DD290412A5 - CYCLIC MULTICOLOR PHENOLES - Google Patents

Abstract

The invention relates to a process for the preparation of cyclic polynuclear phenols and their use in natural, styrene-butadiene, acrylonitrile-butadiene and chloroprene rubber-based rubbers, thereby providing high antioxidant activity with long-term action, protection against fatigue and ozone attack, and against rubber poisons and the "crazing" effect is achieved. Their action is synergistically enhanced by mercaptobenzimidazoles. {Cyclic multicore phenols; calixarenes; Rubber materials; Rubber; Natural rubber; Synthetic rubber; Antioxidant; Rubber poison; crazing effect; mercaptobenzimidazole}

Description

Explanation of the essence of the invention

It was therefore the object of the sulfuric acid-catalyzed condensation of polyhydric phenols, which may optionally be substituted by alkyl groups and acetaldehyde to modify so that the object of the invention can be achieved in a simple manner.

The object of a process for preparing 2,8,14,20-tetramethyl-pentacyclo [19.3.1.1 ^{3 # 7} .1 ^{9 '13} .1 ^15iie ] octacosa-1 (25), 3,5,7 (26) , 9,11,13 (27), 15,17,19 (28), 21,23-dodecenes of the general formula,

in which R ² = H, OH or alkyl

Oaf the way of the condensation of polyhydric phenols catalyzed by sulfuric acid, which may optionally be substituted by alkyl groups to develop with acetaldehyde, according to the invention is achieved in that under the surface of the reaction mixture to the 95 ⁰ C hot solution of the phenolic component in the course of For 1 to 2 hours, the required amount of acetaldehyde or paraldehyde or their aqueous solutions are metered, stirred for 30 minutes at 9ü ° C, cooled to room temperature and worked up in a conventional manner.

The inventive method provides calix [4] arenausbeuten of 91 to 97% of theory; The products are so pure that a recrystallization from alcohol is not required. In addition, the reaction time can be significantly reduced and an after-reaction over several days is not required.

Another advantage is the fact that the elimination of sulfuric acid in the preparation of the acetaldehyde solution in the technical process improves the wastewater situation.

embodiments

The examples are intended to explain the process of the invention in more detail.

example 1 Preparation of 2,8 _/ 14 ^ 0-tetramethylpentacyclo [19.3.1.i ".1 ^ws .1 ^lw *] octacosa-1 (25) A5.7 {2e), 9,11,13 (27), 15 _/ 17,19 (28), 21,23 ·

dodecaene-4,6,10,12,16,18 ^ 2 ^ 4-octol

20.0 g of acetaldehyde are dissolved in 200 ml of water at room temperature. At the same time dissolve 50.0 g of resorcinol in 500 ml of 10% sulfuric acid and heated to 95 ⁰ C.

In this reaction mixture, the aqueous acetaldehyde solution is added within 60 minutes so that the feed takes place below the surface of the reaction mixture.

After completion of the reaction is stirred for 30 minutes bsi 95 ⁰ C, then cooled to room temperature, filtered off with suction, washed free of acid with water and dried at 150 ⁰ C to constant weight.

Yield: 56.73 g = 91.6% of theory

When using cooled, non-aqueous acetaldehyde, a yield of 55.61 g = 90.8% of theory is achieved.

Mp:> 240 ° C (decomposition)

(544.61 g / mol) Boron: C 70.56 H 5.93 Found: C 70.30 H 6.01 'H NMR (acetone de) cccc isomers 9.90 br (2, OH ), 7.60 s (1 H ^b ), 6.19 s (1 H ^c ), 4.50 q (1H ^{1 B} J = 7 Hz), 1.73 d (3CH ₃ , ³ J = 7 Hz)

Example 2 Preparation of 2,8,14-o-tetramethylpentacyclo [19.3.1.i ".1" ^{/ IJ} .1 ¹⁵ "] octaco-a-1 (25), 3,5,7 (26), 9,11, 13 (27), 15,17,19 (28UUJ-

dodecaene-4, e, 10,12, ie, 18,22,24-octol

20 g of paraldehyde are added dropwise via dropping funnel to a 95 ° C solution of 50 g of resorcinol in 500 ml of 10% sulfuric acid within 60 minutes so that the feed 'inter-surface of the reaction mixture is carried out. After completion of the reaction is stirred for 30 minutes at 95 ⁰ C, then cooled to room temperature, filtered off with suction, washed free of acid with water and dried at 150 ° C to constant weight.

Yield: 58.4 g A 95.3% of theory

When using an aqueous solution of paraldehyde, a yield of 59.1 g A 96.6% of theory is obtained under the same conditions.

Example 3 Preparation of 2,8,14-o-tetramethyl-pentacyclo [19.3.1.i ".1 ^f ' ¹ ' .1 ^ie - ¹ »] octacosa-1 (25), 3 _/ 5,7 (26), 9 , 11.13 (27), 15,17,19 (28) i1i3 ·

The procedure is analogous to Example 1, but substitutes instead of 50g resorcinol 57.3Pyrogallol. Yield: S6g & 95.5% of theory mp:> 240 ° C (decomposition) EA: C ₃₂ H ₃₂ O ₁₂ (608.64 g / mol)

Calcd .: C63.14 H5,31Gef .: C63,04 H5,42 ¹ H-NMR (Acoton ^ e) cccc-lsomere8,16s (2, OH), 7.158 (1, H ^b), 4,54q (1 , HV ¹ J - 7Hz), 1.72d (3, CH ₃ , ³ J = 7Hz)

Example 4 Production of 2,5,6,11,14,1

1 (25), 3,5,7 (2e), 9,11,13 (27), 15,17,19 (28), 2U3-dodecaene-4, e, 10,12,16,18 ^ 2 ^ 4-octol

The procedure is analogous to Example 1, supra starts 50 g of resorcinol 66.4g 2-Methylresorcinol. Yield: 64.1 g a 96% of theory The invention further relates to a process for the preparation of macrocyclic bodies of the general formula.

in the

R ² = OH or CH ₃ . In the literature, it is believed that by the acidic condensation of formaldehyde and

polyhydric phenols can not synthesize polycyclic systems of the above formula. Become known

Reactions of this type have hitherto always led to crosslinked phenol-formaldehyde resins. Also, the alkaline condensation of polyhydric phenols with formaldehyde gives resinous products; only at Use of p-alkylated phenols gives comparable macrocyclic structures under special conditions.

