). The solution waε cooled to 100"C and the solvent εtripped under reducεd pressure. The residue weighεd 20.7g and was pulvεrizεd in a mortar and pestle to form a light yellow powder (18.8g). The infrared spectrum (xylenε solution) showεd a εtrong carbonyl band at 1725 cm (imide) . The presεnt invεntion may bε embodied in_ other specific forms without departing from the spirit or essential attributes therεof and, accordingly, rεfεrεnce should be made to thε

appendεd claims, rathέr than to thε forεgoing εpecification aε indicating the εcope of the invention.