DE3725926A1 - Mixture for the stabilisation of polyurethanes - Google Patents
Mixture for the stabilisation of polyurethanesInfo
- Publication number
- DE3725926A1 DE3725926A1 DE19873725926 DE3725926A DE3725926A1 DE 3725926 A1 DE3725926 A1 DE 3725926A1 DE 19873725926 DE19873725926 DE 19873725926 DE 3725926 A DE3725926 A DE 3725926A DE 3725926 A1 DE3725926 A1 DE 3725926A1
- Authority
- DE
- Germany
- Prior art keywords
- tert
- butyl
- bis
- hydroxy
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/3495—Six-membered rings condensed with carbocyclic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Polyurethane werden bekanntermaßen sehr rasch durch Lichteinwirkung zerstört. Diese Zerstörung zeigt sich üblicherweise in einer Vergilbung bzw. Verfärbung sowie in einer Versprödung des polymeren Materials. In der Patentliteratur sind für Polyurethane bereits eine Reihe von Lichtschutzmitteln beschrieben worden, die aus den Verbindungsklassen der sterisch gehinderten Amine, der UV-Absorber und der Antioxidantien stammen. Jedoch konnte mit den beschriebenen Verbindungen in Polyurethanen kein zufriedenstellender Schutz gegen die Zerstörung durch Lichteinwirkung erzielt werden. Durch Verwendung von Gemischen aus Verbindungen der genannten Klassen wurden zwar Verbesserungen in der Lichtstabilisierung erreicht, jedoch führten die zu einem wirksamen Schutz notwendigen hohen Konzentrationen an Additiven oft zu unerwünschten Veränderungen in den Eigenschaften der Polymeren und zu Problemen hinsichtlich der Verträglichkeit (z. B. Ausschwitzen, Kreiden, Belagbildung, farbliche Veränderungen).It is known that polyurethanes are destroyed very quickly by exposure to light. This destruction usually shows up in yellowing or Discoloration and embrittlement of the polymeric material. In the Patent literature is already a series of light stabilizers for polyurethanes have been described which come from the compound classes of steric hindered amines, the UV absorber and the antioxidants. However could not be satisfactory with the compounds described in polyurethanes Protection against destruction by exposure to light will. By using mixtures of compounds of the above Classes, while improvements in light stabilization were achieved, however, the high concentrations necessary for effective protection resulted of additives often lead to undesirable changes in properties of the polymers and compatibility problems (e.g. sweating, chalking, coating, color changes).
Aufgabe dieser Erfindung war es, Stabilisatormischungen bereitzustellen, die Polyurethane wirkungsvoll gegen Licht ohne die unerwünschten Nebenerscheinungen schützen.The object of this invention was to provide stabilizer mixtures, the polyurethanes are effective against light without the undesirable side effects protect.
Es wurde überraschend gefunden, daß Mischungen,It has surprisingly been found that mixtures,
-
a) die mindestens ein sterisch gehindertes Amin der Formel (I)
in der
R¹ und R² unabhängig voneinander Wasserstoff, Methyl oder Phenyl bedeuten, und eine weitere Komponente aus den Gruppena) the at least one sterically hindered amine of the formula (I) in the
R¹ and R² independently of one another are hydrogen, methyl or phenyl, and a further component from the groups - b) der UV-Absorber und/oderb) the UV absorber and / or
- c) der Antioxidantien aus den Klassen der sterisch gehinderten Phenole, der Phosphite oder des Vitamins E und seiner Derivate enthalten,c) the antioxidants from the classes of the sterically hindered phenols, containing phosphites or vitamin E and its derivatives,
Polyurethane in ausgezeichneter Weise gegen die Einwirkung von Licht und Sauerstoff stabilisieren. In dieser Hinsicht sind die Gemische gemäß der vorliegenden Erfindung den Gemischen des Standes der Technik deutlich überlegen. Polyurethanes in an excellent way against the effects of light and Stabilize oxygen. In this regard, the mixtures are in accordance of the present invention the mixtures of the prior art clearly think.
Die erfindungsgemäßen Stabilisatormischungen zeichnen sich durch eine gute Lichtschutzwirkung für Polyurethane, durch keine oder geringe Nebenwirkungen auf die Polymereigenschaften und durch ein synergistisches Zusammenwirken der einzelnen Komponenten aus.The stabilizer mixtures according to the invention are notable for good Sun protection effect for polyurethanes, through no or little side effects on the polymer properties and through a synergistic interaction of the individual components.
Die sterisch gehinderten Amine (I) sind in der EP-A-2 13 570 beschrieben. Für die Gemische gemäß der Erfindung ist für (a) das Amin (I) mit R¹=R²=H bevorzugt.The sterically hindered amines (I) are described in EP-A-2 13 570. For the mixtures according to the invention, for (a) the amine (I) is also present R1 = R2 = H preferred.
