DD251762A1 - METHOD FOR PRODUCING WEATHER-, OZONE- AND WATER-AGING-RESISTANT RUBBER MATERIALS - Google Patents

Abstract

The invention relates to a process for producing weather, ozone and heat aging resistant rubber materials containing elastomers, various fillers and plasticizers, organic accelerators and sulfur vulcanizing agents, protective waxes and other necessary compounding ingredients. In general, aminic and phenolic anti-aging agents are used to prepare weather, ozone and heat aging resistant rubbers. According to the invention, a process is developed in which simple-built amines from the class of aliphatic, aromatic and heterocyclic compounds are incorporated as effective antioxidants and antiozonants in the production of weather, ozone and heat aging resistant rubber materials. It is possible to use the amines, their salts or magadiite-type synthetic phyllosilicates loaded with amines or their salts.

Description

The amines and their salts have, as adsorptive carrier substances, phyllosilicate-type phyllosilicates. The phyllosilicates have the general formula

M ₂ O · y SiO ₂ · ζH ₂ O, where M is an alkali ion or proton, y is a number between 4 and 48 and ζ is a number between 5 and 25.

They can be dehydrated by drying at 180 ^° C. Sodium magadiite has the composition Na ₂ O-14SiO ₂ -9H ₂ O.

The loaded with the relevant amines or their salts magadiite is in a dosage of 0.2 to 50 parts by mass, preferably 2.5 to 20 parts by mass based on 100 parts by mass of elastomer, as little or no discoloring Antiozonant or antioxidant used in the mixing process of rubber compounds.

As reinforcing fillers, precipitated silica or carbon black is added to the rubber mixture.

embodiments

example 1

Recipe of a light colored profile material of synthetic rubber base with the Shore hardness 55 ± 5:

Styrene-butadiene copolymer * 100.00 parts by weight

Amine / magadiite adduct. 10.00 Ma. Parts

(Degree of loading: 20% by weight)

Zinc oxide 5.00 Ma. Parts

precipitated silica 40.00 Ma. »parts

Chalk '11,00 Ma. Parts

Titanium dioxide 5.00 Ma. Parts

Petroleum softener 35.00 Ma. Parts

Facts 50.00 Ma. Parts,

Stearic acid 2.00 Ma. Parts

Ozone protection wax 5.00 Ma. Parts

Sulfur 2.60 parts by mass

N-cyclohexyl-2-benzothiazyl sulfenamide 1.30 parts by weight

Tetramethylthiuramidesulfide 0.20 parts by mass

Diphenylguanidine 0.20 parts by mass

259.30 parts * Note: Copolymer with a styrene content of about 25% and a stabilizer content of 0.5% to 0.6% di-tert-butyl-4-methylphenol.

Substituted heterocyclic amines such as derivatives of morpholine, piperidine and pyridine are used

substituted aromatic amines such as derivatives of benzylmethylamine and N-methyl-N-benzylaniline.

The influence of these amines on the ventilation behavior is beyond the test criteria

Initial strain D, [%]

- number of cracks A

- Crack depth T

and zone Z and the sun and shadow side of the test specimen and refers to a ventilation time of 30 days under the standard meteorological conditions:

Daily average concentration of ground-level ozone = 1.4pphm Daily average of air temperature = 8.5 ⁰ C

Daily sum of sunshine duration = 4.7 h

The determination of the weathering behavior was carried out according to (TGL 16890) 0 to 50% continuously expanded hollow cylindrical specimens, which were vulcanized according to the optimal vulcanization time at 150 ° C.

Weathering condition of the specimen - sunny side

di Z1 T Z2 T Z3 T Z4 T Z5 T Amin [%] A 1 A 2 A 2 A 3 A 3 without 5 3 0 3 0 4 0 4 0 3 1 morpholine 49 0 0 0 0 0 0 0 0 1 1 piperidine 49 0 0 0 0 0 0 0 0 1 1 pyridine 49 0 0 0 0 0 0 0 0 1 1 benzylmethylamine 45 0 0 0 0 0 0 0 0 1 1 N-methyl-N-benzylaniline 46 0 0 0 0 0 0 0 0 1 2 Ν, Ν-dimethylbenzylamine 49 0 0 0 0 0 0 0 0 1 1 N-cyanoethyl-N-ethylaniline 49 0 0 0 0 0 0 0 0 1 2 N-oxyethyl-N-cyanethylanilin 48 0 0 0 0 1 1,1-bis (4,4'-aminophenyl) 0 0 0 0 1 cyclohexane 49 0 0 0 0 1 1,1-bis (4-amino-3-ethyl- 0 0 0 0 1 phenyl) -cyclohexane: 49 0 0 0 0 1 2-methylmercapto-4,6-bis 0 0 0 0 1 isopropylamino-1,3,5-triazine 49 0 0 0 0 1

