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JEuropâischesEuropean Patent Office ® Publication number: 0 042 589

Office européen des brevets B1

® EUROPEAN PATENT SPECIFICATION

(45) Dateof publication of patent spécification: 19.06.85 ® Int. Cl.4: C 08 L 65/00, C 08 K 5/17, C 08 K 5/13 ^ ® Application number: 81104672.1 ® Dateoffiiing: 17.06.81

(H) Norbornene polymers stabilized with hindered aromatic alcohols.

(D Priority: 23.06.80 US 162300 (73) Proprietor: The B.F. GOODRICH Company Dept. 0015 WHB-6 500 South Main Street Akron,Ohio 44318 (US) (43) Date of publication of application: 30.12.81 Bulletin 81/52 (72) Inventor: Layer, Robert Wesley 3184 -9th Street (45) Publication of the grant of the patent: Cuyahoga Falls Ohio 44221 (US) 19.06.85 Bulletin 85/25

(74) Représentative: von Kreisler, Alek, Dipl.-Chem. (§) Designated Contracting States: et al BEDE FRGBITNL Deichmannhaus am Hauptbahnhof D-5000 Kôln 1 (DE) (5Ï) Références cited: FR-A-2 366329 US-A-3 098 841 US-A-3 729433 US-A-4028416 CD

O) 00 m CM o o Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall O. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1 ) European convention). LU patent Courier Press, Leamington Spa, England. BACKGROUND OF THE INVENTION Preparation of the norbornene monomers is well known. Dicyclopentadiene can be made by dimerizing cyclopentadiene by a Diels-Alder reaction whereas dihydrodicyclopentadiene can be made by the Diels-Alder reaction of cyclopentadiene and cyclopentene. Norbornenes can also be prepared by the Diels-Alder reaction of cyclopentadiene with selected olefins to yield either norbornene or substituted norbornenes. Tetracyclododecene compounds are by-products formed from the Diels-Alder reaction of cyclopentadiene and norbornenes. Symmetrical and unsymmetrical trimers and tetramers of cyclopentadiene can, likewise, be prepared by the Diels-Alder reaction of cyclopentadiene. Norbornene polymeric materials, i.e., those prepared from monomers containing a norbornene moiety, are well known. They can be prepared as elastomers, which are flexible at room temperature, or as plastics, which are rigid at room temperature. Although essentially all of the important physical properties of the norbornene polymeric materials are outstanding, their resistance to oxidation is less than desired: Although antioxidants, which stabilize polymers are known, for example in US-A-3 098 841 polynuclear polyamines are described which are useful for the stabilization of synthetic rubber-like elastomers as SBR, polybutadiene and polyisoprene; and in US-A-4 028 416 a class of compounds, namely bis(2- hydroxyalkylbenzyl)-diamino alkenes are described as stabilizers for synthetic rubber compositions, in particular for ABS-resins, there exists still a lack of stabilizers, which satisfactory stabilize norbornene polymeric materials. It is, therefore, an object of this invention to stabilize norbornene polymeric materials against oxidative degradation.

SUMMARY OF THE INVENTION This invention relates to a composition of matter which comprises a reaction product of an elastomeric norbornene polymeric material and a sufficient amount of an antioxidant selected from hindered aromatic alcohols to improve resistance thereof to oxidation.

DETAILED DESCRIPTION OF THE INVENTION Pursuant to the invention described and claimed herein, norbornene polymeric materials are treated with Mannich bases of aromatic alcohols in order to impart antioxidant property to such materials. The Mannich bases will also be referred to herein as hindered aromatic alcohols or hindered phenols. Although Mannich bases of aromatic alcohols have been used in the past with other polymeric materials to improve antioxidant property thereof, the extent of improvement in polymeric norbornene materials treated with Mannich bases of aromatic alcohols was dramatic and totally unexpected. The class of norbornene polymeric materials referred to herein includes homopolymers and polymers of two or more of the monomers that contain the norbornene moiety, defined structurally as follows:

Pursuant to this definition, norbornene polymeric materials include homopolymers, copolymers, terpolymers, and generally polymers of substituted and unsubstituted norbornenes, dicyclopentadienes, dihydrodicyclopentadienes, and tetracyclodecenes. Norbornene polymeric materials can also have polymerized therein small amounts of non-norbornene monomers. Norbornene, or bicycloheptene-2 monomers, which are included within the scope of this invention, are defined as follows:

where each, R, R1, R2, R3 and R4 can separately be hydrogen, alkyl or alkenyl group containing 1 to 20 carbon atoms, and where R3 and R4 can be joined to form an aryl group of 6 to 18 carbon atoms or a cycloalkyl or cycloolefin group of 5 to 6 carbon atoms. Preferably, R, R1 and R2 are hydrogens and R3 and R4 are individually selected from hydrogen and alkyl or alkenyl groups of 1 to 5 carbon atoms. The alkyl and alkenyl groups can be substituted with ester, nitrile, substituted and unsubstituted phenyl and halogen groups. Examples of such norbornene monomers include 2-norbornene (where all Rs are hydrogens), 5- methyl-2-norbornene, 6-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-pentadecyl-2-norbornene, 5- ethyl-2-norbornene, 5-butyl-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl- 2-norbornene. Dicyclopentadiene and dihydrodicyclopentadiene monomers have the following structural formulas:

where R, R1 and R2 are defined as above and there can be up to three R7 groups which are defined as R1. Tetracyclododecene monomers and symmetrical trimers of cyclopentadiene have the following respective structural formulas:

where R, R1, R2, R3, R4 and R7 are defined as above whereas R5 and R6 are individually selected from hydrogen, alkyl and alkenyl groups of 1 to 20 carbon atoms, preferably R5 and R6 are hydrogens. Other monomers can be polymerized with norbornene-type monomers. Such other monomers include cyclopentene and other monocyclic mono and diolefins. Amount of such monomers in the polymerization recipe can vary from 10 to 50 parts by weight per 100 parts of the norbornene polymeric material. Polymerization of the norbornene-type monomers is conducted in the presence of a catalyst mixture which comprises (a) at least one organoaluminium halide and (b) at least one tungsten or molybdenum salt or a mixture of these salts. The organoaluminium halide which is utilized in the catalyst mixture can be either a dihalide of the formula RAIX2 or aluminum sesquihalide of the formula R3A12X3, wherein R is an alkyl radical containing from 1 to about 12 carbon atoms, preferably about 2 to 4 carbon atoms, and X is a; halogen. The organoaluminum halides or mixtures of organoaluminum halides are employed at a level of from about 0.01 to about 20 or more millimoles per mole of monomer, and the molybdenum or tungsten salts are employed at a level of from about 0.001 to about 1.0 millimoles per mole of monomer mixture. The molar ratio of organoaluminum halide to molybdenum and/or tungsten salt(s) is not critical and may range from about 200:1 or more to about 1:10 although a ratio within the range of from 4:1 to about 2:1 is preferred. In a preferred embodiment, the organoaluminum halide and the salts of tungsten and molybdenum are dissolved in a solvent prior to incorporation into the monomer mixture. The addition of the catalyst components as solutions facilitates the handling thereof and also results in a brief induction period after addition to the monomer mixture which permits the addition of all of the components of the reaction mixture before substantial polymerization begins. The result is a more uniform process control, and ultimately, reduced gel formation. Generally, the organoaluminum halide will be predissolved in the same hydrocarbon solvent as used for conducting the polymerization reaction. Thus, preferred solvents for the organoaluminum halides are the aromatic solvents such as benzene, and toluene. The preferred solvents for the molybdenum and tungsten compounds comprise at least one alkylester of a saturated carboxylic or dicarboxylic acid. The concentration of the salts in the ester solvents may vary from as low as about 0.1 molar. Examples of the preferred ester solvents include methyl formate, ethyl formate, methyl chloroformate, ethyl chloroformate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate and dimethyl malonate. Excellent results have been obtained with ethyl acetate. A polymerization activator may be used but is not generally required. Excellent activation is obtained by using air or a peroxide or hydroperoxide, and especially the organic peroxide such as benzoyl peroxide. The activator may be added at any point in the charging procedure, but is more preferably added last. The molecular weight of the copolymers prepared in accordance with the process of the invention can be controlled or modified when the reaction is conducted in the presence of at least one non-conjugated acyclic olefin containing from two to about 12 carbon atoms and having at least one hydrogen on each double-bonded carbon atom. Examples of suitable compounds include the 1-olefins such as 1-butene, 3- methyl-1 -butene, 1-hexene; the 2-olefins such as 1-butene, 4-methyl-2-pentene; 3-olefins such as 5-ethyl-3- octene; non-conjugated diolefins such as 1,6-hexadiene; and non-conjugated triolefins such as 1,4- octatriene. The preferred non-conjugated acyclic olefins are the 1-olefins of the type described above. It is believed that the acrylic olefins act as molecular weight modifiers which provide an easily workable and generally hydrocarbon-soluble polymer. The non-conjugated acyclic olefin or a mixture of such olefins is used in a molar ratio of olefin to total monomer charge of from about 0.0001 : to about 0.3:1. The non-conjugated acyclic olefins can be charged directly or in solution at any point in the charging procedure, but it is preferred that the olefins be charged along with the monomers. The polymerization reaction can be performed as a batch or continuous process. The reaction mixture in the reaction vessel may be cooled or heated to the polymerization temperature at the start of the additions or at any point during the addition of the various reactants. Polymerization temperatures of from about -80°C to about 100°C are utilized although the reaction generally proceeds satisfactorily at about room temperature. If desired, the polymerization reaction can be shortstopped by the addition of alcohols, amines or carboxylic acids such as ethanol, t-butyl phenol, diethylamine or acetic acid. At the conclusion of the polymerization reaction, the copolymer product may be isolated by any of the methods known in the art such as by direct drying under reduced pressure, by precipitation or by steam or by stripping with hot water. The polymer is recovered and may be washed further and dried. The copolymers of the invention are substantially gel-free, and generally are rigid plastics or glass-like at room temperature. When extended with an oil, the copolymers behave as elastomers. The Mannich bases of aromatic alcohols, especially phenols and naphthols, suitable for purposes herein include hindered aromatic alcohols, such as hindered phenols and hindered naphthols. The term "hindered" denotes that at least one position adjacent to the hydroxyl group, the ortho position, is substituted. Hindered phenols suitable for purposes herein are defined by the following structural formula:

where there can be 1 to 5, preferably 2 to 3 R1' groups on the phenyl ring each individually selected from alkyl, alkoxy, hydroxyl and hydroxyalkyl groups wherein the carbon chains contain 1 to 12, preferably 1 to 6, carbon atoms; and where at least one and up to three R1' groups are selected from alkylaminoalkyl groups, i.e., -CH2N(R2')(R3'), where R2' and R3' groups are individually selected from hydrogen and substituted and unsubstituted normal and branched alkyl groups containing 1 to 12, preferably 1 to 6, and more preferably 1 to 2 carbon atoms, provided that not more than one of R2' and R3' groups is hydrogen, and where R 2', R3' and N of the alkylaminoalkyl group form a heterocyclic ring containing 5 to 7 atoms selected from carbon, oxygen, nitrogen and sulfur atoms, provided that the alkylaminoalkyl group or groups are located only ortho and/or para to the hydroxyl group on the phenyl ring. Bis compounds of the aforementioned Mannich bases are also suitable as antioxidants for norbornene polymeric materials. Such bis compounds are bridged through the nitrogen atom of the aminomethyl moiety by means of a chain of 2 to 12, preferably 2 to 6 carbon atoms, or by means of a heterocyclic structure containing 5 to 7 atoms, 2 of which, preferably, are nitrogen atoms and 3 to 5 are carbon atoms. Also suitable as effective stabilizers for polymeric norbornene-type materials are Mannich bases of naphthols, which are defined similarly as the above Mannich bases of phenols. Although both of the phenyl groups in these naphthols can be substituted in a similar manner as the single phenyl group of the Mannich bases of phenols, preferably, each phenyl group is unsubstituted. Mannich bases of naphthol are defined by the following structural formula:

where there can be up to six R1' groups on the naphthyl group, preferably up to 2, which are individually selected from hydrogen, alkyl, alkoxy, hydroxyl and hydroxyalkyl wherein the alkyl groups contain 1 to 12, preferably 1 to 6 carbon atoms; and R" and R3' are as defined above in connection with Mannich bases of phenols. In a more preferred embodiment, all R1' groups are hydrogens and R2' and R3' are selected from alkyl groups of 1 to 4 carbon atoms. In a preferred embodiment, the antioxidant is selected from hindered phenols which have the following structural formula:

where there are three R1' groups on the phenyl ring in the two ortho and the one para positions to the hydroxyl group, said R1' groups are individually selected from alkyl, alkoxy, and dialkylaminomethyl groups wherein said alkyl, alkoxy and the two alkyl groups in the dialkylaminomethyl groups each contain 1 to 6 carbon atoms, at least one of the R1' group being a dialkylaminomethyl group. In a more preferred embodiment, 1 to 2 R1' groups are seleceted from dialkylaminomethyl groups positioned ortho to the hydroxyl group, the two alkyl groups of which individually contain 1 to 2 carbon atoms. Specific examples of suitable Mannich bases of phenols and naphthols are given in the accompanying examples. The Mannich reaction is well known and consists of condensation of ammonia or a primary or a secondary amine, with formaldehyde and a compound containing at least one reactive hydrogen atom, usually in the presence of an acid catalyst, such as hydrochloric acid. The essential feature of the reaction is the replacement of the active hydrogen atom by an aminomethyl or substituted aminomethyl group. The ortho and para hydrogens in phenols are sufficiently active to enter into a Mannich reaction. Products from phenol, 4-acetaminophenol, ortho and para cresols, meta cresol, 3,5-dimethylphenol, 2-methyl-4- ethylphenol, 2- and 4-methoxyphenol, beta-naphthol, and 8-hydroxyquinoline with formaldehyde and diethylamine or piperidine or morpholine are well known. From ortho and para cresol, mono and disubstitution products can be obtained whereas from phenol and metacresol, trisubstitution products can be made. Mannich bases of phenols and naphthols have been used as antioxidants in connection with other polymeric materials. To demonstrate relative effectiveness of the Mannich bases as antioxidants in other polymeric materials as compared to known commercial antioxidants, 0.68 g of a Mannich base antioxidant was mixed with 68 g of reprecipitated SN rubber in a Brabender Plasticorder for 2 minutes at 80°C. Mooney buttons were then made, aged at 70°C for 10 days and tested at 10 minute shearing time to determine retained Mooney viscosity. Two controls containing BHT and AO 2246 had retained viscosity of 96% and 89%, respectively, whereas Mannich base of phenol, which corresponds to compound 10 in the examples herein, had retained Mooney viscosity of only 58%; Mannich base of phenol, which corresponds to compound 9 in the examples herein, had retained Mooney viscosity of only 23%; and Mannich base of naphthol, which corresponds to compound 6 in the examples herein, had retained Mooney viscosity of 75%. Two other Mannich bases of phenols were tested which do not have counterparts in the examples herein although they are. very similar in structure to the tested compounds. These two compounds are identified below with the indicated retained Mooney viscosity of SN rubber samples containing same: Based on the results presented above, it should be apparent that Mannich bases of phenols and naphthols in SN rubber perform considerably poorer than the conventional commercial stabilizers. Examples presented below illustrate the invention claimed herein by demonstrating effectiveness of Mannich bases of phenols and naphthols as antioxidants in polymeric norbornene-type polymeric materials.

Examples A large number of the subject antioxidants (AO) were tested in polymeric norbornene material which was prepared by polymerizing 55 parts dicyclopentadiene and 45 parts 5-methyl-2-norbornene. Samples were prepared by casting a film from a toluene solution containing the norbornene polymeric material and the antioxidant dissolved therein. The film was cast by depositing the toluene solution on a Mylar sheet and evaporating toluene. Thickness of the stabilized norbornene-type polymeric film was approximately 0,5 mm. Samples of the film were placed in an air oven maintained at 70°C and the carbonyl region of the infrared spectrum at 1630 cm-1 was monitored for oxidative failure. Days of testing to develop a fair amount of carbonyl is indicated as "Yes" and days of testing to failure or formation of a large carbonyl band is indicated as "Fail" in Table I, below:

At the of the above Table I, several commercial antioxidants 1-5 are noted which were used as top in controls for comparison purposes. Film samples containing the commercial antioxidants were prepared Table II below the same manner as the film samples containing Mannich bases of phenols and naphthols. identifies these commercial antioxidants by name and structural formulas: A careful study of Table I, above reveals that the commercial antioxidants developed a fair amount of carbonyl from 5 to 8 days and failed in 6 to 9 days. Of the Mannich bases of phenols and naphthols tested, the worst was No. 14, a Mannich base of a lower alkyl substituted naphthol, which developed a fair amount of carbonyl in 5 days and failed in 7 days. This performance is about equivalent to the commercial antioxidants. Samples which performed excellently are those which contained antioxidants Nos. 6, 7, 8, 9, 10, 11, 13, 15, 18, 19, 20 and 21. For this group, a fair amount of carbonyl was formed in a period ranging from 29 days to in excess of 262 days and for most of these materials, failure occurred in a period of time in excess of 49 days. Antioxidant 18 was truly exceptional and the test was terminated before failure after only a small amount of carbonyl had developed in 212 days. Antioxidant performance of Mannich bases of phenols and naphthols in norbornene polymeric materials is totally unexpected when compared to the performance of same and similar Mannich bases of phenols and naphthols in SN rubber, which is described above.

1. Composition comprising an elastomeric norbornene polymeric material and an antioxidant in amount sufficient to provide the desired degree of protection from oxidation degradation, said norbornene polymeric material is prepared from norbornene monomers that contain the following moiety: where each R, R1, R2, R3 and R4 is selected from hydrogen, alkyl and alkenyl groups of 1 to 20 carbon atoms, and groups formed by joining R3 and R4 to form an aryl group of 6 to 18 carbon atoms or a cycloalkyl or cycloolefin group of 5 to 6 carbon atoms; said antioxidant is selected from (A) hindered phenols, (B) bis-compounds of said hindered phenols, (C) hindered naphthols, and mixtures of said antioxidants, said hindered phenols are selected from compounds falling within the definition of the following structural formula:

where R1'D, represents 1 (n=1) to 5 (n=5) individual R1' groups on the phenyl ring each individually selected from substituted and unsubstituted alkyl, alkoxy, hydroxyl, and hydroxyalkyl groups wherein the carbon chains therein contain 1 to 12 carbon atoms, and from alkylaminoalkyl groups defined as

where R2' and R3' groups are individually selected from hydrogen and hydroxy substituted and unsubstituted normal and branched alkyl groups of 1 to 12 carbon atoms and where the R2', R3' and N of said alkylaminoalkyl groups can form a heterocyciic ring containing 5 to 7 atoms selected from carbon, nitrogen, oxygen, and sulfur atoms, provided that not more than one of R2' and R3' groups is hydrogen, that at least one and up to three of said R1' groups are selected from said alkylaminoalkyl groups, and that said alkylaminoalkyl group or groups are located only ortho and/or para to said hydroxyl group on the phenyl ring; said bis compounds of said hindered phenols are bridged through the one nitrogen atom of said alkylaminoalkyl groups by a carbon chain containing 2 to 12 carbon atoms or by a heterocyclic structure of 5 to 7 atoms selected from carbon, nitrogen, oxygen, and sulfur atoms, two of which preferably are nitrogen atoms and three to five are carbon atoms; and said hindered naphthols have the following structural formula:

where there can be up to six R1' groups on the naphthyl group and R1', R2' and R3' are defined as in the case of hindered phenols. 2. Composition of claim 1 wherein the formula for the norbornene monomers, R, R1 and R2 are hydrogens and R3 and R4 are individually selected from hydrogen and alkyl and alkenyl groups of 1 to 5 carbon atoms; and where in said hindered phenols there are 2 to 3 R1' groups on the phenyl ring wherein the carbon chain in said R1' group or groups contains 1 to 6 carbon atoms, said R2' and R3' contain 1 to 6 carbon atoms, not more than one of R2' and R3' groups is hydrogen, said alkylaminoalkyl group or groups are located only ortho and/or para to the hydroxyl group on said phenyl ring, said carbon chain in said bis compounds contains 2 to 6 carbon atoms. 3. Composition of claim 2 wherein at least one and up to three R1 groups are selected from alkylamine groups; and said antioxidant is selected from said hindered phenols and mixtures thereof. 4. Composition of claim 2 wherein R2' and R3' groups of said hindered phenols contain 1 to 2 carbon atoms. 5. Composition of claim 4 wherein said norbornene polymeric material is selected from homopolymers and polymers of two or more substituted and unsubstituted monomers selected from norbornenes, di- cyclopentadienes, dihydrodicyclopentadienes, tetracyclodecenes, and symmetrical and unsymmetrical trimers and tetramers of cyclopentadiene wherein substituents on said monomers are selected from alkyl and alkenyl groups of 1 to 5 carbon atoms containing ester, nitrile, substituted and unsubstituted phenyl, and halogen groups. 6. Composition of claim 5 wherein said norbornene polymeric material contains polymerized therein additional monomers selected from monocyclic monoolefins and diolefins in amount of 10 to 50 parts by weight per 100 parts of said norbornene polymeric material and non-conjugated acyclic olefins containing 2 to 12 carbon atoms, amount of such additional monomers can vary from 0,0001 to 0,3 moles per mole of total monomer charge. 7. Composition of claim 5 wherein said norbornene monomers are selected from 2-norbornene, 5- methyl-2-norbornene, 6-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-propenyl-2-norbornene, 5- butenyl-2-norbornene, and mixtures thereof; and said antioxidant is selected from hindered phenols falling within the following structural formula, and mixtures of such phenols

where there are three R1' groups on the phenyl ring in the two ortho and the one para positions to the hydroxyl group, that R1' groups are selected from alkyl, alkoxy, and dialkylaminomethyl groups wherein said alkylhydroxylalkyl and said two alkyl groups in said dialkylaminomethyl group each contain 1 to 6 carbon atoms. 8. Composition of claim 6 wherein said two alkyl groups in said dialkylaminomethyl group contain 1 to 2 carbon atoms, and said acyclic olefins are selected from non-conjugated olefins. 9. Composition of claim 7 wherein said alkoxy group contains 1 to 2 carbon atoms and wherein 1 to 2 R'' groups are selected from dialkylaminomethyl groups which are positioned in the ortho position to the hydroxyl group.

1. Zusammensetzung, enthaltend ein elastomeres, von Norbornen abgeleitetes polymeres Material und ein Antioxidationsmittel in einer für den gewünschten Grad des Schutzes vor oxidativem Abbau ausreichenden Menge, wobei das von Norbornen abgeleitete polymere Material aus Norbornen- Monomeren hergestellt ist, die die folgende Struktureinheit enthalten

in der, R, R1, R2, R3 und R4 jeweils ausgewählt sind aus Wasserstoff, Alkyl- und Alkenyl-Gruppen mit 1 bis 20 Kohlenstoff-Atomen und Gruppen, die durch Vereinigung von R3 und R4 in der Weise entstanden sind, daß sie eine Aryl-Gruppe mit 6 bis 18 Kohlenstoff-Atomen oder eine Cycloalkyl- oder Cycloolefin-Gruppe mit 5 bis 6 Kohlenstoff-Atomen bilden, wobei das Antioxidationsmittel ausgewählt ist aus (A) gehinderten Phenolen, (B) Bis-Verbindungen dieser gehinderten Phenole, (C) gehinderten Naphtholen und Mischungen dieser Antioxidationsmittel, wobei die gehinderten Phenole ausgewählt sind aus unter die Definition der folgenden Strukturformel fallenden Verbindungen

in der R1' 1 (n = 1) bis 5 (n = 5) individuelle Gruppen R1' an dem Phenyl-Ring bezeichnet, die jeweils einzeln ausgewählt sind aus substituierten und unsubstituierten Alkyl-, Alkoxy-, Hydroxyl- und Hydroxyalkyl- Gruppen, worin die Kohlenstoff-Ketten 1 bis 12 Kohlenstoff-Atome enthalten, und aus als definierten Alkylaminoalkyl-Gruppen, worin die Gruppen R2' und R3' einzeln ausgewählt sind aus Wasserstoff und hydroxy-substituierten und unsubstituierten normalen und verzweigten Alkyl-Gruppen mit 1 bis 12 Kohlenstoff-Atomen und worin R2', R3' und N der Alkylaminoalkyl-Gruppen einen heterocyclischen, 5 bis 7 Atome ausgewählt aus Kohlenstoff-, Stickstoff-, Sauerstoff- und Schwefel-Atomen enthaltenden Ring bilden können, mit den Maßgaben, daß nicht mehr als eine der R2' und R3' Wasserstoff ist, daß wenigstens eine und bis zu drei der Gruppen R1' aus den Alkylaminoalkyl-Gruppen ausgewählt sind und daß die Alkylaminoalkyl-Gruppe oder -Gruppen nur in den o- und p-Stellungen zu der Hydroxyl- Gruppe an dem Phenyl-Ring angeordnet sind, wobei das Bis-Verbindungen der gehinderten Phenole über das eine Stickstoff-Atom der Alkylaminoalkyl-Gruppe durch eine 2 bis 12 Kohlenstoff-Atome enthaltende Kohlenstoff-Kette oder durch eine heterocyclische Struktur mit 5 bis 7 Atomen ausgewählt aus Kohlenstoff-, Stickstoff-, Sauerstoff- und Schwefel-Atomen, wovon vorzugsweise zwei Stickstoff-Atome und drei bis fünf Kohlenstoff-Atome sind, verbrückt sind und wobei die gehinderten Naphthole die nachstehende Strukturformel besitzen.

worin sich bis zu sechs Gruppen R1' an der Naphthyl-Gruppe befinden können und R1, R2 und R3 den für den Fall der gehinderten Phenole angegebenen Definitionen entsprechen. 2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß in der Formel für die Norbornen- Monomeren R, R1 und R2 Wasserstoff sind und R3 und R4 einzeln ausgewählt sind aus Wasserstoff, Alkyl- und Alkenyl-Gruppen mit 1 bis 5 Kohlenstoff-Atomen und und in den gehinderten Phenolen sich zwei bis drei Gruppen R1' an dem Phenyl-Ring befinden, wobei die Kohlenstoff-Kette in dieser Gruppe oder diesen Gruppen R1' 1 bis 6 Kohlenstoff-Atome enthält, wobei die R2' und R3' 1 bis 6 Kohlenstoff-Atome enthalten, nicht mehr als eine der Gruppen R2' und R3' Wasserstoff ist, wobei die Alkylaminoalkyl-Gruppe oder -Gruppen nur in den o- und p-Stellungen zu der Hydroxyl-Gruppe an dem Phenyl-Ring angeordnet sind und wobei die Kohlenstoff-Kette in den Bis-Verbindungen 2 bis 6 Kohlenstoff-Atome enthält. 3. Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daß wenigstens eine und bis zu drei der Gruppen R1' aus Alkylamin-Gruppen ausgewählt sind und das Antioxidationsmittel aus gehinderten Phenolen und deren Gemischen ausgewählt ist. 4. Zusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daß die Gruppen R2' und R3' der gehinderten Phenole 1 bis 2 Kohlenstoff-Atome enthalten. 5. Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß das von Norbornen Abgeleitete polymere Material ausgewählt ist aus Homopolymerisaten und Polymerisaten aus zwei oder mehr sub- stituierten und unsubstituierten Monomeren ausgewählt aus Norbornenen, Dicyclopentadienen, Dihydro- dicyclopentadienen, Tetracyclododecenen und symmetrischen und unsymmetrischen Trimeren und Tetra- meren des Cyclopentadiens, wobei die Substituenten an diesen Monomeren ausgewählt sind aus Alkyl- und Alkenyl-Gruppen mit 1 bis 5 Kohlenstoff-Atomen, die Ester-, Nitril-, substituierte und unsubstituierte Phenyl- und Halogen-Gruppen enthalten. 6. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß das von Norbornen abgeleitete polymere Material einpolymerisierte zusätzliche Monomere, die ausgewählt sind aus mono- cyclischen Monoolefinen und Diolefinen, in einer Menge von 10 bis 50 Gew.-Teilen auf 100 Gew.-Teile des von Norbornen abgeleiteten polymeren Materials und nicht-konjugierte acyclische Olefine mit 2 bis 12 Kohlenstoff-Atomen enthält, wobei die Menge solcher zusätzlichen Monomeren von 0,0001 bis 0,3 mol pro 1 mol des gesamten Monomeren Ansatzes variieren kann. 7. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß die Norbornen-Monomeren ausgewählt sind aus 2-Norbornen, 5-Methyl-2-norbornen, 6-Methyl-2-norbornen, 5,6-Dimethyl-2- norbornen, 5-Propenyl-2-norbornen, 5-Butenyl-2-norbornen und Mischungen aus diesen und das Anti- oxidationsmittel ausgewählt ist aus unter die nachstehende Strukturformel fallenden Phenolen und Mischungen aus diesen Phenolen worin drei Gruppen R1' an dem Phenyl-Ring in den beiden o- und der einen p-Stellung zu der Hydroxyl- Gruppe vorliegen und diese Gruppen R1' augewählt sind aus Alkyl-, Alkoxy- und Dialkylaminomethyl- Gruppen, wobei die Alkylhydroxyalkyl-Gruppe und die beiden Alkyl-Gruppen in der Dialkylaminomethyl- Gruppe jeweils 1 bis 6 Kohlenstoff-Atome enthalten. 8. Zusammensetzung nach Anspruch 6, dadurch gekennzeichnet, daß die zwei Alkyl-Gruppen in der Dialkylaminomethyl-Gruppe 1 bis 2 Kohlenstoff-Atome enthalten und die acyclischen Olefine aus nicht- konjugierten Olefinen ausgewählt sind. 9. Zusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß die Alkoxy-Gruppe 1 bis 2 Kohlenstoff-Atome enthält und eine bis zwei Gruppen R1' ausgewählt sind aus Dialkylaminomethyl- Gruppen, die in o-Stellung zu der Hydroxy-Gruppe angeordnet sind.

1. Composition comprenant une matière polymère élastomère de type norbornène et un antioxygène présent en une quantité suffisante pour conférer le degré voulu de protection contre une dégradation par oxydation, ladite matière polymère de type norbornène est préparée à partir de norbornènes monomères qui contiennent le fragment suivant:

dans lequel chaque symbole R, R1, R2, R3 et R4 est choisi parmi un atome d'hydrogène, des groupes alkyles et alcényles de 1 à 20 atomes de carbone, et des groupes formés par la jonction de R3 et de R4 pour former un groupe aryle de 6 à 18 atomes de carbone ou un groupe cycloalkyle ou cyclooléfine de 5 à 6 atomes de carbone; ledit antioxygène est choisi parmi (A) des phénols à empêchement stérique, (B) des bis-composés desdits phénols à empêchement stérique, (C) des naphtols à empêchement stérique, et des mélanges desdits antioxygènes, lesdits phénols à empêchement stérique sont choisis parmi des composés se situant dans le cadre de la définition de la formule suivante de structure:

dans laquelle Rn1' représente 1 (n = 1) à 5 (n = 5) groupes R1' fixés sur le noyau phényle, chacun étant individuellement choisi parmi des groupes alkyles, alcoxy, hydroxyles, et hydroxyalkyles substitués et non substitués dans lesquels les chaînes carbonées contiennent 1 à 12 atomes de carbone, et parmi des groupes alkylaminoalkyles définis par

où les groupes R2' et R3' sont choisis individuellement parmi un atome d'hydrogène et des groupes alkyles normaux et ramifiés hydroxy substitués et non substitués de 1 à 12 atomes de carbone et où R2', R3' et N desdits groupes alkylaminoalkyles peuvent former un noyau hétérocyclique contenant 5 à 7 atomes choisis parmi des atomes de carbone, d'azote, d'oxygène et de soufre, à la condition que pas plus d'un des groupes R2' et R3' ne soit de l'hydrogène, qu'au moins un et jusqu'à trois desdits groupes R1' soient choisis parmi lesdits groupes alkylaminoalkyles et que le ou lesdits groupes alkylaminoalkyles soient situés seulement en ortho et/ou en para par rapport audit groupe hydroxyle fixé sur le noyau phényle; lesdits bis- composés desdits phénols à empêchement stérique sont pontés par l'intermédiaire de l'atome d'azote desdits groupes alkylaminoalkyles, par une chaîne carbonée contenant 2 à 12 atomes de carbone ou par une structure hétérocyclique de 5 à 7 atomes choisis parmi des atomes de carbone, d'azote, d'oxygène, et de soufre, dont deux sont de préférence des atomes d'azote et trois à cinq sont des atomes de carbone; et lesdits naphtols à empêchement stérique ont la formule de structure suivante:

dans laquelle il peut y avoir jusqu'à six groupes R1' sur le groupe naphtyle et R1', R2' et R3' sont définis comme dans le cas des phénols à empêchement stérique. 2. Composition selon la revendication 1, dans laquelle dans la formule des norbornènes monomères, R, R1 et R2 sont des atomes d'hydrogène et R3 et R4 sont choisis individuellement parmi un atome d'hydrogène et des groupes alkyles et alcényles de 1 à 5 atomes de carbone; et dans laquelle, dans lesdits phénols à empêchement stérique, il y a 2 à 3 groupes R1' sur le noyau phényle et la chaine carbonée du ou desdits groupes R1' contient 1 à 6 atomes de carbone, lesdits groupes R2' et R3' contiennent 1 à 6 atomes de carbone, pas plus d'un des groupes R2' et R 3' est un atome d'hydrogène, le ou lesdits groupes alkylaminoalkyles sont situés seulement en ortho et/ou en para par rapport au groupe hydroxyle fixé sur ledit noyau phényle, ladite chaine carbonée desdits bis-composés contient 2 à 6 atomes de carbone. 3. Composition selon la revendication 2, dans laquelle au moins un et jusqu'à trois groupes RI sont choisis parmi des groupes alkylamines; et ledit antioxygène est choisi parmi lesdits phénols à empêchement stérique et leurs mélanges. 4. Composition selon la revendication 2, dans laquelle les groupes R2' et R3' desdits phénols à empêchement stérique contiennent 1 à 2 atomes de carbone. 5. Composition selon la revendication 4, dans laquelle ladite matière polymére de type norbornène est choisie parmi des homopolymères et des polymères de deux ou plus de deux monomères, substitués et non substitués, choisis parmi des norbornènes, des dicyclopentadiènes, des dihydrodicyclopentadiènes, des tétracyclododécènes, et des trimères et tétramères, symétriques et asymétriques, du cyclopentadiène et dans laquelle les substituants fixés sur lesdits monomères sont choisis parmi des groupes alkyles et alcényles de 1 à 5 atomes de carbone contenant des groupes ester, nitrile, phényle substitué et non substitué, et halogéno. 6. Composition selon la revendication 5, dans laquelle ladite matière polymère de type norbornène contient, à l'état polymérisé, des monomères supplémentaires choisis parmi des monooléfines et dioléfines monocycliques, présents en des quantités de 10 à 50 parties en poids pour 100 parties de ladite matière polymère de type norbornène, et des oléfines acycliques non conjuguées contenant 2 à 12 atomes de carbone, la quantité de tels monomères supplémentaires pouvant varier entre 0,0001 et 0,3 mole par mole de charge monomère totale. 7. Composition selon la revendication 5, dans laquelle lesdits norbornènes monomères sont choisis parmi le 2-norbornène, le 5-méthyl-2-norbornène, le 6-méthyl-2-norbornène, le 5,6-diméthyl-2-norbornène, le 5-propényl-2-norbornène, le 5-butényl-2-norbornène, et leurs mélanges; et ledit antioxygène est choisi parmi des phénols à empêchement stérique se situant dans le cadre de la formule suivante de structure:

dans laquelle il y a trois groupes R1' sur le noyau phényle sur les deux positions ortho et sur la position para par rapport au groupe hydroxyle, les groupes R1' sont choisis parmi des groupes alkyles, alcoxy et dialkyl- aminométhyles, et des mélanges de tels phénols, et lesdits groupes alkylhydroxyalkyles et les deux groupes alkyles du groupe dialkylaminométhyle contiennent chacun 1 à 6 atomes de carbone. 8. Composition selon la revendication 6, dans laquelle lesdits deux groupes alkyles du groupe dialkyl- aminométhyle contiennent 1 à 2 atomes de carbone, et lesdites oléfines acycliques sont choisies parmi des oléfines non conjuguées. 9. Composition selon la revendication 7, dans laquelle ledit groupe alcoxy contient 1 à 2 atomes de carbone et les 1 à 2 groupes R1' sont choisis parmi des groupes dialkylaminométhyles qui sont placés en position ortho par rapport au groupe hydroxyle.