Komponente (a) kann neben dem sterisch gehinderten Amin (I) auch noch andere sterisch gehinderte Amine in untergeordneten Mengen enthalten.Component (a) can in addition to the sterically hindered amine (I) other sterically hindered amines contained in minor amounts.
Als sterisch gehinderte Amine, die zusätzlich in der Komponente (a) enthalten sein können, kommen z. B. in Betracht:As sterically hindered amines, which are additionally present in component (a) may be included, come z. B. Consider:
Bis-(1,2,2,6,6-pentamethylpiperidyl)-ester, wie Bis-(2,2,6,6-tetramethyl piperidyl)-sebacat, Bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacat, das Kondensationsprodukt aus 1-Hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy piperidin und Bernsteinsäure, das Kondensationsproukt aus N,N′-(2,2,6,6-Tetramethylpiperidyl)-hexamethylendiamin und 4-tert.-Octyl amino-2,6-dichlor-1,3,5-s-triazin, Tris-(2,2,6,6-Tetramethylpiperidyl)- nitrilotriacetat, Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-bu tantetracarbonsäureester und 1,1′-(1,2-Ethandiyl)-bis-(3,3,5,5-tetra methylpiperazinon).Bis (1,2,2,6,6-pentamethylpiperidyl) esters such as bis (2,2,6,6-tetramethyl) piperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, the Condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy piperidine and succinic acid, the condensation product N, N '- (2,2,6,6-tetramethylpiperidyl) hexamethylene diamine and 4-tert-octyl amino-2,6-dichloro-1,3,5-s-triazine, tris- (2,2,6,6-tetramethylpiperidyl) - nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-bu tantetracarboxylic acid ester and 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetra methylpiperazinone).
Für die Komponente (b) der UV-Absorber kommen z. B. solche aus den Klassen der Benzotriazole und des N-Cyanoethylen-indolins in Betracht.For component (b) of the UV absorbers, z. B. those from the classes of benzotriazoles and N-cyanoethylene indoline.
Im einzelnen sind z. B. zu nennen das 5′-Methyl-, 3′,5′-Di-tert.-butyl-, 5′-tert.-Butyl-, 5′-(1,1,3,3-Tetramethylbutyl)-, 5-Chlor-3′,5′-di- tert.-butyl-, 5-Chlor-3′-tert.-butyl-5′-methyl-, 3′-sec.-Butyl-5′-butyl-, 4′-Octoxy-, 3′,5′-Di-tert.-amyl-, 3′,5′-Bis(α,α-dimethylbenzyl)-Derivat des 2-(2′-Hydroxyphenyl)-benztriazols.In particular, e.g. B. to call the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec.-butyl-5'-butyl-, 4'-octoxy-, 3 ', 5'-di-tert-amyl-, 3', 5'-bis ( α, α -dimethylbenzyl) derivative of 2- (2'-hydroxyphenyl) benzotriazole.
Als Indolinverbindung kommt z. B.As an indoline compound comes e.g. B.
in Betracht. into consideration.
Als Komponente (c) der Antioxidantien kommen in Betracht:Possible components (c) of the antioxidants are:
-
c1) Phenolische Antioxidantien:
- c1.1) alkylierte Monophenole, wie z. B. 2,6-Di-tert.-butyl-4-methylphenol, 2-tert.-Bu tyl-4,6-dimethylphenol, 2,6-Di-tert.-butyl-4-ethylphenol, 2,6-Di-tert.-butyl-4-n-butylphenol, 2,6-Di-tert.-bu tyl-4-i-butylphenol, 2,6-Di-cyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-Di-octa decyl-4-methylphenol, 2,4,6,Tri-cyclohexylphenol, 2,6,Di-tert.-butyl-4-methoxymethylphenol.
- c1.2) alkylierte Hydrochinone, z. B. 2,6-Di-tert.-butyl-4-methoxyphenol, 2,5-Di-tert.-bu tyl-hydrochinon, 2,5-Di-tert.-amylhydrochinon, 2,6-Di- phenyl-4-octadecyloxyphenol.
- c1.3) hydroxylierte Thiodiphenylether, wie z. B. 2,2′-Thio-bis-(tert.-butyl-4-methylphenol), 2,2′-Thio-bis-(4-octylphenol), 4,4′-Thio-bis-(6-tert.-bu tyl-3-methylphenol), 4,4′-Thio-bis-(6-tert.-butyl-2-methyl phenol).
- c1.4) Alkyliden-Bisphenole, z. B.
