CA2026522A1 - Hydroxyphenylcarboxylic acid esters as stabilizers - Google Patents
Hydroxyphenylcarboxylic acid esters as stabilizersInfo
- Publication number
- CA2026522A1 CA2026522A1 CA002026522A CA2026522A CA2026522A1 CA 2026522 A1 CA2026522 A1 CA 2026522A1 CA 002026522 A CA002026522 A CA 002026522A CA 2026522 A CA2026522 A CA 2026522A CA 2026522 A1 CA2026522 A1 CA 2026522A1
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- Prior art keywords
- tert
- butyl
- bis
- ethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
A-17774/=
HydroxyPhenylcarboxylic acid esters as stabilizers Abstract of the disclosure The novel compounds of the formulae Ia and Ib , (Ia) (Ib) in which the radicals R are identical or different and are a group of the formula II
(II) in which X is a direct bond, methy1ene, ethylene or a group
HydroxyPhenylcarboxylic acid esters as stabilizers Abstract of the disclosure The novel compounds of the formulae Ia and Ib , (Ia) (Ib) in which the radicals R are identical or different and are a group of the formula II
(II) in which X is a direct bond, methy1ene, ethylene or a group
Description
2~2~2 A-17774/=
Hvdroxvphenvlcarboxylic acid esters as stabilizers The present invention relates to novel hydroxyphenylcarboxylic acid esters, the organic materials stabilized against thermal, oxidative and actinic degradation using these compounds and the use of the hydroxyphenylcarboxylic acid esters as stabilizers.
DiaLIcyl-hydroxyphenylcarboxylic acid esters of di- and tripentaerythritol and their use as stabilizers are described, for exarnple, in US-A-3,642,868. DiaL~cyl-hydroxyphenyl-carboxylic acid esters are furthermore disclosed in EP-A-366,040 and Derwent abstract 87-105824/15.
The present invention relates to compounds of the formulae Ia andlor Ib OR fR OR OR OR fR CH~OR
H2C--CH--CH2--0--CHr CH--CH2 , H2C--CH--- CH2--O--CH
(Ia) (Ib) in which the radicals R are identical or different and are a group of the formula II
--C--X {~OH
in which X is a direct bond, methylene, ethylene or a group --CH2--cl H--and Y is Cl-C8alkyl, Rl and R2 independendy of one another are Cl-CI8alkyl, Cs-CI2cycloaL~yl, Cs-C7cycloalkyl which is substituted by Cl-C4alkyl, or are phenyl or CTCIOphenylalkyl, and R2 is additionally hydrogen.
2~2~ 2C~
Cl-C8all~yl Y is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
Straight-chain alkyl, in particular methyl, is preferred.
Cl-CI8alkyl Rl and R2 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Cl-C4alkyl, in particular methyl and tert-butyl, are preferred. Rl and R2 are particularly preferably tert-butyl.
Cs-CI2cycloaL~cyl Rl and R2 are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl cycloundecyl or cyclododecyl. Cs-C7cycloaL~cyl, in particular cyclohexyl, is one of the preferred meanings of Rl and R2.
C5-C7cycloaLkyl Rl and R2 which are substituted by Cl-C4alkyl, preferably methyl, are, for example, methylcyclohexyl.
C7-CIOphenylalkyl Rl and R2 are, for example, b en z y 1 o r p h eny 1 e thy 1 .
Compounds of the formulae Ia and Ib in which the radicals R are identical are preferred.
X is preferably a direct bond, methylene or ethylene, in particular ethylene.
Compounds of dhe formulae Ia and Ib in which Rl and R2 independently of one another are Cl-Cl2al~yl, Cs-C7cycloalkyl, Cs-C7cycloalkyl which is substituted by Cl-C4aLkyl, or are phenyl~ benzyl or phenylethyl and R2 is additionally hydrogen are of interest.
Compounds of the formulae Ia and Ib in which X is a direct bond, medhylene or ethylene, Rl and R2 independendy of one another are Cl-C4alkyl, cyclohexyl, cyclohexyl which is substituted by Cl-C4aL~cyl, or are phenyl or benzyl and R2 is additionally hydrogen are likewise of interest.
Compounds of the formulae Ia and Ib in which X is ethylene, Rland R2 independently of one anodher are Cl-C4alkyl and R2 is addidonally hydrogen are pardcularly prefe~
2Q~2~ .
Examples of compounds of the formulae Ia and Ib are:
1 ,2,6,7-tetrakis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxy]-4-oxaheptane, 1 ,5,~tris[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxyl-2-[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxymethy1]-3-oxahexane, 1,2,6,7-tetrakis[(3'-methyl-5'-tert-butyl-4'-hydroxyphenyl)propionyloxy]~oxaheptane, 1 ,5,6-tris~(3 '-methyl-5 '-tert-butyl-4'-hydroxyphenyl)propionyloxy]-2-~(3 '-methyl-5 '-tert-butyl-4'-hydroxyphenyl)propionyloxymethyl]-3-oxahexane.
The compounds of the formulae Ia and Ib are suitable for stabilizing organic materials against thermal, oxidadve and acdnic degradation.
Examples of such materials are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, polymethylpent-l-ene, polyisoprene or polybutadiene, and poly ners of cycloolefins, for example of cyclopentene or norbornene; and furthermore polyethylene (which can be non-crosslinked or crosslinked), for example high density polyethylene (HDPE), low density polyethylene (I,OPE) and linear low density polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE or PP/IDPE) and mixtures of various types of polyethylene (for example LDPE/HDPE).
Hvdroxvphenvlcarboxylic acid esters as stabilizers The present invention relates to novel hydroxyphenylcarboxylic acid esters, the organic materials stabilized against thermal, oxidative and actinic degradation using these compounds and the use of the hydroxyphenylcarboxylic acid esters as stabilizers.
DiaLIcyl-hydroxyphenylcarboxylic acid esters of di- and tripentaerythritol and their use as stabilizers are described, for exarnple, in US-A-3,642,868. DiaL~cyl-hydroxyphenyl-carboxylic acid esters are furthermore disclosed in EP-A-366,040 and Derwent abstract 87-105824/15.
The present invention relates to compounds of the formulae Ia andlor Ib OR fR OR OR OR fR CH~OR
H2C--CH--CH2--0--CHr CH--CH2 , H2C--CH--- CH2--O--CH
(Ia) (Ib) in which the radicals R are identical or different and are a group of the formula II
--C--X {~OH
in which X is a direct bond, methylene, ethylene or a group --CH2--cl H--and Y is Cl-C8alkyl, Rl and R2 independendy of one another are Cl-CI8alkyl, Cs-CI2cycloaL~yl, Cs-C7cycloalkyl which is substituted by Cl-C4alkyl, or are phenyl or CTCIOphenylalkyl, and R2 is additionally hydrogen.
2~2~ 2C~
Cl-C8all~yl Y is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
Straight-chain alkyl, in particular methyl, is preferred.
Cl-CI8alkyl Rl and R2 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Cl-C4alkyl, in particular methyl and tert-butyl, are preferred. Rl and R2 are particularly preferably tert-butyl.
Cs-CI2cycloaL~cyl Rl and R2 are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl cycloundecyl or cyclododecyl. Cs-C7cycloaL~cyl, in particular cyclohexyl, is one of the preferred meanings of Rl and R2.
C5-C7cycloaLkyl Rl and R2 which are substituted by Cl-C4alkyl, preferably methyl, are, for example, methylcyclohexyl.
C7-CIOphenylalkyl Rl and R2 are, for example, b en z y 1 o r p h eny 1 e thy 1 .
Compounds of the formulae Ia and Ib in which the radicals R are identical are preferred.
X is preferably a direct bond, methylene or ethylene, in particular ethylene.
Compounds of dhe formulae Ia and Ib in which Rl and R2 independently of one another are Cl-Cl2al~yl, Cs-C7cycloalkyl, Cs-C7cycloalkyl which is substituted by Cl-C4aLkyl, or are phenyl~ benzyl or phenylethyl and R2 is additionally hydrogen are of interest.
Compounds of the formulae Ia and Ib in which X is a direct bond, medhylene or ethylene, Rl and R2 independendy of one another are Cl-C4alkyl, cyclohexyl, cyclohexyl which is substituted by Cl-C4aL~cyl, or are phenyl or benzyl and R2 is additionally hydrogen are likewise of interest.
Compounds of the formulae Ia and Ib in which X is ethylene, Rland R2 independently of one anodher are Cl-C4alkyl and R2 is addidonally hydrogen are pardcularly prefe~
2Q~2~ .
Examples of compounds of the formulae Ia and Ib are:
1 ,2,6,7-tetrakis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxy]-4-oxaheptane, 1 ,5,~tris[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxyl-2-[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyloxymethy1]-3-oxahexane, 1,2,6,7-tetrakis[(3'-methyl-5'-tert-butyl-4'-hydroxyphenyl)propionyloxy]~oxaheptane, 1 ,5,6-tris~(3 '-methyl-5 '-tert-butyl-4'-hydroxyphenyl)propionyloxy]-2-~(3 '-methyl-5 '-tert-butyl-4'-hydroxyphenyl)propionyloxymethyl]-3-oxahexane.
The compounds of the formulae Ia and Ib are suitable for stabilizing organic materials against thermal, oxidadve and acdnic degradation.
Examples of such materials are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, polymethylpent-l-ene, polyisoprene or polybutadiene, and poly ners of cycloolefins, for example of cyclopentene or norbornene; and furthermore polyethylene (which can be non-crosslinked or crosslinked), for example high density polyethylene (HDPE), low density polyethylene (I,OPE) and linear low density polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE or PP/IDPE) and mixtures of various types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (lDPE), propylene-but-1-ene copolymers, propylene-isobutylene copolymers, ethylene-but-1-ene copolymers, ethybne-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 or ethylene-acrylic acid copolyrners and salts thereof (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and furthermore mixtures of such copolymers with one another and with the polymers mentioned under 1), for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPElethylene-acrylic acid 2 ~ 'i 2'~
copolymers, LLDPE/ethylene-vinyl acetate copolymers and LLDPE/ethylene-acrylic acid copolymers.
3a. Random or alternating copolymers of a-olefins and carbon monoxide.
3b. Hydrocarbon resins (for example Cs-Cg), including hydrogenated modificationsthereof (~or example tackifying resins).
4. Polystyrene, poly-(p-methylstyrene) and poly(a-methylstyrene).
3a. Random or alternating copolymers of a-olefins and carbon monoxide.
3b. Hydrocarbon resins (for example Cs-Cg), including hydrogenated modificationsthereof (~or example tackifying resins).
4. Polystyrene, poly-(p-methylstyrene) and poly(a-methylstyrene).
5. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile, styrene-aL~cyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-maleic anhydride and styrene-acrylonitrile-methyl acrylate; mixtures of high irnpact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, for example styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-s~rene or styrene-ethylene/propylene-styrene.
6. Graft copolymers of styrene or ~-methylstyrene, for exarnple styrene on polybutadiene, styrene on polybutadiene-styrene copolymers or polybutadiene-acIylonitrile copolymers, and styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acIylonitrile and maleic anhydride or maleimide on polybutadiene;
styrene and maleimide on polybutadiene, styrene and aL~cyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylontrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on a~rylate-butadiene copolyrners, and mixtures ~hereof with the copolymers mendoned under 5), such as are known, for exarnple, as so-called ABS, MBS, ASA or AES polymers.
styrene and maleimide on polybutadiene, styrene and aL~cyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylontrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on a~rylate-butadiene copolyrners, and mixtures ~hereof with the copolymers mendoned under 5), such as are known, for exarnple, as so-called ABS, MBS, ASA or AES polymers.
7. Halogen~ontaining polymers, for example polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene and epichlorohydrin homo- and copolymers,in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride and polyvinylidene fluoride; and copolymers thereof, such as 202~ 3 22 vinyl chloride-vinylidene chloride, vinyl cbloride-vinyl acetate or vinylidene chloride-vinyl acetate.
8. Polyrners whlch are derived from c~,~-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.
9. Copolymers of the monomers mentioned under 8) with one another or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-aL~cyl acrylate copolymers, acrylonit~ile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolyrners or acrylonitrile-alkyl methacrylate-butadiene terpolyrners.
10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, polyvinyl butyral, polyallyl phthalate and polyallylmelamine; and copolymers thereof with the olefins mendoned in point 1).
11. Homopolymers and copolymers of cyclic ethers, such as polyaL~cylene glycols,polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
12. Polyacetals, such as polyoxymethylene, and those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals which are modified with thermop1astic polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides, and mixtures thereof with styrene polymers or polyamides.
14. Polyurethanes which are derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphadc or aromadc polyisocyanates on ~e other hand, and precursors thereof.
15. Polyamides and copolyarnides which are derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactarns, such as polyarnide 4, polyamide 6, polyamide 616, 6/10, 6/9, 6/12 or 4/6, polyamide 11, polyamide 12 and aromadc polyamides starting from m-xylene, diamine and adipic acid; polyarnides prepared from hexamethylenediarnine and isophthalic and/or terephthalic acid and if 2Q~ 22 desired an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenylene-isophthalamide; block copolymers of the abovementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethy1ene glycol; and furthermore polyarnides or copolyamides modified with EPDM or ABS; and polyamides which are fused during processing ("RIM polyamide systems").
16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
17. Polyesters which are derived from dicarboxylic acids and dialcohols andlor from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly- 1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block polyether esters derived from polyethers having hydroxyl end groups; and furthermore polyesters modified with polycarbonates or MBS.
18. Polycarbonates and polyester carbonates.
19. Polysu1fones, po1yether sulfones and polyether ketones.
20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, such as also halogen~ontaining modifications thereof of lowflammability.
23. Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, for example from epoxy acrylates, urethane acrylates or polyester ylates.
24. Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine 2~2~22 resins, urea resins, polyisocyanates or epoxy resins.
25. Crosslinked epoxy resins which are derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
26. Naturally occurring polymers, such as cellulose, natural rubber, gelatin andpolymer-homologous chemically modified derivatives thereof, such as cellulose acetates, propionates and butyrates, and the cellulose ethers, such as methylcellulose, as well as colophony resins and derivatives.
27. Mixtures (polyblends) of the abovementioned polymers, for example PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVCtABS, PVC/MBS, PCtABS, PBTPtABS, PC/ASA, PCtPBT, PVCtCPE, PVClacrylates, POh~lthermoplastic PUR, PC/therrnoplastic PUR, POMtacrylate, POM/MBS, PPO/H[PS, PPO/PA 6.6 and copolymers, PA/HDPE, PAtPP and PA/PPO.
28. Naturally occurring and synthetic organic substances which are pule monomeric compounds or mixtures of these, for example mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates), as well as blends of synthetic esters u~th mineral oils in any weight ratios, such as are used, for example, as spinning preparations, and aqueous emulsions thereof.
29. Aqueous emulsions of naturally occurring or synthetic rubbers, for example natural rubber latex or latices of carboxylated styrene-butadiene copolyrners.
The invendon ~us furthcrmore relates to composihons containing an organic material which is sensidve againts oxidative, thermal or actinic degradahon and at least one compound of thc formulae Ia andlor Ib, as well as the use of compounds of the formulae Ia and Ib for stabilizing organic mate~ial against oxidative, thermal or acdnic deg~adadon.
Preferred organic matcrials are polymers, for cxample synthedc polymers, in particular thermoplastic polymers. Pardcularly p~cfeITed organic materials are polyolefins, for examplc those mendoned above under points 1 to 3, in particular polyethylene andpolypropylene.
2~2~)~2~
The compounds of the formulae Ia and Ib are in general added to the material to be stabilized in amounts of 0.01 to 10 %, preferably 0.01 to 5 %, in pardcular 0.01 to 2 %, based on the total weight of the material to be stabilized.
In addidon to the compounds of the formulae Ia and/or Ib, the compositions according to the invention can addidonal1y contain conventional additives, for example those mentioned below.
1 Antioxidants 1.1. ~lkvlated monoPhenols, for example 2,~di-tert-butyl-~methylphenol, 2-tert-butyl-4,~dimethylphenol, 2,~di-tert-butyl-4-ethylphenol, 2,6 di-tert-butyl-4n-butylphenol, 2,~di-tert-butyl~i-butylphenol, 2,~di-cyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl~4,6 dimethylphenol, 2,6 di-octadecyl-4-methylphenol, 2,4,~tri-cyclohexylphenol, 2,~di-tert-butyl-4-methoxymethylphenol and 2,~di-nonyl-~methylphenol.
1.2. ALlcvlated hvdroquinones, for example 2,6 di-tert-butyl-~methoxyphenol, 2,5~i-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone and 2,~diphenyl-4-octadecyloxyphenol.
1.3. Hvdroxvlated diphenYI thioethers, for example 2,2'-thio-bis-(~tert-butyl ~- methylphenol), 2,2'-thi~bis-(4-octylphenol), 4,4'-thio-bis-(~tert-butyl-3-methylphenol) and 4,4' -thio-bis-(~tert-butyl-2-methylphenol).
1.4. AlkYlidene bisDhenols, for example 2t2'-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(~tert-butyl-4-ethylphenol), 2,2'-methylene-bis-~4-methyl-~(a-methylcyclohexyl)-phenol], 2,2'-methylene-bis-(4-methyl-~cyclohexylphenol), 2,2'-methylene-bis-(~nonyl-4-methylphenol), 2,2'-methylene-bis-(4,~di-tert-butylphenol), 2,2'-ethylidene-bis-(4,~di-tert-butylphenol), 2~2'-ethylidene-bis-(~
tert-butyl-4-isobutylphenol), 2,2'-methylene-bis-[~(a-methylbenzyl)4-nonylphenol], 2,2'-methylene-bis-[~(a,-dirnethylbenzyl)4-nonylphenol], 4,4'-methylene-bis-(2,~di-tert-butylphenol), 4,4'-methylene-bis-(~tert-butyl-2-methylphenol), 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,~bis-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methylphenol, 1,1,3-tris-(5-tert-butyl-4 hydroxy-2-methylphenyl)-butane, 2 ~ 2 2 g 1,1-bis-(5-tert-butyl4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate], bis-(3-tertbutyl-4-hydroxy-S-methylphenyl)~icyclopentadiene and bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-~tert-butyl-4-methylphenyl] terephthalate.
1.5. Benzvl comPounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl~hydroxy-benzyl)-2,4,~
trimethylbenzene, bis-(3,5-di-tert-butyl~-hydroxybenzyl)-sulfide, isooctyl 3,S-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiolterephthalate, 1,3,5-tris-(3,5-di-tert-butyl 4 hydroxybenzyl)-isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,~dimethylbenzyl)-isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the Ca salt of 3,5-di-tert-butyl~
hydroxybenzylphosphonic acid monoethyl ester and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. Acvlaminophenols, for example 4-hydroxylaurylanilide, 4-hydroxystearylanilide, 2,4-bis-(ocylmercapto)-~(3,5-di-tert-butyl-4-hydroxyanilino )-s-triazine and octyl N-(3,5-di-tert-buyl-4hydroxyphenyl)-carbamate.
1.7. Esters of B-(3.5-di-tert-butvl~-hydroxvPhenvl~propionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,~hexanediol, neopenylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl) isocyanurate and N,N'-bis-~hydroxyethyl~oxalic acid diamide.
1.8. Esters of ~-(5-tert-butyl~hvdroxv-3-methvlphenyl)-propionic acid with mono- or polyhydric alcohols, for example with methanol, octa-decanol, 1,~hexanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy)ethyl isocyanurate and N,N'-bis-(hydroxyethyl)-oxalic acid diamide.
1.9. Esters of B-(3.5-dicYclohexYI-4-hvdrox~rphenvl)-~roPionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,~hexanediol, neopenylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydl~oxy)ethyl isocyanurate and N,N'-bis-(hydroxyethyl~oxalic acid diamide.
202~X2 1.10. Amides of ~-(3,5-di-tert-butvl-4-hvdroxv~henyl)-propionic acid, for example N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexarnethylenediamine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine and N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2. W absorbers and li~ht stabilizers 2.1. 2-(2'-HvdroxvPhenY!)-benzotriazoles, forexarnple the S'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis-(,a-dimethylbenzyl) derivatives.
2.2. 2-HvdroxvbenzoPhenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-te~t-butyl~hydroxybenzoate.
2.4. Acrvlates, for example ethyl or isooctyl a~-cyano-,~"B~iphenylacrylate, methyl -carbomethoxycinnamate, methyl or butyl cc-cyano-~-methyl-p-methoxycinnamate, methyl c~-carbomethoxy-p-methoxycinnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel comPounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl~phenols], such as the l: l or 1:2 complex, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of ~hydroxy-3,5~i-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxime and nickel complexes of l-phenyl-4-lauroyl-S-hydroxy-pyrazole, if desired with additional ligands.
2.6. Stericallv hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-( 1 ,2,2,6,~pentamethylpiperidyl) sebacate, bis-(l ,2,2,6,6-pentamethylpiperidyl) 202~ ;~2~
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexarnethyl-enediamine and 4-tert-octylarnino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetrarnethyl-4-piperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetrarnethyl 1 piperidyl)-1,2,3,4-butanetetraoate and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl-piperazinone).
2.7. Oxalic acid diarnides, for example 4,4'~ioctyloxyoxanilide, 2,2'-dioctyloxy-S,S'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-S,S'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylarninopropyl)-oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o-and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-HYdroxYPhenYl)-l~3~s-triazines~ for exarnple 2,4,~tris(2-hydroxy-4-octyloxy-phenyl~-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl) ~I,~bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4~ihydroxyphenyl)4,~bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis-(2-hydroxy-~propyloxyphenyl)-~(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)4,~bis-(4-methylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-dodecyloxyphenyl)-4,~bis-(2,4-dirnethylphenyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diarnide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis-(salicyloyl)-hydr~zine, N,N'-bis-~3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamin~1,2,~triazole and bis-(benzylidene)-oxalic acid dihydrazide.
4. Phosphites and phosphonites, for exarnple triphenyl phosphite, diphenyl alkylphosphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, ~is-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis-(2,~di-tert-butylphenyl)-pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 3,9-bis-(2,4-di-tert-butylphenoxy)-2,4,8,1~tetraoxa-3,9-diphosphaspiro[5.5~undecane.
5. Peroxide-destro~/in~ compounds, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt 202~ 1 22 of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis-(,B-dodecylmercapto)-propionate.
6. Polvamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivadves, amines, polyarnides,polyurethanes and alkali metal salts and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, andmony pyrocatecholate or tin pyrocatecholate.
8. Nucleatin agents, for example 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.
9. Fillers and reinforcin~ a~ents, for example calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
10. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, fluorescent brighteners, flameproofing agents, antistatic agents and blowing agents.
The conventional additives are added, for example, in concentrations of 0.01 to 10 %, based on the total weight of material to be stabilized.
The compounds of the formulae Ia and Ib and if desired other additives are incorporated into the organic material by known methods; for example, the incorporation into the polymeric material can be caIried out before or during shaping or by applying the dissolved or dispersed compounds to the polymeric material, if desired with subsequent evaporation of the solvent. The compounds of the formulae Ia and Ib can also be added in the form of a masterbatch, which contains these, for example, in a concentration of 2.5 to 25 % by weight, to the materials to be stabilized.
The compounds of the formulae Ia and Ib can also be added before or during the polymerization or before the crosslinking.
2 ~ 2 2 The compounds of the formulae Ia and Ib can be incorporated in the pure forrn or in a form encapsulated in waxes, oils or polymers into the material to be stabilized.
The materials stabilized in this way can be used in widely varying forms, for example as films, fibres, tapes, moulding composidons or profiles, or as binders for surface coatings, adhesives or putty.
The compounds of the formulae Ia and Ib can be prepared by processes analogous to known processes, for example by reacdng a diglycerol with a compound of the formula m uo~x-~l-Z (m) o in which Rl, R2 and X are as defined above and Z is, for example, Cl-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
If Z is Cl-C4alkoxy it is advantageous to use dibutyltin oxide, dtanium tetraisopropoxide, LiNH2, LiH, LiOA, KOA or NaOA, in which A is, for example, hydrogen, Cl-Cloalkylor a phenyloxy group which is unsubstituted or substituted by 1 to 3 Cl-Cloalkyl radicals, as catalysts. In this case, the reacdon is preferably carried out in an organic solvent, for example benzene, toluene, xylene, dimethylformamide and the like. It is furthermore advantageous for the reactants to be introduced into the reacdon vessel in an inert gas, for example nitrogen or argon, and for the alcohol fonned during the reacdon to be distilled off. The reacdon mixture can be further heated, for example, at 1 80-220C under a pressure of 10-1013 mbar for 8-20 hours to bring the reacdon to completion.
If Z is hydroxyl, an acid, for example p-toluenesulfonic acid, is advantageously used as the catalyst. If Z is chlorine, it is advantageous for the reaction to be carried out in the presence of an acid acceptor, for example pyridine, triethylamine, NaOH or KOH. In this case, the reaction can be carried out, for example, at a temperature of -10 to 150C.
The compounds of the formula m are known and, if they are not commercially available, 2 0 2 ~ , 2 ~J
can be prepared by processes analogous to known processes, such as are described, for example, in EP-A-219,459.
If a mixture of 1,2,6,7-tetrahydroxy-4-oxaheptane and 2-hydroxymethyl-l,S,~trihydroxy-3-oxahexane is employed as the diglycerol, a mixture of the compounds of the forrnulae Ia and Ib, which can be separated by chromatographic methods, is obtained.
The invention thus furthermore relates to a mixture of the compounds of the forrnulae Ia and Ib.
The invention also relates to a mixture of the compounds of the formulae Ia and Ib which is obtainable by reaction of diglycerol with an ester of the formula m R
HO ~X--C--Z
~
in which Rl, R2 and X are as defined in claim 1 and Z is Cl-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
The ratio of the compounds Ia/Ib in the mixture is, for example, 100/1 to 1/100, preferably 100/1 to 60/10 and in particular 90/10 to 80/10.
The following examples illustrate the invention in more detail. The parts and percentage data in these examples relate to the weight, unless stated otherwise.
xamDle 1: Preparation of 1,2,6,7-tetrakis[(3',5'-di-tert-butyl-4'-hydroxy-phenyl)-propionyloxy]-4-oxaheptane C(CH3)3 OR OR OR OR ,--~/
HzC--CH- -CHz--0--CHrCH--CH2 whe R _ ICl--CHZ--CH2{~OH
C(CH3)3 2t~7~ ,~2 121.6 g (0.42 mol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and 13.3 g (0.08 mol) of diglycerol are initially introduced into a 350 ml sulfonating flask and are heated to 90C under nitrogen. 0.16 g of dibutyltin oxide (= 0.8 mol %, based on the diglycerol employed) is then added as a catalyst and the reaction mixture is further heated to 180C, methanol distilling of After 75 minutes, the apparatus is slowly placed under a vacuum (13.3 mbar) and is heated at 185C for 12 hours. The reaction mixture is cooled and the excess methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate employed is distilled off under a high vacuum (2.67 x 10-5 bar) at 123-127C. Purification of the crude product by column chromatography gives 77.5 g (= 83 % of theory) of a colourlessamorphous powder having a melting point of 57C.
Elemental analysis:
Calculated: 73.60 % C; 9.18 % H
Found: 73.83 % C; 9.15 % H
ExamDle 2: Preparation of 1,2,6,7-tetrakis[(3'-methyl-5'-tert-butyl-4'-hydroxy-phenyl)-propionyloxy]4-oxaheptane OR OR OR OR = ~~ CH3 H2C--CH--CHz--0--CHr CH--CH2 where R - ICI--CH2 CH~OH
C(CH3)3 45 g (0.18 mol) of methyl 3-(3'-methyl-5'-tert-butyl4'-hydroxyphenyl)propionate and 6.65 g (0.04 mol) of diglycerol are inidally introduced into a sulfonadng flask and heated to 100C 0.1 g of dibutyldn oxide (= 1 mol %, based on the diglycerol employed) is then added as a catalyst. The reacdon mixture is heated to 180C and kept at this temperature in vacuo (133 mbar) for 13 hours. Working up is ca~ied out analogously to the method described in Example 1. 28.2 g (= 68 % of theory) of an arnorphous powder which has a meldng point to 55C are obtained.
Elemental analvsis:
Calculated: 71.65 % C; 8.34 % H
Found: 71.31 % C; 8.53 % H
2 ~ 2 /~J
Example 3: Stabilization of polypropylene 100 parts of polypropylene powder containing 0.1 % of calcium stearate are mixed with 0.3 % of dilauryl thiodipropionate and 0.1 % of the stabilizer shown in Table 1 and the mixture is then kneaded at 200C for 10 minutes in a Brabender Plastograph. The composidon thus obtained is pressed to sheets 1 mm thick in a press at a surfacetemperature of 260C, and strips 1 cm wide and 10 cm long are cut from these sheets. One or more such strips from each sheet are suspended in a circulating air oven heated to 135C or 149C and observed at regular intervals of dme. Oxidadve decomposition of these strips can be recognized by a yellow discoloration starting as a circle. The duration of dme in days before decomposidon occurs is a measure of the stability of the sample.
Table 1:
Compound Number of days of oven ageing before decomposition from Example 135C 149C
2 189 ~0
The invendon ~us furthcrmore relates to composihons containing an organic material which is sensidve againts oxidative, thermal or actinic degradahon and at least one compound of thc formulae Ia andlor Ib, as well as the use of compounds of the formulae Ia and Ib for stabilizing organic mate~ial against oxidative, thermal or acdnic deg~adadon.
Preferred organic matcrials are polymers, for cxample synthedc polymers, in particular thermoplastic polymers. Pardcularly p~cfeITed organic materials are polyolefins, for examplc those mendoned above under points 1 to 3, in particular polyethylene andpolypropylene.
2~2~)~2~
The compounds of the formulae Ia and Ib are in general added to the material to be stabilized in amounts of 0.01 to 10 %, preferably 0.01 to 5 %, in pardcular 0.01 to 2 %, based on the total weight of the material to be stabilized.
In addidon to the compounds of the formulae Ia and/or Ib, the compositions according to the invention can addidonal1y contain conventional additives, for example those mentioned below.
1 Antioxidants 1.1. ~lkvlated monoPhenols, for example 2,~di-tert-butyl-~methylphenol, 2-tert-butyl-4,~dimethylphenol, 2,~di-tert-butyl-4-ethylphenol, 2,6 di-tert-butyl-4n-butylphenol, 2,~di-tert-butyl~i-butylphenol, 2,~di-cyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl~4,6 dimethylphenol, 2,6 di-octadecyl-4-methylphenol, 2,4,~tri-cyclohexylphenol, 2,~di-tert-butyl-4-methoxymethylphenol and 2,~di-nonyl-~methylphenol.
1.2. ALlcvlated hvdroquinones, for example 2,6 di-tert-butyl-~methoxyphenol, 2,5~i-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone and 2,~diphenyl-4-octadecyloxyphenol.
1.3. Hvdroxvlated diphenYI thioethers, for example 2,2'-thio-bis-(~tert-butyl ~- methylphenol), 2,2'-thi~bis-(4-octylphenol), 4,4'-thio-bis-(~tert-butyl-3-methylphenol) and 4,4' -thio-bis-(~tert-butyl-2-methylphenol).
1.4. AlkYlidene bisDhenols, for example 2t2'-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(~tert-butyl-4-ethylphenol), 2,2'-methylene-bis-~4-methyl-~(a-methylcyclohexyl)-phenol], 2,2'-methylene-bis-(4-methyl-~cyclohexylphenol), 2,2'-methylene-bis-(~nonyl-4-methylphenol), 2,2'-methylene-bis-(4,~di-tert-butylphenol), 2,2'-ethylidene-bis-(4,~di-tert-butylphenol), 2~2'-ethylidene-bis-(~
tert-butyl-4-isobutylphenol), 2,2'-methylene-bis-[~(a-methylbenzyl)4-nonylphenol], 2,2'-methylene-bis-[~(a,-dirnethylbenzyl)4-nonylphenol], 4,4'-methylene-bis-(2,~di-tert-butylphenol), 4,4'-methylene-bis-(~tert-butyl-2-methylphenol), 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,~bis-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methylphenol, 1,1,3-tris-(5-tert-butyl-4 hydroxy-2-methylphenyl)-butane, 2 ~ 2 2 g 1,1-bis-(5-tert-butyl4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate], bis-(3-tertbutyl-4-hydroxy-S-methylphenyl)~icyclopentadiene and bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-~tert-butyl-4-methylphenyl] terephthalate.
1.5. Benzvl comPounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl~hydroxy-benzyl)-2,4,~
trimethylbenzene, bis-(3,5-di-tert-butyl~-hydroxybenzyl)-sulfide, isooctyl 3,S-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiolterephthalate, 1,3,5-tris-(3,5-di-tert-butyl 4 hydroxybenzyl)-isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,~dimethylbenzyl)-isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the Ca salt of 3,5-di-tert-butyl~
hydroxybenzylphosphonic acid monoethyl ester and 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. Acvlaminophenols, for example 4-hydroxylaurylanilide, 4-hydroxystearylanilide, 2,4-bis-(ocylmercapto)-~(3,5-di-tert-butyl-4-hydroxyanilino )-s-triazine and octyl N-(3,5-di-tert-buyl-4hydroxyphenyl)-carbamate.
1.7. Esters of B-(3.5-di-tert-butvl~-hydroxvPhenvl~propionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,~hexanediol, neopenylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl) isocyanurate and N,N'-bis-~hydroxyethyl~oxalic acid diamide.
1.8. Esters of ~-(5-tert-butyl~hvdroxv-3-methvlphenyl)-propionic acid with mono- or polyhydric alcohols, for example with methanol, octa-decanol, 1,~hexanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy)ethyl isocyanurate and N,N'-bis-(hydroxyethyl)-oxalic acid diamide.
1.9. Esters of B-(3.5-dicYclohexYI-4-hvdrox~rphenvl)-~roPionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,~hexanediol, neopenylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydl~oxy)ethyl isocyanurate and N,N'-bis-(hydroxyethyl~oxalic acid diamide.
202~X2 1.10. Amides of ~-(3,5-di-tert-butvl-4-hvdroxv~henyl)-propionic acid, for example N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexarnethylenediamine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine and N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2. W absorbers and li~ht stabilizers 2.1. 2-(2'-HvdroxvPhenY!)-benzotriazoles, forexarnple the S'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis-(,a-dimethylbenzyl) derivatives.
2.2. 2-HvdroxvbenzoPhenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-te~t-butyl~hydroxybenzoate.
2.4. Acrvlates, for example ethyl or isooctyl a~-cyano-,~"B~iphenylacrylate, methyl -carbomethoxycinnamate, methyl or butyl cc-cyano-~-methyl-p-methoxycinnamate, methyl c~-carbomethoxy-p-methoxycinnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel comPounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl~phenols], such as the l: l or 1:2 complex, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of ~hydroxy-3,5~i-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxime and nickel complexes of l-phenyl-4-lauroyl-S-hydroxy-pyrazole, if desired with additional ligands.
2.6. Stericallv hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-( 1 ,2,2,6,~pentamethylpiperidyl) sebacate, bis-(l ,2,2,6,6-pentamethylpiperidyl) 202~ ;~2~
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexarnethyl-enediamine and 4-tert-octylarnino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetrarnethyl-4-piperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetrarnethyl 1 piperidyl)-1,2,3,4-butanetetraoate and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl-piperazinone).
2.7. Oxalic acid diarnides, for example 4,4'~ioctyloxyoxanilide, 2,2'-dioctyloxy-S,S'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-S,S'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylarninopropyl)-oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o-and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-HYdroxYPhenYl)-l~3~s-triazines~ for exarnple 2,4,~tris(2-hydroxy-4-octyloxy-phenyl~-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl) ~I,~bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4~ihydroxyphenyl)4,~bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis-(2-hydroxy-~propyloxyphenyl)-~(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)4,~bis-(4-methylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-dodecyloxyphenyl)-4,~bis-(2,4-dirnethylphenyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diarnide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis-(salicyloyl)-hydr~zine, N,N'-bis-~3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamin~1,2,~triazole and bis-(benzylidene)-oxalic acid dihydrazide.
4. Phosphites and phosphonites, for exarnple triphenyl phosphite, diphenyl alkylphosphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, ~is-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis-(2,~di-tert-butylphenyl)-pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 3,9-bis-(2,4-di-tert-butylphenoxy)-2,4,8,1~tetraoxa-3,9-diphosphaspiro[5.5~undecane.
5. Peroxide-destro~/in~ compounds, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt 202~ 1 22 of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis-(,B-dodecylmercapto)-propionate.
6. Polvamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivadves, amines, polyarnides,polyurethanes and alkali metal salts and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, andmony pyrocatecholate or tin pyrocatecholate.
8. Nucleatin agents, for example 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.
9. Fillers and reinforcin~ a~ents, for example calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
10. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, fluorescent brighteners, flameproofing agents, antistatic agents and blowing agents.
The conventional additives are added, for example, in concentrations of 0.01 to 10 %, based on the total weight of material to be stabilized.
The compounds of the formulae Ia and Ib and if desired other additives are incorporated into the organic material by known methods; for example, the incorporation into the polymeric material can be caIried out before or during shaping or by applying the dissolved or dispersed compounds to the polymeric material, if desired with subsequent evaporation of the solvent. The compounds of the formulae Ia and Ib can also be added in the form of a masterbatch, which contains these, for example, in a concentration of 2.5 to 25 % by weight, to the materials to be stabilized.
The compounds of the formulae Ia and Ib can also be added before or during the polymerization or before the crosslinking.
2 ~ 2 2 The compounds of the formulae Ia and Ib can be incorporated in the pure forrn or in a form encapsulated in waxes, oils or polymers into the material to be stabilized.
The materials stabilized in this way can be used in widely varying forms, for example as films, fibres, tapes, moulding composidons or profiles, or as binders for surface coatings, adhesives or putty.
The compounds of the formulae Ia and Ib can be prepared by processes analogous to known processes, for example by reacdng a diglycerol with a compound of the formula m uo~x-~l-Z (m) o in which Rl, R2 and X are as defined above and Z is, for example, Cl-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
If Z is Cl-C4alkoxy it is advantageous to use dibutyltin oxide, dtanium tetraisopropoxide, LiNH2, LiH, LiOA, KOA or NaOA, in which A is, for example, hydrogen, Cl-Cloalkylor a phenyloxy group which is unsubstituted or substituted by 1 to 3 Cl-Cloalkyl radicals, as catalysts. In this case, the reacdon is preferably carried out in an organic solvent, for example benzene, toluene, xylene, dimethylformamide and the like. It is furthermore advantageous for the reactants to be introduced into the reacdon vessel in an inert gas, for example nitrogen or argon, and for the alcohol fonned during the reacdon to be distilled off. The reacdon mixture can be further heated, for example, at 1 80-220C under a pressure of 10-1013 mbar for 8-20 hours to bring the reacdon to completion.
If Z is hydroxyl, an acid, for example p-toluenesulfonic acid, is advantageously used as the catalyst. If Z is chlorine, it is advantageous for the reaction to be carried out in the presence of an acid acceptor, for example pyridine, triethylamine, NaOH or KOH. In this case, the reaction can be carried out, for example, at a temperature of -10 to 150C.
The compounds of the formula m are known and, if they are not commercially available, 2 0 2 ~ , 2 ~J
can be prepared by processes analogous to known processes, such as are described, for example, in EP-A-219,459.
If a mixture of 1,2,6,7-tetrahydroxy-4-oxaheptane and 2-hydroxymethyl-l,S,~trihydroxy-3-oxahexane is employed as the diglycerol, a mixture of the compounds of the forrnulae Ia and Ib, which can be separated by chromatographic methods, is obtained.
The invention thus furthermore relates to a mixture of the compounds of the forrnulae Ia and Ib.
The invention also relates to a mixture of the compounds of the formulae Ia and Ib which is obtainable by reaction of diglycerol with an ester of the formula m R
HO ~X--C--Z
~
in which Rl, R2 and X are as defined in claim 1 and Z is Cl-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
The ratio of the compounds Ia/Ib in the mixture is, for example, 100/1 to 1/100, preferably 100/1 to 60/10 and in particular 90/10 to 80/10.
The following examples illustrate the invention in more detail. The parts and percentage data in these examples relate to the weight, unless stated otherwise.
xamDle 1: Preparation of 1,2,6,7-tetrakis[(3',5'-di-tert-butyl-4'-hydroxy-phenyl)-propionyloxy]-4-oxaheptane C(CH3)3 OR OR OR OR ,--~/
HzC--CH- -CHz--0--CHrCH--CH2 whe R _ ICl--CHZ--CH2{~OH
C(CH3)3 2t~7~ ,~2 121.6 g (0.42 mol) of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and 13.3 g (0.08 mol) of diglycerol are initially introduced into a 350 ml sulfonating flask and are heated to 90C under nitrogen. 0.16 g of dibutyltin oxide (= 0.8 mol %, based on the diglycerol employed) is then added as a catalyst and the reaction mixture is further heated to 180C, methanol distilling of After 75 minutes, the apparatus is slowly placed under a vacuum (13.3 mbar) and is heated at 185C for 12 hours. The reaction mixture is cooled and the excess methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate employed is distilled off under a high vacuum (2.67 x 10-5 bar) at 123-127C. Purification of the crude product by column chromatography gives 77.5 g (= 83 % of theory) of a colourlessamorphous powder having a melting point of 57C.
Elemental analysis:
Calculated: 73.60 % C; 9.18 % H
Found: 73.83 % C; 9.15 % H
ExamDle 2: Preparation of 1,2,6,7-tetrakis[(3'-methyl-5'-tert-butyl-4'-hydroxy-phenyl)-propionyloxy]4-oxaheptane OR OR OR OR = ~~ CH3 H2C--CH--CHz--0--CHr CH--CH2 where R - ICI--CH2 CH~OH
C(CH3)3 45 g (0.18 mol) of methyl 3-(3'-methyl-5'-tert-butyl4'-hydroxyphenyl)propionate and 6.65 g (0.04 mol) of diglycerol are inidally introduced into a sulfonadng flask and heated to 100C 0.1 g of dibutyldn oxide (= 1 mol %, based on the diglycerol employed) is then added as a catalyst. The reacdon mixture is heated to 180C and kept at this temperature in vacuo (133 mbar) for 13 hours. Working up is ca~ied out analogously to the method described in Example 1. 28.2 g (= 68 % of theory) of an arnorphous powder which has a meldng point to 55C are obtained.