D ₁ Z1 Z2 Z3 T Z4 T Z5 T 100.00 Ma. Parts -3- 251 762 [%] A DID A 2 A 3 A 4 10.00 Ma. Parts 16 0 0 1 1 3 0 3 1 3 2 33 0 0 0 0 0 0 1 1 4 2 5.00 Ma. Parts Weathering condition of the specimen - shadow side 31 0 0 0 0 0 0 1 1 3 2 52.00 Ma. Parts 37 0 0 0 0 0 0 ' 2 1 2 3 40.00 Ma. Parts Amin 28 0 ο Ό ο 0 0 1 1 2 3 2.00 Ma. Parts without 36 0 0 0 0 0 0 1 1 2 2 50.00 Ma. Parts morpholine 38 0 0 0 0 0 0 2 1 2 2 5.00 Ma. Parts piperidine 39 0 0 0 0 0 1 2 2 2 3 2.30 Ma. Parts pyridine 30 0 0 0 0 1 2 3 1.00 Ma. Parts benzylmethylamine 0 0 2 0.10 Ma. Parts 1-2-N-methyl-N-benzyl aniline 46 0 0 0 0 0. 0 1 259.40 Ma. Parts Ν, Ν-dimethylbenzylamine 0 0 3 N-cyanoethyl-N-ethylaniline 42 0 0 0 0 0 0 1 N-oxyethyl-N-cyanoethylaniline 0 1 2 1,1-bis (4,4'-aminophenyl) 40 0 0 0 0 0 1 2 cyclohexane Recipe of a carbon black-filled synthetic rubber-based profile material with a Shore hardness of 55 ± 5: 1,1-bis (4-amino-3-ethyl- Styrene-butadiene copolymer * phenyl) -cyclohexane Amine / magadiite adduct 2-methyl-mercapto-4,6-bis- (Degree of loading: 20% by weight) isopropylämino-1,3,5-triazine zinc oxide Example 2 soot Petroleum softener stearic acid Fact is Ozone protection wax sulfur N-cyclohexyl-2-benzothiazylsulfenamide Tetramethylthiuramidsulfid

* Note: Copolymer with a styrene content of approx. 25% and a stabilizer content of 0.5% to 0.6% di-tert-butyl-4-methylphenol.

The amines mentioned in Example 1 are used; their influence on the weathering behavior again refers to a weathering time of 30 days under the stated meteorological standard conditions.

Weathering condition of the specimen - sunny side

D ₁ D ₁ Z1 T T Z2 T Z3 T Z4 T Z5 T Amin [%] [%] A 1 1 A 2 A 2 A 3 A 2 without 13 13 1 0 0 2 1 4 2 4 2 4 2 morpholine 18 18 0 0 0 1 1 3 2 4 2 4 2 piperidine 18 19 0 0 0 1 0 4 2 4 2 4 2 pyridine 26 28 0 0 0 0 1 1 1 2 1 4 1 benzylmethylamine 16 22 0 0 0 1 0 3 1 3 1 3 1 N-methyl-N-benzyl aniline 20 20 0 0 0 0 0 2 0 3 0 3 1 Ν, Ν-dimethylbenzylamine 42 26 0 0 0 0 0 0 0 1 2 2 N-cyanoethyl-N-ethylaniline 38 0 0 0 0 0 0 1 0 2 1 N-oxyethyl-N-cyanethylanilin 46 0 0 0 0 1 " 1,1-bis (4,4'-aminophenyl) 0 0 0 0 0 cyclohexane 50 0 0 0 0 0 1,1-bis (4-amino-3-ethyl- 0 0 0 0 0 phenyl) -cyclohexane 50 0 0 0 0 0 2-methylmercapto-4,6- 0 0 0 0 1 isopropylamino-1,3,5-triazine 44 '0 shady side 0 0 0 2 Weathering condition of the specimens - Z1 A Z2 T Z3 T Z4 'T Z5 T Amin 1 A 3 A 3 A 3 A 3 without 0 3 1 4 2 4 2 3 2 morpholine 0 1 1 2 2 2 2 4 2 piperidine 0 1 0 3 1 3 1 4 2 pyridine 0 0 0 1 1 2 1 4 2 benzylmethylamine 0 0 1 2 1 2 1 3 2 N-methyl-N-benzyl aniline 0 1 0 2 1 2 2 2 2 Ν, Ν-dimethylbenzylamine 0 1 3 4

D ₁ Z1 T Z2 T Z3 T Z4 T Z5 T [%] A 0 A 0 A 0 A 1 A 2 30 0 0 0 0 0 0 2 1 4 1 36 0 0 0 0 0 0 1 0 2 0 50 0 0 0 0 0 0 0 0 0 1 49 0 0 0 0 0 0 0 1 1 2 34 0 0 0 2 2

N-cyanoethyl-N-ethylaniline

N-oxyethyl-N-cyanethylanilin

1,1-bis (4,4'-aminophenyl)

cyclohexane

1,1-bis (4-amino-3-ethyl

phenyl) -cyclohexane

2-methylmercapto-4,6-bis

isopropylamino-1,3,5-triazine

Example 3

Formulation of a soot-filled rubber material based on natural rubber with the Shore hardness 60 ± 5:

Natural Rubber RSS 1. 100.00 Ma. Parts

Amine / magadiite adduct 12.00 parts by weight

(Degree of loading: 17% by weight)

Zinc oxide 5.00 Ma. Parts

Soot »40.00 Ma. Parts

Stearic acid · 2.00 parts by weight

Petroleum softener 5.00 Ma. Parts

Ozone protection wax 3.00 Ma. Parts

Sulfur 2.40 Ma. Parts

N-cyclohexyl-2-benzothiazyl sulfenamide 0.80 parts by mass

159.20 Ma. Parts

Substituted heterocyclic / aromatic amines such as derivatives of piperidines or substituted aliphatic amines such as n-propylamine are used.

The influence of these amines on the heat aging behavior is beyond the test criteria:

Δδ _Β

- relative change in tensile strength -100%

sb

Δε _Β

Relative change of the breaking elongation 100%

ε _Β Δ5100 '

Elongation 100% ·

8100.

- Absolute change in Shore hardness ΑΔΗ compared to unaged vulcanizate.

The artificial heat aging test was carried out at an aging temperature of 100 ° C ± 1 K and an aging time of days. Tensile strength, elongation at break and stress value were determined (according to TGL 14366) on the ring specimen with a thickness of 6 mm and the Shore hardness was measured on a plate of 6 mm.

Relative change in tensile strength, elongation at break and stress value as well as absolute change in Shore hardness during artificial heat aging (3 days at 100 ° C)

^Δδ10 ° ₁₀₀ i *. 100 - ^ - 100 ΔΗ

δ 100 δ _Β ε _Β

without -40 -49 +42 +3 piperidine -15 -27 + 19 + 1 N-propylamine -32 -42 + 32 + 1

Claims (1)

A process for the preparation of weather, ozone and heat aging resistant rubber materials containing natural and / or synthetic rubber, various fillers, support material and plasticizer, organic accelerators and sulfur as vulcanizing agents, protective waxes and other necessary mixture components, wherein in the mixing process of the rubber compound substituted heterocyclic Amines, preferably derivatives of morpholine, quinoline, piperidine or pyridine, substituted aromatic amines, preferably derivatives of benzylamine and aniline, substituted aliphatic monoamines, substituted aliphatic polyamines, mixtures of heterocyclic and aromatic amines or heterocyclic and aliphatic amines, aromatic and aliphatic amines in an amount of from 0.05 to 10 parts by mass, preferably from 0.5 to 4.0 parts by mass, based on 100 parts by mass of elastomer, of which the antiozonant or antioxidant is not slightly or slightly discolored, g Characterized in that are used as carrier material for the amines phyllosilicates of the magadiite type. Field of application of the invention The invention relates to a process for producing weather, ozone and heat aging resistant rubber materials containing various fillers and plasticizers, organic accelerators and sulfur vulcanizing agents, protective waxes and other necessary compounding ingredients. These rubber compounds are used wherever static ozone is present in the presence of static and dynamic stress and where ambient temperatures above normal room temperature prevail. Characteristic of the known technical solutions For the production of weather, ozone and aging resistant rubber materials are generally used aminic and phenolic anti-aging agents, which are added during the mixing process of the rubber compound. The commonly used amines, such as phenyl-ß-naphthylamine, substituted diphenylamines and p-phenylenediamines, although in most cases, are effective antioxidants, but they are because of their discoloration properties and the resulting lack of color fastness of light colored rubber materials or because of their tendency from the Rubber material also in adjacent paint and paint transfers, only to a limited extent operational. On the other hand, phenols that are predestined for use in non-discolouring rubber materials do not protect against the attack of atmospheric ozone and can accelerate even in the presence of soot the thermo-oxidation-induced destructuring processes in rubber materials. It has also been proposed to use synthetic crystalline zeolites as support material for amines (DD-PS 217228). Object of the invention The aim of the present invention is to develop a process for the preparation of rubber compounds which makes it possible to incorporate simple amines of the class of aliphatics, aromatics and heterocycles as effective antioxidants and antiozonants in rubber materials. Explanation of the essence of the invention The production of weather, ozone and heat aging resistant rubber materials is achieved by the use of amines, which do not require extensive synthesis and which are used in the form of their magadiite adducts. In the blending of the rubber blends are substituted heterocyclic amines, preferably derivatives of morpholine, quinoline, piperidine or pyridine, substituted aromatic amines, preferably derivatives of benzylamine and aniline, substituted aliphatic monoamines, substituted aliphatic polyamines and mixtures of heterocyclic and aromatic amines, heterocyclic and aliphatic Amines in a dosage of 0.05 to 10Ma.-parts, preferably 0.5 to 4.0 parts by mass per 100 parts by mass of elastomer, added as a little or no discoloring Antiozonant or antioxidant. The relevant amines can also be added to the rubber mixtures in the form of their salts in the same dosage.