2,2′-Methylen-bis-(6-tert.-butyl-4-methylphenol),
2,2′-Methylen-bis-(6-tert.-butyl-4-ethylphenol),
2,2′-Methylen-bis-[4-methyl-6-8(α-methylcyclohexyl)-phenol],
2,2′-Methylen-bis-(4-methyl-6-cyclohexyl-phenol),
2,2′-Methylen-bis-(6-nonyl-4-methylphenol),
2,2′-Methylen-bis-(4,6-di-tert.-butylphenol),
2,2′-Ethyliden-bis-(4,6-di-tert.-butylphenol),
2,2′-Ethyliden-bis-(6-tert.-butyl-4-isobutylphenol),
2,2′-Methylen-bis-[6(α-methylbenzyl)-4-nonylphenol],
2,2′-Methylen-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol],
4,4′-Methylen-bis-(2,6-di-tert.-butylphenol),
4,4′-Methylen-bis-(6-tert.-butyl-2-methylphenol),
1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan,
2,6-Di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methyl phenol,
1,1,3-Tris(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butan,
1,1-Bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-3-n- dodecylmercaptobutan,
Ethylenglykol-bis[3,3-bis-(3′-tert.-butyl-4′-hydroxyphenyl)- butyrat],
Di-(3-tert.-butyl-4-hydroxy-5-methylphenyl)-di-cyclopenta dien,
bis-[2-(3′-tert.-butyl-2′-hydroxy-5′methylbenzyl)-6-tert.- butyl-4-methylphenyl]-terephthalat. - c1.5) Benzylverbindungen, z. B.
1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-tri methylbenzol,
Di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-sulfid,
3,5-Di-tert.-butyl-hydroxy-benzyl-mercaptoessigsäure-iso octylester,
Bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol- terephthalat,
1,3,5-Tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-isocyanurat,
1,3,5-Tris-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-iso cyanurat,
3,5-Di-tert.-butyl-4-hydroxybenzyl-phosphonsäuredioctadecyl ester,
3,5-Di-tert.-butyl-4-hydroxybenzyl-phosphonsäure-monoethyl ester-Calcium-Salz. - c1.6) Acylaminphenole, wie z. B.
4-Hydroxy-laurinsäureanilid,
4-Hydroxystearinsäureanilid,
2,4-Bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxyani lino)-s-triazin,
N-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-carbaminsäure-octyl ester. - c1.7) Ester der
β-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen,
z. B. mit Methanol, Octadecanol, 1,6-Hexandiol, Neopentyl glykol, Thiodiethylenglykol, Diethylenglykol, Triethylen glykol, Pentaerythrit, Tris-hydroxyethyl-isocyanurat, Di-hydroxyethyl-oxalsäurediamid. - c1.8) Ester der
β-(5-tert.-Butyl-4-hydroxy-3-methylphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen,
z. B. mit Methanol, Octadecanol, 1,6-Hexandiol, Neopentyl glykol, Thiodiethylenglykol, Diethylenglykol, Triethylen glykol, Pentaerythrit, Tris-hydroxyethyl-isocyanurat, Di-hydroxy-ethyl-oxalsäureamid. - c1.9) Amide der
β-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propion säure, z. B. N,N′-Di-(3,5-di-tert.-butyl-4-hydroxyphenylpropio nyl)-hexame thylendiamin, N,N′-Di-(3,5-di-tert.-butyl-4-hy droxyphenylpropionyl)-trimet hylendiamin, N,N′-Di-(3,5-di- tert.-butyl-4-hydroxyphenylpropionyl)-hydrazin.
- c1.1) alkylated monophenols, such as. B. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6- Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- ( α- methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octa decyl-4-methylphenol, 2,4,6, tri-cyclohexylphenol, 2,6, di-tert-butyl-4-methoxymethylphenol.
- c1.2) alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tert-amyl hydroquinone, 2,6-di-phenyl- 4-octadecyloxyphenol.
- c1.3) hydroxylated thiodiphenyl ethers, such as. B. 2,2'-thio-bis- (tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6-tert .-Bu tyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol).
- c1.4) alkylidene bisphenols, e.g. B.
2,2'-methylene-bis- (6-tert-butyl-4-methylphenol),
2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol),
2,2′-methylene-bis- [4-methyl-6-8 ( α- methylcyclohexyl) phenol],
2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol),
2,2'-methylene-bis- (6-nonyl-4-methylphenol),
2,2'-methylene-bis- (4,6-di-tert-butylphenol),
2,2'-ethylidene-bis- (4,6-di-tert-butylphenol),
2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol),
2,2′-methylene-bis- [6 ( α- methylbenzyl) -4-nonylphenol],
2,2′-methylene-bis- [6- ( α, α -dimethylbenzyl) -4-nonylphenol],
4,4'-methylene-bis- (2,6-di-tert-butylphenol),
4,4'-methylene-bis- (6-tert-butyl-2-methylphenol),
1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl phenol,
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane,
Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate],
Di- (3-tert-butyl-4-hydroxy-5-methylphenyl) di-cyclopenta diene,
bis- [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate. - c1.5) benzyl compounds, e.g. B.