Elemental analvsis:
Calculated: 71.65 % C; 8.34 % H
Found: 71.31 % C; 8.53 % H
2 ~ 2 /~J
Example 3: Stabilization of polypropylene 100 parts of polypropylene powder containing 0.1 % of calcium stearate are mixed with 0.3 % of dilauryl thiodipropionate and 0.1 % of the stabilizer shown in Table 1 and the mixture is then kneaded at 200C for 10 minutes in a Brabender Plastograph. The composidon thus obtained is pressed to sheets 1 mm thick in a press at a surfacetemperature of 260C, and strips 1 cm wide and 10 cm long are cut from these sheets. One or more such strips from each sheet are suspended in a circulating air oven heated to 135C or 149C and observed at regular intervals of dme. Oxidadve decomposition of these strips can be recognized by a yellow discoloration starting as a circle. The duration of dme in days before decomposidon occurs is a measure of the stability of the sample.
Table 1:
Compound Number of days of oven ageing before decomposition from Example 135C 149C
2 189 ~0
Claims (12)
1. A compound of the formulae Ia or Ib , (Ia) (Ib) in which the radicals R are identical or different and are a group of the formula II
(II) in which X is a direct bond, methylene, ethylene or a group and Y is C1-C8alkyl, R1 and R2 independently of one another are C1-C18alkyl, C5-C12cycloalkyl, C5-C7cycloalkyl which is substituted by C1-C4alkyl, or are phenyl or C7-C10phenylalkyl, and R2 is additionally hydrogen.
(II) in which X is a direct bond, methylene, ethylene or a group and Y is C1-C8alkyl, R1 and R2 independently of one another are C1-C18alkyl, C5-C12cycloalkyl, C5-C7cycloalkyl which is substituted by C1-C4alkyl, or are phenyl or C7-C10phenylalkyl, and R2 is additionally hydrogen.
2. A compound according to claim 1, in which the radicals R are identical.
3. A compound according to claim 1, in which X is a direct bond, methylene or ethylene.
4. A compound according to claim 1, in which Rl and R2 independendy of one another are C1-C12alkyl, C5-C7cycloalkyl, C5-C7cycloalkyl which is substituted by C1-C4alkyl, or are phenyl, benzyl or phenylethyl and R2 is additionally hydrogen.
5. A compound according to claim 1, in which X is a direct bond, methylene or ethylene, R1 and R2 independently of one another are C1-C4allcyl, cyclohexyl, cyclohexyl which is substituted by C1-C4alkyl, or are phenyl or benzyl and R2 is additionally hydrogen.
6. A compound according to claim 1, in which X is ethylene, R1 and R2 independently of one another are C1-C4alkyl and R2 is additionally hydrogen.
7. A compound according to claim 1, in which the radicals R are identical and are 3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy or 3-methyl-5-tert-butyl-4-hydroxyphenylpropionyloxy.
8. A mixture of compounds of the formulae Ia and Ib defined in claim 1.
9. A mixture of compounds of the formulae Ia and Ib according to claim 1, obtainable by reacting diglycerol with an ester of the formula III
(III) in which R1, R2 and X are as defined in claim 1 and Z is C1-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
(III) in which R1, R2 and X are as defined in claim 1 and Z is C1-C4alkoxy, hydroxyl or chlorine, in the presence of a catalyst.
10. A composition containing an organic material which is sensitive to thermal, oxidative or actinic degradation and at least one compound of the formula Ia and/or Ib according to claim 1.
11. A composition according to claim 10, in which the organic material is a polyolefin.
12. A process for stabilizing an organic material against thermal, oxidative or actinic degradation, which comprises incorporating at least one compound of the formula Ia and/or Ib according to claim I into this organic material.
FO 7.3/SR/sf*
FO 7.3/SR/sf*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3583/89-1 | 1989-10-02 | ||
| CH358389 | 1989-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2026522A1 true CA2026522A1 (en) | 1991-04-03 |
Family
ID=4259125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002026522A Abandoned CA2026522A1 (en) | 1989-10-02 | 1990-09-28 | Hydroxyphenylcarboxylic acid esters as stabilizers |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0421928B1 (en) |
| JP (1) | JPH03123757A (en) |
| KR (1) | KR910007862A (en) |
| BR (1) | BR9004907A (en) |
| CA (1) | CA2026522A1 (en) |
| DE (1) | DE59006127D1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9101619A (en) * | 1991-09-25 | 1993-04-16 | Harcros Chemicals Bv | STABILIZERS FOR ORGANIC MATERIALS. |
| DE69703138T2 (en) * | 1996-05-23 | 2001-05-17 | Ciba Sc Holding Ag | Process for the preparation of substituted hydroxy hydrocinnamate esters |
| WO2005007735A2 (en) * | 2003-07-11 | 2005-01-27 | Eastman Chemical Company | Addition of uv absorbers to pet process for maximum yield |
| CN102746154B (en) * | 2012-07-03 | 2014-07-30 | 山东省临沂市三丰化工有限公司 | Crystallizing method of solid antioxidant |
| US11345846B2 (en) | 2019-07-03 | 2022-05-31 | Si Group, Inc. | Alkylphenol copolymer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594444A (en) * | 1983-12-22 | 1986-06-10 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
| JPH0745437B2 (en) * | 1988-03-18 | 1995-05-17 | 吉富製薬株式会社 | Method for producing ester |
-
1990
- 1990-09-25 DE DE59006127T patent/DE59006127D1/en not_active Expired - Fee Related
- 1990-09-25 EP EP90810736A patent/EP0421928B1/en not_active Expired - Lifetime
- 1990-09-26 KR KR1019900015292A patent/KR910007862A/en not_active Application Discontinuation
- 1990-09-28 CA CA002026522A patent/CA2026522A1/en not_active Abandoned
- 1990-10-01 JP JP2263685A patent/JPH03123757A/en active Pending
- 1990-10-01 BR BR909004907A patent/BR9004907A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE59006127D1 (en) | 1994-07-21 |
| BR9004907A (en) | 1991-09-10 |
| JPH03123757A (en) | 1991-05-27 |
| EP0421928B1 (en) | 1994-06-15 |
| EP0421928A3 (en) | 1992-04-22 |
| EP0421928A2 (en) | 1991-04-10 |
| KR910007862A (en) | 1991-05-30 |
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