WO1990009369A1 - Hydrazides d'absorption des u.v. a base d'oxanilide et de benzatriazole - Google Patents

Hydrazides d'absorption des u.v. a base d'oxanilide et de benzatriazole Download PDF

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Publication number
WO1990009369A1
WO1990009369A1 PCT/US1989/000575 US8900575W WO9009369A1 WO 1990009369 A1 WO1990009369 A1 WO 1990009369A1 US 8900575 W US8900575 W US 8900575W WO 9009369 A1 WO9009369 A1 WO 9009369A1
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Prior art keywords
carbonε
carbons
diradical
substituted
aliphatic
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PCT/US1989/000575
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English (en)
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Ronald E. Mac Leay
Terry N. Myers
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Atochem North America, Inc.
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Application filed by Atochem North America, Inc. filed Critical Atochem North America, Inc.
Priority to JP50216989A priority Critical patent/JPH04505002A/ja
Priority to PCT/US1989/000575 priority patent/WO1990009369A1/fr
Priority to EP19890902346 priority patent/EP0409840A4/en
Priority to BR898907374A priority patent/BR8907374A/pt
Publication of WO1990009369A1 publication Critical patent/WO1990009369A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/26—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C243/28—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

  • 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.
  • a successful stabilizer additive In addition .o activity as a stabilizer on a ⁇ olar 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.
  • 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 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:
  • 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
  • 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
  • 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
  • R 2 i.s hydrogen, substituted or unsubstituted aliphatic of 1-8 carbons, or substituted or unsubstituted araliphatic of 7-9 carbons.
  • 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.
  • 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.
  • R 4, R5, R6 and R7 are independently hydrogen, hydroxy, alkyl of 1-8 carbons, alkoxy of
  • 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.
  • R is a direct bond or substituted or unsubstituted alkylene diradical of 1-4 carbons.
  • R is a direct bond, methylene or
  • 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
  • R is hydrogen, substituted or unsubstituted aliphatic of
  • 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.
  • R is a direct bond, aliphatic diradical of 1-8 carbons, 1,3-phenylene diradical or 1,4-phenylene diradical.
  • 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
  • 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.
  • R 12 is hydrogen, subs i ⁇ u ed or unsubstituted aliphatic oj
  • 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,
  • 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.
  • 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' ⁇ )-, with - li ⁇
  • 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.
  • 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
  • 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)-,
  • R 14 and R15 are independently substituted or unsubstituted aliphatic of 1-8 carbons, substituted or unsubstituted alicyclic of
  • 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.
  • 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
  • the cyclic group formed contains 5 or 6 atoms in the ring.
  • 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.
  • 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 ⁇ hat multiple heteroatoms must be seDarated from each other and the diradical ends by at least one carbon atom.
  • 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
  • R is a substituted or unsubstituted aliphatic diradical of
  • 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.
  • 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.
  • 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.
  • 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.
  • aryl diradical of 6-12 carbons
  • alicyclic diradical of 5-14 carbons substituted or unsubstituted araliphatic diradical of 7-22 carbons.
  • 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
  • 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.
  • R is hydrogen, aliphatic of 1 to 8 carbons, aliphatic acyl of 2-6 carbons, or substituted or unsubstituted benzoyl.
  • R is hydrogen, aliphatic of 1 to 8 carbons, aliphatic acyl of 2-6 carbons, or substituted or unsubstituted benzoyl.
  • R is methyl or hydrogen.
  • 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.
  • M is hydrogen or sodium ion.
  • M is hydrogen.
  • 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
  • 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.
  • 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:
  • 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.
  • 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- unde
  • R 1 and R2 are, independently, for example, ethoxy, ethoxy, 2-ethylhexyloxy, isopropoxy, 2-hydroxypropoxy, 2-(acyloyloxy)ethoxy, or sec-butoxy.
  • R 1, R4, R5 and R7 As substituted or unsubstituted alkoxycarbonyl of 2-8 carbons, R 1, R4, R5 and R7
  • 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.
  • R is, for example, methoxysulfonyl, or butoxysulfonyl.
  • 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.
  • 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.
  • 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, toly ⁇ , 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.
  • 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
  • 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.
  • 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,
  • 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.
  • 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.
  • 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,
  • 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-phen
  • 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,
  • 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.
  • 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
  • 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.
  • polymeric composition(s) include homopoly ers or any type of copolymers.
  • 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.
  • the polymeric compositions need not be, and typically are not, coreactive with the stabilizers.