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-tri methylbenzene,
Di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,
3,5-di-tert-butyl-hydroxy-benzyl-mercaptoacetic acid iso octyl ester,
Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -iso cyanurate,
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester,
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcium salt. - c1.6) acylamine phenols, such as. B.
4-hydroxy lauric acid anilide,
4-hydroxystearic acid anilide,
2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine,
N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester. - c1.7) esters of
β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols,
e.g. B. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxyethyl oxalic acid diamide. - c1.8) esters of
β - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols,
e.g. B. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate, di-hydroxy-ethyl oxalic acid amide. - c1.9) Amides of
β - (3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g. B. N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropio nyl) hexamethylene diamine, N, N'-di- (3,5-di-tert-butyl-4 -hy droxyphenylpropionyl) trimethylene diamine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
- c2) Phosphorhaltige Antioxidationsmittel, z. B. Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphos phite, Tri-(nonylphenyl)-phosphit, Trilaurylphosphit, Trioctadecyl phosphit, Distearyl-pentaerythritdiphosphit, Tris-(2,4-di-tert.-bu tyl-phenyl)-phosphit, Diisodecylpentaerythritdiphosphit, Di-(2,4-di-tert.-butylphenyl)-pentaerythritdiphosphit, Tristearyl-sor bit-triphosphit, Tetrakis-(2,4-di-tert.-butyl-phenyl)-4,4′-bi phenylen-diphosphonit, 3,9-Bis-(2,4-di-tert.-butylphenoxy-2,4,8,10- tetraoxy-3,9-diphosphaspiro[5,5]undecan.c2) phosphorus-containing antioxidants, e.g. B. Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphos phite, tri (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris- (2,4-di-tert.-bu tylphenyl) phosphite, diisodecylpentaerythritol diphosphite, Di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sor bit triphosphite, tetrakis (2,4-di-tert-butyl-phenyl) -4,4'-bi phenylene diphosphonite, 3,9-bis (2,4-di-tert-butylphenoxy-2,4,8,10- tetraoxy-3,9-diphosphaspiro [5,5] undecane.
- c3) Vitamin E und dessen Derivate, z. B. Derivate der 6-Hydroxy-2,5,7,8-tetramethylchromans, wie α-Toco pherol, Stearinsäure-(6-hydroxy-2,5,7,8-tetramethylchroman-2-yl)- ethylester, Vitamin-E-acetat und -propionat.c3) Vitamin E and its derivatives, e.g. B. Derivatives of 6-hydroxy-2,5,7,8-tetramethylchromans, such as α -tocopherol, stearic acid (6-hydroxy-2,5,7,8-tetramethylchroman-2-yl) ethyl ester, vitamin E-acetate and propionate.
Weiterhin können für (c) auch Mischungen gleichartiger und verschiedenartiger Antioxidantien in den erfindungsgemäßen Gemischen verwendet werden, z. B. Gemische aus α-Tocopherol und Tri-(nonylphenyl)-phosphit im Verhältnis von 1 : 10 bis 10 : 1 Gewichtsteilen.Furthermore, mixtures of the same and different types of antioxidants can also be used in the mixtures according to the invention for (c), e.g. B. Mixtures of α- tocopherol and tri- (nonylphenyl) phosphite in a ratio of 1:10 to 10: 1 parts by weight.
Für (b) sind UV-Absorber aus der Klasse der 2-(2′-Hydroxyphenyl)-benz triazole und des N-Cyanoethylenindolins bevorzugt. Besonders bevorzugt sind für (b) das 5′-Methyl-, das 3′,5′-Di-tert.-butyl-, das 5′-tert.- Butyl-, das 3′,5′-Di-tert.-amyl, das 5-Chlor-3′,5′-di-tert.-butyl- und das 3′,5′-Bis(α,α-dimethylbenzyl)-Derivat des 2-(2′-Hydroxyphenyl)-benz triazols, die Verbindung der Formel For (b), UV absorbers from the class of 2- (2'-hydroxyphenyl) benzotriazoles and N-cyanoethylene indoline are preferred. Particularly preferred for (b) are 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 3', 5'-di-tert. -amyl, the 5-chloro-3 ', 5'-di-tert-butyl and the 3', 5'-bis ( α, α -dimethylbenzyl) derivative of 2- (2'-hydroxyphenyl) -benz triazoles, the compound of the formula
sowie eine Mischung aus Verbindungen der Formelnand a mixture of compounds of the formulas
undand
bei denen n so gewählt ist, daß das mittlere Molekulargewicht der Mischung über 600 liegt.where n is chosen so that the average molecular weight of the mixture is over 600.
