DE2108893A1 - Vulcanizable rubber compounds - Google Patents

Description

The invention relates to mixtures vulcanizable with sulfur and accelerators, which have at least one weak unsaturated copolymer of ethylene with an α-olefin and at least one diene and a highly unsaturated one Contain rubber and result in vulcanizates with excellent properties.

Elastomeric products made from copolymers of ethylene with an a-01efin and a conjugated or non-conjugated Diene, for example of the linear endomethylene type or tetrahydroindene, with a low content of unsaturated units in the range from 0.1 to 0.5 mol of double bonds / kg Polymer are already known. • Typical examples of such copolymers using propylene as : ct-01efin contain, they are known as EPDM copolymers.

■ th ethylene-propylene-diene rubbers.

These copolymers have a high resistance to Ozone and chemicals, but at the same time poor processability, poor compatibility with certain fillers, insufficient adhesion to atark unsaturated rubbers and fibers and low stickiness

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of the raw mixes. Due to these properties, the copolymers are often used for certain applications, e.g. for Manufacture of tires, unsuitable.

It is known that some properties of the copolymers can be improved if they are highly unsaturated Rubbers, e.g. natural rubber (NR), synthetic cis-l, 4-polyisoprene (IR), cis-l, 4-polybutadiene (BR), Butadiene-styrene copolymers (SBR), butadiene-acrylonitrile copolymers (NBR) and polychloroprene (CR), in suitable amounts. In this way Vulcanizates could be obtained in which the increased aging resistance and ozone resistance of the Copolymers added to the typical properties of the various highly unsaturated rubbers.

However, the production of such mixtures is still associated with disadvantages, for example from the limited Compatibility of the elastomeric components result. It is also known from the literature that two Elastomers can only be vulcanized together if they have comparable vulcanization speeds and have at least partial chemical affinity.

The weakly unsaturated elastomeric copolymers are due to their low vulcanization rate im Compared to the strongly unsaturated rubbers in a mixture with the strongly unsaturated rubbers only within very tolerated by narrow concentration limits. This poor tolerance means that it is not possible Prepare mixtures of the above elastomers in all proportions. Even if such mixtures can be produced were, they resulted in using the usual, from sulfur, tetramethylthiuram monosulfide and mercaptobenzothiazole existing vulcanization systems for weakly unsaturated elastomers to vulcanizates, their mechanical and dynamic properties are insufficient for many applications.

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An improvement in both mechanical and dynamic properties has been greatly increased through use Unsaturated terpolymer achieved in place of the weakly unsaturated terpolymers.

The object of the invention is to eliminate and eliminate the disadvantages of the known processes and products weakly unsaturated copolymers of ethylene with propylene and a diene and to produce mixtures of highly unsaturated rubbers which have good general properties, e.g. homogeneous dispersion of the two elastomeric components and the fillers and good processability in the Mixers, have, and from which vulcanizates can be produced, their mechanical and dynamic properties are just as good or better than the properties of the vulcanizates based on the individual elastomeric components.

It has now surprisingly been found that this object can be achieved when weakly unsaturated copolymers (0.1 to 0.5 mol of double bonds / kg) are used, which are prepared using at least one diene which introduces double bonds into the copolymer, which vulcanize rapidly with sulfur and accelerators, and when a certain type of accelerator selected from the sulfenamide derivatives is used in amounts is that preferably. 1.3 to 3% by weight, based on the elastomers.

As a service, those with sulfur and accelerators quickly introduce vulcanizing double bonds into the copolymer, conjugated diolefins, e.g., 1,3-butadiene and Isoprene, trienes with two conjugated double bonds, e.g. 1 »3,7-octatriene, and non-conjugated dienes with a non-conjugated vinylidene double bond of the isopropenyl norborriene type or an alkylidene double bond of the ethylidene-boron type or a tri- or tetrasubstituted Double bond, e.g. 5- (2'-methyl-2'-butenyl) -

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2-norbornene, 6-methyl-4,7,8,9-tetrahydroindene and 5,6-dimethyl-4,7,8,9-tetrahydroindene.

The invention thus relates to vulcanizable mixtures which "consist of the following components:

A. 20 to 90 weight percent of at least one 0.1 to 0.5 mole unsaturated Units per kg containing copolymers of ethylene with an α-olefin and at least one diene, the double bonds in the copolymer, which vulcanize rapidly in the presence of sulfur and accelerators introduces and from the group conjugated diolefins, trienes with two conjugated double bonds, non-conjugated Serve with vinylidene double bonds, non-conjugated Dienes with alkylidene double bonds and non-conjugated dienes with tri- or tetrasubstituted ones Double bonds is selected;

B. 10 to 80 wt .- # of at least one highly unsaturated Rubber and

6. a vulcanization system, consisting of

a) 1 to 10 parts of sulfur per 100 parts by weight of the total amount of elastomers (copolymer + strong unsaturated rubber),

b) 0.5 to 10 parts of a sulfenamide derivative serving as an accelerator per 100 parts by weight of the elastomers all in all.

For the mixtures according to the invention copolymers are used, which by copolymerization of ethylene with a a-01efin, which contains 3 to 10 carbon atoms, preferably propylene, and at least one diene that quickly vulcanizes Introduces double bonds, are obtained, preferably the following dienes are used: 6-methy1-4,7,8,9-tetrahydroindene, 5,6-dimethy1-4,7,8,9-tetrahydroindene, 2-ethylidene-norbornene-5 »2-isopropenylnorbornene-5 and 4-methyl-tricyclo (6,2,1,0) -undecadiene-4,9.

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These copolymers generally have a molecular weight of 50,000 to 5,000,000 and contain the by the Diene introduced unsaturated units in an amount of 0.1 to 0.5 moles of double bonds per kg of the terpolymer.

For the purposes of the invention, natural rubber and, for example, are suitable as highly unsaturated rubbers Synthetic rubbers made from diolefins (1,3-butadiene, 1,3-isoprene and 2-chlorobutadiene) alone or with others Comonomers (styrene, acrylonitrile, etc.) have been produced, e.g. oil-1,4-polybutadiene, polychlorobutadiene, synthetic cis-1,4-polyisoprene, styrene-butadiene rubbers and butadiene-acrylonitrile rubbers.

The vulcanization systems contain the sulfur in one Amount of 1 to 10 parts, preferably in an amount of 1 to 4 parts per 100 parts of the elastomers.

N-Cyclohexyl-2-benzothiazylsulfenamide, N-tert.r-butyl-2-benzothiazylsulfenamide, N-oxydiethyl-2-benzothiazylsulfenamide, N, N ^l -diethyl-2-benzothiazylsulfenamide and morpholine disulphide are preferably used as sulfenamide accelerators. The amount of accelerator is 0.5 to 10 parts by weight, preferably 1.3 to 3 parts by weight per 100 parts by weight of the elastomers. These sulfenamide compounds are also superior to the typical accelerators for weakly unsaturated elastomers, namely the thiazole and thiuram derivatives, because of their better properties and better compatibility and dispersibility in the mixtures and because of the better control of vulcanization.

• Commercially available natural or synthetic rubbers are generally used as highly unsaturated elastomers, the - the specifications given by the manufacturers for use in the various fields of application to have. Their molecular weight and their molecular weight distribution are not critically important in their choice, however, for obvious reasons, it is

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Availability expedient to use products with a Mooney viscosity (ML 1 + 4 at 100 ⁰ C) of more than 10. The Mooney viscosity should be selected depending on the desired processability.

Oil-extended highly unsaturated rubbers are also suitable, whereby care must be taken that that the type of oil is compatible with the terpolymer used. Suitable for this purpose are paraffinic or naphthenic oils and, in certain cases, aromatic oils. The weight ratio of terpolymer too high unsaturated rubber in the mixture can vary between 20:60 and 95-5. In practice, this ratio will follow selected the desired properties of the vulcanizate. This makes the EPDM terpolymers more oil-resistant, for example acrylonitrile-butadiene copolymers (NBR) are used in a proportion of 10 to 50 wt .- ^. With these Mixtures produced in proportions also show less swelling due to solvents. You stick better on metals, both via adhesive films and adhesives, and on fabrics and have better compatibility with fillers like cork and asbestos.

The mixtures of EPDM terpolymer and butadiene-styrene copolymer (SBR) can be produced with any proportions of the constituents (from 5:95 to 95: 5). Depending on these ratios, improved adhesion to fabrics, better adhesion of rubber to rubber and economy of the mixtures and Vulkaniaate can be achieved. The mixtures can therefore be used in all areas that are intended for the two individual elastomers. The same applies to natural rubber and synthetic cis-1,4-polyisoprene. For example, these rubbers, which are contained in the mixtures in amounts of more than 20 Gevi _t - ^C , i , improve the dispersion of light-colored fillers, the stickiness of the raw mixtures, the adhesion to fabrics, the tear resistance, back-

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resilience and the hysteresis behavior.

Mixtures with chloroprene rubber (CR) result in vulcanizates with better oil resistance, good resistance to Inflammation, improved adhesion of rubber to rubber and rubber to metal and better dispersion of the bright Fillers and pigments.

By adding cis-1, ^ - polybutadiene to EPDM terpolymers their abrasion resistance, elasticity at low temperatures and adhesion to rubber are improved. At high Concentrations of highly unsaturated rubber, however, these mixtures have a poor resistance to aging.

The mixing of two or more elastomeric components can be carried out according to known methods using internal mixers of the Banbury type or on roller mixers. The mixtures according to the invention can fillers and Pigments are admixed within the limits known to the person skilled in the art. For example, 10 to 200 parts activated carbon black and up to 500 parts of thermal black per 100 parts by weight of the elastomer mixture can be added. Commercially available plasticizing oils can also be added prior to vulcanization, their amount and type in Depending on the Mooney viscosity of the mixtures, the chemical nature of the elastomers and the required Properties of the vulcanizates can be selected.

The content of unsaturated units in the ethylene-propylene-diene elastomers, expressed in moles of double bonds per kg of copolymer, was determined by iodometric analysis of the unsaturated units determined by the ICL method, which is described by Siggia (Anal. Chem. 35, 362, 1963) and recently by M.Tunnecliffe and co-workers (Europ.Pol.J. 259, 1965) and by Giuffre-Cassani (Chim. Ind. 806, 1963) has been improved.

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The course of mixed vulcanization can be based on unfilled mixtures in which the elastomers have a weight ratio of 50:50, by measuring the swelling and solubility in certain solvents for those in the Mixture contained elastomers can be determined according to the method used by G.Kerrut and H.Blümel in rubber and Gummi 413-418-8 / 1969.

Examples 1 to 5

Two mixtures of an ethylene-propylene-2-ethylidene norbornene-5 terpolymer (EPDM) containing 40 wt .- ^ propylene and 0.3 mol of double bonds / kg and a Mooney viscosity are placed on roller mixers at temperatures of 40 to 80 C. (ML 1 + 4 at 100 ⁰ C) of 80, and a styrene-butadiene copolymer (SBR 1502), which has a Mooney viscosity (ML 1 + 4 at 100 ⁰ ) of 50, the EPDM / SBR weight ratio for one mixture is 50:50 and for the other mixture is 70:30. Vulcanizable mixtures are produced from these mixtures on roller mixers, on the one hand using the usual accelerators for EPDM rubbers, consisting of mercaptobenzothiazole (MBT) and tetramethylthiuram monosulfide, and on the other hand using a sulfenamide compound as accelerator according to the invention. The mixture has the following composition: elastomer mixture 100, HAP carbon black 50, stearic acid 1.5, ZnO 5, accelerator and sulfur according to Table 1.

The mixtures produced in this way are vulcanized ^{in a press at 160 ° C. for 30 minutes.} The mechanical properties of the vulcanizates were determined according to the ASTM D-412 method. The results are shown in Table 1 below.

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Table 1

example Parts ρ
, kg / cm 1 O, _ 2 3 2.0 5, Accelerator, ρ
, kg / cm 1. 100 5 MBT + your Santo- 243 5 TMTMS 2.2 Sulfur, parts 310 1.5 50 2.5 SBR 133 50 30 50 30th EPDM Q
kg / cm 238 50 70 185 70 Tensile strenght, 98 55 320 207 Elongation at break, $ strain 200 150 106 340 Module at $ 200 strain 98 172 125 Module at $ 300 _ _ 195

Santocure = N-cyclohexyl-2-benzothiazylsulfenamide

Examples 6-15

On the roll mill five mixtures were incubated at temperatures of 40 to 8O ⁰ C with an EPDM / SBR ratio of 50:50 and 70:30 of the said terpolymer and below a styrene-butadiene copolymer (SBR 1502) containing a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 50, produced:

1) Ethylene-propylene-dicyclopentadiene terpolymer (DCP) with a propylene content of 35% by weight, a double bond content of 0.38 mol / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 100 .

2) Ethylene-propylene-1,4-hexadiene terpolymer (ED) with a propylene content of 42% by weight, a double bond content of 0.37 mol / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C) from 80.

3) Ethylene-propylene-6-methyl-4,7,8,9-tetrahydroindene terpolymer (MTHl) with a propylene content of 30% by weight, a double bond content of 0.3 mol / kg and a Mooney viscosity (ML 1 + 4 at 100 ⁰ C) of 105.

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-: o - ■

4) Ethylene-propylene ^ -ethylidene norbornene-S-terpolymer (ENB) with a propylene content of 40% by weight, a double bond content of 0.3 mol / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) ) from 80.

5) Ethylene-propylene-4-methyltricyclo (6,2,1,0 ') undecadiene-4,9-terpolymer (MTCU) with a propylene content of 40 wt .-; o, a content of double bonds of 0.37 mol / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 150.

The mixtures produced in this way became vulcanizable mixtures of the following composition on a roller mixer manufactured:

100 parts by weight of elastomer mixture 50 parts by weight of HAP carbon black 1.5 parts by weight of stearic acid 5 parts by weight of ZnO

2 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide Sulfur in the amounts given in Table 2

These mixtures were vulcanized at 160 ° C for 30 minutes. The mechanical properties of the vulcanizates were the same as for the vulcanizates mentioned in Examples 1 to 5 certainly. The results are given in the table below.

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Tabel

CD CO Ca> CO

Examples 6th 7th "8th 9 10 EPDM / SBR 50/50
2.2 MTHI ENB MTCU * 11 12th 13th 14th ENB 15th Sulfur, parts / 100 parts
Elastomers ED 163
320
112
160 185
320
106
172 255
300
144
255 EPDM / SBR
2.5 207
340
125.
191 70/30 Diene in EPDM terpolymer DCP 108
220
97 DCP ED MTHI MTCU Tensile strength, kg / cm
Elongation of the fracture, ^v jo
Module at $ 200 elongation, kg / cm
Module at $ 300 elongation, kg / pm : 108
240
97 57
200
57 51
220
51 173
420
93
137 285
290
184

O CO OO

"It *"

Examples 16 Ms 24

From the mixtures prepared according to Example 1 "to 5 with EPDM / SBR weight ratios of 70; 30 and 50:50, nine vulcanizable mixtures with different contents of accelerator (N-cyclohexyl-2-benzothiazylsulfenamide" Santocure ") and / or sulfur and The following composition is produced: 100 parts by weight of elastomers, 50 parts by weight of HAF carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO and N-cyclohexyl-2-benzothiazylsulfenaride and sulfur in the in Table 3 The mixtures were vulcanized in a press for 30 minutes at 160 ^° C. The mechanical properties were determined in the same way as for the products produced according to Examples 1 to 5.

Furthermore, the aging resistance according to ASTM D and the compression set 'according to ASTM D 395, method B, certainly.

The results are shown in Table 3 below.

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Table 3

Examples 16 17th 18th - 19th 20th 21st 22nd 23 _ 24 * 185 I. I \ -Cyclohexyl-2-benzothiazyl-
sulfenamide, parts / 100 parts
Elastomers 1.5 1.5 1.75 1.75 2.0 2.5 1.5 1.75 - 2.0 320 92 · Sulfur, parts / 100 parts
Elastic kidney 2.2 2.5 2.2 2.5 2.5 2.5 2.2 2.2 2.2 106 50 mixture 70/30 Gemi sch 50/50 - 172 ¹⁵ N> 2
Tensile strength, kg / cm 200 194 204 204 207 207 204 182 50- * Elongation at break, $ 380 340 370 320 340 340 330 320 Module at $ 200 elongation, kg / cm ² 100 107 104; 118 125 127 114 112 Module at $ 300 elongation, kg / cm ² 160 170 165 184 191 186 182 174 Age resistance
(4 days at 125 ^° C): • Tensile strength in $ of the value
. from aging _ _ 105 MM. 100 _ Elongation at break in $ of the value
from aging - - 65 - 55 - - Compression set, method B
22 hours at 70 ⁰ C, $ 16 70 hours at 125 ⁰ C, $ - - "- 50 - -

CD OO CO

Examples 25 to 30

A mixture prepared according to Examples 1 to 5 with an EPDM / SBR weight ratio of 70:30 became produced a vulcanizable mixture of the following composition: 100 parts by weight of elastomer mixture, 50 parts by weight of HAP carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO, 2 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide, 2.5 parts by weight of sulfur. This mixture has been in a press for different times at temperatures vulcanized at 150 and 160 C. The test of the mechanical properties at 23 ° C according to ASTM had the results given in Table 4.

Table 4

Examples kg / cm 25th 26th 27 28 29 30th Temperature, ⁰ C 150 160 Time, minutes Strain, 30th 60 90 15th 30th 45 Tensile strenght, Strain, 215 210 215 209 198 211 Elongation at break, ^ 380 350 320 380 320 320 Module at $ 200
kg / cm ^ 114 121 124 112 122 123 Module at $ 300
kg / cm2 177 185 202 169 185 193

Examples 31 to 34

In the manner described for Examples 1 to 5, two mixtures of an ethylene-propylene-ethylene norbomene terpolymer containing 40% by weight of propylene and 0.3 mol of double bonds / kg and a Mooney viscosity (ML 1+ 4 was at 100 ⁰ C) of 80 and an acrylonitrile-butadiene-Gopolymeren (NBR Elaprim S and contained 356) containing 45 wt .- $ acrylonitrile having a Mooney viscosity (ML 1 + 4 at 1GO ⁰ C) of 53 had, with the ii] FDM / iIBR - Gev; ichtverältnis for one mixture ^c jC: 50 and for the other mixture 70; 30.

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With these mixtures, vulcanizable mixtures of the following composition were produced on a roller mixer: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO, vulcanizing agent according to Table 5 The mechanical properties of the vulcanizates produced from the mixtures are given in Table 5, which lists the properties of vulcanizates obtained from the individual elastomers in the mixtures mixed with the usual vulcanizing agents for these elastomers for comparison. All mixtures were ^{vulcanized at 160 °} C. for 30 minutes. The mechanical tests given in Table 5 were carried out according to ASTM methods. The oil immersion test was performed according to ASTM D 471.

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Tabel

Examples 31 32 33 34 EPDM, parts per 100 parts
Elastomers
NBR, parts per 100 parts
Elastomers 100 100 50
50 70
30th Accelerator, parts / 100 parts
Elastomers Mercaptobenzothiazole
Tetramethylthiurammono-
sulfide 0.5
1.5

190 274 218 194 340 400 340 330 96 115 112 100 166 200 190 173

MBTS - 1.5

N-cyclohexyl-2-benzothiazyl-

sulfenamide - 2 2

Sulfur, 100/100 parts elastomers 1.5 1.5 2.25 2.5

Tensile strength, kg / cm ² ... elongation at break, $

Module at 200 ^ elongation, kg / cm ² Module at 300 ^ elongation, kg / cm ²

Aging resistance (4 days at 125 C)

Tensile strength, $ of the value above Aging

Elongation at break, fi of the value before aging

Compression set. Method B.
22 hours at 70 ⁰ G, fo
70 hours at 125 ° C, ^c />
Immersion in Oil (ASTM # 2)
Volume change (70 hours at 23 ° C), # 21 immersion in oil (ASTM Er.3)
Volume change (70 hours at 23 ⁰ C) $

116 96 110 102 82 43 55 60 12th 20th 18th 18th 58 81 72 66 21st 0 8th 14th 85 6th 30th 50

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Examples 35 to 38

With the mixtures prepared according to Examples 1 to 5 with EPDM / SBR weight ratios of 70:30 and 50:50, vulcanizable mixtures were prepared using two different plasticizer oils, namely with a naphthenic oil (Necton 60) and an aromatic oil (Sundex 53 ). The mixtures had the following composition: 100 parts by weight of elastomer mixture, 10 parts by weight of plasticizer oil, 50 parts by weight of HAF carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO, 2 parts by weight N-Cyclohexyl-2-benzothiazylsulfenamide and 2.5 parts by weight of sulfur in the 70/30 mixture and 2.2 parts by weight of sulfur in the 5O / 5O mixture. The mixtures were vulcanized in a press for 30 minutes at 16O ⁰ G. The results of the mechanical tests carried out in accordance with ASTM at 23 ⁰ G are given in Table 6 below.

Table 6

Examples kg / cm kg / cm 35 36 172 37 38 50/50 Plasticizer oil kg / cm Necton 60 370 Sundex 53 182 EPDM / SBR Strain, 70/30 50/50 87 70/30 400 Tensile strenght, Strain, 189 136 196 81 Elongation at break, $ 400 420 131 Module at $ 200 78 81 Module at $ 300 130 134

Examples 39 and 40

In the manner described in Examples 1 to 5, two mixtures of an EPDM terpolymer and a highly unsaturated rubber by weight were produced. manufactured by 70:30 "used was an ethylene-propylene-2-A" thyliden-5-norbornene terpolymer containing 40 wt. ~ / o propylene and 0.3 Get double bonds / kg and containing a Mooney viscosity (ML 1 +4 at 100 0) out of 80, and the following two highly unsaturated ones

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Rubbers:

Natural rubber (pale crepe) (NR)

cis-1,4-polybutadiene (BR), Mooney viscosity (ML 1 + 4 at

10O ⁰ C) 50.

Vulcanizable mixtures "having the following composition were prepared from these mixtures: 100 parts by weight Elastomer mixture, 50 parts by weight of HAP carbon black, 1.5 parts by weight Stearic acid, 5 parts by weight ZnO, 2 parts by weight N-cyclohexyl-2-benzothiazylsulfenamide (Santocure), sulfur according to Table 7.

These mixtures were vulcanized for 30 minutes at 160 ^° C. The mechanical tests carried out according to ASTM methods at 23 ° C. had the results given in Table 7.

Table 7 Examples 39 and 42 40 Weight ratio EPDM / strong unsaturated rubber 70/30 70/30 Highly unsaturated rubber NO BR Sulfur, parts / 100 parts Elastomers 3.0 2.2 ο
Tensile strength, kg / cm 180 188 Elongation at break, ° ß> 410 350 Module at $ 200 elongation, kg / cm ² 86 102 Module, at 3005b elongation, kg / cm ² 132 164 Examples 41

The same terpolymer was converted into polychlorobutadiene in the manner described for Examples 39 and 40 and from (CR rubber) (Neoprene WHV) produced two mixtures with EPDM / CR weight ratios of 7O; 3O and 50:50. With these two mixtures, two vulcanizable mixtures with the following composition were made: 100 parts by weight of elastomer mixture, 50 parts by weight HAP carbon black, 1.5 parts by weight stearic acid, 5 parts by weight ZnO,

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70/30 50/50 2.75 2.5 230 236 320 300 128 150 215 236

2 parts by weight of MgO (type D), 2 parts by weight of N-cyclohexyl-2-benzothiazyl-sulfenamide (Santocure), sulfur according to Table 8.

Table 8 Examples 4J 42

EPDM / CR weight ratio
Sulfur, parts / 10C parts elastomers

2
Tensile strength, kg / cm

Elongation at break,>

ο
Module at $ 200 elongation, kg / cm

Module at $ 300 elongation, kg / cm

Examples 43 and 44

In the manner described in Examples 1 to 5, two mixtures of an ethylene-propylene-ethylidene norbornene terpolymer containing 3 "5 wt .- $ propylene and 0.5 mol double bonds / kg and a Mooney viscosity (ML 1 + 4 was at 100 ° C) of 83, and a styrene-butadiene copolymer (SBR 1502), having a Mooney viscosity (ML had at 10O ⁰ C) of 50 1 + 4, with an EPDM / SBR weight ratio of 50: 50 and 70:30 with these mixtures vulcanizable mixtures of the following composition were produced on the roller mixer: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight parts of ZnO, 2 parts by weight of N-cyclohexyl-2-benzothiazyl sulfenamide, 2 parts by weight of sulfur. The mixtures obtained were in a press jJO minutes at 160 ⁰ C vulcanized. The tests carried out in accordance with ASTM methods at 23 ° C mechanical tests had the results given in Table 9.

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Table 9 Examples

EPDM / SBR weight ratio

50/50

70/30

229 198 320 300 128 117 206 198

Tensile strength, kg / cm elongation at break, $

Module at $ 200 elongation, kg / cm '

Module at 300? & Elongation, kg / cm *

Examples 45 to 48

With the mixtures prepared according to Examples 1 to 5 with EPDM / SBR weight ratios of 50:50 and 70:30, four vulcanizable mixtures were made using morpholine disulfide ("Sulfasan R") and N-oxydiethyl-2-benzothiazylsulfenamide (Nobs Special) as Accelerator produced according to the following recipe: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO, accelerator and sulfur as indicated in Table 10. These mixtures were then vulcanized in a press for 30 minutes at 16O ⁰ C. The results of the physical and mechanical tests are shown in Table 10 below.

Tabel Examples 10 212 46 5 215 47 2, 171 48 0 181 EPDM / SBR weight ratio 45 280 70/30 320 50/50 2, 340 70/30 O 400 Accelerator, parts / 100 parts
Elastomers 50/50 147 , 5 130 86 77 Morpholine disulfide - 201 150 132 N-oxydiethyl-2-benzothiazyl-
sulfenamide 2, Sulfur, parts / 100 parts
Elastomers Tensile strength, kg / cm 2 Elongation at break, ^c ß> Module at 200 ^ elongation, kg / cm ² Module at 300 ^ elongation, kg / cm

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example

A vulcanizable mixture according to the following recipe was prepared from a device produced according to Examples 1 to 5 with an EPDM / SBR weight ratio of 70:30: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 1.5 parts by weight . Parts of stearic acid, 5 parts by weight of ZnO, 2 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide, 2.5 parts by weight of sulfur. Piping mixture was vulcanized 30 minutes at 160 ⁰ C with a Reyoncord 1650/2, which was pretreated with a mixed with resorcinol-formaldehyde resin styrene-vinylpyridine-butadiene copolymer latex.

The adhesion between rubber and rayon cord was determined according to the Η test (ASTM D-2138-67) compared to a * Mixture determined that only a styrene-butadiene copolyraeres as an elastomer (SBR 1502) and on a rayon cord pretreated in the manner described above had been vulcanized.

SBR EPDM / SBR

Adhesion values, determined according to

Η test, kg / 6.3 mm at 23 C 18 16

Examples 50 to 52

From the mixtures prepared according to Examples 1 to 5 with EPDM / SBR weight ratios of 50:50 and 70:30, two vulcanizable mixtures were produced on the roller mixer according to the following recipe: 100 parts by weight of elastomer mixture, 75 parts by weight of PEF Carbon black, 25 parts by weight of naphthenic oil (Necton 60), 1.5 parts by weight of stearic acid, 5 parts by weight of ZnO, 2 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide, sulfur according to Table 11. Subsequently, the vulcanization behavior of the mixtures using a rotating disc rheometer ^ (Monsanto) according to the ASTH D 2705 / 68T method at 160 ⁰ C and 10 cycles / minute with one

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Oscillation arc of 3 ° determined.

The T ^ values, ö.h. the time in minutes that is required is until the torsional moment exceeds the minimum value by 2 points, as well as the T9O values, i.e. the time in minutes which is required to be 9C $ of the maximum value of the The vulcanization curve to be achieved was determined in this manner. These values are shown in Table 11 below Comparison to the values given for a mixture based only on EPDM.

Table 11 50 1 51 52 Examples 50 70 100 EPDM terpolymer, Parts 50 30th - SBR, parts 2.2 2.5 2.5 Sulfur, parts / 100 Parts of elastomer Monsanto rheometer 7.8 7.4 6.2 T2, minutes 13.2 5.4 21.2 T90, minutes Example 53 and 54

On the two roll mill mixtures with EPDM / HR-weight ratios of 50:50 AU3 are a natural rubber (HR, type RSS) and each one of the following terpolymers prepared at temperatures of 40 to 80 ⁰ C:

1) ethylene propylene dicyclopentadiene terpolymer (DCP) with 44 wt .- ^ propylene content, 0.50 mol double bonds / kg and a Mooney viscosity (ML 1 + 4 at 10OG C) of 86.

2) ethylene-propylene ~ 2 ~ 5-ethylidenenorbornene Terpoiyrneres (ENB), propylene content 44 wt. -Fi, content of double bonds 0.28 mol / kg, Mooney Viakosität (ML 1 + 4 at 100 ⁰ C) 75.

INSPECTED

10 9839/1534

With these mixtures, vulcanizable mixtures were produced on the roller mixer according to the following recipe: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 2 parts by weight of stearic acid, 5 parts by weight of ZnO, 1.3 parts by weight. -Parts of N, N ^l "r diethyl-2-benzothiazylsulfenamide (Vulkacit AZ), 2.5 parts by weight of sulfur. These mixtures were vulcanized for 60 minutes at H5 ° C. The mechanical properties of the vulcanizates were determined as in Examples 1 to 5 The results are shown in Table 12 below.

Table 12

Examples 5J5 54

Diene in the EPDM terpolymer DGP ENB

Tensile strength, kg / cm elongation at break, i>
Module at 200 $ elongation, kg / cm ² Module at 300 ^ elongation, kg / cm

Examples 55 and 56

On a roller mixer, at temperatures of 40 "to 8O ⁰ C, two mixtures of one ethylene-propylene-2-ethylidene norbornene-5 terpolymer (EPDM), one of which was 44 wt .- ^ propylene and 0.28 mol Contained double bonds / kg and had a Mooney viscosity (ML 1 + 4 at 100 ⁰ G) of 75 and the other 42 wt .-% propylene and 0.65MoI double bonds / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 88, and a natural rubber (HR type RSS) with EPDM / ER weight ratios of 50:50 was produced Elastomer mixture, 50 parts by weight of HAF carbon black, 2 parts by weight of stearic acid, 5 parts by weight of ZnO, 1.3 parts by weight of N, N'-diethyl-2-benzothiazylsulfenamide (Vulkacit AZ) and 2.5 Parts by weight of sulfur »Dieao Vn is vulcanized at 145 ° C for 60 minutes.

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96 160 220 330 87 98 144

160 187 330 340 98 105 144 166

The mechanical properties of the vulcanizates were determined as in the case of Examples 1 to 5. (These examples show that with moderately to slightly unsaturated EPDM terpolymer compared to a highly unsaturated one EPDM terpolymers achieve good mixed vulcanization ») The results are shown in the table below called.

Table 13

Examples 55 56,

Unsaturated units, moles / kg 0.28 0.65

Tensile strength, kg / cm elongation at break, $

Module at 2OO7S elongation, kg / cm

Module at 300 ^ elongation, kg / cm

Examples 57 'to

On the roller mixer ratios NR were stored at temperatures of 40 to 80 ⁰ C for four mixtures with EPDM / 50:50 in each case one of the following ethylene-propylene-2-Kthylidennorbornen-5-terpolymer and a natural rubber (NR, type RSS) manufactured:

1) EPDM terpolymer with 26 wt .- ^. Propylene content, 0.34 mol of double bonds / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 92.

2) EPDM terpolymer with 30% by weight propylene content, 0.3 mol double bonds / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 78.

3) EPDM terpolymer with 33 wt .- # propylene content,

0.37 mol of double bonds / kg and a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 82.

4) EPDM terpolymer with 44% by weight propylene content, 0.28 mol double bonds / k »and a Mooney viscosity (ML 1 + 4 at U) O ⁰ C) of 75.

1Q9.839 / 1 5 34

With these mixtures, vulcanizable mixtures were produced on the roller mixer according to the following recipe: 100 parts by weight of elastomer mixture, 50 parts by weight of HAF carbon black, 2 parts by weight of stearic acid, 5 parts by weight of ZnO, 1.3 parts by weight. -Parts of N, N'-diethyl-2-benzothiazylsulfenamide (Vulkazit AZ), 2.5 parts by weight of sulfur. These mixtures were vulcanized for 60 minutes at 145 ^° C. The mechanical properties of the vulcanizates were determined in accordance with ASTM-D-412. The results are shown in Table 14 below.

Table 14 Examples 57 58 59 60 Propylene salary, $ 26th 30th 44 Unsaturated units, moles / kg 0.34 0.30 0.37 0.28 ο
Tensile strength, kg / cm 231 190 192 160 Elongation at break, fo 340 340 390 330 Module at $ 200 elongation, kg / cm 130 103 92 98 Module at $ 300 elongation, kg / cm 210 163 148 144 Examples 61 up to 65

On the roller mixer C five mixtures of an A'thylen-propylene-ethylidenenorbornene-2-5-terpolymers (EPDM) containing 30 wt .- $ propylene and 0.3 mol of unsaturated units were at temperatures of 40 to 80 ⁰ / kg containing and had a Mooney viscosity (ML 1 + 4 at 100 ^° C.) of 78, and a synthetic cis-1,4-polyisoprene (IR) with EPDM / IR weight ratios of 90:10, 75:25, 50:50 , 25:75 and 10:90.

Vulcanizable mixtures were prepared using a naphthenic plasticizer oil (Circosol 4240) according to the following recipe: 100 parts by weight of elostomerone mixture, 50 parts by weight of plasticizer oil, 70 parts by weight of f'EJj 'carbon black, 2 parts by weight Stearic acid, 5 wt _; -Parts ZnO, N, N'-diethyl-2-benzothiazylaul fenami d (Vulkac.it ΛΖ) and

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8AD OWGHNAL

Sulfur in the amounts given in Table 15.

The mixtures were vulcanized in a press at 16O ⁰ G 'in the above Table 15 in time. The mechanical properties of the vulcanizates were determined in accordance with ASTM D 412. The following properties were also determined:

Compression set according to ASTM D 395, method B Tear resistance according to ASTM D 624 Tensile set according to ASTM D 412, hardness according to ASTM D 1415

Vulcanization behavior with the Monsanto rheometer, such as in Examples 50 to 52 described.

The results are shown in Table 15 below.

Table 15

Examples 61 62 63 64

EPDM terpolymer, parts by weight 90 75 50 25

cis-1,4-polyisoprene, wt.

Parts 10 25 50 75

N, N'-diethyl-2-benzothiazvl-

sulfenaraid (Vulkacit AZ) 2.0 1.6 1.15 1.1 1.0

Parts / 100 parts elastomers

Sulfur, parts / 100 Parts 2.5 2 , 5 2 • 2 , 5 2, 5 Elastomers 9 7th , 5 6th , 75 6th , 75 6, 5 Monsanto rheometer: T2, min. 24.25 17th , 75 15th .75 12th , 5 13th T90, min. 40 30th ,8th 20th 20th Vulcanization time, Mi η _o 30th

Tensile strength, kg / cm ² 180 150 130 120 145

Elongation at break, $ 550 520 520 540 560

Module at $ 300 elongation,

kg / cr / 96 83 75 70 72

Tensile set, ^c / o 10 12.5 13.5 10 7.5

IRHD hardness 63 56 57 52 52

Tear resistance, kg / cm 55 38 37 37 37

DruckveriOrmunnsi-esi ;,

Method B (22 5 Ui, at 7C ⁰ G),

? o 39 39 '50 26 23

109839/1534

Claims (6)

Patent claims A) 20 to 90% by weight of at least one 0.1 to 0.5 col unsaturated units per kg containing copolymers of ethylene with an α-olefin and at least a diene that quickly vulcanizes double bonds in the presence of sulfur and accelerators introduces into the copolymer and from the group conjugated diolefins, trienes with two conjugated Double bonds, non-conjugated dienes with vinylidene double bonds, non-conjugated dienes with alkylidene double bonds and non-conjugated dienes with tri- or tetrasubstituted double bonds is selected, B) 10 to 80% by weight> at least one highly unsaturated. ten rubber and C) a vulcanization system a) 1 to 10 parts by weight of sulfur per 100 parts by weight of the elastomers in total (copolymer plus highly unsaturated rubber), b) 0.5 to 10 parts of a sulfenamide derivative serving as an accelerator per 100 parts by weight of the Total elastomers. 2) Vulcanizable rubber mixtures according to claim 1, characterized in that the copolymer is used as the oc-olefin Propylene and as diene 6-methyl-4,7,8,9-tetrahydroindene, 5,6-dimethyl-4,7,8,9-tetrahydroindene, 2-ethylidene norbornene-5, 2-isopropenylnorbornene-5 or 4-methyl- contains tricyclo (6,2,1,10 "* ') - undecadiene-4,9 3) Vulcanizable rubber mixtures according to claim 1 and 2, characterized in that they are highly unsaturated Rubber natural rubber, cis-1,4-polybutadiene, Polychlorobutarias, synthetic cis-1, /! - polyisoprene, Styrene-butadiene rubber or butadicn-acr.yl 109839/1534 contain nitrile rubber. 4) Vulcanizable rubber mixtures according to claim 1 to 3i, characterized in that they are 1 to 4 parts by weight Contain sulfur per 100 parts by weight of the elastomers in total. 5) Vulcanizable rubber mixtures according to claim 1 to 4, characterized in that they act as an accelerator serving sulfenamide in an amount of 1.3 to 3 parts by weight per 100 parts by weight of the elastomers included in total. 6) Vulcanizable rubber mixtures according to claim 1 to 5, characterized in that they are used as accelerators N-Cyclohexyl-2-benzothiazylsulfenamide, K-tert, -Butyl-2-benzothiazylsulfenamide, N-oxydiethyl-2-benzothiazylsulfenamide, N, N'-diethyl-2-benzothiazylsulfenamide or morpholine disulfide .contained. 109839/153 *