  • the stabilizers of the present invention are effective UV stabilizers even when mixed with inert polymers.
  • 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.
  • 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.
  • 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.
  • novel compounds of Formula III are ester precursors used as intermediates to make certain hydrazides of Formula 1 ⁇ having corresponding structures and substituents.
  • 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.
  • Polyolefins derived from diolefins such as polybutadiene and polyisoprene.
  • Copolymers of monoolefins or diolefins such as ethylene-propylene, propylene- butene-1, propylene-isobutylene and ethylene- butene-1 copolymer.
  • EPDM ethylene and propylene with dienes
  • 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.
  • Styrenic polymers such as polystyrene (PS) and poly(p_-methylstyrene) .
  • 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- ⁇ tyrene block copolymers (StereonTMproducts available from Fire
  • Synthetic Rubber and Latex Co. graft copolymers of styrene-acrylonitrile on rubbers, such as butadiene (ABS) , polyisoprene or ⁇ tyrene- butadiene-styrene block copolymers, graft copolymers of styrene-methyl methacrylate on rubbers, such as polybutadiene (MBS) , butadiene- ⁇ tyrene radial block copolymers (e.g. KRO 3TM of Phillips Petroleum Co.), selectively hydrogenated butadiene-styrene block copolymers (e.g. Kraton GTM from Shell Chemical Co.), and mixtures thereof.
  • ABS butadiene
  • MVS polybutadiene
  • butadiene- ⁇ tyrene radial block copolymers e.g. KRO 3TM of Phillips Petroleum Co.
  • 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.
  • Halogenated rubbers such as chlorinated and/or brominated butyl rubbers or polyolefins and fluoroelastomers.
  • Polymer ⁇ and copolymer ⁇ derived from alpha, beta-unsaturated acids, anhydrides, esters, amides and nitriles or combinations thereof, such as polymer ⁇ 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.
  • 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.
  • Polymer ⁇ and copolymers derived from unsaturated amines such as poly(allyl melamine) .
  • Polycarbonates and especially the aromatic polycarbonates such a ⁇ those derived from phosgene and bisphenols such as bisphenol-A, tetrabromobi ⁇ phenol-A and tetramethylbi ⁇ phenol-A.
  • Polye ⁇ ter derived from dicarboxylic acid ⁇ and diols and/or hydroxycarboxylic acids or their corresponding lactones such a ⁇ polyalkylene phthalates (e.g. polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , and poly(l,4- dimethylcyclohexane terephthalate) or copolymers thereof) and polylactones ⁇ uch as polycaprolactone.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • poly(l,4- dimethylcyclohexane terephthalate) or copolymers thereof and polylactones ⁇ uch as polycaprolactone.
  • Polyarylates derived from bisphenols e.g. bisphenol-A
  • various aromatic acid ⁇ ⁇ uch as isophthalic and terephthalic acids or mixtures thereof.
  • Aromatic copolyestercarbonates having carbonate a ⁇ well a ⁇ e ⁇ ter linkage ⁇ pre ⁇ ent in the backbone of the polymer ⁇ such as those derived from bisphenol ⁇ , i ⁇ o- and terephthaloyl chlorides and phosgene.
  • Polyacetals such as polyoxy ethylenes and polyoxy ethylenes which contain ethylene oxide a ⁇ a comonomer.
  • Polya ides and copolyamide ⁇ which are derived from diamine ⁇ and dicarboxylic acids and/or from aminocarboxylic acid ⁇ or the corresponding lactones, such as the following nylons: 6, 6/6, 6/10, 11 and 12.
  • Cross-linked polymers which are derived from aldehydes on the one hand and from phenols, urea ⁇ and melamine on the other hand, such a ⁇ phenol-formaldehyde, urea-formaldehyde and melamine-formaldehvde resins.
  • Alkyl resin ⁇ such as glycerol- phthalic acid re ⁇ in ⁇ and mixtures thereof with melamine-formaldehyde resin ⁇ .
  • Blends of vinyl monomers and un ⁇ aturated polyester resins which are derived from copolyester ⁇ of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as from vinyl compounds (cro ⁇ slinking agents) and al ⁇ o halogen-containing, flame re ⁇ istant modifications thereof.
  • Natural polymer ⁇ ⁇ uch as cellulose and natural rubber, a ⁇ well as the chemically modified homologous derivatives thereof, such as cellulose acetate ⁇ , cellulose propionate, cellulose butyrate and the cellulose ethers, such as methyl and ethyl cellulose.
  • novel stabilizer ⁇ of thi ⁇ invention may be u ⁇ ed to ⁇ tabilize various combination ⁇ or blends of the above polymers or copoly er ⁇ . They are particularly u ⁇ eful in the ⁇ tabilization of polyolefins, acrylic coatings, ⁇ tyrenic ⁇ , 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.
  • antioxidants such as alkylated monophenols, alkylated hydroquinone ⁇ , hydroxylated thiodiphenyl ether ⁇ , alkylidene-bis- phenol ⁇ , hindered phenolic benzyl compound ⁇ , acylaminophenol ⁇ , e ⁇ ter ⁇ 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 e ⁇ ter ⁇ , e ⁇ ter ⁇ of ⁇ ub ⁇ tituted or un ⁇ ub ⁇ tituted benzoic acid ⁇ , diphenyl acrylate ⁇ , nickel chel
  • the novel UV absorber hydrazides are prepared by reacting UV absorber-substituted carboxylic acid e ⁇ ter ⁇ and halides, sulfonic acid esters and ⁇ ulfonyl halide ⁇ with hydrazine or hydrazine hydrate.
  • e ⁇ ter i ⁇ di ⁇ olved in a polar ⁇ olvent 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.
  • 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.
  • solvents such as isopropanol or ethylene glycol, are also acceptable.
  • the resulting hydrazides can be purified by recry ⁇ tallization from the lower alcohols.
  • Substituted hydrazides can be prepared by reacting the esters with substituted hydrazines.
  • Suitable benzotriazole-sub ⁇ tituted carboxylic acid ester ⁇ and oxaniiide-substituted carboxylic acid e ⁇ ter ⁇ are de ⁇ cribed 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 ester ⁇ may be prepared according to the following example ⁇ .
  • an acid acceptor e.g. potassium carbonate, tertiary amine
  • alkylation catalysts e.g. aminopyridine ⁇ , potassium iodide
  • Z' is -0-, -N(R 7)- or -S-, R l ⁇ lower alkyl of 1-4 carbon ⁇ or phenyl and R 1 and R4 are a ⁇ previou ⁇ ly defined.
  • R' is lower alkyl of 1-4 carbon ⁇ or allyl
  • R 1, R2 and R4 are as previously defined.
  • 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.
  • R is a direct bond
  • ⁇ uch esters may also be prepared by reaction with lower dialkyl oxalate or diphenyl oxalate.
  • Non-limiting example ⁇ of ⁇ u table hydrazines include hydrazine, hydrazine hydrate, 35-85% hydrazine hydrate, methylhydrazine, ethylhydrazine, propylhydrazine, isopropylhydrazine, n-butyIhydrazine, sec- butylhydrazine, n-amylhydrazine, ⁇ ec-amylhydrazine, n-hexylhydrazine and n-octylhydrazine, t- butyIhydrazine, phenyIhydrazine, benzylhydrazine and sec-octyIhydrazine.
  • Hydrazone derivative ⁇ of this invention are prepared by reacting the hydrazides with ketones, aldehyde ⁇ or formaldehyde in inert solvents, preferably in hydrocarbon solvents under azeotropic conditions. They may also be prepared by reacting hydrazone ⁇ of ketone ⁇ or aldehyd ⁇ with UV absorber-containing esters.
  • novel carbamoyl and thiocarbamoyl derivatives are prepar ⁇ d by reacting the hydrazides with isocyanates, di ⁇ cyanate ⁇ , i ⁇ othiocyanates or diisothiocyanates in aprotic polar solvents, such as tetrahydrofuran or dimethylformamide.
  • the coreactant is a compound that can ea ⁇ ily b ⁇ r ⁇ mov ⁇ d 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-sub ⁇ tituted amic acid esters in lower alcohol solutions to form 1,2-amoyl hydrazines.
  • Th ⁇ r ⁇ actions ar ⁇ normally carried out in refluxing alcohol (i.e. methanol) but may be carried out in higher boiling aprotic ⁇ olvent ⁇ or without ⁇ olvent by heating a mixture of the two components above their melting points.
  • the methyl and ethyl esters of N- ⁇ ubstituted oxamates and succinamates are the pref ⁇ rr ⁇ d cor ⁇ actants.
  • Th ⁇ novel acyl derivatives of the hydrazide may be prepared by reacting the esters with acid hydrazides in refluxing alcohol (i. ⁇ . methanol) .
  • the novel alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl and . aralkoxycarbonyl derivatives of the hdyrazide ⁇ 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).
  • thes ⁇ derivatives may be prepared by reacting the hydrazide with a disubstituted carbonate or ⁇ ub ⁇ tituted haloformate.
  • an additional base inorganic or amine
  • the novel sulfonyl derivatives of the hydrazides may be prepared by reacting the ester ⁇ with the corresponding sulfonyl hydrazide.
  • the novel alkyl derivatives of the hydrazid ⁇ s may be prepared by reacting the hydrazides with epoxide ⁇ .
  • 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 un ⁇ ubstituted hydrazid ⁇ to th ⁇ monoalkylated and dialkylated products is depend ⁇ nt upon the mole ratio of epoxid ⁇ to hydrazid ⁇ , th ⁇ temperature and the concentration, if the reaction is run in a solvent.
  • Non-limiting exampl ⁇ s of suitable ketones include acetone, methyl ethyl keton ⁇ , 2-p ⁇ ntanon ⁇ , 2-hexanone, 3-h ⁇ xanon ⁇ , 2-decanone, 3-methyl-2- pentanone, 4-methyl-2-pentanone, 4-methoxy-4- m ⁇ thyl-2-pentanone, cyclopentanone, cyclohexanone, 2,4-dimethyl-4-heptanon ⁇ , 3,5-dimethyl-4-heptanone, 2,4-dimethyl-3-p ⁇ ntanon ⁇ , 1,3-diphenylaceton ⁇ , 2- octanon ⁇ , 3-octanon ⁇ , dihydroi ⁇ ophoron ⁇ , 4-t- butylcycloh ⁇ xanon ⁇ , m ⁇ thyl cycloh ⁇ xyl ketone, ac ⁇ tophenone, 2,2,6,6-tetramethyl-4-piperidone and 2,6-di ⁇ thyl-2
  • Non-limiting exampl ⁇ of ⁇ uitabl ⁇ ald ⁇ hyd ⁇ included ⁇ formaldehyde, acetald ⁇ hyd ⁇ , butyraldehyde, dod ⁇ cyl ald ⁇ hyde, 2- ethylbutyraldehyde, heptald ⁇ hyde, isobutyraldehyde, i ⁇ ovaleraldehyde, octyl ald ⁇ hyde, propionaldehyde, benzaldehyde, 3,5-di-t-butyl-4-hydroxybenzaldehyde, 2,3-dimethyl-p_-ani ⁇ aldehyde, 3-hydroxybenzaldehyde, 1-naphthaldehyd ⁇ , ⁇ alicylald ⁇ hyde, p-tolualdehyd ⁇ and 2,3,4-trimethoxyb ⁇ nzald ⁇ hyde.
  • Non-limiting example ⁇ of ⁇ uitable i ⁇ ocyanat ⁇ s included ⁇ allyl isocyanat ⁇ , b ⁇ nzyl isocyanate, n-butyl isocyanat ⁇ , s ⁇ c-butyl i ⁇ ocyanate, isobutyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate, isopropyl isocyanate, 4-methoxyphenyl isocyanate, methyl isocyanate, octadecyl isocyanat ⁇ , 1-naphthyl isocyanate, phenyl isocyanate, o_-tolyl isocyanate, m-tolylisocyanate and p_-tolyl isocyanate, dimethyl-m- i ⁇ oprop ⁇ nylb ⁇ nzyl i ⁇ ocyanate and 2-isocyanatoethyl m ⁇ thacryl
  • Non-limiting ⁇ xampl ⁇ s of suitabl ⁇ isothiocyanat ⁇ s included ⁇ allyl isothiocyanat ⁇ , b ⁇ nzyl isothiocyanate, 4-bromophenyl i ⁇ othiocyanate, n-butyl i ⁇ othiocyanat ⁇ , s ⁇ c-butyl isothiocyanat ⁇ , isobutyl isothiocyanat ⁇ , t-butyl isothiocyanat ⁇ , 3-chloroph ⁇ nyl i ⁇ othiocyanat ⁇ , cycloh ⁇ xyl isothiocyanate, ethyl isothiocyanate, methyl isothiocyanate, propyl i ⁇ othiocyanat ⁇ , isopropyl isothiocyanat ⁇ , 1-naphthyl isothiocyanate, t-octyl isothiocyanate, phenethyl isothiocyanat ⁇ , phenyl iso
  • Non-limiting example ⁇ of suitable amic acid ester ⁇ include m ⁇ thyl oxamate, ⁇ thyl oxamat ⁇ , propyl oxamate, i ⁇ opropyl oxamate, n-butyl oxamate, phenyl oxamate, methyl ⁇ uccinamat ⁇ , ⁇ thyl succinamate, propyl ⁇ uccinamate, i ⁇ opropyl ⁇ uccinamat ⁇ , n-butyl ⁇ uccinamat ⁇ , ph ⁇ nyl ⁇ uccinamat ⁇ , ⁇ thyl N-(2,2,6,6-t ⁇ tram ⁇ thyl-4- piperidinyl)oxamate, methyl N-(2,2,6,6- t ⁇ tramethyl-4-piperidinyl)oxamat ⁇ , ethyl N- (2,2,6,6-tetramethyl-4-pip ⁇ ridinyl) ⁇ uccinamat ⁇ ,
  • Non-limiting ⁇ xampl ⁇ s of suitabl ⁇ acid hydrazid ⁇ s included ⁇ ac ⁇ tyl hydrazide, propionic hydrazide, butyric hydrazide, isobutyrichydrazide, val ⁇ ric hydrazid ⁇ , isoval ⁇ ric hydrazid ⁇ , caproic hydrazid ⁇ , d ⁇ canoic hydrazid ⁇ , lauric hydrazide, stearic hydrazide, benzhydrazide, 3,5-di-t-butyl- 4-hydroxyb ⁇ nzhydrazid ⁇ , 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)propi
  • Non-limiting exampl ⁇ s of suitabl ⁇ carbazat ⁇ include ethyl carbazate, methyl carbazate, propyl carbazate, isopropyl carbazate, butyl carbazate, cyclohexyl carbazate, cyclopentyl carbazat ⁇ , cyclodod ⁇ cyl carbazate, phenyl carbazate, b ⁇ nzyl carbazate, 4-t-butylcyclohexyl carbazat ⁇ , 2- ⁇ thylh ⁇ xyl carbazat ⁇ , 4-m ⁇ thylph ⁇ nyl carbazat ⁇ and 3-methoxypheny1 carbazate.
  • Non-limiting examples of suitable diaryl carbonates include diphenyl carbonate, di-(4- methylphenyl) carbonate, di-(3-methylph ⁇ nyl) carbonate, di-(3-methoxypheny1) carbonate, di- (2,6-dimethylph ⁇ nyl) carbonate and di-(2,5-di-t- butylph ⁇ nyl) carbonate.
  • Non-limiting examples of suitable sulfonyl halid ⁇ s include benzenesulfonyl hydrazide, 4-bromobenz ⁇ n ⁇ ulfonyl hydrazid ⁇ , 1-butan ⁇ ulfonyl hydrazide, 4-t-butylbenzenesulfonyl hydrazide, t>- toluene ⁇ ulfonyl hydrazide, ethane ⁇ ulfonyl hydrazide, ⁇ than ⁇ sulfonyl hydrazid ⁇ , 4- fluorobenz ⁇ ne ⁇ ulfonyl hydrazide, 1- h ⁇ xad ⁇ canesulfonyl hydrazid ⁇ , isopropan ⁇ sulfonyl hydrazid ⁇ and 1-naphthal ⁇ n ⁇ ulfonyl hydrazid ⁇ .
  • Non-limiting ⁇ xampl ⁇ s of suitable epoxid ⁇ s included ⁇ 1,2- ⁇ poxybutane, 2,3-epoxybutan ⁇ , 1,2- ⁇ poxycyclodod ⁇ can ⁇ , 1,2- ⁇ poxycycloh ⁇ xan ⁇ ,1,2- ⁇ poxyoctan ⁇ , 1,2- ⁇ poxyd ⁇ can ⁇ , 1,2- ⁇ poxydodecane, 1,2-epoxyoctadecan ⁇ , l,2- ⁇ poxy-3-ph ⁇ noxypropane, 2,3-epoxypropyl acrylat ⁇ , 2,3-epoxypropyl methacrylat ⁇ , 2,3- ⁇ poxypropyl 4-m ⁇ thoxyph ⁇ nyl ⁇ th ⁇ r, glycidyl isopropyl ⁇ th ⁇ r, glycidyl n-h ⁇ xyl ⁇ th ⁇ r, glycidyl dod ⁇ cyl ⁇ th ⁇ r and glycidyl octad ⁇
  • Th ⁇ following ⁇ xamples are pre ⁇ ent ⁇ d to provide a more detailed explanation of the pre ⁇ nt inv ⁇ ntion and ar ⁇ int ⁇ nd ⁇ d a ⁇ illu ⁇ tration ⁇ and not limitations of th ⁇ inv ⁇ ntion. Unless otherwis ⁇ stated herein, the t ⁇ mp ⁇ ratur ⁇ s ar ⁇ in d ⁇ gr ⁇ C ⁇ ntigrade and all parts are by weight.
  • the reaction was maintained at this temp ⁇ ratur ⁇ for 24 hr ⁇ .
  • the reaction mixture wa ⁇ ⁇ tirred with 250 ml water and 250 ml methylen ⁇ chlorid ⁇ .
  • Th ⁇ phas ⁇ s w ⁇ r ⁇ separated and the organic phas ⁇ wash ⁇ d twic ⁇ with 200 ml portions of water.
  • the organic solution was dried with anhydrous ⁇ odium ⁇ ulfate and magne ⁇ ium ⁇ ulfate and stripped using a ⁇ pirator vacuum.
  • Liquid chromatographic assay ⁇ how ⁇ d about 60% of th ⁇ title compound, about 30% n-butanol and about 4% starting benzotriazol ⁇ .
  • Polyethyl ⁇ ne glycol e ⁇ ter 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 mix ⁇ d with 335 ml m ⁇ thanol (two liquid phas ⁇ ) .
  • To thi ⁇ wa ⁇ add ⁇ d 54% aq. hydrazin ⁇ (60g, 0.1 mol ⁇ ).
  • Th ⁇ reaction wa ⁇ heated to 40 C, forming a homogeneou ⁇ solution. This temperature was maintained for 1 hr.
  • Example (13.95g, 0.038 mole) was slurri ⁇ d in 150 ml of m ⁇ thanol in a 500 ml fla ⁇ k. Added to the e ⁇ t ⁇ r was 54% hydrazine (5g, 0.084 mole). Shortly after addition th ⁇ reaction gelled. Methanol (50 ml) was added to dilute the reaction. The r ⁇ action was heated to reflux, and refluxed for 1.5 hrs., then cooled and allowed to stand 16 hrs. The r ⁇ action was again h ⁇ ated to reflux and reflux ⁇ d for 2 hrs. Th ⁇ insolubl ⁇ s w ⁇ r ⁇ filt ⁇ r ⁇ d from th ⁇ hot (60°C) ⁇ olution.
  • Th ⁇ filtrat ⁇ wa ⁇ r ⁇ duc ⁇ d in volume by distillation 144 ml remov ⁇ d
  • Th ⁇ solution was cool ⁇ d to 60 C, and solids filt ⁇ r ⁇ d. A pr ⁇ cipitate formed in the filtrate and this was isolated by another filtration.
  • the combined solids were air dried and weigh ⁇ d 1.5g and had a m.p. of 212-216°C.
  • Th ⁇ infrar ⁇ d spectrum ⁇ howed a ⁇ trong OH band at 3295 cm , a ⁇ trong ⁇ harp carbonyl band at 1635 cm , and a m ⁇ diu ⁇ harp carbonyl band at 1550 cm , with a w ⁇ ak ⁇ houlder at 1510 cm
  • Kraton FG 1901 XTM (a sytren ⁇ /butadiene block copolymer grafted with 2% maleic anhydride, a product of Shell Chemical Company) (30.Og, 0.006 maleic anhydride eguiv.) was add ⁇ d to 300 ml of hot xylene (122°C) . After the polym ⁇ r dissolv ⁇ d, the hydrazide of Example IV (2.2g, 0.006 mole) was added. The mixture was heat ⁇ d to reflux, and azeotropically distilled for 3 hrs. (no water formation noted) . The xylene (125 ml) was distilled from th ⁇ r ⁇ action.
  • Th ⁇ mixtur ⁇ was cooled and stirred with 700 ml methanol for 1 hr. Th ⁇ solids which formed were ⁇ filt ⁇ r ⁇ d. Th ⁇ solids were ⁇ proc ⁇ ssed for 2 min. in 500 ml methanol using a Waring blender. The solid ⁇ w ⁇ r ⁇ filt ⁇ red, giving a weight of 22.6g. The infrar ⁇ d spectrum (nujol mull) show ⁇ d an imide band at 1730 cm . EXAMPLE VIII
  • Example IV The hydrazide of Example IV (17.05g, 0.05 mole) and 250 ml xylene were combined in a flask.
  • PA-18TM an octadecene-maleic anhydride copolymer product of Chevron Ch ⁇ mical Company
  • SMA 3000TM (a styren ⁇ /mal ⁇ ic anhydrid ⁇ copolym ⁇ r product of ARCO Ch ⁇ mical Company) (26.8g,
  • Epolene E-43TM (50g, 0.018 mole) was added to 500 ml hot xylen ⁇ (100°C) .
  • Th ⁇ hydrazid ⁇ of Exampl ⁇ III (6.2g, 0.018 mole) wa ⁇ added at 110°C.
  • reaction was azeotropically distilled for 1.5 hrs. (collected 0.6g water). Th ⁇ reaction mixtur ⁇ wa ⁇ cooled and th ⁇ precipitate filtered. The product w ⁇ ighed 27.4g and had a m.p. of 139-144 C.
  • Example III 250 ml THF were combined in a 500 ml flask equipped with a Dean Stark water separation ass ⁇ mbly.
  • the hydrazide of Example III (8.5g, 0.025 mole) was added accompanied by a ri ⁇ e in temperature from
  • Th ⁇ filtrate was stripped under reduc ⁇ d pr ⁇ ssur ⁇ , leaving a viscous liquid.
  • the liquid was ⁇ olidifi ⁇ d by cooling on dry ice for 30 min.
  • the fine light yellow ⁇ olid weigh ⁇ d 19.Og and had a m.p. of 106-110"C.
  • Th ⁇ co bin ⁇ d product weighed 25.9g.
  • the infrared spectrum (xylene solution) showed two sharp carbonyl bands at 1735 and 1685 cm
  • Example III The hydrazide of Example III (8.6g, 0.025 mol) was slurried with 200 ml THF in a 500 ml flask. Butyl isocyanat ⁇ (2.5g, 0.025 mole) in 25 ml THF was added and the mixture heated to reflux for 3 hrs. The mixture was cool ⁇ d and the solid filter ⁇ d. The solid was allowed to air dry yi ⁇ lding 8.Og of product having a m.p. of 201- 203"C. Th ⁇ infrared spectrum showed a weak carbonyl band at 1725 cm " and two strong carbonyl bands at 1690 and 1645 cm " .
  • Example III The hydrazide of Example III (8.6g, 0.025 mol) was slurried with 250 ml THF in a 500 ml flask. Octadecyl isocyanat ⁇ (7.4g, 0.025 mole) in
  • PA-18TM (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 h ⁇ at ⁇ d to reflux for th ⁇ addition of th ⁇ hydrazide of Exampl ⁇ II (9.5g, 0.025 mole) in 3 portions over 30 min.
  • th ⁇ r ⁇ action was azeotropically distilled to remov ⁇ water for 90 min. (0.4-0.45 ml water collected).
  • the solution wa ⁇ cooled to 100"C and the solvent ⁇ tripped under reduc ⁇ d pressure.
  • the residue weigh ⁇ d 20.7g and was pulv ⁇ riz ⁇ d in a mortar and pestle to form a light yellow powder (18.8g).
  • the infrared spectrum (xylen ⁇ solution) show ⁇ d a ⁇ trong carbonyl band at 1725 cm (imide) .
  • the pres ⁇ nt inv ⁇ ntion may b ⁇ embodied in_ other specific forms without departing from the spirit or essential attributes ther ⁇ of and, accordingly, r ⁇ f ⁇ r ⁇ nce should be made to th ⁇ append ⁇ d claims, rath ⁇ r than to th ⁇ for ⁇ going ⁇ pecification a ⁇ indicating the ⁇ cope of the invention.

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Abstract

On décrit des agents d'absorption d'ultraviolets à base d'oxanilide et de benzatriazole à fonction hydrazide (formules I et II), utiles pour stabiliser des compositions de polymères coréactives ou inertes, ainsi que des intermédiaires nouveaux (formules III servant à produire certains types de composés de la formule I), dont les formules générales sont les suivantes: (I) ou (II) ou (III) où R?1, R2, R3, R4, R5, R6, R7, R8, R9¿, X, Y, tous leurs substituants, et n, ont la valeur décrite dans le descriptif de l'invention.
PCT/US1989/000575 1989-02-13 1989-02-13 Hydrazides d'absorption des u.v. a base d'oxanilide et de benzatriazole WO1990009369A1 (fr)

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JP50216989A JPH04505002A (ja) 1989-02-13 1989-02-13 ベンゾトリアゾール及びオキサニリドｕｖ吸収ヒドラジド
PCT/US1989/000575 WO1990009369A1 (fr) 1989-02-13 1989-02-13 Hydrazides d'absorption des u.v. a base d'oxanilide et de benzatriazole
EP19890902346 EP0409840A4 (en) 1989-02-13 1989-02-13 Benzotriazole and oxanilide uv absorber hydrazides
BR898907374A BR8907374A (pt) 1989-02-13 1989-02-13 Composto quimico

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4008799A1 (de) * 1989-03-21 1990-09-27 Ciba Geigy Ag Verfahren zum modifizieren von acrylatcopolymeren
EP0593936A1 (fr) * 1992-09-24 1994-04-27 Elf Atochem North America, Inc. N-2-hydroxy-3-(2H-benzotriazolyl-2)benzyl oxamides comme stabilisateurs à la lumière
US5516914A (en) * 1991-02-12 1996-05-14 Ciba-Geigy Corporation Compositions stabilized with 5-thio-substituted benzotriazole UV-absorbers
US5683861A (en) * 1996-10-23 1997-11-04 Eastman Kodak Company Benzotriazole-based UV absorbers and photographic elements containing them
US5739348A (en) * 1996-10-23 1998-04-14 Eastman Kodak Company Method of synthesizing tert-amido-substituted 2-(2'-hydroxyphenyl) benzotriazole compounds in a one-step process
EP2949732A1 (fr) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Utilisation d'un composé de oxanilide dans une composition de carburant diesel dans le but de modifier le retard d'allumage et/ou la durée de combustion
EP2949733A1 (fr) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Compositions d'essence contenant d'absorbants uv de type oxanilide

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US4172188A (en) * 1971-12-23 1979-10-23 Bayer Aktiengesellschaft Difunctional polymers with terminal hydrazide groups
US3894083A (en) * 1972-09-21 1975-07-08 Sandoz Ltd Amides
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US4041044A (en) * 1974-11-25 1977-08-09 Ciba-Geigy Corporation Process for the production of 2-aryl-2H-benzotriazoles
US4258059A (en) * 1978-12-15 1981-03-24 Usv Pharmaceutical Corporation Amino-benzamides
US4533612A (en) * 1983-04-27 1985-08-06 Basf Aktiengesellschaft Electrophotographic recording materials containing special charge carrier-transporting compounds
US4642350A (en) * 1983-06-01 1987-02-10 Ciba-Geigy Corporation Novel process for preparation of benzotriazoles using aryldiols and quinones
US4675352A (en) * 1985-01-22 1987-06-23 Ciba-Geigy Corporation Liquid 2-(2-hydroxy-3-higher branched alkyl-5-methyl-phenyl)-2H-benzotriazole mixtures, stabilized compositions and processes for preparing liquid mixtures

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4008799A1 (de) * 1989-03-21 1990-09-27 Ciba Geigy Ag Verfahren zum modifizieren von acrylatcopolymeren
DE4008799C2 (de) * 1989-03-21 1999-07-22 Ciba Geigy Ag Verfahren zum Modifizieren von Acrylatcopolymeren
US5516914A (en) * 1991-02-12 1996-05-14 Ciba-Geigy Corporation Compositions stabilized with 5-thio-substituted benzotriazole UV-absorbers
US5942626A (en) * 1991-02-12 1999-08-24 Ciba Specialty Chemicals Corporation Process for making 5-thio-substituted benzotriazole UV absorbers
EP0593936A1 (fr) * 1992-09-24 1994-04-27 Elf Atochem North America, Inc. N-2-hydroxy-3-(2H-benzotriazolyl-2)benzyl oxamides comme stabilisateurs à la lumière
US5683861A (en) * 1996-10-23 1997-11-04 Eastman Kodak Company Benzotriazole-based UV absorbers and photographic elements containing them
US5739348A (en) * 1996-10-23 1998-04-14 Eastman Kodak Company Method of synthesizing tert-amido-substituted 2-(2'-hydroxyphenyl) benzotriazole compounds in a one-step process
EP2949732A1 (fr) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Utilisation d'un composé de oxanilide dans une composition de carburant diesel dans le but de modifier le retard d'allumage et/ou la durée de combustion
EP2949733A1 (fr) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Compositions d'essence contenant d'absorbants uv de type oxanilide

Also Published As

Publication number Publication date
BR8907374A (pt) 1991-04-23
EP0409840A4 (en) 1991-09-04
EP0409840A1 (fr) 1991-01-30
JPH04505002A (ja) 1992-09-03

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