Aus der Reihe der Antioxidantien sind 2,6-Di-tert.-butyl-4-methylphenol, 2-tert.-Butyl-4,6-dimethylphenol, Triethylenglykol-bis-3-(3-tert.-butyl- 4-hydroxy-5-methylphenyl)-propionat, Pentaerythrit-tert.-3-(3-tert.- butyl-4-hydroxy-5-methylphenyl)-propionat, a-Tocopherol, Stearinsäure-(6- hydroxy-2,5,7,8-tetramethyl-chroman-2-yl)-ethylester, Tri-(nonylphenyl)- phosphit sowie Tetra-bis-(2,4-di-tert.-butylphenyl)-4,4′-biphenylen- diphosphonit bevorzugt.From the series of antioxidants are 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, triethylene glycol-bis-3- (3-tert-butyl-4- hydroxy-5-methylphenyl) propionate, pentaerythritol tert-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, a -tocopherol, stearic acid (6-hydroxy-2,5, 7,8-tetramethyl-chroman-2-yl) ethyl ester, tri- (nonylphenyl) phosphite and tetra-bis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite are preferred.
Bevorzugt ist weiterhin eine Mischung aus α-Tocopherol und Tri-(nonyl phenyl)-phosphit im Gewichtsverhältnis von 1 : 10 bis 10 : 1, insbesondere im Verhältnis von 1 : 10 Gewichtsteilen.A mixture of α- tocopherol and tri- (nonyl phenyl) phosphite in a weight ratio of 1:10 to 10: 1, in particular in a ratio of 1:10 parts by weight, is also preferred.
Die Komponenten (a), (b) und (c) der erfindungsgemäßen Stabilisatormischungen können als solche einzeln oder als Mischung dem Polyurethan in Mengen von jeweils 0,01 bis 5, vorzugsweise von jeweils 0,05 bis 2,5, insbesondere von jeweils 0,1 bis 2 Gew.-%, bezogen auf das zu stabilisierende Material, zugemischt werden. Components (a), (b) and (c) of the stabilizer mixtures according to the invention can as such individually or as a mixture in the polyurethane Quantities of 0.01 to 5, preferably 0.05 to 2.5, in particular from 0.1 to 2% by weight, based on that to be stabilized Material to be mixed.
Üblicherweise erfolgt die Zugabe der Stabilisatormischung durch Lösen der einzelnen Verbindungen oder des Gemisches aus (a), (b) und/oder (c) in der Polyolkomponente des Polyurethans gegebenenfalls unter leichtem Erwärmen. Das erfindungsgemäße Gemisch kann aber auch durch Einmischen der einzelnen Verbindungen oder des fertigen Gemisches in die Schmelze nach der in der Technik üblichen Methode vor oder während der Formgebung eingebracht werden. Das Stabilisieren kann aber auch durch Aufbringen der gelösten oder dispergierten Verbindungen (a), (b) und/oder (c) auf das Polymere oder durch Einmischen in eine Lösung, Suspension oder Emulsion des Polymeren, gegebenenfalls unter nachträglichem Verdunsten des Lösungsmittels, erfolgen.The stabilizer mixture is usually added by dissolving the individual compounds or the mixture of (a), (b) and / or (c) in the Polyol component of the polyurethane, if necessary with gentle heating. However, the mixture according to the invention can also be mixed in by mixing the individual Compounds or the finished mixture in the melt after the in the Technique usual before or during the molding introduced will. Stabilization can also be done by applying the loosened ones or dispersed compounds (a), (b) and / or (c) on the polymer or by mixing in a solution, suspension or emulsion of the Polymers, optionally with subsequent evaporation of the solvent, respectively.
Die folgenden Beispiele sollen die Erfindung zusätzlich erläutern und verdeutlichen.The following examples are intended to illustrate the invention and clarify.
