EP0994855A1 - Melanges synergiques photostabilisants pour des polymeres organiques - Google Patents

Melanges synergiques photostabilisants pour des polymeres organiques

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Publication number
EP0994855A1
EP0994855A1 EP98932149A EP98932149A EP0994855A1 EP 0994855 A1 EP0994855 A1 EP 0994855A1 EP 98932149 A EP98932149 A EP 98932149A EP 98932149 A EP98932149 A EP 98932149A EP 0994855 A1 EP0994855 A1 EP 0994855A1
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EP
European Patent Office
Prior art keywords
group
general formula
compounds
organic polymers
alkyl group
Prior art date
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Application number
EP98932149A
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German (de)
English (en)
Inventor
Carlo Neri
Fabio Broussard
Luciana Crisci
Mauro Adovasio
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Lanxess Switzerland GmbH
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Great Lakes Chemical Europe GmbH
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Publication of EP0994855A1 publication Critical patent/EP0994855A1/fr
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    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Definitions

  • the present invention relates to light-stabilizing synergic mixtures for organic polymers. More specifically, the present invention relates to stabilizing mixtures for organic polymers comprising one or more compounds belonging to the group of enami- nes, consisting of derivatives of ?-keto-esters, or /3-keto-amides or 1, 3-diketones with primary or second- ary aliphatic or aromatic amines and one or more compounds belonging to the group of sterically hindered amines (HALS) known in the art and their use in the light-stabilization of organic polymers.
  • HALS sterically hindered amines
  • the present invention also relates to the poly er- ic compositions light-stabilized with the above mixtures and the end-articles obtained from these compositions.
  • organic polymers undergo degradation over a period of time as a result of exposure to atmospheric agents and mainly to ultraviolet radiation, and they also easily undergo thermoxidative degradation during processing and transformation processes.
  • This degradation results in a deterioration in the physical characteristics of organic polymers such as, for example, a decrease in the impact strength and flexure, as well as alterations in the optical properties of the end-article.
  • stabilizing compounds are usually introduced into the organic polymers.
  • HALS sterically hindered amines
  • the present invention therefore relates to stabilizing mixtures for organic polymers comprising: (a) one or more compounds belonging to the group of enamines, consisting of derivatives of 3-keto- esters, or ?-keto-amides or 1, 3-diketones with primary or secondary, aliphatic or aromatic amines, having general formula (I) :
  • n represents an integer from 1 to 4 , extremes included
  • R 1 represents a triazine having one of the following general formula (II) , (III) or
  • R ⁇ represents a hydrogen atom ; a linear or branched C,-C 1a alkyl group; a -NHR 6 amine group or a -SR 6 group wherein R 6 represents a hydrogen atom or a linear or branched C.-C jg alkyl group; 5 - R.
  • R 2 represent a hydrogen atom; a linear or branched C.,-C 18 alkyl group; a linear or branched C 2 -C 3 alkoxyalkyl group; a C 5 -C 8 cycloalkyl group optionally containing a heteroatom selected 10 from oxygen, nitrogen and sulfur; a C 6 -C ⁇ a aryl group; a C 7 -C 20 arylalkyl or alkylaryl group; a group having general formula (V):
  • R 7 represents a hydrogen atom; a linear or branched C ⁇ C. g alkyl group, said alkyl group optionally substituted with an
  • R_ represents a hydrogen atom, a linear or branched C.-C jg alkyl group, or a C 6 -C 18 aryl group; an -OR, group wherein R ⁇ represents a hydrogen atom, or a linear or branched C ⁇ C. g alkyl
  • R 3 and R 4 represent a linear or branched C.-C 18 alkyl group; a C 6 -C 18 aryl group; a C 7 -C 20 alkylaryl or arylalkyl group; a linear or branched ⁇ -C 8 alkoxyl 10 group; or, R 4 represents a group having general formula (VI) :
  • R 7 has the same meanings defined above ; or, R 4 represents an NR ⁇ R.. group wherein R 10
  • R ⁇ represent a hydrogen atom; a linear or branched C.-C ⁇ alkyl group; a linear or branched C 2 -C 8 alkoxyalkyl group; a C 5 -C 3 cycloalkyl group optionally containing a heteroatom selected
  • R 7 has the same meanings defined above ; or, R 10 and R ⁇ considered jointly with the nitrogen atom, represent a 5 -C 8 heterocyclic
  • R 4 represents a group having one of the following general formulae (VII) , (VIII) or (IX) :
  • R 12 represents a hydrogen atom; or a linear or branched C ⁇ C jg alkyl group; R 13 represents a linear or branched C,-C 18 alkyl group; a -COCH 2 COCH 3 group; or a direct bond; (b) one or more compounds belonging to the group of sterically hindered amines.
  • R, , R 2 , R 10 and R ⁇ groups, as well as a hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl , 4- (2 , 2 , 6 , 6-tetramethyl) piperidinyl, 4- (2 , 2 , 6, 6-tetramethyl) -1-butoxyethylpiperidinyl, 4- (2 ,2, 6, 6-tetramethyl) -1-butoxypiperidinyl, 4- (2, 2, 6, 6-tetramethyl) -1-methylpiperidinyl, 3 , 5-dioctylaminotriazine, 3 , 5-dibutylaminotriazine, etc..
  • Examples of C 5 -C 8 heterocyclic groups, when R. and R 2 or R 10 and R.,. are considered jointly with the nitrogen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazol- idine, etc..
  • R 3 and R 4 groups are: methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybu- tyl, etc..
  • R 4 groups when R represents a group having general formula (VI), are: 4- (2, 2, 6, 6-tetramethyl)piperidinoxy, N-methyl-4-(2,2, 6, 6-tetramethyl) pi- peridinoxy, N-methoxyethyl-4- (2 , 2,6, 6-tetramethyl) pipe- ridinoxy, N-methylaminoethyl-4-(2,2, 6, 6-tetramethyl)pi- peridinoxy, etc..
  • R 4 groups when R 4 represents a group having general formula (VII) , (VIII) or (IX) and n is 2, are:
  • R 4 groups when R 4 represents a group having general formula (VII) , (VIII) or (IX) and n is 3, are:
  • R 4 groups when R 4 represents a group having general formula (VII) , (VIII) or (IX) and n is
  • R 7 groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, ⁇ -hydroxyethyl , /?-methoxyethyl, ?-butoxyethyl, methylaminoethyl, etc.
  • R j , R 6 , R g , R 9 , R 12 and R 13 groups when said groups represent a linear or branched C.-C. g alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc..
  • the compounds having general formula (I) described above can be obtained by means of various processes.
  • One process for the synthesis of the compounds having general formula (I) comprises the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having general formula (X) : HNR j R-, (X) wherein R 1 and R 2 have the same meanings defined above, with 1-3 moles of a 3-keto-ester, or a /3-keto-amide, or a 1,3-diketone having general formula (XI): ( R 3 —C—CH 2 —C—) n —R 4 (XI) w ⁇ . 0 0 wherein R 3 , R 4 and n have the same meanings defined above .
  • the above reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature ranging from 60 °C to 160 °C, preferably from 115 °C to 150 °C, at atmospheric pressure, and for a time ranging from 0.5 to 24 hours, preferably from 3 to 10 hours.