(Topics in Current Chemistry, 123 [1984], 1)

The aim of the invention is a process which makes it possible to formaldehyde and polyhydric phenols calix [4] arenpolyole

to produce defined structure in good yields.

It was therefore the task to develop pentacyclo [19.3.1.1 ³⁷ .1 ⁹ "" .1 ^{l6 '19} l in a technically simple and easy-to-control manner.

octacosa-1 (25), 3,5,7 (26), 9,11,13 (27), 15,17,19 (28), 21,23-dodecenes.

This object is achieved in that substituted in the 2-position by OH or CH ₃ groups

1,3-Dihydroxybenzene in aqueous acidic solution at room temperature with formaldehyde, wherein the mass ratio between the phenol used and formaldehyde (as formalin solution) is 4: 3.

embodiments The examples are intended to explain the erfii: Jungle-wet method in more detail. Example 5 Preparation of Pentecyclo [19.3.1.i ".1 ^t " .1 ^161t ] octerosa-1 (25), 3,5,7 (2e), 9,11,13 (27), 15 _/ 17,19 (28 ), 21,23-dodecaen-

4,5,6,10,11,12,16,17,18,22,23,24-dodecol6,3 g of pyrogallol are dissolved in 80 ml of water and 1,12 g of formaldehyde (as a 30% solution) are added. 20 ml of concentrated hydrochloric acid are added while stirring and the reaction solution is allowed to stand at room temperature for 1 hour. The precipitated product is filtered off with suction and washed free of acid.

Yield: 3.5 g (»67.5% of theory, based on CH ₂ O) The characterization of the new compound was carried out by the conversion into the dodecaacetate and into the dodecabutyrate:

a) Dodecaacetate of Pentacycle Fp: 155-158 ⁰ CEA: C ₆₂ H ₄₈ O ₂₄

(1056.95 g / mol) Calc .: C59.09 H4.58 Found: C, 58.91, H4.67 ¹ H-NMR (acetone-dg) 6.93 ppm s (1H), 3.71 ppm s ( 2H), 2.18 ppm s (3H)

b) dodecabutyrate mp: 138-14O ⁰ C EA: C ₇₆ H ₉₄ O ₂₄

(1393.60 g / mol) Calc .: C65.50 H6.94 Found: C65.55 H7.06 ¹ H-NMR (acetone-de) 6.87 ppm s (1 H), 3.66 ppm (2H) , 2.36-2.47 ppm s (6H), 1.51-1.69 ppmm (6H), 0.73-1.01 ppm m (9H)

Examples Preparation of 2, B, 8,11,14,17 ^ 0,23-Ootometh-pentecyclo [19.3.1.i ".1 ^l ' ¹ ' .1 ¹ ""] ootacosa ·

1 (25), 3,5,7 (2e), 9,11,13 (27), 15,17,19 (28) ^ U3 dodeceen-4,6,10,12, ie, 18 ^ 2 ^ 4-octol

The procedure is analogous to Example 1; instead of pyrogallol, 6.2 g of 2-methylresorcinol are used. There are obtained 3.3 g (= 65% of theory, based on CH ₂ O) of calix [4] arenpolyols. The invention also relates to a process for the preparation of brominated cyclic multicore phenols of the general

Formula.

in the

R ¹ β is alkyl, preferably CHj, or aryl, which may optionally also be substituted. From J. Am. Chem. Soc. 104 (1982), 5826 it is known, 2,8,14,20-tetramethyl-pentacyclo-l19.3.1.1 ³ ' ⁷ .1 ^e ' ⁿ .1 ^{1B> 1} 'loctacosaa-

1 (25), 3,5,7 (26), 9,11,13 (27), 15,17,19 (28), 21,23-dodecaen4,6,10,12, ie, 18.22, To react 24-octol with N-Bromsukzinimid to obtain umromomierte cyclic Mehrkemphenole above structure. However, yields of only 4% of theory are achieved, and in addition brominations using N-bromo succinimide are quite cost-prohibitive.

The aim of the invention is a process which makes it possible to produce brominated calix [4] arenes in good yields. It was therefore an object to provide 5,11,17,23-tetra-bromo-pentacyclo '19 .3.1.1 ^{3 | 7} .1 ^an .i '^{6> 19} ] octacosa-

1 (25), 3,5,7 {26), 9,11,13 (27), 15,17,19 {28), 21,23-dodecaene-4,6,10,12,1ö, 18, 22,24-octole in a technically simple and easy to produce overwhelming.

This problem, brominated, cyclic Mehrkernphenole the general formula,

in the

R ¹ = alkyl or aryl, which may optionally also be substituted, meaning "',

is prepared according to the invention by reacting calix [4] arene λ general formula,

in which R ^{1 has} the abovementioned meaning, suspended in glacial acetic acid and reacted at 20 ° C to 40 ⁰ C with elemental bromine.

The starting calix [4] arenes are known to be formed by acid condensation from 1,3-dihydroxybenzene

and aldehydes are produced.

The process according to the invention leads to yields between 95% and 99% of theory, whereby the products are replaced by a

high purity.

This smooth course of the reaction is extremely surprising since the chlorination under comparable conditions for Degradation of the macrocyclic system leads. embodiments The examples are intended to explain the process of the invention in more detail. Example 7

1 (25), 3,5,7 (2e), 9,11,13 (27), 15,17,19 (28), 2U3-dodecaene-4, e, ^ 10 ^ 2 ^ 2,16,18 4-octol into a suspension of 5,44g (0,01 mol) of 2,8,14,20-tetramethyl-pentacyclo [19.3.1.1 ^{3 '7} .1 ^{9' 13} .1 ^{1e 'l9]} -octacosa-1 ( 25), 3,5,7 (26), 9,11,13 (27), 15,17,19 (28) ₍ 21,23-dodecaene-4,6,10,12,16,18,22, 24-octol in 60ml of glacial acetic acid are added dropwise at about 3C ⁰ C 6.4 g (0.04 mol) of bromine in 10ml of glacial acetic acid. Until the completion of the evolution of HBr ruh to π after, the product filtered off and washed with water until acid free.