Eine Polyolkomponente, bestehend aus 41,9 Teilen eines Polyetherols (OH-Zahl: 29,0; erhalten durch Addition von Propylenoxid und Ethylenoxid an Propylenglykol und das ungefähr 84% primäre Hydroxylgruppen besitzt) und 42,5 Teile eines Polyetherols (OH-Zahl; 27,0; erhalten durch Addition von Propylenoxid und Ethylenoxid an Trimethylpropan, das ungefähr 88% primäre Hydroxylgruppen besitzt), 8,1 Teilen 1,4-Butandiol, 1724 Teile einer 25%igen Lösung von Diazabicyclooctan in 1,4-Butandiol und 0,016 Teile Dibutylzinndilaurat, 0,1 Teilen Siliconstabilisator OS 710 (Bayer AG), 5,49 Teilen Frigen 11 und 0,17 Teilen Wasser wurde mit den angegebenen Stabilisatoren versetzt und im Mischungsverhältnis 100 : 48,5 mit einem 23,0% Isocyanatgruppen enthaltenden Präpolymeren bei 25°C Komponenten- und Werkzeugtemperatur zu Prüfplatten verschäumt.A polyol component consisting of 41.9 parts of a polyetherol (OH number: 29.0; obtained by adding propylene oxide and ethylene oxide of propylene glycol and about 84% primary hydroxyl groups owns) and 42.5 parts of a polyetherol (OH number; 27.0; obtained by adding propylene oxide and ethylene oxide to trimethyl propane, which has about 88% primary hydroxyl groups), 8.1 parts 1,4-butanediol, 1724 parts of a 25% solution of diazabicyclooctane in 1,4-butanediol and 0.016 part dibutyltin dilaurate, 0.1 part Silicone stabilizer OS 710 (Bayer AG), 5.49 parts Frigen 11 and The specified stabilizers were added to 0.17 part of water and in a mixing ratio of 100: 48.5 with a 23.0% isocyanate group containing prepolymers at 25 ° C component and tool temperature foamed to test plates.
Das NCO-Präpolymer wurde hergestellt aus 87,17 Teilen 4,4′-Diphenyl methandiisocyanat und 4,83 Teilen eines Polyetherols mit der OH-Zahl von 250 (erhalten durch Addition von Propylenoxid an Propylenglykol) und 8,0 Teilen Dipropylenglykol.The NCO prepolymer was made from 87.17 parts of 4,4'-diphenyl methane diisocyanate and 4.83 parts of a polyetherol with the OH number of 250 (obtained by adding propylene oxide to propylene glycol) and 8.0 parts dipropylene glycol.
Die Proben werden im Xenotest® 450 belichtet und an den Proben der Yellowness Index nach ASTM D 1925 bestimmt.The samples are in the Xenotest® 450 exposed and on the samples the Yellowness Index according to ASTM D 1925 certainly.
Die verwendeten Gemische sowie die Ergebnisse der Belichtung sind in der folgenden Tabelle zusammengestellt. The mixtures used and the results of the exposure are shown in compiled in the following table.
Claims (3)
- a) mindestens ein sterisch gehindertes Amin der Formel (I)
in der
R¹ und R² unabhängig voneinander Wasserstoff, Methyl oder Phenyl bedeuten, und eine weitere Komponente aus den Gruppen - b) der UV-Absorber und/oder
- c) der Antioxidantien aus den Klassen der sterisch gehinderten Phenole, der Phosphite und/oder des Vitamin E und seiner Derivate.
- a) at least one sterically hindered amine of the formula (I) in the
R¹ and R² independently of one another are hydrogen, methyl or phenyl, and a further component from the groups - b) the UV absorber and / or
- c) the antioxidants from the classes of sterically hindered phenols, phosphites and / or vitamin E and its derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873725926 DE3725926A1 (en) | 1987-08-05 | 1987-08-05 | Mixture for the stabilisation of polyurethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873725926 DE3725926A1 (en) | 1987-08-05 | 1987-08-05 | Mixture for the stabilisation of polyurethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3725926A1 true DE3725926A1 (en) | 1989-02-16 |
Family
ID=6333079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19873725926 Withdrawn DE3725926A1 (en) | 1987-08-05 | 1987-08-05 | Mixture for the stabilisation of polyurethanes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3725926A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2682392A1 (en) * | 1991-10-11 | 1993-04-16 | Sandoz Sa | NOVEL COMPOSITIONS FOR STABILIZING POLYMER MATERIALS. |
| EP0705872A2 (en) * | 1994-10-04 | 1996-04-10 | Bayer Ag | Use of alpha- and/or beta-tocopherol (vitamin E) for the stabilisation of polyether polyols |
