DE2230311A1 - DIPHENYLAMINE AND THEIR USE AS AN AGE PROTECTION AGENTS - Google Patents

Description

¹¹ Diphenylamines and their use as anti-aging agents "

Priority: June 21, 1997I, V.St.A., No. 155 297

The invention relates to diphenylamines, * ^% especially N, N-di- (oxyalkylene) -4-aniino-diphenylamines, and their use as anti-aging agents.

Suitable antioxidants for organic compounds with unsaturated carbon-carbon bonds, such as rubber or other plastic material, these compounds not only protect against the effects of atmospheric oxygen, ozone or others Oxidizing agents, but also do not change them in terms of handling, premature hardening or physical properties » The anti-aging agent prevents the substrate from being oxidized, discolored or otherwise over a long period of time

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Ice flower pattern
Changes, formation of / or cracking on the surface »By combining it with other anti-aging agents against heat, light, aging, oxidation and cracking in the stretched state, the applicability of an anti-aging agent increases.

Although the ozonization of an unsaturated carbon-carbon-> stoff-Bindimg is an oxidation of the substrate, it can.

taking place formation of

¹ / Ozonides and / or Hydr operoxiden generally not

be prevented by antioxidants. This means, Protection agents against ozonization are a special group of anti-aging agents that may also be used against the Protect from oxidation by atmospheric oxygen.

The role of ozone in the formation of fatigue cracks in rubber has been studied in detail since 1945. There were different ones Protective agents are produced which extend the life of the rubber exposed to the ozone by delaying and reducing it prolong the formation of cracks “Many of the protective agents available on the market against ozonation conduct deviates from N-substituted p-phenylenediamines «.

These N-substituted p-phenylenediamines, e.g. 4-isopropylamino-diphenylamine, are made by the alkylation of a p-aminodiphenylamine with a ketone. They are powerful Protection agents against ozonization, which do not cause premature vulcanization of rubber or the rate of vulcanization delay. However, these 4-alkylaminodiphenylamines are colored and therefore also color the

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-D-

Chew it up.

In general, the antioxidants are added to the latex. A solid antioxidant is dispersed in the latex in such a way that the mixture is as homogeneous as possible, a liquid antioxidant is emulsified. At this point it is very important to have the antioxidant No premature coagulation of the rubber or a framing of the latex (Eht stabilization of the rubber and separation of the Water from the Lat ° r.) After the addition of the antioxidant the rubber is coagulated in order to separate it from the water as an elastomeric dry material. The rubber now appears as small agglomerates, which are dried to crumbs of rubber by hot air · You can use the antioxidant also the rubber crumbs or the pressed ones

to the

Crumbs of rubber during! Grinding, spraying or other manufacturing processes to add.

The object of the invention was to produce anti-aging agents used for polyolefins, fats, oils or synthetic fats and do not discolour the connections to be protected.

The invention thus relates to diphenylamines of the general formula (i)

/ V

x * "^ - ^R1 -

(R0) _y ~ C - R '_

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in which χ and y each have 1 Ms 12, Z is a hydrogen atom, an alkali metal, an NH, lower alkyl or hydroxyalkyl group, R is ethylene, 1,2-propylene, 1,2-butylene -, 2,3-butylene or styrene group and R ^{1 is} an arylene, alkylene, alkenylene, cycloalkenylene or cycloalkylene group with 2 to 24 ring carbon atoms, which are optionally substituted by halogen atoms, carboxy or lower alkyl groups, means

Preference is given to compounds of the formula (i) in which

(a) R ^{1 is} a divalent cyclopentane, cyclohexene, cyclohexane, bicyclo (2,2,1) -5-heptene and hydrophenanthrene group;

(b) R ^{1 is} an o-phenylene or peri-substituted naphthylene group;

(c) R 'is a divalent alkylene or alkenylene group having 2 to 24 carbon atoms.

The anti-aging agents according to the invention are suitable before especially for polyolefins such as polyethylene, polypropylene, polybutylene, Polybutadiene, polystyrene or their copolymers. The polyolefins generally have a molecular weight of 1000 to about 1,000,000 and can range from high, medium, or be low density. Those with the anti-aging agents according to the invention stabilized polyolefins are suitable both as coating compounds and as thermoplastic molding compounds » In particular those containing the anti-aging agents according to the invention Polyethylenes are used as insulators in electronics

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■ - 5 or cotidensers very suitable.

The compounds according to the invention can also be used for stabilization of lubricants, such as synthetic or natural fats and oils, synthetic esters, polyalkylene oxides, silicones, Phosphoric acid esters, silicic acid esters and polyfluorinated hydrocarbons are used »Petroleum-based lubricants, to which the anti-aging agents according to the invention can be added are engine oils, transmission oils, cutting oils and Pressure oils.

- ^ - j> · j "·· TT-uj η · ■ · jt λ. · , Lubricating greases The compounds according to the invention can be synthetic / such as fats in solid or semi-solid gel form based on alkali metal, alkaline earth metal and aluminum, or fuels which Containing saturated and unsaturated hydrocarbon mixtures, are added.

The diphenylamines according to the invention are also suitable for stabilization any other material containing carbon-carbon unsaturated bonds, such as waxes and synthetic resins, natural and especially synthetic rubber, ZoB «styrene-bitadiene rubber

Non-discoloring styrene-butadiene rubbers generally contain an anti-aging agent made from either an aralkyl phosphite or an alkylated or aralkylated phenol consists. Discolouring styrene-butadiene rubber contains p-phenylenediamines as anti-aging agents in quantities of 0.2 up to about 2.5 parts per 100 parts rubber. Although the

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diphenylamines according to the invention from the coloring anti-aging agents derive, they are not or only weakly discoloring and therefore only cause negligible discoloration of rubber »

The anti-aging agents according to the invention are in acid or Ester form used to prepare dispersions, emulsions or solutions with the rubber latex during the Coagulation are mixed and in this way protect the latex during the subsequent treatment.

In the case of styrene-butadiene rubber, the must according to the invention Diphenylamines are not necessarily added to the latex, they can also be crumbled or balled into the rubber during the Add grinding or other manufacturing steps.

The inventive diphenylamines are the organic Compounds containing carbon-carbon unsaturated bonds in amounts from about 0.01 to about 5 parts per 100 parts organic compound added.

The diphenylamines according to the invention are acidic esters of N, N-di (oxyalkylene) -4-aminodiphenylamine. The amine component the ester is prepared by known processes (see US Pat. No. 3,330,777). In general, the oxyalkylene group is des 4-aminodiphenylamine with ethylene oxide, propylene oxide, 1,2-butyl oxide, Introduced 2,3-butylene oxide or styrene oxide. In this way at least two hydroxyalkyl groups are obtained on the free one

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Amino group, creating a tertiary amine »By adding a basic catalyst and a further amount of alkylene oxide the chain of the N-hydroxyalkylated group is extended »You then get a derivative of a tertiary amine with up to 12 repeating alkoxy groups and one terminal Hydroxyl group β

The N, N-di- (oxyalkylene) -4-amino-diphenylamines formed as an intermediate are then esterified with a stoichiometric amount of a carboxylic acid anhydride in order to obtain the half-esters of the diphenylamines according to the invention. ^{The reaction takes place according to methods known per} se. The free carboxylic acid group of the acid ester thus obtained can be converted into the alkali metal salt with sodium hydroxide,% into the ammonium salt with ammonium hydroxide or into a simple ester with an alcohol such as methanol, ethanol, propanol, butyl alcohol, amyl alcohol or a lower alkylene oxide carbonate. Preferred are carboxylic acid anhydrides which provide free carboxyl, salt or ester groups that are either sufficiently hydrophilic to use the anti-aging agent in water-containing systems or are sufficiently hydrophobic to be used in hydrocarbon or similar anhydrous mixtures »Specific examples of carboxylic acid anhydrides are the reaction product from a Diels-Alder condensation of _; Maleic anhydride with rosin, phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, malic anhydride, camphor anhydride, citraconic anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohex-4-ene ~

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1,2-dicarboxylic acid anhydride, 3,4,5,6-tetrachlorophthalic acid auhydriö, Cyclopentane-1,2-dicarboxylic acid anhydride, mellophanic acid anhydride (1, 2, 3, 4-benzene-tetracarboxylic acid), methylic acid anhydride (benzene hexacarboxylic acid), Trimellitic anhydride and hexachloroendomethylene tetrahydrophthalic anhydride.

The examples explain the invention ο

Example 1 ^, N-M-hydroxyethyl-N'-pheriyl-p-phenylenediamine

22.7 kg of p-amino-diphenylamine are heated to H2 ° C. at 384 Torr in a reaction vessel. The reaction vessel is then closed, 12.2 kg of ethylene oxide are fed in over the course of 52 minutes at a temperature of 142 to 172 ^° C. in such a way that a weak reaction pressure builds up. Since the reaction is exothermic, the reaction mixture has to be cooled in order to keep the temperature in the desired range (Mn ', number average) of 286 has ο The product contains no primary amine, 0.34 milliequivalents per gram of secondary amine and 3.38 milliequivalents per gram of tertiary amine.

Example2

N, N-Dihydroxyäthyl-N'-phenyl-p-phenylenediamine A 2 liter flask equipped with a mechanical

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A stirrer, a nozzle for the passage of gas, a thermometer and a capillary immersed in oil as a vent valve are charged with 552.6 g of p-aminodiphenylamine. The amine is heated to 133 ° G and 293.6 g of ethylene oxide are added over the course of 1 hour and 10 minutes at a temperature of 133 to 174 ° C so that the reaction mixture does not boil too much. In addition, the reaction mixture has to be cooled to keep the temperature in the desired range. After cooling, a dark colored solid with a hydroxyl number of 495 and a molecular weight (Mn, number average) of 287 is obtained. The product does not contain a primary amine , 0.17 meq / g secondary amine and 3) 35 meq / g tertiary amine. _;

Example 3 N 1 - Dihydroxypropyl-N'-phenyl-p-phenylenediamine

A 2 liter flask equipped with a pressure indicator; equal dropping funnel, a feed connection for nitrogen, a mechanical stirrer, thermometer with temperature control and a water-cooled ball condenser is charged with 552.6 g of p-aminodiphenylamine charged "The amine is heated under a nitrogen blanket to 168 ⁰ C and in the course of 7 hours with 357 , 2 g of propylene oxide are added so that the mixture does not boil too much. The reaction mixture is stirred for a further 58 minutes. After cooling, a dark solid is obtained with a hydroxyl number of 423 and a molecular weight (Mn, number average) of 308. The product does not contain any primary amine,

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0.22 milliequivalents / g secondary amine and 3 »23 milliequivalents / g tertiary amino o

Example 4 NjN-Dihydroxypropoxypropyl-IT'-phenyl-p-phenylenediamine

According to Example 3, 552.6 g of p-aminodiphenylamine are present in the presence of 2.8 g of anhydrous sodium acetate with 697 g of propylene oxide ο After cooling, you get a very highly viscous liquid with a hydroxyl number of 334 and one Molecular weight (Mn, number average) of. 397. The product contains no primary amine, 0.36 meq / g secondary amine and 2.57 meq / g tertiary amino

Example-15

N, N—. Dihydroxyethyl-N * -phenyl-p-phenylenediamine-colophony-maleic acid adduct-Halljester ο

34.9 kg rosin are in a reaction vessel under nitrogen protection · heated to 131 ⁰ C, was added in the course of 35 minutes with 11.3 kg of maleic anhydride in four portions "The temperature of the reaction mixture increases after the second dose of 187 ⁰ C and controlled by Kühleu .0 After the addition of maleic anhydride, the temperature of the reaction mixture is kept at 180 to 188 ° C for two hours »Then 12.7 kg of N, N-dihydroxyethyl-N'-phenyl-p-phenylenediamine, prepared according to Example 1, no primary amine, 1.16 milliequivalents / g secondary amine and 2.64 milliequivalents / g tertiary amine containing, with a

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Hydroxyl number of 489 and a molecular weight (Mn, number average) of 263 ₅ added. "There is" no exothermic reaction. The reaction mixture is kept at 174 to 182 ^° C. for 1 hour. The end product has an acid number of 226 (theoretical: 219.7 ) and melts at 110 "to 124 ⁰ C.

Example 6

Acid phthalic acid ester of Έ , H-dihydroxyethyl-ftP-phenyl-ppheny1endiamine

34.9 kg of N, E-dihydroxyethyl-N-phenyl-p-phenylenediamine from Example 1 are added under nitrogen at a temperature of 150 ⁰ C in the course of 33 minutes with 43.3 ^ g of phthalic anhydride in four portions so that only small Temperature fluctuations occur «. The reaction mixture is then stirred at 140 to 165 ° C. for 1 hour and 47 minutes. The end product has an acid number of 207 (theoretical: 209 »7) and melts at 96.4 to 104 ^° C.

Example 7

Acid phthalic acid ester of Ν, Ν-dihydroxypropyl-N'-phenyl-p- '' phenylenediamine

165.2 g (2 hydroxyl equivalents) of N, N-dihydroxypropyl-N • -phenylp-phenylenediamine of Example 3 are heated in a 1 liter three-necked flask under a nitrogen blanket to 146 ⁰ C ₉ slowly at Hl to 146 ° C with 296 2 g (2 mol) of phthalic anhydride are added. The reaction mixture is another hour

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"maintained at 141-155 ⁰ C. The final product has an acid number of 195.9 to 203.7 (theoretical: 199.9), and melts at 119 to ⁰ Gc

Examples

Acid phthalic acid ester of Ν, Ν-dihydroxypropoxypropyl-N'-phenyl-p _T phenylenediamine

According to Example 7, 335.9 g (2-hydroxyl-uinuivalente) Ν, Ν-dihydroxypropoxypropyl-N ¹ -phenyl-p-phenylenediamine from Example 4 with 296.2 g (2 mol ) Phthalic anhydride implemented «The end product has an acid number of 184.5 (theoretical: 177.5) and melts at 103 to 106 ⁰ Cc

Example 9

Acid succinic acid ester of N, N-dihydroxyethyl-N'-phenyl-pphenylenediamine

A 500 ml three-necked flask, equipped with an inlet connection for nitrogen, a glass stirrer, a thermometer and a ball reflux condenser, is filled with 113.3 g (1.00 hydroxyl equivalent) Ν, Ν-dihydroxyethyl-N'-phenyl-p-phenylenediamine of example 2 and 100.1 g (1.00 mol) of succinic anhydride charged This reaction mixture is heated under stirring and under nitrogen protection 1 hour and 49 Minuteti long heated to 142.7 to 163 ⁰ ° C. The final product has an acid value of 259.7 (theoretical: 262.9) and melts at 44 to 54 ⁰ C

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_ ₁₃ _

Example 10 and 11
Acid hexahydrophthalic and Za-tetrahydrophthalic esters

of NJfl-Ijihydroxyäthyl-IT'-phenyl-p-phenylenediamine

According to Example 9, further acidic esters of N, N-dihydroxyethyl-F'-phenyl-p-phenylenediamine from Example 2 are prepared »
The reaction conditions and the properties of the end products are summarized in Table I ο

Table I. example

10

11

Product of Example 2, parts by weight

Hexahydrophthalic anhydride, parts by weight

A ⁴ -tetrahydrophthalic anhydride,
Parts by weight

Acid number,. calculated found

reaction time

113.3

154.2

209.7 241.8

68-77

Hour, min.

56.6

76.0

211.3 233

75-83

1 hour, 48 min.

Reaction temperature ^{, 0 C}

147-168.8 145.1-172.2

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-H-

Example 12

Acid hexachloroendomethylene tetrahydrophthalic acid ester of N, N-dihydroxyethyl-N * -phenyl-p-phenylenediamine

A 1 liter three-necked flask is filled with 28.3 g (0.25 hydroxyl equivalents) of N, N-dihydroxyethyl-N-phenyl-p-phenylenediamine from Example 2 and 92.7 g (0.25 mol) of 1.4 , 5,6,7,7-Hexachlorbicyclo - / ?, 2, J_7-5-hepten-2,3-dicarboxylic anhydride charged ο 250 ml of chemically pure acetone are added to the reaction mixture and, under nitrogen protection and stirring, am Heated to reflux. The acetone is distilled off in vacuo ο The final product has an acid number of 137.6 (theoretical: 115.9), melting with decomposition at 136-152 ⁰ C, at 136 to veifärbt H8 ° C and melts with foaming at 148-152 ⁰ Co

Example 13

Acid 3,4,5,6-tetrachlorophthalic acid ester of N, N-dihydroxyethyl-N'-phenyl-p-phenylenediamine

According to Example 13, 28.3 g (0.25 hydroxyl equivalents) N, N-dihydroxyethyl-N ¹ -phenyl-p-phenylenediamine from Example 2 and 71.5 g (0.25 mol) 3.4, Dissolved 5,6-tetrachlorophthalic anhydride in 500 ml of acetone and refluxed for 4 hours. The reaction mixture is poured into distilled water, the end product precipitating, which is then filtered and dried. The acid number is 185.8 (theoretical: HO.5), melting point 131 bis

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Example 14

Maleic acid ester of !!, H-dihydroxypropoxypropyl-N'-phenyl-p-phenylenediamine

A 500 ml three-necked flask, equipped with an inlet connection for nitrogen, a glass stirrer, a thermometer with temperature control and a water-cooled ball condenser, is filled with 168.0 g (1.0 hydroxyl equivalent) of N, N-dihydroxypropoxypropyl-Ef'-phenyl- p-phenylenediamine of example 4 and 98.1 g (1.0 mole) of charged Maieinsäureanhydrid The reaction mixture is first heated to 151 C, then held for 1 hour at 148-155 ⁰ g ". The end product melts at 81 to 93 ° C.

Example 15 2-Hydroxyethyl ester from Example 5

A three-necked flask equipped with an inlet pipe for nitrogen, a stirrer, a thermometer and a ball condenser is charged with 300 I of the product of Example 5 (1.24 * carboxyl equivalents), 3.0 g of potassium carbonate and 108.7 g (1 , 24 mol) ethylene carbonate charged. The reaction mixture is first heated to 165 ⁰ C, then for 3.5 hours, kept at 127 to 133 ° C, the final solid product, m.p. «71-82 ⁰ C, has an acid number of Oc

Example 16

2-Hydroxyethy3 ester from Example 6

According to Example 15, 274 g (1 ₅ 0 carboxyl equivalent) of the product from Example 6, 2.7 g of potassium carbonate and 88> 1 g {1 mol)

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Ethylene carbonate heated to 165 to 168 ⁰ C for 3 hours 40 minutes. The solid end product melts at 55 to 67 ^° C. and has an acid number of Oo

Example 17 Preparation of the methyl esters

The methyl esters of the foregoing acids can be prepared using standard procedures are produced »A particularly suitable process is the following:

400 ml of 20 percent potassium hydroxide solution and 400 ml of cooled ether are slowly added to a 1 liter Erlenmeyer flask 2o g'N-methyl-N'-nitro-N-nitrosoguanidine were added. This diazomethane solution slowly becomes a solution of 0.1 to 0.2 parts of the acid to be esterified in a methanol / ether (1: 1) mixture admitted? until the diazomethane color persists. The solution is allowed to stand for 10 to 15 minutes, then the solvent distilled off in a weak stream of nitrogen, desired methyl ester remains.

Example 18 The ammonium salt of Example 6

A 1-liter flask, equipped with a mechanical stirrer, a thermometer and a water cooled reflux condenser is charged with 374.7 g of distilled v / ater and 25.3 g of concentrated ammonium hydroxide (28.0 to 30.0 i <> ammonia) charged 100 g of the powdered product of Example 6 become

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added to this mixture over 2 minutes with stirring. The reaction is exothermic, the temperature rises from 25 ⁰ C to 34.5 Co ⁰ The solution is filtered and filled into a bottle, is stable

Example 19 Ms 23 Preparation of ammonium salts

According to Example 18, further ammonium salts are used in the previous Examples ^ c ^ chritteneu acidic esters produced. The reaction conditions are summarized in Table II.

Product of example product, weight steep '

Distilled water, weight steep

Table II

19 20

example

21

22nd

Ammonium hydroxide

(28.0-30.0 1o NH ₅ ) 6.0 5.6 5.4

All solutions are clear, dark in color and stable.

9 10 11 12th 13th 20th 20th 20th 20th .. 20

74.0 74.4 74.6 176.8 75.7

3.2 4.3

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Example 24 Preparation of the potassium salts

162 g of distilled water and 438 g of a 2.0182 η potassium hydroxide solution are mixed with 200 g of powdered product from Example 6 while stirring over the course of 5 minutes. The mixture is stirred and shaken to dissolve the resin. The solution is filtered However, there are no insoluble Peststoffe existing The final solution has a pH of 8.86 at 26.5 ⁰ C

The compounds prepared according to Examples 18 to 24 are soluble in latex-water emulsions and adhere to the rubber during coagulation »

Example 25

Acid maleic acid ester of Ν, Ν-Dihy'äroxyäthyl-N'-phenyl-ppheny1endiamine

A mixture of 100 g (0.681 hydroxyl lquivalente) N, N ^f dihydroxyethyl-N'-phenyl-p-phenylenediamine and 66.8 g maleic anhydride (0.681 mol) is added under a nitrogen blanket for about 1.5 hours to about 110 to 120 ⁰ C heated. The end product melts at 90 to 92 ⁰ G and has an acid number of 205.7 (theoretical: 229.0) o

The anti-aging agents according to the invention are made according to known methods Process dispersed, emulsified or dissolved and the

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Rubber latex added. This latex is coagulated by adding sodium chloride and acid; a dried, crumbled rubber material is obtained which contains the anti-aging agents in quantities of one, two or 3 parts per 100 parts of rubber. For comparison, N-phenyl-N ¹ -cyclohexyl-p-phenylenediamine is used _{as the standard control 0}

The anti-aging properties of the compounds according to the invention are explained with reference to the compounds of Examples 5, 6 and 8. Table III shows the results of heat aging tests on styrene-butadiene rubber to which anti-aging agents according to the invention have been added. The anti-aging agent was used in amounts of 3 parts per 100 parts of rubber in Example 5 (Mixture A), Example 6 (Mixture B) and in the control with N-phenyl-EP-cyclohexyl-pphenylenediamine (Mixture G), and in an amount of one part per 100 parts of rubber in Example 8 (mixture D) was added. The rubber is in a flow-through air oven at 100 ⁰ C in the specified in Table III Time heat aged _o Stated value: the percentage of formed GeIo

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Table III heat-aging in a flow-through of air oven at 10O ⁰ Q

A. G-emis
. B. ch
C. D. Aging protection agent e1
(Parts per 100 parts rubber) 3 3 3 3 not aged, $ gel O O O O aged, fo gel 8 days O O 2.0 O 7 days O ■ 5.0 17.0 3.0 9 days 4.0 20.0 56.0 20.0

Vulcanized products of the following are made from the same rubber material Composition made:

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Crumbled styrene butadiene

*) Rubber '

Naphthen oil Buss (highly abrasion-resistant oil soot) Zinc oxide stearic acid sulfur N-t-butylbenzothiazole-2-sulfenamide Mixture E,

Composition as in example 5

Mixture Ί ?,

Composition - as in Example 6

Mixture G,

N-phenyl-N'rcyclohexyl-p-phenylenediamine

^: *) Developed when the latex is coagulated by adding sodium chloride and acid.

Thought parts

100

25 62.5

1.75

1.25

After Vermis.chen and grinding, these batches are vulcanized for 50 and 90 minutes at 145 ° C. The properties of the Vulcanizates, not aged and aged, are tested in accordance with ASTM test standard D 15-70. The results are in Table IV summarized »

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Valley IV

Vulcanizate properties, not aged and aged

Elongation, $ 50 minutes E. mixture G 90 minutes Έ Not aged Tensile strength, kg / cm 193 202.4 •' 50 minutes 196 194.4 205.7 90 minutes 208.4 200 io module 650 920 50 minutes 740 790 935 90 minutes 900 Elongation, % 620 515 50 minutes 560 520 515 90 minutes 505 aged, 3 days at 100 ⁰ G Tensile strength, kg / cm 197.2 .197.5 50 minutes 210 192 193.3 90 minutes 177.4 200 ° / o modulus] 1605 1305 50 minutes 1380 1900 1395 90 minutes 1565 335 415 395 285 365 305

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Claims (1)

Claims ο) Diphenylamines of the general formula (I) in which χ and y each have the value 1 to 12, Z is a hydrogen atom, an alkali metal, an ammonium, lower alkyl or hydroxyalkyl group, R is an ethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene or styrene-G group and R ^{1 is} an arylene, alkylene, alkenylene, cycloalkenylene or cycloalkylene group with 2 to 24 ring carbon atoms, which are optionally substituted by halogen atoms, carboxy or lower alkyl groups, meant ο Diphenylamines according to claim 1, formula (i), in which R 'is a divalent cyclopentane, cyclohexane, cyclohexene or hydropenanthrene group meant '. c Diphenylamine "according to claim 2 of the formula ?, H
CH ₂ CH ₂ OC - C HC _ 209883/12 50 4 · Diphenylamines according to Claim 2 of the formula \ 1 _H - 0 V CI CI
JL ₂ CH ₂ OC I. HO ₂ C Cl CH (III) 5 ο diphenylamines according to claim 2 of the formula O CH ₂ CH ₂ OC HO ₂ C (IV) 6 ο diphenylamines according to claim 2 of the formula CH ₀ CH ₉ OC 2 / (V) 7-diphenylamines according to claim 1, formula (i), in which R ¹ signifies an ortho-substituted phenylene or a peri-substituted naphthylene group " 209883/1 250 8o diphenylamines according to claim 7 of the formula ^H0 2 ^C (VI) 9 »Diphenylamines according to claim 7 of the formula Il .CH CHOCH CH-O'C Z ₁ Z, CH CH ₃ , Ό. (VII) Diphenylamines according to Claim 7 of the formula 0 __ CH "CH-O-C CH, 11. Diphenylamines according to claim 7 of the formula (VIII) CI CI CI CI (IX) 12. Diphenylamines according to claim 1, formula (I), in which R ^{1 is} a divalent alkylene or alkenylene group. 209 88 3/12 50. ο Diphenylamine according to claim 12 of the formula ti - CH = CH - COH 14 · Diphenylamines according to Claim 12 of the formula 0 CH ₂ CH ₂ OC «Diphenylamines according to claim 12 of the formula (X) 0 0 CH CH-O-CH ^ CH - OCCH = CH C - OH 2, CH. CH, (XI) (XII) 16o Use of the diphenylamines according to claims 1 "to 15 as anti-aging agents for organic compounds, in particular for polyolefins, lubricating greases, oils, natural and synthetic fats _{or the like} 17 · Embodiment according to claim 16, characterized in that the diphenylamines in an amount of 0.10 to 0.5 parts per 100 parts of organic compounds are used. 209883/1 250 18ο embodiment according to claim. 16, characterized in that that the organic compounds styrene-butadiene-polymers or are polyisoprene " 2 09-883 / 1250