  • an inert organic solvent preferably a hydrocarbon, in particular toluene
  • Acetic acid can optionally be added as catalyst to this reaction.
  • reaction water is released which is separated by azeotropic distillation using an apparatus for azeotropic distillation, whereas the organic solvent is recycled.
  • the desired compound having general formula (I) is purified from the raw product thus obtained by fractionated distillation, operating under vacuum, at a pressure ranging from 0.1 mm/Hg to 50 mm/Hg and a temperature ranging from 40 °C to 200 "C. Or, said compound having general formula (I) is separated by crystallization using techniques known in the art.
  • Examples of primary or secondary, aliphatic or aromatic amines, having general formula (X) which can be used for the purposes of the above reported process are: cyclohexylamine, n-butylamine, tert-butyla ine, n-octy-lamine, tert-octylamine, n-octadecylamine, n-do- decylamine, benzylamine, 2-methoxyethylamine, 2-furfu- rylamine, pyrrolidine, piperidine, morpholine, dibenzy- la ine, aniline, diphenylamine, melamine, 4-amino-2,2, 6 , 6-tetramethylpiperidine, 4-amino-2 ,2,6, 6-te-trameth- yl-1-methylpiperidine, 4-amino-2 ,2,6, 6-tetramethyl-l- butoxyethylpiperidine, l-amino-3 , 5-d
  • Examples of /3-keto-esters or 3-keto-amides, or 1, 3-diketones having general formula (XI) which can be used for the purposes of the above reported process are: ethyl acetoacetate, ethyl benzoylacetate, acetyla- cetone, benzoylacetone, p-toluylacetone, 4-(2, 2,6,6- tetramethyl) piperidinyl acetoacetate, N-methyl-4- (2 , 2 , 6, 6-tetramethyl) piperidinyl acetoacetate, aceto- acetamide, acetoacet-4- (2,2,6,6, -tetra ethylpiperidi- ne) amide, acetoacet- (3 , 5-dibutyltriazine) -1-amide, etc.
  • Sterically hindered amines (b) which can be used for the purposes of the present invention can be selected from compounds (b-l)-(b-25) indicated hereunder.
  • Compounds (b-l) can be selected from: bis (1,2, 2, 6 , 6-pentamethyl-4-piperidinyl) -n-butyl-3 , 5- di-t-butyl-4-hydroxybenzylmalonate, tris (2,2,6,6- tetramethyl-4-piperidinyl) nitrilotriacetate, tetrakis- (2,2,6, 6-tetramethyl-4-piperidinyl) -1,2,3 , 4-butanete- tracarboxylate, 1, 1'- (1, 2-ethanediyl) -bis- (3 , 3 , 5, 5- tetramethylpiperazinone) , 4-benzoyl-2 , 2 , 6, 6-tetrame- thylpiperidine , 3-n-o ⁇ ty
  • R'. represents a hy ⁇ rogen atom; a C.-C 18 alkyl group; a ⁇ -C ⁇ 2 cycloalkyl group optionally substituted with a C ⁇ -C ⁇ alkyl group; n 1 represents 1, 2, or 4 ; when n 1 is 1, R' 2 represents a C ⁇ -C z5 alkyl group; when n. is 2, R' 2 ' represents a C ⁇ -C ⁇ alkylene group; when n 1 is 4, R' 2 represents a C ⁇ -C ⁇ tetrayl-alkane group.
  • R' 3 and R' 7 represent a hydrogen atom; or a ⁇ -C alkyl group; - R r R's anc * R 6 tne same or different, represent a C 2 -c 10 alkylene group ; and
  • X. , X 2 , X 3 , X 4 , X s , X 6 , X 7 and X 8 represent a group having general formula (XIV) :
  • R' 8 represents a hydrogen atom; a C - ⁇ z alkyl group; a C 5 -C 12 cycloalkyl group optionally substituted with a ⁇ -C ⁇ alkyl group; a phenyl group optionally substituted with an -OH group and/or a ⁇ -C ⁇ alkyl group; a C 7 -C 9 phenylalkyl group optionally substituted in the phenyl group with an -OH group and/or a
  • R' 9 and R' 10 the same or different, have the same meanings as R' r
  • Compounds (b-4) can be selected from the compounds having general formula (XVI) :
  • Compounds (b-5) can be selected from the compounds having general formula (XVII) :
  • R' , R' 13 , R' ⁇ and R' 15 represent a hydrogen atom; a C.-C. j alkyl group; a C 3 -C 12 cycloalkyl group optionally substituted with a C 1 -C 4 alkyl group; a phenyl group optionally substituted with an -OH group and/or a C.,-C 10 alkyl group; a C 7 -C 9 phenylalkyl group optionally substituted in the phenyl group with an -OH group and/or a C ⁇ C ⁇ alkyl group; or they represent a group having general formula (XV) ;
  • R' 12 represents a C 2 -C ⁇ a alkylene group; a C 5 -C 7 cycloalkylene group; or a ⁇ -C ⁇ alkylene di(C 5 -C 7 cycloalkylene) group; or R' ⁇ , R' 12 and R' 13 considered jointly with the nitrogen atom to which they are bound, represent a C 5 -C 1Q heterocyclic ring; or R' 14 and R' 1S , considered jointly with the nitrogen atom to which they are bound, represent a C 5 -C 10 heterocyclic ring; n 2 is a number between 2 and 50 and at least one of the substituents R' , R' 13 R' 14 and R' 15 , represents a group having general formula (XV) .
  • Compounds (b-6) can be selected from the compounds having general formula (XVIII) :
  • R' 1 ⁇ represents:
  • R' 23 represents a hydrogen atom
  • C -C ⁇ 2 alkyl group a C 5 ⁇ C 12 cycloalkyl group optionally substituted with a C.-C 4 alkyl group; a -CH 2 CN group; a C 3 -C 6 alkenyl group; a C 7 -C 9 phenyl- alkyl group optionally substituted in the phenyl group with a C 1 -C alkyl group;
  • R' 24 represents a linear or branched C ⁇ C j alkyl group ;
  • R' 17 , R' 19 and R' 20 the same or different, repre- sent a linear or branched C ⁇ C ⁇ group; a C 5 -C 10 cycloaliphatic or alkylcycloaliphatic group; an aromatic group with 6 carbon atoms, said aromatic group optionally substituted with linear or branched 0,,-C.,-, alkyl or alkenyl groups;
  • - R' 18 represents a linear or branched C.-C 10 alkylene group or one of the following groups:
  • n represent an integer so that 4 ⁇ m+n ⁇ 60;
  • R' 22 represents a hydrogen atom or a
  • R' 17 has the same meaning defined above ; or, R' 21 and R' 22 jointly represent a direct bond, giving rise to a cyclic structure.
  • Compounds (b-7) can be selected from the compounds obtained as follows:
  • n 4 , n 7 and n 4 represent a number between 2 and 12 ; and R' 27 represents a hydrogen atom; a C ⁇ C ⁇ alkyl group; a C 3 -C 12 cycloalkyl group; a phenyl group; a C 6 -C 9 phenylalkyl group; and
  • R' 2S has the same meaning as R 7 ..
  • R' 29 and R' 34 represent a direct bond; or a -N(Y.) -C0-Y 2 -C0-N(Y 3 ) - group wherein:
  • Y 1 and Y 3 represent a hydrogen atom; a C,-C 8 alkyl group; a C 5 -C 12 cycloalkyl group ; a phenyl group ; a C 7 -C 9 phenylalkyl group; or a group having general formula (XV) ⁇
  • Y 2 represents a direct bond; or a C 1 -C 4 alky- lene group
  • Compounds (b-9) can be selected from the compounds having general formula (XXIII) :
  • R 7 37 represents a C.,-C 24 alkyl group
  • R' 38 has the same meaning as R 7 1
  • Compounds (b-10) can be selected from the compounds having general formula (XXIV) :
  • R' 39 has the same meaning as R ⁇ ; and - n 6 is a number between 2 and 50.
  • Compounds (b-11) can be selected from the compounds having general formula (XXV) :
  • R' 40 and R 41 together form a C 2 ⁇ C 14 alkylene group
  • - R' 42 represents a hydrogen atom or a -Z ⁇ COO-Z j group wherein Z. represents a C 2 -C 14 alkylene group and Z 2 represents a C ⁇ C ⁇ alkyl group;
  • R' 43 has the same meaning as R 7 -.
  • Compounds (b-12) can be selected from the com- pounds having general formula (XXVI) :
  • R' 49 has the same meaning as R 7 ,; and n 7 is a number between 1 and 50.
  • Compounds (b-13) can be selected from the compounds having general formula (XXVII) :
  • a 1 represents a hydrogen atom; a ⁇ -C 8 alkyl group
  • a 3 and A 7 represent a hydrogen atom; or a C.-C 12 alkyl group; - A 4 , A 5 and A 6 , the same or different, represent a C 2 -C 10 alkylene group; and
  • T., T 2 , T 3 , T 4 , T 5 , T 6 , T 7 and T 8 represent a group having general formula (XXXI) :
  • a 8 represents a hydrogen atom; a C,-C 12 alkyl group; a C 5 -C 12 cycloalkyl group optionally substituted with a C ⁇ -C ⁇ alkyl group; a phenyl -group optionally substituted with an -OH group and/or a C.,-C 10 alkyl group; a C 7 -C 9 phenylalkyl group optionally substituted in the phenyl group with an -OH group and/or a C. j -C. jQ alkyl group; or it represents a group having general formula (XXXII)
  • Compounds (b-16) can be selected from the compounds having general formula (XXXIII) :
  • T 9 , T 10 and T.,., the same or different, represent a group having general formula (XXXI) .
  • Compounds (b-17) can be selected from compounds having general formula (XXXIV) :
  • A.., A 13 , A. 4 and A 15 represent a hydrogen atom; a C ⁇ -C 2 alkyl group; a C 5 -C 2 cycloalkyl group optionally substituted with a C 1 -C 4 alkyl group; a phenyl group optionally substituted with an -OH group and/or a C.-C. g alkyl group; a C 7 -C 9 phenylalkyl group optionally substituted in the phenyl group with an -OH group and/or a C ⁇ C. Q alkyl group; or they represent a group having general formula (XXXII) ;
  • a 12 represents a C 2 -C 18 alkylene group; a C 5 -C 7 cycloalkylene group; or a C 1 -C 4 alkylene di(C 5 -C 7 cycloalkylene) group; - or A , A 12 and A 13 , considered jointly with the nitrogen atom to which they are bound, represent a C 5 -C 10 heterocyclic ring; or A 14 and A 15 , considered jointly with the nitrogen atom to which they are bound, represent a C 5 -C 10 heterocyclic ring; b 2 is a number between 2 and 50 and at least one of the substituents A , A 13 , A 14 and A 15 , represent a group having general formula (XXXII) .
  • Compounds (b-18) can be selected from the com- pounds obtained as follows:
  • b 4 , b 4 and b 4 represent a number between 2 and 12 ;
  • a 19 represents a hydrogen atom; a C.-C.., alkyl group; a C 5 -C 12 cycloalkyl group; a phenyl group; or a C ⁇ -C 9 phenylalkyl group; and
  • a 20 has the same meaning as A 1 .
  • Compounds (b-19) can be selected from the compounds having general formula (XXXVII) :
  • a 21 and A 2 ⁇ represent a direct bond; or a -N(E.) -CO-E 2 -CO-N(E 3 ) - group wherein :
  • E 1 and E 3 represent a hydrogen atom; a C ⁇ C g alkyl group; a C 5 -C 12 cycloalkyl group; a phenyl group; a C 7 -C 9 phenylalkyl group; or a group having general formula (XXXII) ;
  • E 2 represents a direct bond; or a C.-C 4 alkylene group; - A 22 has the same meaning as A 1 ; - A 23 , A 24 , A, 7 and A 28 , the same or different, represent a hydrogen atom; a C.-G- g alkyl group; a C -C, 2 cycloalkyl group; or a phenyl group; A 25 represents a hydrogen atom; a C ⁇ -C ⁇ alkyl group; a C -C cycloalkyl group; a phenyl group; a ⁇ 7 ⁇ ⁇ ) phenylalkyl group; or a group having general formula (XXXII) ; and b 5 represents a number between 1 and 50.
  • Compounds (b-20) can be selected from the compounds having general formula (XXXVIII) :
  • a 29 represents a C.-C. ⁇ alkyl group; and - A 3Q has the same meaning as A..
  • Compounds (b-21) can be selected from the compounds having general formula (XXXIX) :
  • a 31 has the same meaning as A 1 ; and b 6 is a number between 2 and 50.
  • Compounds (b-22) can be selected from the com- pounds having general formula (XL) :
  • a 32 and A 33 together form a C 2 -C 14 alkylene group;
  • a 34 represents a hydrogen atom; or a -G ⁇ COO-G-, group wherein G 1 represents a C 2 -C 14 alkylene group and G 2 represents a C 1 -C 24 alkyl group; and . 35 has the same meaning as A.
  • Compounds (b-23) can be selected from the compounds having general formula (XLI) :
  • a 3 ⁇ , A 37 , A 38 , A 39 and A 4Q represent a direct bond; or a C-
  • Compounds (b-24) can be selected from the compounds having general formula (XLII) :
  • T 12 , T 13 and T 14 represent a group having general formula (XLIII) : —CH. -CH—CH 2 —L (XLIII)
  • a 42 represents a hydrogen atom; or a methyl group
  • a '43 represents a direct bond; or a C.-C 10 alkylene group
  • b 3 represents a number between 2 and 50.
  • alkyl groups having up to 30 carbon atoms are: methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2-ethylbutyl , n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl,
  • the substituents A 1 , K g , A 10 , A 18 , A 20 , A 22 , A 30 , A 31 , A 35 and A 41 preferably represent a C 1 -C 4 alkyl group, even more preferably a methyl group.
  • the substituents R 31 , ' 35 , A 23 and A 27 preferably represent a C,-C 25 alkyl group, even more preferably a C 15 ⁇ C 25 a lkyl group such as, for example, hexadecyl and C 18 -C 22 alkyl group.
  • the substituents R 7 33 and A 25 preferably represent a C.,-C 25 alkyl group, even more preferably an octadecyl group.
  • the substituents R' 8 , R 7 27 , A 8 and A 19 represent a C,-C 4 alkyl group, even more preferably an n-butyl group.
  • C 5 -C 12 cycloalkyl groups are: cyclopen- tyl, cyclohexyl, cycloheptyl, cyclo-octyl, cyclodode- cyl, etc.
  • C 5 -C 8 cycloalkyl groups are preferred, cyclohexyl is even more preferred.
  • Examples of C 5 -C 12 cycloalkyl groups substituted with a C 1 -C 4 alkyl group are: methylcyclohexyl, di e- thylcyclohexyl, etc.
  • Examples of phenyl groups substituted with an -OH group and/or a C j -C. ⁇ alkyl group are: methylphenyl , dimethylphenyl, trimethylphenyl, t-butylphenyl, 3,5-di- t-butyl-4-hydroxyphenyl , etc.
  • C 6 -C 9 phenylalkyl groups are: benzyl, phenylethyl, etc.
  • Examples of C 6 -C 9 phenylalkyl groups optionally substituted in the phenyl group with an -OH group and/or a C.-C ⁇ alkyl group are: methylbenzyl , dimethyl- benzyl, trimethylbenzyl , t-butylbenzyl, 3 , 5-di-t-butyl- 4-hydroxybenzyl, etc.
  • Examples of C 3 -C 6 alkenyl groups are: allyl, 2- methallyl, butenyl, pentenyl, hexenyl, etc. Allyl is the preferred group.
  • the carbon in position 1 is preferably saturated.
  • Examples of alkylene groups having up to 18 carbon atoms are: methylene, ethylene, propylene, trimethyl- ene, tetramethylene, pentamethylene, 2 , 2-dimethyltrime- thylene, hexamethylene, trimethylhexamethylene, octame- thylene, decamethylene, etc.
  • the substituents R 7 12 and A 12 are preferably hexamethylene; the substituent A 43 is preferably ethylene; the substituents R' 44 , R' 46 , R ' ⁇ 2 ' A 36 and A 38 are preferably methylene; the substituents R 47 and A 39 are preferably 2, 2-dimethylethylene; and the substituents R' 48 and A 40 are preferably 1, 1-dimethyle- thylene.
  • C 4 -C 10 tetrayl-alkane group is 1 , 2 , 3 , 4 -tetrayl-butane .
  • An example of a C 5 -C 7 cycloalkylene group is cyclohexylene .
  • An example of a C 1 -C 4 alkylene di ( C 5 -C 7 -cycloalkyle- ne) group is methylenedicyclohexylene.
  • Heterocyclic rings with 6 carbon atoms are preferred.
  • substituents R 14 and R 15 or A, 4 and A 15 form, together with the nitrogen atom to which they are bound, a C 5 -C 1Q heterocyclic ring
  • examples of this ring are: 1-pyrrolidine, piperidine, morpholine, 1-piperazi- nyl, 4-methyl-l-piperazinyl, l-hexahydroazepinyl, 5,5, 7-trimethyl-l-homopiperazinyl , 4,5,5, 7-tetrameth l- 1-homopiperazinyl, etc.
  • the morpholine group is preferred.
  • the substituents R' 31 , R' 3S/ A 23 and A ⁇ preferably represent a phenyl group.
  • the substituents Y 2 , E 2 , R' 45 and A 37 preferably represent a direct bond.
  • the substituents Y 1 , Y 3 , E 1 , E 3 , A 1 , A,, A 1Q , A 18 , A 20 , A 22 , A 30 , A 31 , A 35 , A 41 and A 42 preferably represent hydrogen.
  • n 2 and b 2 are preferably between 2 and 25.
  • n 3 and b 3 are preferably between 1 and 25, even more preferably between 2 and 20 or between 2 and 10.
  • n 4 , n 4 , n 4 , n 4 , b 4 , b 4 , and b'" 4 are preferably between 2 and 4.
  • n 5 and b 5 are preferably between 1 and 25, even more preferably between 2 and 20 or between 1 and 10.
  • n 6 and b 6 are preferably between 2 and 25, even more preferably between 2 and 20 or between 2 and 10.
  • n 7 and b 7 are preferably between 1 and 25, even more preferably between 1 and 20 or between 1 and 10.
  • b 8 is preferably between 2 and 25, even more preferably between 2 and 20 or between 2 and 10.
  • Compounds (b-18) can be prepared analogously to known processes, for example, by the reaction of a polyamine having general formula (XXXV) with cianuryl chloride, in a molar ratio ranging from 1:2 to 1:4, in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate, in an organic solvent such as, for example, 1, 2-dichloroethane, toluene, xylene, benzene, dioxane or t-amyl alcohol, at a temperature ranging from -20 °C to +10 °C, preferably between -10 °C and +10 °C, even more preferably between 0°C and +10 °C, for a time ranging from 2 to 8 hours, followed by the reaction of the resulting product with a 2 , 2 , 6, 6-tetramethyl-4-piperidylamine having general formula (XXXVI) .
  • an organic solvent such as, for example, 1, 2-dichloroethane, to
  • the molar ratio between 2 , 2 , 6, 6-tetra- methyl-4-piperidylamine and the polyamine having general formula (XXXV) used is, for example, between 4:1 and 8:1.
  • the quantity of 2 , 2 , 6 , 6-tetramethyl-4- piperidyla ine can be added in a single portion or in various portions at intervals of a few hours.
  • the ratio between the polyamine having general formula (XXXV), the cianuryl chloride and 2,2,6,6-te- tramethyl-4-piperidylamine having general formula (XXXVI) is preferably between 1:3:5 and 1:3:6.
  • the following example illustrates a method for preparing a (b-18) compound.
  • a further 18 g (0.13 moles) of anhydrous potassium carbonate are added and the resulting mixture is heated to 60 °C for a further 6 hours.
  • the solvent is eliminated by distillation, under a light vacuum (200 mbars) and replaced with xylene.
  • 18.2 g (0.085 moles) of N- (2, 2, 6, 6-tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 moles) of sodium hydroxide in granules are added, the mixture is heated to reflux temperature for 2 hours and, for a further 12 hours, and the water formed during the reaction is removed by azeotropic distillation.
  • the mixture is filtered.
  • the solution obtained is washed with water and dried on sodium sulfate.
  • the solvent is evaporated and the residue is dried, under vacuum (0.1 mbars) , at 120" C-130 ° C .
  • the compound obtained, which is among the (b-18) compounds, is a colourless resin.
  • a (b-18) compound can generally be represented, for example, by one of the compounds having the formula ( ⁇ -18) , (b 2 -18) or (b 3 -18) , or a mixture of the three compounds :
  • the preferred (b.,-18) compound is the following:
  • the preferred (b,-18) compound is the following:
  • the preferred (b-18) compound is the following:
  • b A is preferably between 1 and 20.
  • Compounds (b-l) are known compounds and, in some cases, are commercially available.
  • Compounds (b-2) to (b-13) can be prepared starting from the compounds described from (b-14) to (b-24) whose nitrogen atom of the 2 , 2 , 6, 6-tetramethylpiperid- 4-yl group is not substituted, operating analogously to known processes, for example, in U.S. patent 5.204.473, by oxidation of the corresponding 2 , 2, 6, 6-tetramethyl- piperidine derivative with a suitable peroxide such as, for example, hydrogen peroxide or t-butyl hydroperoxi- de, in the presence of a metal carbonyl or a metal oxide as catalyst, followed by the reduction of the oxyl intermediate to the desired N-hydroxyl derivative, preferably by catalytic hydrogenation.
  • a suitable peroxide such as, for example, hydrogen peroxide or t-butyl hydroperoxi- de
  • 0-alkyl derivatives can be synthesized in various ways.
  • N-hydroxyl derivatives can be alkylated with sodium hydride and halogenated hydrocarbons such as, for example, ethyl iodide.
  • N-methoxyl variants can be prepared by thermolysis of a chlorobenzene solution of the nitroxyl radical and di-t-butyl peroxide.
  • the product is formed by "coupling" reaction between the nitroxyl radical and the methyl radical which is formed by breakage in ⁇ position of the t- butoxyl radical .
  • N-alkoxyl variants can be synthesized by a "coupling" reaction of the nitroxyl radicals with the hydrocarbon radicals, which are formed during the thermal decomposition of di-t-butyl peroxide in the presence of a hydrocarbon solvent such as, for example, cyclohexane, toluene and ethylbenzene.
  • a hydrocarbon solvent such as, for example, cyclohexane, toluene and ethylbenzene.
  • l-cycloalkyloxy-2 , 2 , 6, 6-tetramethyl- piperid-4-yl derivatives can be prepared by the reaction of the corresponding 2 , 2 , 6, 6-tetramethylpiperid-4- yl derivative with t-butyl hydroperoxide in the pres- ence of molibden oxide (Mo0 3 ) and a cycloalkane.
  • some (b-6) compounds are known compounds and, in some cases, are commercially available and can be prepared with known processes as described, for example, in European patent EP 162.524 and in U.S. patent 4.946.880.
  • the compound (b-7) can, for example, also be represented by one of the compounds (b.,-18) , (b 2 -18) or (b 3 -18) , in which the A 20 radical is an -OR 28 group, or a mixture of the three.
  • the compounds described in (b-7) can, for example, also be obtained by the reaction of the product obtained by the reaction of a polyamine having general formula (XIX) and cyanuryl chloride, with a compound having general formula (XX'): H 2 N ⁇ (CH 2 ) n/ ,--NH— (CH 2 ) n;/4 --NH--(CH 2 ) n/; , 4 —NH 2
  • n 4 , n 4 and n 7 ' 4 represent a number between 2 and 12;
  • - R/ 27 represents a hydrogen atom; a ⁇ -C 2 alkyl group; a C 5 -C 12 cycloalkyl group; a phenyl grou ; or a C 6 -C 9 phenylalkyl group; and
  • R 28 has the same meaning as R'-,.
  • sterically hindered amines (b) which can be used for the purposes of the present invention are: TINUVIN 123 ® among compounds (b-2); MARK LA 52 ® or MARK LA 57 ® among compounds (b-14) ; CHIMASSORB 119 ® among compounds (b-15) ; CHIMASSORB 944 ® , CYASORB UV 3346 ® and DASTIB 1082 ® among compounds (b-17) ; UVASIL 299 ® corresponding to poly-methylpropyl-3-oxy[4- (2 , 2 , 6, 6-tetramethyl) piperidinyl] siloxane, among compounds (b-6) ; UVASORB HA 88 ® among compounds (b-18) ; UVINUL 5050 H ® , LICHTSCHUTZSTOFF UV 31 ® or LUCHEM HA-B 18 ® among compounds (b-19
  • sterically hindered amines (b) which can be used for the purposes of the present invention are selected from compounds (b-14) : TINUVIN 770 ® corresponding to bis (2 , 2,6, 6-tetramethyl-4-piperidinyl) seba- cate, LOWILITE 76 ® corresponding to bis ( 1, 2 , 2 , 6, 6- pentamethyl-4-piperidinyl) sebacate; or among compounds (b-25) : LOWILITE 62 ® corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperi- dine with succinic acid.
  • DASTIB 845 among compounds (b-14)
  • LICHTSCHUTZMITTEL S 95 among compounds (b-20)
  • HOSTAVIN N20 or SANDUVOR 3050 ® among compounds (b-22) .
  • Compound (b-7) which can be used for the purposes of the present invention is UVASORB HA 88 ® , in which the 2 , 2 , 6, 6-tetramethylpiperidin-4-yl radical is substituted with a group having general formula (XXI) .
  • radical A 31 in the compound having general formula (XXXIX) represents a hydrogen atom
  • said compound can be in the form of a mixture with a compound having formula (XXXIX 7 ):
  • ratio compound having general formula (XXXIX) /compound having formula (XXXIX 7 ) is between, for example, 20:1 and 1:20 or between 1:10 and 10:1.
  • the end groups can also be modified after the preparation of the above compounds.
  • X represents, for example, a halogen atom, preferably chlorine, and R 14 and R' 15 have the same meanings described above, with a compound having general formula:
  • X represents a halogen atom
  • it is advanta- geous to substitute it, for example, with an -OH group, or with an amine group at the end of the reaction.
  • amine groups which can be used for the purposes of the present invention are: pyrrolidin-1-yl ; morpholine; -NH 2 ; -N(C,-C 3 -alkyl) ; -NR(C 1 -C 8 -alkyl) wherein R represents a hydrogen atom, or a group having general formula (XV) .
  • the end group bound to the triazine radical is, for example, a chlorine atom, or a group having general formula:
  • the end group bound to the amine radical is, for example, a hydrogen atom, or a group having general formula:
  • the end group bound to the 2 , 5-dioxopyrrolidine ring is, for example, a hydrogen atom and the end group bound to the radical -C(R 35 ) (R 7 3 ⁇ ) - is, for example, one of the following groups having general formula:
  • the end group bound to the 2 , 5-dioxopyrrolidine ring is, for example, a hydrogen atom and the end group bound to the -C(A 27 ) (A 28 ) - radical is, for example, one of the following groups having general formula:
  • the end group bound to the dimethylene radical can be, for example, an -OH group and the end group bound to the oxygen atom can be, for example, a hydrogen atom.
  • the end groups can also be polyether radicals.
  • the end group bound to the nitrogen atom can be, for example, a hydrogen atom and the end group bound to the 2-hydroxypropylene radical can be, for example, a group having formula:
  • the end group bound to the carbonyl radical is, for example, a group having general formula:
  • the end group bound to the carbonyl radical is, for example, a group having general formula:
  • a 42 has the same meanings defined above, with a dicarboxyl diester having general formula
  • Q-00C-A 43 -C00-Q wherein Q is, for example, methyl, ethyl or propyl and A 43 has the same meanings described above, the end group bound to the 2 , 2 , 6 , 6-tetramethyl-4-oxypi- perid-1-yl radical is a hydrogen atom, or a
  • R a represents a hydrogen atom or a meth ⁇
  • R b represents one of the following groups: -C 2 H 5 ; -C 4 H 9 ; -C 8 H 17 ; -C 12 H 25 ; and R' b represents one of the following groups: -CH 2 -CO-CH 3 ; -CH 3 ; -C 2 H 5 ; -C 4 H 9 ; - x represents an integer between 1 and 4, extremes included; y represents an integer between 0 and 3 , extremes included; enamine having formula (a 7 ) : enamine having general formula (a 8 ) :
  • R' d represents one of the following groups:
  • Sterically hindered amines (b) which are preferred for the purposes of the present invention are: LOWILITE 76 ® corresponding to bis (1, 2 , 2, 6, 6-pentamethyl-4-pipe- ridinyl) sebacate; LOWILITE 62 ® corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4- hydroxypiperidine with succinic acid; UVASIL 299 ® corresponding to poly-methylpropyl-3-oxy [4- (2 , 2 , 6, 6- tetramethyl)piperidinyl]siloxane; TINUVIN 770 ® corresponding to bis (2,2,6, 6-tetramethyl-4-piperidinyl) seba- cate.
  • Preferred stabilizing mixtures for the purposes of the present invention are those in which: the compound belonging to the group of enamines (a) is selected from the following compounds: - enamine having formula (a 7 .,) :
  • CH 3 —C CH—COOC 18 H 37 (a 3 ) ;
  • CH 3 — C CH — CO — CH 3 (a 7 4 ) ;
  • the sterically hindered amine (b) is selected from the following compounds:
  • the two components (a) and (b) are used in a weight ratio ranging from 1:10 to 10:1, preferably from 1:4 to 1:1.
  • Organic polymers capable of being light-stabilized by the addition of the stabilizing mixtures of the present invention are:
  • polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyiso- prene or polybutadiene; as well as polymers of cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be optionally cross-linked) such as, for example, high density polyethylene (HDPE) , high density polyethylene and polyethylene with a high molecular weight (HDPE-HMW) , high density polyethylene and polyethylene with an "ultra-high" molecular weight (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , branched low density polyethylene (BLDPE) .
  • HDPE high density polyethylene
  • HDPE-HMW high molecular weight
  • polyethylene and polypropylene can be prepared with various methods known in literature, preferably using the following methods:
  • radicalic polymerization generally carried out at a high pressure and high temperature
  • a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals generally have one or more ligands such as, for example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -co-ordinated.
  • ligands such as, for example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -co-ordinated.
  • These metal complexes can be in free form or supported in substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide.
  • These catalysts can be soluble or insoluble in the reaction medium.
  • the catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, lla and/or Ilia of the Periodic Table.
  • the activators can be conveniently modified with other ester, ether, amine or silyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (DuPont) , metallocene or "single site cata- lyst" (SSC) .
  • Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE) , propylene/but-1- ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethyl- ene/acryl
  • Hydrocarbon resins for example, C 5 ⁇ C 9
  • hydrogenated modifications for example, tackifiers
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/al- kyl acrylate, styrene/butadiene/alkyl methacry- late, styrene/maleic anhydride, styrene/acrylo- nitrile/methylacrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacry- late, a polymer of a diene or an ethylene/propyle- ne/diene ter
  • Grafted copolymers of styrene or ⁇ -methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene or polybutadiene-acrylo- nitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl ethacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and male- imide on polybutadiene; styrene and alkylacrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and
  • Polymers containing halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, poly- vinylidenechloride, polyvinyl fluoride or polyvin- ylidenefluoride; and also their copolymers such as, for example, vinyl chloride/vinylidenechlo- ride, vinyl chloride/vinyl acetate or vinylidene- chloride/vinyl acetate.
  • halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular
  • unsaturated alcohols and amines or their acyl or acetal derivatives such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrral , polyallyl phthalate or polyallyl melamine; and also their copolymers with the olefins listed under point (1).
  • Polyacetals such as, for example, polyoxymethylene and polyoxymethylenes which contain ethylene oxide as comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene or polyamide polymers are examples of polyacetals such as, for example, polyoxymethylene and polyoxymethylenes which contain ethylene oxide as comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides deriving from diamines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from -xylene diamine and adipic acid; poly- amides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2 , 4 , 4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with polyole- fins, olefinic copolymers, ionomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polyt
  • Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephtha- late and polyhydroxybenzoates, as well as block copolyether esters deriving from polyethers with hydroxyl-terminated groups ; and also polyesters modified with polycarbonates or MBS.
  • dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephtha- late and polyhydroxybenzoates, as well as block copolyether esters deriving from polyethers with hydroxyl-terminated groups ; and also polyesters modified with polycarbonates
  • cross-linkable acrylic resins deriving from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates.
  • cross-linked epoxy resins deriving from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidic compounds such as, for example, di-glycidylethers of bisphenol A and bisphenol F, which are cross- linked with the usual hardeners such as, for example, anhydrides or amines, in the presence of or without accelerating agents.
  • aliphatic, cycloaliphatic, heterocyclic or aromatic glycidic compounds such as, for example, di-glycidylethers of bisphenol A and bisphenol F, which are cross- linked with the usual hardeners such as, for example, anhydrides or amines, in the presence of or without accelerating agents.
  • Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and buty- rates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins”) and their derivatives.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS , PC/ABS , PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates , POM/ther- moplastics PUR, PC/thermoplastics PUR, POM/acryla- tes, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, or PBT/PET/PC.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS , PC/ABS , PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates , POM/ther- moplastics
  • Natural or synthetic organic materials which are pure monomeric compounds or mixtures of these compounds such as, for example, mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (for example, phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratio, typically those used as compositions for spinning and also aqueous emulsions of these materials.
  • Aqueous emulsions of natural or synthetic rubbers for example, natural latex or latexes of carboxyl- ated styrene-butadiene copolymers.
  • organic polymers which can be light-stabilized by the addition of the mixtures of the present invention, are polyolefins, preferably polypropylene and polyethylene.
  • the addition of the stabilizing mixtures of the present invention to the above organic polymers, is carried out according to methods known in the art.
  • the stabilizing mixtures of the present invention can be added as such or in their single components [compound (a) and compound (b) ] , to the organic polymers, optionally in the presence of other additives, in the step following their preparation, or immediately before the transformation process.
  • the stabilizing mixtures of the present invention are added to the polymer to be stabilized in a quantity ranging from 0.05% to 5% by weight, preferably between 0.1% and 2%.
  • the total quantity is the same as that described above.
  • the polymers stabilized as described above have a high resistance to degradation caused by light, in particular, ultraviolet radiation. They are therefore capable of maintaining their colour and brightness for a long period even when exposed to external agents.
  • compositions for coating or painting such as, for example, paints, lacquers, plastic-based compositions.
  • coating or painting compositions are preferred in which the organic polymer is selected from:
  • thermoplastic polymer selected from thermoplastic polymers containing heteroatoms, in particular nitrogen, sulfur and/or oxygen, in the main chain, styrene copolymers, grafted styrene polymers and polymethyl methacrylates (PMMA) ; or
  • thermoplastic polymers (a) containing heteroatoms, in particular nitrogen, sulfur and/or oxygen, in the main chain are listed above under points 13 to 20.
  • polycarbonates polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides are preferred; particularly preferred are polycarbonates, polyesters such as, for example, polyethylene terephthalate (PET) , and polyamides (PA) such as, for example, PA 6 and PA 6/6; polycarbonates are even more preferred.
  • Paint ligands (b) can comprise at least one of the organic polymers specified above.
  • Paints containing specific ligands are: 1. paints based on alkyd resins, acrylic resins, polyester resins, epoxy resins or melamine resins, which can be cross-linked at a low or high temperature, or mixtures of these resins, to which a cross-linking agent is optionally added; 2. polyurethane paints with two components based on acrylic resins containing hydroxyl groups, polyester resins or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocya- nates ; 3. polyurethane paints with one component based on block isocyanates, isocyanurates or polyisocyana- tes which are unblocked during oven treatment;
  • paints with two components based on acrylic resins containing an anhydride group and a polyhydroxyl or polyamine compound 7. paints with two components based on acrylic resins containing an anhydride group and a polyhydroxyl or polyamine compound; 8. paints with two components based on (poly)oxazo- line and acrylic resins containing an anhydride group or unsaturated acrylic resins or aliphatic or aromatic isocyanates, or isocyanurates or poly- isocyanates ;
  • thermoplastic polyacrylic paints based on thermoplastic acrylic resins or non-self-crosslinking acrylic resins combined with etherified melamine resins;
  • one- or two-coat of coating and the stabilizing mixtures of the present invention are preferably added to the upper colourless coating.
  • the paints can be applied to the substrate (metal, plastic, wood, etc.) using the conventional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis.
  • a preferred embodiment of the present invention consists in paints or coatings (for example car coatings) comprising at least one stabilizing mixture of the present invention.
  • Ligands which can be used for the purpose are, for example, those listed above.
  • the above stabilizing mixtures can be combined, as already mentioned above, with other conventional additives or their mixtures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example.
  • Antioxidants 1.1 Alkylated monophenols such as, for example:
  • Alkylthiomethylphenols such as, for example: 2 , 4-dioctylthiomethyl-6-t-butylphenol ;
  • Hydroquinones and alkylated hydroquinones such as, for example:
  • Tocopherols such as, for example: ⁇ -tocopherol , 3-tocopherol, ⁇ -tocopherol, 5-tocopherol and their mixtures (Vitamin E) .
  • Hydroxylated thiodiphenyl ethers such as, for example :
  • Hydroxybenzylated malonates such as, for example: dioctadecyl-2 , 2-bis ( 3 , 5-di-t-butyl-2-hydroxyben- zyl) malonate; dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylben- zyl)malonate; didodecylmercaptoethyl-2 , 2-bis (3 , 5-di-t-butyl-4- hydroxybenzyl ) malonate ; bis[4-(l,l,3, 3-tetramethylbutyl) phenyl] -2,2- bis (3 , 5-di-t-butyl-4-hydroxybenzyl) alonate.
  • Aromatic hydroxybenzyl compounds such as, for example:
  • Triazine compounds such as, for example:
  • 1,3, 5-tris ( 3 , 5-di-t-butyl-4-hydroxyphenylpropio- nyl) hexahydro-1, 3 , 5-triazine; l,3,5-tris-(3, 5-dicyclohexy 1-4 -hydroxy ben- zyl) isocyanurate.
  • Benzylphosphonates such as, for example: dimethyl-2 , 5-di-t-butyl-4-hydroxybenzylphosphona- te; diethyl-3 , 5-di-t-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3 , 5-di-t-butyl-4-hydroxybenzylphospho- nate ; dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylpho- sphonate ; calcium salts of monoethyl ester of 3,5-di-t- butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols such as, for example: 4-hydroxylauranilide ; 4-hydroxystearanilide ; octyl-N- ( 3 , 5-di-t-butyl-4-hydroxyphenyl) carbamate.
  • esters of ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) ro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3- thiopentadecanol, trimethylhexandiol, tri ethyl- olpropane, 4-hydroxymethyl-l-phospho-2 , 6 , 7-trioxa- bicyclo[2.2.
  • esters of ⁇ - (5-t-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy- lolpropane, 4-hydroxymethyl-l-phospho-2 , 6 , 7-trio- xabicyclo [2.2.2]
  • esters of j3-(3, 5-dicyclohexyl-4-hydroxyphenyl)pro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N -bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy- lolpropane , 4-hydroxymethyl-l-phospho-2 ,6,7- trioxabicyclo[2.2.2 ] octane.
  • esters of (3 , 5-di-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol , trimethylhexandiol, trimethy- lolpropane, 4-hydroxymethyl-l-phospho-2 ,6,7- trioxabicyclo [2.2.2] octane .
  • monohydric or polyhydric alcohols such
  • Amine antioxidants such as, for example, N,N 7 -di- isopropyl-p-phenylenediamine, N,N -di-s-butyl-p- phenylenediamine, N,N 7 -bis (1, 4-dimethylpentyl) -p- phenylenediamine, N,N -bis (l-ethyl-3-methylpen- tyl) -p-phenylene-diamine, N,N 7 -bis (1-methyl- heptyl) -p-phenylenediamine, N, N ' -dicyclohexyl-p- phenylenediamine, N,N -diphenyl-p-phenylenedi- a ine, N,N 7 -bis(2-naphthyl) -p-phenylenediamine, N- isopropyl-N'-phenyl-p-phenylenediamine, N- is
  • 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4- decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2 ,4 - trihydroxy- ; 2 ' -hydroxy-4 , 4 ' -dimethoxy.
  • Esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4-t- butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol, bis (4-t-butylbenzoyl) -resor- cinol, dibenzoyl-resorcinol, 2,4-di-t-butylphenyl- 3 , 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3 , 5- di-t-butyl-4-hydroxybenzoate, octadecyl-3,5-di-t- butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-t-butyl- phenyl-3 , 5-di-t-butyl-4-hydroxybenzoate.
  • benzoyl-resorcinol bis (4-t-butylbenzoyl) -resor-
  • Acrylates such as, for example, ethyl or isoctyl ⁇ -cyano-/3,/3-diphenylacrylate; methyl ⁇ -carbometho- xycinnamate, methyl or butyl ⁇ -cyano-?-methyl-p- methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxy- cinnamate, N-(9-carbomethoxy- / 3-cyanovinyl) -2-me- thylindoline.
  • Nickel compounds such as, for example, complexes of 2, 2 7 -thio-bis-[4- (1,1,3, 3-tetramethylbutyl) phenol], for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3 , 5-di-t-butyl- benzyl-phosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2- hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazol with or without additional ligands.
  • Oxamides such as, for example: 4 , 4 ' -dioctyloxyoxanilide;
  • Metal-deactivators such as, for example: N,N- diphenyloxamide, N-salicylal-N 7 -salicyloyl-hydra- zine, N,N -bis (salicyloyl) hydrazine; N,N -bis (3 , 5- di-t-butyl-4-hydroxyphenylpropionyl) hydrazine , 3- salicyloylamino-1, 2 , 4-triazole, bis (benzylidene) o- xalyl dihydrazide, oxanilide, isophthaloyl dihy- drazide, sebacoyl bisphenylhydrazide, N,N -diace- tyladipoyl dihydrazide, N,N'-bis (salicyloyl
  • Phosphites and phosphonites such as, for example: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2 , 4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2 , 4-di-t-butyl- phenyl) pentaerythritol diphosphite, bis (2 , 5-di-t- butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite,
  • Hydroxylamines such as, for example: N, N-dibenzyl- hydroxylamine, N,N-diethylhydroxylamine, N,N- dioct lhydroxylamine, N,N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N- hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N,N-dialkylhydroxylamine deriving from the amine from hydrogenated tallow.
  • Nitrons such as, for example: N-benzyl- ⁇ -phenyl- nitron, N-ethyl- ⁇ -methyl-nitron, N-octyl- ⁇ -heptyl- nitron, N-lauryl- ⁇ -undecyl-nitron, N-tetradecyl- ⁇ - tridecyl-nitron, N-hexadecyl- ⁇ -pentadecyl-nitron, N-octadecyl- ⁇ -heptadecyl-nitron, N-hexadecyl- ⁇ - heptadecyl-nitron, N-octadecyl- ⁇ -pentadecyl- nitron, N-heptadecyl- ⁇ -heptadecyl-nitron, N- octadecyl- ⁇ -hexadecyl-nitron, nitron deriving from N,N-dialkylhydroxy
  • Agents which are capable of destroying peroxides such as, for example, esters of 3-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide pentaerythritol tetrakis (/3-dodecylmercapto) propionate.
  • esters of 3-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole zinc dibutyldithiocarbamate
  • Stabilizers of polyamides such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
  • Basic co-stabilizers such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, deriva- tives of hydrazine, amines, polyamides, polyurethanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimo- nium-pyrocatecholate, tin-pyrocatecholate.
  • Basic co-stabilizers such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, deriva- tives of hydrazine, amines, polyamides, polyurethanes, salts of alkaline
  • Nucleating agents such as, for example: inorganic substances such as talc, metal oxides such as titanium dioxide or manganese oxide, phosphates, carbonates or sulphates preferably of earth- alkaline metals; organic compounds such as, for example: mono- or poly-carboxylic acids and their salts, for example, 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers”) .
  • inorganic substances such as talc, metal oxides such as titanium dioxide or manganese oxide, phosphates, carbonates or sulphates preferably of earth- alkaline metals
  • organic compounds such as, for example: mono- or poly-carboxylic acids and their salts, for example, 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copo
  • Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, "glass bulbs", asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
  • additives such as, for example: plastici- zers, lubricants, emulsifying agents, pigments, rheological additives, catalysts, "flow-control" agents, optical brighteners, flame-retardants (for example, bromides, chlorurates, phosphorates and phosphorous/halogen mixtures) , antistatic agents, blowing agents, thiosynergizing agents such as, for example, dilauryl thiodipropionate or diste- aryl thiodipropionate.
  • reaction mass is maintained under stirring and reflux heated for 1 hour and 45 minutes, to a temperature ranging from 118 °C to 130 °C. During this period there is the formation of reaction water which is separated by azeotropic distillation: 3.5 g of reaction water are separated.
  • reaction temperature 4.5 hours at 118°C-132°C.
  • the product is isolated as boiler residue, after distillation under vacuum of the solvent and acetic acid.
  • the homogeneous mixtures, from (A) to (G) , thus obtained is subjected to extrusion in a Brabender extruder having a diameter of 19 mm and a length about 25 times the diameter, equipped with a screw and nozzle of 2 mm, with a compression ratio of 1:4 and with a temperature profile of 190°C, 210°C, 215°C, 215°C.
  • the extruder is activated at 50 rpm and the filament leaving the extruder is cut into granules which are subsequently transformed into films with a "Plasticizer" operating at a temperature of 220°C.
  • the films are then subjected to compression until films with a thickness of 60 ⁇ m are obtained, operating under the following conditions: 2 minutes of preheating and 2 minutes of compression 100 Kg/cm 2 at 200 °C.
  • the films thus obtained are subjected to ultraviolet radiation in UV-CON under the following conditions:
  • a film obtained from polypropylene without light-stabilizers is prepared.
  • Polyethylene of the type Riblene FC20 produced and sold by Polimeri Europa, is used for the purpose. 100 g of the above polyethylene in the form of granules are mixed with 0.25 g of the following co - pounds :
  • the homogeneous mixtures, from (A) to (G) , thus obtained is subjected to extrusion in a Brabender extruder having a diameter of 19 mm and a length about 25 times the diameter, equipped with a screw and nozzle of 2 mm, with a compression ratio of 1:4 and with a temperature profile of 190°C, 210°C, 215"C, 215°C.
  • the extruder is activated at 50 rpm and the filament leaving the extruder is cut into granules which are subsequently transformed into films with a "Plasticiz- er" operating at a temperature of 220 °C.
  • the films are then subjected to compression until films with a thickness of 100 ⁇ m are obtained, operating under the following conditions: 2 minutes of preheating and 2 minutes of compression 100 Kg/cm 2 at 200 °C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

Mélanges stabilisants pour des polymères organiques contenant: (a) un ou plusieurs composés appartenant au groupe des énamines constitué par des dérivés de β-céto-esters ou β-céto-amides ou 1,3-dicétones avec des amines aliphatiques ou aromatiques primaires ou secondaires, et représentés par la formule suivante (I):(I) (b) un ou plusieurs composés appartenant au groupe d'amines à empêchement stérique.
EP98932149A 1997-07-10 1998-06-12 Melanges synergiques photostabilisants pour des polymeres organiques Withdrawn EP0994855A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI971641 1997-07-10
IT97MI001641A IT1293317B1 (it) 1997-07-10 1997-07-10 Miscele sinergiche stabilizzanti alla luce per polimeri organici
PCT/EP1998/003506 WO1999002495A1 (fr) 1997-07-10 1998-06-12 Melanges synergiques photostabilisants pour des polymeres organiques

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TW401437B (en) * 1995-02-10 2000-08-11 Ciba Sc Holding Ag Synergistic stabilizer mixture
DE10124332A1 (de) 2001-05-18 2002-11-21 Basf Ag Kosmetische oder pharmazeutische Zubereitungen, die Enaminotriazine als Lichtschutzmittel enthalten und neue Enaminotriazine
US20030225191A1 (en) 2002-04-12 2003-12-04 Francois Gugumus Stabilizer mixtures
WO2004009690A2 (fr) 2002-07-18 2004-01-29 Exxonmobil Chemical Patents Inc. Polyolefines stabilisees par rayons ultraviolets
WO2009082019A1 (fr) * 2007-12-21 2009-07-02 Sumitomo Chemical Company, Limited Composition et moulages de résine de polypropylène
ITMI20110802A1 (it) * 2011-05-10 2012-11-11 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri

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DE2849444A1 (de) * 1978-11-15 1980-05-29 Hoechst Ag Beta aminocrotonsaeurepiperidylester, verfahren zu ihrer herstellung und ihre verwendung als lichtschutzmittel
CH666028A5 (de) * 1985-08-27 1988-06-30 Vladimir Ivanovich Paramonov 2,2,6-6-tetramethylpiperidylamide substituierter karbonsaeuren und die mit ihnen stabilisierten lichtbestaendigen polymermischungen.
IT1203354B (it) * 1987-02-26 1989-02-15 Ciba Geigy Spa Composti piperidinici atti all'impiego come stabilizzanti per polimeri e copolimeri sintetici
IT1217742B (it) * 1988-05-31 1990-03-30 Ciba Geigy Spa Poliammine parzialmente sostituite con piperidin triazine

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Title
See references of WO9902495A1 *

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JP2001509521A (ja) 2001-07-24
WO1999002495A1 (fr) 1999-01-21
IT1293317B1 (it) 1999-02-16

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