| EP0717069A2 (en) * | 1994-12-15 | 1996-06-19 | Elastogran GmbH | Stabilized, thermoplastic polyurethanes |
| EP0712887A3 (en) * | 1994-10-07 | 1997-09-17 | Davidson Textron Inc | Light stable aliphatic thermoplastic urethane elastomers and method of making same |
| FR2760005A1 (en) * | 1997-02-21 | 1998-08-28 | Ciba Geigy Ag | STABILIZED COMPOSITION, MIXTURE OF STABILIZERS, AND PROCESS FOR STABILIZING ORGANIC MATTER |
| WO2002088236A1 (en) * | 2001-04-27 | 2002-11-07 | Basf Aktiengesellschaft | Mixture of substances for the uv-stabilisation of synthetic materials and the production thereof |
| WO2003031506A1 (en) * | 2001-10-02 | 2003-04-17 | Basf Aktiengesellschaft | Stabilizer mixture and stabilized polyurethanes |
| WO2004046234A2 (en) * | 2002-11-21 | 2004-06-03 | Basf Aktiengesellschaft | Use of polymer powder containing uv absorber for the stabilisation of polymers against the effects of uv radiation |
| EP1788015A1 (en) * | 2002-11-21 | 2007-05-23 | BASF Aktiengesellschaft | Use of polymer powder containing UV absorber for the stabilisation of polymers against the efects of UV radiation |
| US20140073458A1 (en) * | 2012-09-13 | 2014-03-13 | Michael Michalewich | Golf ball compositions |
| US9808675B2 (en) | 2012-09-13 | 2017-11-07 | Acushnet Company | Golf ball compositions |
| US10035043B2 (en) | 2016-12-15 | 2018-07-31 | Acushnet Company | Golf ball incorporating highly crosslinked thermoset fluorescent microspheres and methods of making same |
| US10252112B2 (en) | 2017-03-20 | 2019-04-09 | Acushnet Company | Golf ball composition |
| US11697048B2 (en) | 2021-08-12 | 2023-07-11 | Acushnet Company | Colored golf ball and method of making same |
-
1987
- 1987-08-05 DE DE19873725926 patent/DE3725926A1/en not_active Withdrawn
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2260764A (en) * | 1991-10-11 | 1993-04-28 | Sandoz Ltd | Stabilizing composition for polymers |
| FR2682392A1 (en) * | 1991-10-11 | 1993-04-16 | Sandoz Sa | NOVEL COMPOSITIONS FOR STABILIZING POLYMER MATERIALS. |
| US5695689A (en) * | 1994-10-04 | 1997-12-09 | Bayer Aktiengesellschaft | Polyether polyols stabilized with tocopherol |
| EP0705872A2 (en) * | 1994-10-04 | 1996-04-10 | Bayer Ag | Use of alpha- and/or beta-tocopherol (vitamin E) for the stabilisation of polyether polyols |
| EP0705872A3 (en) * | 1994-10-04 | 1996-05-08 | Bayer Ag | |
| US6187859B1 (en) | 1994-10-07 | 2001-02-13 | Davidson Textron Inc. | Light stable aliphatic thermoplastic urethane elastomers and method of making same |
| EP0712887A3 (en) * | 1994-10-07 | 1997-09-17 | Davidson Textron Inc | Light stable aliphatic thermoplastic urethane elastomers and method of making same |
| EP0972784A2 (en) * | 1994-10-07 | 2000-01-19 | Davidson Textron Inc. | Light stable aliphatic thermoplastic urethane elastomers and method of making same |
| EP0972784A3 (en) * | 1994-10-07 | 2000-05-17 | Davidson Textron Inc. | Light stable aliphatic thermoplastic urethane elastomers and method of making same |
| EP0717069A3 (en) * | 1994-12-15 | 1997-06-11 | Elastogran Gmbh | Stabilized, thermoplastic polyurethanes |
| EP0717069A2 (en) * | 1994-12-15 | 1996-06-19 | Elastogran GmbH | Stabilized, thermoplastic polyurethanes |
| FR2760005A1 (en) * | 1997-02-21 | 1998-08-28 | Ciba Geigy Ag | STABILIZED COMPOSITION, MIXTURE OF STABILIZERS, AND PROCESS FOR STABILIZING ORGANIC MATTER |
| NL1008373C2 (en) * | 1997-02-21 | 1999-04-19 | Ciba Geigy Ag | Stabilizer mixture for organic materials. |
| BE1011643A3 (en) * | 1997-02-21 | 1999-11-09 | Ciba Sc Holding Ag | Composition stabilized, mixture of stabilizers and method for stabilizing an organic matter. |
| ES2138926A1 (en) * | 1997-02-21 | 2000-01-16 | Ciba Sc Holding Ag | Stabilizer mixture for organic materials |
| WO2002088236A1 (en) * | 2001-04-27 | 2002-11-07 | Basf Aktiengesellschaft | Mixture of substances for the uv-stabilisation of synthetic materials and the production thereof |
| WO2003031506A1 (en) * | 2001-10-02 | 2003-04-17 | Basf Aktiengesellschaft | Stabilizer mixture and stabilized polyurethanes |