Yield: 8.4 g (& 97.6% of theory)

The characterization of the substance was carried out by elemental analysis, NMR spectroscopy and by conversion into the

Octabutyrat.

Mp:> 360 "C

EA: C ₃₂ H ₂₈ O ₈ Br ₄

(860.21 g / mol)

Calcd .: C44.68 H3.28 Br37.16 Found: C44.82 H 3.38 Br36.86 ¹ H-NMR (DMSO-de) 7.06 ppm s (1H), 4.93 ppm q (1H, ³ J »6Hz), 1.63ppm d (3H, ³ J - 6Hz)

Octabutyrat:

Mp: 324-327'C

EA: CMH ₈₄ O ₁₈ Br ₄

(1420,95g / mol)

Calc .: C54.10 H5.39 Br22.49 Found: C54.28 H5.23 Br22.36 ¹ H-NMR (acetone-d _e ) 7.6 oppm s (Ί H), 6.43 ppm s (1 H ), 4.21 ppm Q (2H, ³ J = 7Hz), 2.30 to 2.78 ppm m (8H), 1,38-1,94ppm m (8H), 1,60ppm d (6H, ³ J = Hz), 1.02ppmt ( ³ J = 6Hz)

Examples

5,11,17,23-tetrabromo-2,8,14 ^ 0-tetra- (2-hydroxy) -phenyl-penta-cyclo [19.3.1.1 ^v . 1 ^{] -1} 1ls -1 lctacosa-1 (25) , 3,5,7 (26), 9,11,13 (27), 15,17,19 (28), 2U3-dodecaene-4,6,10,12,16,18,22,24-octol a suspension of 8.57 g (0.01 mol) of 2,8,14,20-tetra- (2-hyiroxy) phenyl-penta-cycloI19.3.1.1 ³ - ⁷ .1 ^{e> 13} .1 ¹⁶ - ¹⁹ loctacosa -1 (25), 3,5,7 (26), 9,11,13 (27), 15,17,19 (28), 21,23-4,6,10,12,16,18-dodecacn , 22.24-octol in 60 ml of glacial acetic acid are added dropwise at about 3OX 19.2 g (0.12 mol) of bromine in 10 ml of glacial acetic acid.After completion of the HBr development, the mixture is stirred, filtered off with suction and the product is washed with water until free of acid : 17.7g (£ 98.1% of theory) mp:> 360 "C

Identification as octabutyrate mp: 236-240X EA: C ₁₀₀ H ₁ OoO ₂₄ Br ₁ I (2844.81 g / mol)

C45.41 H3.81 Br36.26 Found: C45.53 H3.78 Br35.91 ¹ H-NMR (acetone-d _e ) 7.76 ppm s (2H); 6,59ppm s (2H); 6.19ppm s (1H); 5.81 ppm s (1H); 5.46ppm s (2H); 2.46-2.63 ppm m (12H); 1.46-1.81 ppm m (12H); 0.81-1.07ppm m (18H)

Finally, the invention relates to a process for the preparation of macrocyclic bodies of the general formula I.

in the 1? * »CH ^ - N (

"CH

or

IM I

CH,

CH,

and R ¹ and R ² , which may be the same or different, represent alkyl or aryl groups. The serving as Ausgar.gssubstanz body of the general formula Il

According to available experimental investigations, aromatic electrophilic substitution reactions are known to be difficult to access. (Monatshefte Chem. 89 [1958], 135, Topics in Current Chemistry 123 [1984], 1)

The only known substitution in the 2-position on the phenolic main body of the macrocyclic system is the Bromination (J. Am. Chem. Soc., 104 [1982], 5826). Alkylation reactions to obtain sterically hindered multinuclear phenols are in the 2-position of the resorcinol building blocks of

macrocyclic system has so far been unsuccessful.

The aim of the invention is a process which makes it possible sterically hindered cyclic Mehrkernphenole of the general formula I.

to produce in good yields.

So there was the task? 5,11,17,23-tetra-substituted 5,6,6,6-trisubstituted and easily controlled

aminomethyl-2,8,14,20-tetra-methyl-pentacyclo [19.3.1.i ".1 ^{e '13} .1 ¹⁶ ' ^1e ] octacosa-1 (25), 3,5,7 (26), 9 , 11,13 (27), 15,17,19 (28), 21,23-dodecaenA6,10,12,16,18,22,24-octols.

This object is achieved in that calix [4] arenpolyo! E the structure

in methariuiischer solution aminomethylated at boiling temperature by reaction with secondary amines and paraformaldehyde or with alicyclic systems such as piperidone, morpholine or piperazines and paraformaldehyde.

embodiments

The examples are intended to explain the process of the invention in more detail.

Example 9

1 (25) ^ ₍ 5,7 (2e), 9,11,13 (27), 15,17,19 (28), 21i3-dodecaene-4, e, 10,12, ie _/ 18 ^ 2,24 -octol In a solution of 6,44g (0,01 mol) of 2,8,14,20-tetramethyl-pentacyclo [19.3.1.1 ³⁷ .1 ^{9 '13} .'i ^{1B' ie]} octaco8a-1 _(25)> 3 _< 5 _> 7 _> (26) _> 9,11> 13 (27), 15,17,19 (28), 21 _< 23-dodecaene-4 _> e, 10,12 _> 16 _> 18 _l 22,24- octol in 100ml of methanol at 6O ⁰ C with stirring 3,40g (0.04 mol) of piperidine are added. it sets the suspension 1.20 g (0.04 mol) of paraformaldehyde added upon which the ammonium salt is in solution, and after a few minutes, the The final product begins to separate.

The mixture is stirred at 60 ° C for 2 hours, the product is filtered off with suction, washed until neutral and the precipitate is dried.

The yield is 6.20 g [& 67% of theory].

The characterization of the new substance was carried out in addition to the NMR spectroscopy by the conversion into the Octabutyrai.

Mp: 24O ⁰ C (decomposition) EA: C ₆₆ H ₇₆ O ₈ N ₄ (933.36 g / mol)

Boron .: C72,05 H8,22 N6,00 Found .: C71.74 H8.51 N6,21 ¹ H-NMR (DMSO-d ₆₎ 7,76ppm s (1H); 4.06ppm s (2H); 2.66-2.90 ppm (4H); 175-2.05 ppm (9H)

Octabutyrate mp: 190-192 ° C EA: C ₈₈ H ₁₂₄ O ₁₈ N ₄

(1493.99 g / mol) Calc .: C 70.75 H 8.37 N 3.75 Found: C 70.48 H 8.47 N 3 / J 3 ¹ H-NMR (acetone-d ₆ , 7.52 ppm (1 H); 6,25ppm s (1H); 4,10ppm q (2H, ³ J = 7 Hz), 2.97 ppm s (4H); 1,45ppm d ⁽³ J = 7Hz)

Example 10 S, 11,17,23-Tetra [N, N -dimethylamino) methyl] -2,8,14 ^ 0-tetramethylpentacyc) o [19.3.1.1 ⁹ - ⁷ .i'- ¹³ .1 ^1s - ¹ *] octacosa ·

1 (25) ^, 5.7 (2e), 9,11,13 (27), 15.17,19 (28), 2U3-dodecaene-4, e, 10,12, ie, 18.22 ^ 4-octol

In a solution of 5.44 g (0.01 ».n ^. UU-O-tetramethyl-pentacycloHg.SII ^ .I ^^ V ^^ loctacosa-1 (25), 3,5,7 (26), 9 , 11,13 (27), 15,17,13 (28), 21,23-dodecene-4,6,10,12, ie, 18,22,24-octol (starting material of Example 1) in 100 ml of methanol C. 2.90 g (0.24 mmol) of diethylamine are added while stirring at 60 ° C. 1.20 g (0.04 mol) of paraformaldehyde are added to the resulting suspension, whereupon the ammonium salt goes into solution and the end product is dissolved after a few minutes to start separating.

The mixture is stirred at 6O ⁰ C for 4 hours, the product filtered off, washed until neutral and dried the precipitate.

The yield is 5.75 g (= 65% of theory) mp:> 360 ° C EA: C ₆₂ H ₇₆ O ₈ N ₄ (885.32 g / mol)

Calcd .: C70.54 H8.67 N6.32 Found .: C70.31 H8,81 N6,39 ¹ H-NMR (DMSO ^ g) 7,50ppms (1H); 4,51ppmq (1H, ³ J = 7 Hz ); 3,77ppm8 (2H); 2,75ppmq (4H, ³ J = 7Hz); 1,72ppmd (3H, ³ J = 7Hz); 1,01ppmt (6H, ³ J = 7Hz)

Example 1

1 (25), 3,5,7 (26), 9,11,13 (27), 15,17,19 (28) ^ U3-dodecaene-4,6,10,12,16,18 ^ 2, 24-octol The procedure is analogous to Example 2 and enters into the methanolic solution of the precursor 1.8Og (0.04 mol) of dimethylamine. This gives 5.3 g of yield (69% of theory) mp:> 360 ° C EA: C ₄₄ H ₆₀ O ₈ N ₄ (773.08 g / mol)

Calc .: C68.35 H7.83 N7.24 Found: C68.26 H7.94 N7.31 ¹ H NMR (DMSO ^ ₆ ) 7.64 ppm s (1H); 4.68ppm br (1H); 4.01 ppm s (2H); 2,62ppm s (6H) 1,97ppm s (3, ³ J = 6Hz)

Example 12

5,11,17 _I 23.Tetra [moΓphollnomβthvlJ · 2,8,14ί0 · tetramethvl · pβntacyclo [19.3.1.1 ". ^{1 t} · ¹ ^ 1 ¹ '· ^1l ] octaco $ a · 1 (25) ^, 5, 7 (2e), 9,11,13 (27), 15,17,19,128) ^ U3-dodecaene-4, e, 10,12, ie _/ 18 ^ 2,24-octol The procedure is analogous to Example 1, but it is set instead of the piperidines, 3.49 g (0.04 mol) of morpholene.

The yield is 6.3 g (67% of theory)

Mp:> 360 ° C

EA: C ₆₂ HmO ₁₂ N ₄

(941,24g / mol)

Bar .: C66.35 H7.25 N5.95 Found: C66.01 H7.54 N6.18 ^ H-NMR (DMSO-d _e )

7,58ppm s (1 H) 4,43ppm q (1 H, ³ J = 7Hz) 3,70ppm s (2H) 3,51-3,65m (4H) 2.39 to 2.50 ppm (4H) 1, 72ppm d (3H ₁ ³ J = 7Hz)

For the production of heat-resistant, weather-resistant and ozone-resistant rubber materials based on natural, styrene-butadiene, acrylonitrile-butadiene and chloroprene rubber, it is preferable to add amalgam aging inhibitors to the elasto-mixtures during the mixing process. However, these substances, in the practical use of the gum products in question, cause discoloration of the gum or of other materials in contact with it.

On the other hand, sterically hindered mono- or bisphenols as anti-aging agents cause no contact discoloration and no or only slight yellowing of the vulcanizates exposed to the light; However, the antioxidant activity of the phenolic compounds is limited due to their volatility in the vulcanization process of the rubber blanks and / or at high use temperatures of the rubber articles due to strong pre-emptive concentration. Like many amines in rubber, they are subject to a wash-out process by water and extraction by fuels, alkalis and aqueous solutions of basic salts.

A long-term effect of these products is therefore not available. Otherwise, in the case of thermally highly stressed rubber articles, expensive special rubbers such as e.g. Ethylene-propylene terpolymers, epichlorohydrin, silicone or hydrogenated Acryliiitril-styrene rubber are used, which require special vulcanization curing systems. It is therefore a further object of the present invention to find non-volatile and difficult-to-extract anti-oxidant antioxidants which can be used to prepare heat-aging and weather-resistant non-contact-staining rubbers.

It has been found that by the use of cyclic Kordensationsprodukten polyhydric phenols with carbonyl compounds in particular of calix [4] arenpolyolen instead of mono- and bisphenols in rubber mixtures based on natural and / or synthetic rubber, various fillers, plasticizers, accelerators and sulfur an increase in thermal oxidation resistance of the rubbers occurs at elevated temperatures, while improving their weatherability and maintaining good protection against the destructive effects of dynamic mechanical forces and certain heavy metal compounds acting as so-called rubber poisons in the presence of oxygen

 Calix [4] arene polyols, metacyclophanes of the general formula I

Formula I

Due to their molecular structure, they are characterized by high antioxidant activity, low volatility and heavy extractivity due to water and non-polar hydrocarbons.

According to the invention as antioxidants for rubbers, especially the diene compounds; \ Ά R ¹ = CH _3, R ² = H

and with

R ¹ = CH ₃ , R ² = CH ₂ N (C ₂ H ₆ I ₂ or CH ₂ NC ₆ H ₁₀ or CH ₂ NC ₄ H ₈ O

suitable.

It has been found that the improvement of the properties of rubber vulcanizates on the basis of NR, SBR, NBR, HR, CR and EPDM after thermooxidative and dynamic mechanical stress can be achieved by reducing cracking bbi of static ozone suppression and outdoor ventilation, when 0.05 to 10 parts by volume, preferably 0.5 to 4.0 parts by mass of a calix [4-ytalcohol polyol per 100 parts by weight of elastomer to which the rubber compound is added.

The achieved by the erfindungsgemäSen method Kennw3rte the vulcanizates, such as. B. tensile strength of elongation at break after heat aging at 70 ° C and 100 ° C, initial elongation, number of cracks and crack depth after one Γ; ¹ Ii: ot ventilation or artificial ozone aging and the average cracking resistance after a Stauch-Biegc Prlif'wi.j dosen cheaper than the vulcanizates containing a mono or bifunctional phenolic antioxidant at the same concentration.

The following examples are intended to illustrate the procedure of the invention without limiting sin.

embodiments

The rubber compounds are produced in a laboratory internal mixer of the type GK4 N according to a uniform mixing procedure. The characteristic values are determined and evaluated according to the listed TGL regulations.

Example 13 Formulation of a beige rubber material based on natural ZBadieneStyrene rubber base of Shore hardness A60 ± 6

test formulation not according to the invention 2 erfindungsge mixtures Ma. parts suitable mixture mixture 1 51.00 3 Ma. parts 49,00 Ma. parts natural rubber 51.00 9.20 51.00 ölverstreckterButadien-styrene rubber 49,00 11,80 49,00 high molecular weight butadiene-styrene plasticizer 9.20 29,60 9.20 zinc oxide 11,80 28,90 11,80 kaolin 29,60 37.50 29,60 precipitated silica 28,90 4.90 28,90 Zinc sulfide / barium sulfate filler 37.50 2.30 37.50 Fact is 4.90 5.30 4.90 stearic acid 2.30 4.90 2.30 rosin 5.30 0.00 5.30 Ozone protection wax 4.90 2.00 4.90 2,6-di-t-butyl-4-methyl-phenol 2.00 0.00 0.00 2,2'-methylene-bis- [4-methyl-6-t-butylphenol] 0.00 0.20 0.00 Tetramethyl calix (4] arenoctol 0.00 0.72 2.00 Oiphenylguanidin 0.20 0.85 0.20 tetramethylthiuram 0.72 2.60 0.72 mercaptobenzothiazole 0.85 240.77 0.85 sulfur 2.60 2.60 240.77 240.77

Vulcanization of the Elnstomerrohmischungen: 10 minutes at 15O ⁰ C

1. Percentage loss of tensile strength (--- * 100%) and elongation at break {- · 100%) of the vulcanizato of the mixtures 1,2

Whether εβ

and 3 after a heat aging of 7 days at 70 ° C and 100 ⁰ C according to TGL14366, determined on ring specimens of 6mm thickness:

property

Material of mixture

 100 [%]

Sb Δε _Β

ε _Β after 7 days at 70 ⁰ C.

-15 -28

-12 -22

100 [%] 100 [%] after 7 days at 100 ^° C.

-37-59

-35 -54

2. Mean cracking resistance RBW as the decadic logarithm of the kilocycles until the crack formation step C of the vulcanizates of the mixtures 1, 2 and 3 in a compression bending test according to TGL14378, determined on test specimens of the form 1:

property

Material of mixture

0.89

0.93

3. Ozone aging behavior according to TGL 24418 (initial elongation D | [%], number of cracks A and crack depth T in the expansion zone Z2), determined on 0 to 0% continuous hollow cylindrical specimens of 3 mm thickness at an ozone concentration of 50 × 10 ^-8 vol. %, a temperature of 40 ° C and a test period of 72 hours:

property

Material of mixture

Initial elongation D | [%] number of cracksA crack depth T

14 3-4

19 2 1

4. Gates according to TGL16890 (initial strain D ₁ [%], number of cracks A and crack depth T in the strain zone Z5), determined at 0 at 50% continuously stretched hollow cylindrical specimens of 3 mm thickness after a soaking period of 29 days under the following central European meteorological standards. Conditions: mean ozone concentration: 29μς / ηη ³

average air temperature: 8,5 ⁰ C

average daily sunshine duration: 4.7 hours

Werkstoffaus 1 2 3 mixture property Sunny side of the specimen 30 40 45 Initial strain D, [%] 3 2 2 Number of cracks A 2-3 2 2 Crack depth T Shadow side of the specimens 28 33 41 Initial strain D, (%) 3 2-3 2 Crack number A 2 2 2 crack depth

Explanation of the terms initial strain, number of cracks and depth of crack: initial strain D ₁ [%] is the static strain at which the

first crack occurs; a Dp value of 30% means that the stretch area lying between 0 and 29% remains crack-free.

Number of cracks A and crack depth T will.) Are classified as follows: AO no cracks TO no cracks A1 1-5 cracks surface cracks (about 0.1-0.5 mm deep) A 2 6-40 cracks T 2 cracks, approx. 1 mm deep A 3 41-120 cracks T 3 cracks, over 1 mm deep A4over120 cracks T4 openwork specimens

5. Testing of paint discoloration (contact discoloration of white alkyd resin paint) to factory standard GKTS 802-3 / 01 on test specimens of dimensions 100 mm χ 20 mm x 2 mm

property

Material of mixture

Discoloration after 21 days exposure outdoors (July, 1987) in 916mNN

none

none

Test formulation for tetra-isopentylcalix [4] arenoctol (column 4) and tetra-isepylcalix [4] arenoctol (column 5) test formulation

inventive mixture

mixture 4 5 concentration Ma. parts Ma. parts natural rubber 51.00 51.00 ÖlgestreckterButadien-styrene rubber 49,00 49,00 hochmolekularerButadien-styrene plasticizers 9.20 9.20 zinc oxide 11,80 11,80 kaolin 29,60 29,60 precipitated silica 28,90 28,90 Zinc sulfide / barium sulfate filler 37.50 37.50 Fact is 4.90 4.90 stearic acid 2.30 2.30 rosin 5.30 5.30 Ozone protection wax 4.90 4.90 2,6-di-tert-butyl-4-methylphenol 2,2'-methylenebis [4-methyl-6-t · 0.00 0.00 butylphenol] 0.00 0.00 Tetra Isopqntylcalix [4] arenoctol 2.00 0.00 Tetraheptylcalix [4] arenoctol 0.00 2.00 diphenylguanidine 0.20 0.20 Tetramethylthiuramidsulfid 0.72 0.72 mercaptobenzothiazole 0.85 0.85 sulfur 2.60 2.60 240.77 240.77

-13- 290412 vulcanization of Elastomerrohmischungen: 10min at 15O ⁰ C

1. Percentage loss of tensile strength (-R - ^ - · 100%) and elongation at break {- · 100%) of the vulcanizates of mixtures 4 and

Whether εβ

5 after heat aging of 7 days at 7O ⁰ C and 100 ⁰ C according to TGL14366, determined on ring specimens of 6mm thickness.

Werkstoffaus

Mixture 4 5

, Property

δ _Β

ε _Β after 7 days at 70 ⁰ C.

10 -9 17 -14 32 -31 49 -46

δ _Β

ε _Β after 7 days at 100 ° C

The following describes the thermal and photostabilization of discoloring emulsion and solution polymers by means of calix [4] arene-ols.

Use of calix [4] arene-ols, preferably of tetramethylcalix (4) -arene-octol, as primary stabilizer in a concentration of 0.5 to 3%, preferably of 1.5 to 2.5%, for thermal and photostabilization from

• Emulsification polymers (cold and hot polymers):

· Butadiene-styrene rubber (having a styrene content of 23 t's 50% and a Mooney viscosity of 40 to 62 ME) ·· oil-extended butadiene-styrene rubber (having a styrene content of 13 to 25% and a Mooney viscosity of 40 to

56M ·)

·· Butadiene-acrylonitrile rubber (having an acrylonitrile content of 16 to 41% and a Mooney viscosity of 33 to 70 ME) ·· butadiene-acrylonitrile rubber / PVC compound (having an acrylonitrile content of 17 to 22%, a PVC Content from 37 to

44% and a Mooney viscosity of 50 to 70ME).

Solution polymers:

Isoprene rubber with a cis content of about 96% and a Mooney viscosity of 70-80ME. Use of calix [4] arene-ols, preferably of tetramethyl-calix [4] -areno-octol, in combination with

• Ν, Ν'-Oialkyl-p-phenylenediamines

• N-alkyl-N'-aryl-p-phenylenediamines

• Ν, Ν'-Diaryl-p-phenylenediamines

• liquid diphonylamine-acetone condensation products

in the ratio 5: 1 to 1: 2 at a total concentration of 0.5 to 3.0%, preferably from 1.5 to 2.5%, as a primary stabilizer in emulsion and solution polymers.

Preparation of the stabilized rubbers

- Mixing of the stabilizers or stabilizer mixtures in prestabilized rubber (emulsion polymer) on oinem laboratory roll mill with 450mm roll length and 200mm roll diameter

Incorporation of the tetramethylcalix [4] -arenoctol or of the mentioned combinations into a solution polymer stabilized with 1,2% 2,6-di-tert-butyl-4-methylphenol (isoprene rubber)

Assessment of the thermal and photostability of rubbers

Determination of the viscosity change of the rubbers according to TGL 25689 with the Mooney viscometer at a temperature of

100 ^° C:

- before and after storage in a warming cabinet with fresh and circulating air operation at + 7O ⁰ C.

- before and after outdoor storage at an altitude of 916m asl.

Example No. 14 for stabilization of butadiene-styrene rubber (cold polymer)

not inventively stabilized rubbers according to the invention

stabilized rubbers

1 2 3 4 5 6 7 8

Butadiene-styrene rubber * 100.0 100.0 100.0

Phenyl-.beta.-naphthylamine 0.5

Tetramethylcalix [4] -arenoctole - - -

N-isopropyl-N'-phenyl-p-phenylene

diamine - 0.5

N, N'-bis (1,4-dimethyl-pentyl -) -

p-phenylenediamine - - 0.5

• Styieim "! -: 23.1% Mooney-ViekositSt M _u « 41100 · «: 4 / ME

"Mass parts

Change in the viscosity of the rubbers after a 14-day aging at + 70'C:

100.0 100.0 100.0 100.0 100.0 0.5 0.4 0.3 0.25 0.2 » - 0.1 0.2 0.25 - 0.2 »

AM ₁₁ + 4MOO ¹ C) (ME) +4 +5 +4 +2 +1 +3 +4 +3

Viscosity change of the rubbers after 56 days storage at 916m above sea level under meteorological conditions:

• average temperature of the weathering bead: 10.7 ° C

• Sunshine duration of the ventilation period: 389 hours

• Rainfall of the ventilation period: 170 liters prom ²

J234567 8

100.0 100.0 100.0 100.0 · " 0.5 0.25 0.25 0.25 " 0.25 _

T3I +2 (3 +24 +48 +18 +16 +18 +15

Example No. 15 for stabilization of butadiene-styrene rubber (hot polymer)

not inventively stabilized rubbers according to the invention

stabilized rubbers

12345678

Butadiene-styrene rubber * 100.0 100.0 100.0, 100.0

Phenyl-ß-naphthylamine 0,5 -

Tetramethylcalix [4] -arenoctole N-isopropyl-N'-phenyl-p-

phenylenediamine - 0.5 N, N'-bis (1,4-dimethylpentyl) -

p-phenylenediamine - - 0.5 - - - 0.25 'diphenylamine-acetone

Condensation product - 0.5 - - - 0.25 ^#

Styren content: 25.4%

Mooney-Vlekosltät M _L , _(mxi : 40ME ·· Ma. Parts

Change in viscosity of the rubbers after 14 days heat aging at 7O ⁰ C:

12 3 4 5 6 7 8

AM _{u <} .4 ₍ , oo _c , [MEl +8 +12 +11 +14 +7 +11 +9 +12

Viscosity change of the rubbers after storage for 13 days at an altitude below the meteorological

Conditions:

»Average temperature of the ventilation period: 0.7 ⁰ C

• Sunshine duration of the ventilation period: 193 hours

• Rainfall of the ventilation period: 680Literprom ^J

1234561 7 8

4 (ΐοο · ο (MEl +5 +6 +5 +7 +16 +3 +2 +4

Example No. 16 for stabilization of oil-extended butadiene-styrene rubber (cold polymer)

not according to the invention stabilized rubbers stabilized rubbers

1 2 3 4

Butadiene-styrene rubber *

Phenyl-beta-naphthylamine

Tetramethylcalix [4] arene octol

N-isopropyl-N'-phenyl-p-phenylenediamine diphenylamine-acetone condensation product

Styrene content: 23.4%

Mooney viscosity M _u 141100x1: 40ME ·· m. Parts

Viscosity change of the rubbers after heat aging at 70 ° C for 14 days

1 2 3 ^ 4

AMu ₊ 4 (tooxi [ME]. +3 +2 +6 +5

100.00 100.00 100.00 100.00 »· 0.50 - - - - 0.50 0.25 0.25 ·· - - 0.25 - - - - 0.25 **

Viscosity change of the rubbers after 56 days storage at 916m above sea level under meteorological conditions:

• Average air temperature of the heating period: 10.7 ^° C

• Sunshine duration of the ventilation period: 389 hours

• Rainfall of the ventilation period: 140 liters per m ² .

1 2 3

+43

Example No. 17 for butadiene-acrylonitrile rubber (hot polymer)

+43

+34

not according to the invention stabilized rubber stabilized rubber

Butadiene-acrylonitrile rubber * Phenyl-beta-naphthylamine Tetramethylcalix [4] arene octol N-isopropyl-N'-phenyl-p-phenylenediamine N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine Diphenylamine-acetone condensation product

100.00 100.00 100.00 100.00 100,00 " 0.50 - - - - - 0.50 0.25 0.25 0.25 - - 0.25 - - - - 0.25 -

: 45ME

³ Acrylic Content: 26.2% Moonoy viscosity M _u "parts by weight

Change in viscosity of the rubbers after 14 days heat aging at 7O ⁰ C

1 2

AMli + 4 (100 * 0 [Ml

+ 8 + 7

+5

+6

+6

Viscosity change of the rubbers after storage for 16 days at an altitude of 916m NN under the meteorological conditions:

• Average temperature of the ventilation period: 7.3 "C

• Sunshine duration of the ventilation period: 701 hours

• Rainfall of the ventilation period: 280 liters prom ²

1 2 3 4

_{+ 4} (IOo-C) [ME

+45

+65

+36

+38

+41

Example No. 18 for butadiene-acrylonitrile rubber / PVC compound

not according to the invention stabilized rubber stabilized rubber

Butadiene rubber Acrylnit.il · Phenyl-beta-naphthylamine Tetramethylcallx [4) arene octol N-isopropyl-N'-phenyl-p-phenylenediamine N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine Diphenylamine-acetone condensation product

* Acrylic nitrate content: 21.7% PVC content: 39.3% Mooney viscosity M _L1 miiwci: 61ME

100.00 100.00 100.00 100.00 100.00 0.50 - - - - - 0.50 0.25 0.25 0.25 - - 0.25 - - - - _ 0.25 _

Viscosity change of the rubbers after heat aging at 70 ^° C. for 14 days:

1 2

+ 6 + 5

+6

+5

+5

Viscosity change of the rubbers after storage for 116 days at an altitude of 916m NN under the meteorological conditions:

• average temperature of the ventilation perloid: 7.3 ^° C

• Sunshine duration of the grazing period: 701 hours

• Rainfall of the ventilation period: 280 liters prom ²

1 2 3 4 5

AMi _{1 +} 4 (100-C) (ME) +8 +15 +6 +7 +7

Example No. 19 for Isoprene car chuk (solution polymer)

not according to the invention stabilized rubber stabilized rubber

1 2 3 4 isoprene rubber * 100.00 100.00 100.00 100.00 »· Phenyl-beta-naphthylamln 0.50 - - - Tetramethylcalix [4] arene octol - 0.50 0.25 0.25 "· N-isopropyl-N'-phenyl-p-phenylenediamine - - 0.25 - N, N'-diphenyl-p-phenylenediamine -, - - 0.25 ··

• stabilized with 1.2% 2,6-di-tert-butyl-4-methylphenol

Mooney composition M _{L1 f} 4I ₁ M ¹ Ci = ME * * measure

Viscosity change of the rubbers after a 7-day heat aging at 70 ⁰ C:

1 2

-5 -4 -2 -3

Viscosity change of the rubbers after 95 days of storage at an altitude of 916m NN under the meteorological conditions:

• average temperature of the ventilation period: 6.1 ⁰ C

• Sunshine duration of the weathering period: 553 hours

• Precipitation during the ventilation period: 222 liters prom ²

1 2 3 4_

-15 -4 -2 -3

Claims (3)

claims: 1. A process for preparing cyclic Mehrkernphenole, characterized
that 5,11,17,23-tetrabromo-pentacycloH9.3.1.1 ³ ' ⁷ .1 ⁹ ' ¹³ .1 ^1M9 ] -octacosa-1 (25), 3 _/ 5,7 {26), 9,11,13 ( 27), 15,17,19 (28), 21,23-dodecaene-4 _/ 6,10,12,16,18,22 _/ 24-octolender
general formula, br in which R ¹ = alkyl or aryl, which may optionally also be substituted, are prepared by reacting calix [4] arenes of the general formula in which R ^{1 has} the abovementioned meaning, suspended in glacial acetic acid and reacted at 2O ⁰ C to 4O ⁰ C with elementcrem bromine, that for the preparation of substituted BjH.n ^ S-tetraaminomethyl ^^. M ^ O-tetramethyl pentacyclol 19.3.1.1 ³ ' ⁷ .1 ⁹ ' ¹³ .1 ^{16 '19} ] octacosa-1 (25), 3,5,7 (26), 9,11,13 (27), 15,17,19 ( 28), 21,23-dodecaene-4,6,10,12,16,18,22,24-octols of general Fortviel, R2 : ^CH 3 in which R ² = CHr-N (CH ₃ J ₂ , = CH- -N (C ₂ H ₅ J ₂ , CH ₂ CH ₂ or CH ₃ CH2 means calix [4] arene polyols of the structure in methanolic solution at boiling temperature by reaction with secondary amines and paraformaldehyde or with cyclic systems such as piperidine, morpholine or piperazine and paraformaldehyde aminomethylated, that for the preparation of pentacyclo [19.3.1.1 ³ ' ⁷ .1 ^{9 <13} .1 ¹⁶ ' ¹⁹ ] octacosa-1 (25), 3,5,7 (26), 9,11,13 (27), 15 , 17,19 (28), 21,23-dodecenes of the general formula in which R ¹ = H, R ² = CH ₃ or OH, substituted in the 2-position by OH or CH ₃ groups substituted 1,3-Dihydroxybenzene in aqueous acid solution with formaldehyde at room temperature, the mass ratio between the used phenol and formaldehyde (as formalin solution) is 4: 3, that for the preparation of 2,8,14,20-tetramethyl-pentacyclo [19.3.1.1 ^3l7 .1 ⁹ⁱ¹³ .1 ^{16> 19} ] octacosa-1 (25), 3,5,7 (26), 9,11, 13 (27), 15, 17, 19 (28), 21,23-dodecenes of the general formula, in which R ² = H, OH or alkyl, by way of the sulfuric acid-catalyzed condensation of polyhydric phenols, which may optionally be substituted by alkyl groups, with acetaldehyde, below the surface of the reaction mixture to the 95 ⁰ C hot solution of the phenolic component added in the course of 1 to 2 hours, the required amount of acetaldehyde or paraldehyde or their aqueous solutions, stirred for 30 minutes at 95 ⁰ C, cooled to room temperature and worked up in a conventional manner. 2. Use of cyclic Mehrkernphenole according to claim 1, characterized in that they are used as anti-aging agents in rubber materials. 3. Use of cyclic Mehrkernphenole according to claim 2 as an anti-aging agent in rubber materials, characterized in that in addition Mercaptobenzimidazol and / or substituted p-phenylenediamine is added. Field of application of the invention The invention relates to a process for the preparation of macrocyclic bodies of the general formula in the R = H, OH or alkyl. Characteristic of the known state of the art The acid-catalyzed reaction between polyhydric phenols and aldehydes has long been known. Already isolated in 1883 Michael (Am. Chem. J. 5,338 [1883]) describes two crystalline compounds by reacting resorcinol with benmzaldehyde. The Clarification of the structure of these substances has been the focus of much work. The reaction between resorcinol and acetaldehyde was more closely understood by Niederl and Vogel (J. Am. Chem. Soc., 62, 2512 [1940]) examined. For the first time, these authors proposed a cyclic tetrameric structure with 8extraannular hydroxyl groups for the reaction product. The reaction was later reported by A. G.S. Högberg (J. Org. Chem. 45,4498 [1980]; J. Am. Chem. Soc. 102, 6046 [1980]), who proved the cyclic structure to be calix [4] arene. For the preparation of the calix | 4] arene from resorcinol and acetaldehyde, there are two regulations in the literature, namely the Condensation in the presence of sulfuric acid according to J.B. Niederl and H.J.Vogel (J. Am. Chem. Soc., 62, 2512 (194O)) and the Condensation in the presence of hydrochloric acid described by Högberg (J. Org. Chem. Vol. 45, 22, 4499 [1980]). The reaction of a solution of resorcinol in 10% sulfuric acid with a solution of acetaldehyde in dilute Sulfuric acid requires a reaction time of three days and gives a yield of 79.1% as an air-dried product. This value determined by Högberg also corresponds to the yields we have found. The acid condensation in the presence of hydrochloric acid requires only a few hours, but leads to our findings always to large proportions of hanartiger products. Already in the literature there are indications that the yield data fluctuate due to the changing water content of the products pipe and can hardly be compared. For example, the reported yield of 79.1% refers to air-dried product. If you dry it Precipitate at 15O ⁰ C to constant weight, so the yield for that accessible from recorcinol and acetaldehyde Calix [4] is only 71% of theory. Object of the invention The object of the invention is 2,8,14,20-tetramethyl-pentacyclo [19.3.1.1 ³ " ⁷ .1 ^{e '13} .1 ¹⁶ ] octaco3a 1 (25), 3,5,7, (26), 9,11,13 (27), 15,17,19 (28), 21,23-dodecenes in improved yield and with shorter reaction times.