| WO2004046234A2 (en) * | 2002-11-21 | 2004-06-03 | Basf Aktiengesellschaft | Use of polymer powder containing uv absorber for the stabilisation of polymers against the effects of uv radiation |
| WO2004046234A3 (en) * | 2002-11-21 | 2005-03-03 | Basf Ag | Use of polymer powder containing uv absorber for the stabilisation of polymers against the effects of uv radiation |
| EP1788015A1 (en) * | 2002-11-21 | 2007-05-23 | BASF Aktiengesellschaft | Use of polymer powder containing UV absorber for the stabilisation of polymers against the efects of UV radiation |
| US7728057B2 (en) | 2002-11-21 | 2010-06-01 | Basf Aktiengesellschaft | Use of polymer powder containing UV absorber for the stabilisation of polymers against the effects of UV radiation |
| US8461235B2 (en) | 2002-11-21 | 2013-06-11 | Basf Se | Use of polymer powder containing UV absorber for the stabilisation of polymers against the effects of UV radiation |
| US20140073458A1 (en) * | 2012-09-13 | 2014-03-13 | Michael Michalewich | Golf ball compositions |
| US9227109B2 (en) * | 2012-09-13 | 2016-01-05 | Acushnet Company | Golf ball compositions |
| US9808675B2 (en) | 2012-09-13 | 2017-11-07 | Acushnet Company | Golf ball compositions |
| US10035044B2 (en) | 2012-09-13 | 2018-07-31 | Acushnet Company | Golf balls incorporating regenerating-type multi-functional antioxidants |
| US10035043B2 (en) | 2016-12-15 | 2018-07-31 | Acushnet Company | Golf ball incorporating highly crosslinked thermoset fluorescent microspheres and methods of making same |
| US10252112B2 (en) | 2017-03-20 | 2019-04-09 | Acushnet Company | Golf ball composition |
| US11697048B2 (en) | 2021-08-12 | 2023-07-11 | Acushnet Company | Colored golf ball and method of making same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3856082T2 (en) | Polyethylene stabilizer compositions from compounds with piperidine groups and metal compounds | |
| DE3725926A1 (en) | Mixture for the stabilisation of polyurethanes | |
| EP0080431B1 (en) | Synergistic mixture of low and high molecular weight polyalkyl piperidines | |
| CA1272832A (en) | Polyolefin compositions stabilized against degradation using hydroxylamine derivatives | |
| EP0200684B1 (en) | Method for stabilizing spherical polymerized polyolefins | |
| EP0053098B1 (en) | Alkanol-amine esters of cyclic 1,1'-biphenyl-2,2'-diyl and alkylidene-1,1'-biphenyl-2,2'-diyl phosphites | |
| EP0119160B1 (en) | N-substituted 4-hydroxyphenylthiomethyl amines or urides | |
| JP2594105B2 (en) | Organic polymer composition and method for stabilizing it against photodegradation | |
| EP0107615A1 (en) | Polyolefins stabilized by bis or tris (polyalkylpiperidinyl-amino) 1,3,5-triazines | |
| JP3106213B2 (en) | Method for recycling colored polyolefins. | |
| DE4202276A1 (en) | STABILIZED POLYOLEFIN | |
| EP0142467A1 (en) | Polymer compounds containing piperidyl groups and their use as stabilisers in synthetic polymers | |
| DE3713375A1 (en) | 1,3,2-OXAZAPHOSPHOLIDINE STABILIZERS | |
| DE3426137A1 (en) | POLYMERIC COMPOUNDS CONTAINING PIPERIDINE RESIDES AND THEIR USE FOR STABILIZING SYNTHETIC POLYMERS | |
| EP0090770B1 (en) | Phosphoric-acid compounds as costabilizers for me(ii) carboxylates and/or me(ii) phenolates in polyvinyl chloride | |
| DE2365382A1 (en) | STABILIZED POLYMER MATERIALS AGAINST DEGRADATION DUE TO THE EFFECT OF LIGHT AND HEAT | |
| EP0246189A2 (en) | Compositions stabilized by aminoxyalkyl amines | |
| EP0155912A2 (en) | Radiation-stabilized polymer compositions | |
| EP0233153B1 (en) | Stabilization of polyphenylene ethers with macrocyclic polyalkyl piperidinyl compounds | |
| EP0079855A1 (en) | Alkylated hydroxyphenylthioalcanoic esters | |
| DE3500016A1 (en) | Synergistic mixtures | |
| DD263295A5 (en) | STABILIZED THERMOPLASTIC POLYMER AGAINST LIGHT INFLUENCE | |
| EP0324106B1 (en) | Use of a polyolefin moulding composition for long term contact with an extracting medium | |
| DE2433639A1 (en) | NEW PIPERIDE DERIVATIVES FOR THE STABILIZATION OF SYNTHETIC POLYMER COMPOSITIONS | |
| DE3426121C2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |