DE2658693C3 - Rubber compound that can be vulcanized in heat - Google Patents

Description

It was previously assumed that vulcanization accelerators were used in sulfur vulcanization and activators together with sulfur is essential. The vulcanization accelerator is one Substance which, if used in small quantities, can increase the extent of vulcanization and which leads to Vulcanization can reduce the required temperature and time. The accelerator is also beneficial with regard to the improvement of the physical properties of vulcanized rubber compounds, such as tensile strength or modulus, reducing blooming or improving aging resistance. The activators are substances that when used together with the vulcanization accelerators enable them to demonstrate their activities effectively and the extent of vulcanization and the affect the physical properties and aging properties of the rubber. A vulcanization with Sulfur alone without an accelerator is hardly acceptable for technical operations, because of the rate of vulcanization is lower and the vulcanized rubber compositions obtained have poor physical properties Possess properties. However, the usual accelerators must be used together with activators in order to achieve satisfactory acceleration effects, and in the absence of activators the results extremely unsatisfactory. It was therefore believed that sulfur, accelerators and Activators are the three essential components in the vulcanization of rubber compounds.

Typical examples of vulcanization pads heretofore used in the art are Guanidines, such as diphenylguanidine, aldehyde-amine, such as Condensation products of n-butyraldehyde and butylideneaniline, Aldehyde ammonia such as hexamethylenetetramine and acetaldehyde ammonia, thiazole such as 2-mercaptobenzothiazole, sulphonamides, such as benzothiazyl-2-diethyl sulfenamide and N-cyelahexyl-2-benzothiazylsulfenamide, Thiurams, such as tetramethylthiurarn disulfide and dipentamethylene thiuram hexasulfide, dithioearb-

ϊ amates, such as sodium dimethyldithiocarbamate and zinc dimethylriithioearbamate and xanthates such as sodium isopropyl xanthate. These accelerators must always be in Compound with activators, especially zinc oxide, can be used. Some of these usual Bc-accelerated

Longer are toxic and there is an interest in them Development of harmless accelerators that guarantee a high level of safety. Common activators include zinc oxide, black lead, magnesium oxide, organic amines, alkali carbonates and alkali hydroxides. Of these, zinc oxide is the best activator and it has been used in the rubber industry especially used because of the tendency for the zinc oxide to scatter around in the form of dust however, pollution problems arise. The zinc oxide added as an activator remains in the finished vulcanized rubber product and dissolves out when used. Hence the Application of zinc oxide particularly unfavorable when vulcanized rubber products in medical Therapy and for food, for example as bottle stoppers, nipples on feeding bottles or lids, be used. There is therefore an interest in the development of vulcanized Accelerators that do not require the joint use of zinc oxide as an activator.

On the other hand, it is known that when a sulfur donor used as a vulcanizing agent alone or in combination with sulfur, the simultaneous Application of zinc oxide is essential. As a result, the same problems also arise in this case with regard to environmental pollution, as described above.

In accordance with the invention, it has been found that certain amino acids have very good vulcanization accelerating effects show when the rubber compounds are vulcanized with sulfur and / or a sulfur dispenser. Surprisingly, it was there found that when using the amino acids a use of activators, which in the case of usual vulcanization accelerators are required, is avoided.

The invention relates to a mass vulcanizable in the heat, consisting of

, o (A) at least one rubber selected from styrene-butadiene, acrylonitrile-butadiene, polybutadiene, Acrylonitrile-isoprene, alfine, butadiene-methyl methacrylate, polyisoprene, acrylonitrile-butadiene-isoprene, carboxylated acrylonitrile butadiene,

-, -, propylene oxide, propylene butadiene rubber

and / or natural rubber,

(B) 0.1 to 20 parts by weight per part by weight of the compound (C) sulfur and / or usual Sulfur donors as vulcanizing agents and

μ, (C) 0.1 to 30 parts by weight per 100 parts by weight Rubber, at least one compound selected from arginine, lysine, hydroxylsine, ornithine, Proline, hydroxyproline, leucine. Isoleucine, Histidine, Tryptophan, Serine, Homoserine, Alanine, Phcnylala-

"-, nin, valine, methionine, citrulline, tyrosine, asparagine,

Aspartic acid, glutamine, glutamic acid and / or salts of these amino acids as vulcanization accelerators, which do not require an activator.

In the drawing, F g, t to 11 show vulcanization curves the rubber compositions used in the examples.

The rubbers used according to the invention are known per se. For example, styrene-butadiene rubber is a synthetic rubber that is obtained by copolymerizing styrene and butadiene by an emulsion or solution polymerization process. Acrylonitrile-butadiene rubber is mainly obtained by emulsion copolymerization of acrylonitrile and butadiene. Polybutadiene rubber is obtained by solution polymerization or emulsion polymerization of butadiene in the presence of an organometallic compound as a catalyst. Acrylonitrile-isoprene rubber is a synthetic rubber with superior instability obtained by copolymerizing acrylonitrile and isoprene. Styrene / butadiene rubber or isoprene / butadiene rubber are synthetic rubber compounds which are produced by solution polymerization using an alfine catalyst (alfin> o = alcohol + olefin). Butadiene-methyl methacrylate rubber is obtained by copolymerizing butadiene and methyl methacrylate, optionally together with a third component, such as a carboxylic acid. Polyisoprene rubber, which has a chemical composition similar to that of natural rubber, is obtained by polymerizing isoprene and includes both cis-type and trans-type. Acrylonitrile / butadiene / isoprene rubber is a ternary copolymer rubber that is made up of acrylonitrile, yes butadiene and isoprene.A carboxylated acrylonitrile / butadiene rubber is a synthetic rubber that consists of a ternary copolymer of butadiene, acrylonitrile acid and a small amount of an acidic monomer, such as Methacrylic acid j5 or maleic acid. Propylene oxide rubber and propylene butadiene rubber are each relatively new rubber compounds. Propylene oxide rubber is a copolymer of propylene oxide and allyl glycidyl ether and propylene-butadiene rubber is a block copolymer of propylene and butadiene with thermal stability and low permanent compression set. These rubbers can be used in various fields of application. Natural rubber is a naturally occurring rubber that is made up of a -r. Polymers of isoprene, and includes both natural rubber of the cis type and natural rubber of the trans type, for example gutta-percha and balata.

The rubbers listed above can -> o either in solid form or in latex form can be used according to the invention. It can also be a Mixture of two or more rubbers in a desired mixing ratio can be used. Styrene-butadiene rubber, acrylonitrile-butadiene rubber and polybutadiene rubber are particularly preferred.

The vulcanizing agent [component (B)] consists of either sulfur alone or a mixture of Sulfur and sulfur donors. The specification sulfur t, o Donor denotes a substance that contains sulfur in an active state at the vulcanization ion temperature and which can therefore be used as a vulcanizing agent for rubber compounds.

The sulfur donors are known and include, for example, sulfur compounds such as sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylohenol disulfide, N, N'-uithiobis- (hexahydro-2H-a / cpinon-2) and phosphorus-containing polysulfides, thiazole compounds such as 2- (4 ' -Morpholindithio) -benzothiazole and thiuram polysulphide compounds, such as tetramethylthiuram disulphide, activated tetrathiuram disulphide, tetraethylthiuram disulphide, tetrabutylthiuram disulphide, N ₁ N'-dimethyl-N, N'-diphenylthiuramethylpenthiuramethylenthiuramethylenthi, N'-diphenylthiuramentyculphide, D-dipetramentyculfide thiuramentyculphide, Dipamentamethylenthi, D

amethylene thiuram disulfide and mixed alkyl thiuram disulfates.

The third component (C) of the vulcanizable composition consists according to the invention of at least one of the listed amino acids or their salts and acts as a vulcanization accelerator. The salts are metal salts, preferably alkali salts, especially sodium salts.

According to the invention, arginine, lysine, ornithine and proline are particularly preferred as component (C)

In GB-PS 12 41493 halogen-containing Rubber masses described that -.;. '»Anti-singeing agent may contain an amino compound.,

It has been suggested that certain amino acids have superior vulcanization effects for brominated butyl rubber (cf. DE-OS P 25 48 5165), Epichloride rubber (DE-OS P 26 48 515.8), polybutadiene rubber with bromine at the terminals (DE-OS P 26 02 9885) and chloroprene rubber (DE-OS P 26 04 0533) and that therefore without use of other known vulcanizing agents, these vulcanizing agents consisting only of amino acids give satisfactory effects. In contrast, those indicated according to the invention show Amino acids have practically no significant vulcanization effects for those used according to the invention Rubber compounds, but show superior vulcanization acceleration effects for sulfur and / or sulfur donors, as was first established according to the invention. That according to the invention Amino acids used have a superior vulcanization accelerating effect without at the same time an activator, such as zinc oxide, is also used, is surprising. The present invention is also surprising in view of the fact that, as follows on the basis of a comparative experiment occupies, for example 3,5-diiodotyrosine, an amino acid outside the scope of the invention, at all no vulcanization acceleration effect despite their very close resemblance to the chemical structure of tyrosine, which according to the invention is used as an amino acid, shows and that, as well As shown on the basis of the comparative example, the amino acids specified according to the invention do not have any vulcanization acceleration effects for rubber materials not listed within the scope of the invention, for example Butyl caoutchouc or ethylene propylene terpolymer rubber, demonstrate.

The vulcanization of the composition according to the invention can be carried out at temperatures, for example 140 to 180 ^° C., and pressures, for example 100 to 230 kg / cm ² , which are customarily used for the various rubber compositions listed in the context of the invention.

The amino acid content in the compositions according to the invention is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight to 100 parts by weight of rubber. Of the The content of sulfur and / or sulfur donors as vulcanizing agents is 0.1 to 20 parts by weight.

preferably 0.5 to 10 parts by weight, per 1 part by weight of the entire amino acid component.

It is possible to use the usual compounding chemicals. such as reinforcing agents, processing aids. Pigments, Plasticizers, plasticizers and antioxidants for the vulcanizable compositions according to the invention to incorporate. If desired, the customary vulcanization accelerators can also be used will.

The rubber compositions according to the invention are in the various fields of application, in which the usual rubber compounds are used, usable. For example, they can be used for bicycle and Motor vehicle tires. Window frames, shoe soles, ribbons. Hoses. Pressure rollers and oil seals used will. Since the amino acids used as vulcanization accelerators are still non-toxic are and not activators, such as zinc oxide, the gcsuncliieiiSgcfdMMiCn SiHu, cfiufucrfi, 'κΰϊϊΠΟΠ the MäaSCfi according to the invention in a favorable manner as nipples on feeding bottles, stoppers for with the medicinal product Therapy and food related items. Tubes for milk and milking machines. Tapes and Hoses for food manufacture or transportation and linings for caps for beer and beer Juice bottles can be used.

The following examples and comparative examples illustrate the present invention. In every example the numerical values in the tables denote the parts by weight of the constituents.

The rubber compounds were made according to the ASTM prescribed, listed below Process made:

ASTM D15-68a Part B 17

for natural rubber and polyisoprene rubber

ASTMDI5-68aPartB 19

for styrene / butadiene rubber, polybutadiene rubber. Propylene / butadiene rubber, butadiene / methyl methacrylate rubber and propylene oxide rubber

ASTMDI5-68aPartB22

for acrylonitrile / butadic rubber, acrylonitrile / isoprene rubber, Acrylonitrile / butadiene / isoprene rubber and carboxylated acrylonitrile / butadiene rubber

The vulcanization curves of the compositions were determined using an oscillating rheometer Disc made.

Tensile strength, elongation and modulus of the vulcanized rubbers were determined according to J [S K-6301 using a tensile measuring device of the Schopper type with a withdrawal speed of 500 mm / min, through-

The determination of the hardness was carried out in accordance with JIS K-6301 using a hardness tester from Type IIS-A carried out.

example 1

Masses that contain styrene / butadiene rubber as a rubber component: rite were prepared according to the approaches listed in Table I. The crowds were vulcanized under the specified conditions using a steam press. The properties of the The vulcanized rubber compositions obtained are listed in Table I.

The vulcanization curves obtained at 170 ° C. for the masses of tests 1, 2, 9, 10 and 11 are shown in FIG. I. shown. The numbers on the curves correspond to the trial numbers.

Table I.

Experiment no.

1 2 (comp.)

Styrene butadiene rubber

SRF-L carbon black ¹ )

Alkali salt of a higher fatty acid ² )

sulfur

50% aqueous lysine solution

50% aqueous omithin solution

Arginine

Proline

3,5-diiodotyrosine

DBTD ³ )

Stearic acid

Vulcanization temperature f C)
Vulcanization time (minutes)

300% modulus (kg / cm ² )
Tensile strength (kg / cm ² )
Strain (%)
hardness

100
40
2.5
1

2.5

160
30th

50

153

670

55

100 100 100 100 40 40 40 40 2.5 2.5 2.5 - 1 1 1 2 - 2.5 - 2.5 _ _ 3

2.5

2.5

160 160 170 160 30th 30th 30th 20th 43 51 58 63 158 173 195 211 720 670 700 640 52 55 52 56

Table I (loitscl / uiii;)

Experiment no.
7 (cf.)

9 (cf.)

10 (cf.)

11 (cf.)

Styrene butadiene rubber 100 100 SRF-L carbon black ¹ ) 40 40 Alkali salt of a higher fatty acid ² ) - - sulfur 2 I. 50% aqueous lysine solution - 1.5 50% aqueous ornithine solution - - Arginine - 1.5 Proline - - 3,5-diiodotyrosine - - DBTD ¹ ) - - ZnO - - Stearic acid - - Vulcanization temperature (C) 160 160 Vulcanization time (minutes) 20th 20th 300% modulus (kg / cm ² ) 4th 53 Tensile strength (kg / cm ² ) 6th 192 Strain(%) 1360 860 hardness 38 38

100
40

100
40

160

20th

34

165

860

49

') Loaf-reinforcing furnace black with a low structure, added as a reinforcing agent.

² ) Rollability improving agent.

') Dibenzothiazyl disulfide as a common vulcanization accelerator. 2
5
1

160
20th

22nd
153
940
44

100
40
2.5
1

2.5

160
30th

5
8th

1240
36

It is clear from the test results shown in Table I that, if styrene / butadiene rubber vulcanized with a mixture of sulfur and the amino acids specified according to the invention the vulcanized rubber obtained has good properties. The vulcanization curve 1 of F i g. Fig. 1 clearly shows that the vulcanization process was very satisfactory at this point. If whereas vulcanization was carried out using only sulfur, those obtained had vulcanized rubber compounds had very poor properties (tests no. 2 and 7) and the vulcanization rate was very slow (see vulcanization curve 2 in Fig. 1). Experiment No. 11 and vulcanization curve 11 of FIG. 1 show that 3,5-diiodotyrosine, an amino acid not to be used according to the invention, no vulcanization acceleration effect at all shows case vulcanization using

50

55 of a mixture of sulfur and a vulcanization accelerator and an activator has been carried out, which is the case with current technical practice in the art (Experiment No. 11). the properties of the vulcanized rubber and the vulcanization curve 10 were both satisfactory. However, if vulcanization was carried out using sulfur and a vulcanization accelerator in the absence of an activator (Experiment No. 9), the vulcanization rate was very slow as shown by vulcanization curve 9 and the method is not technically useful. The amino acids specified according to the invention are far superior to the usual vulcanization accelerators in that they show a superior vulcanization acceleration effect in the absence of activators.

example

Using the compositions according to the approaches listed in Table II, the acrylonitrile / butadiene rubber Contained as a rubber component, the same tests as in Example i were carried out physical properties of the vulcanized rubber compositions obtained are shown in Table II. The vulcanization curves obtained at 160 ° C. for the compounds of tests 1, 2, 8 and 9 are shown in FIG F i g. 2 It can be seen from Table II and F i g. 2 that with regard to acrylonitrile / butadiene rubber the same Experimental results can be obtained as in the case of styrene / butadiene rubber.

ίο

Table II

Experiment no. 2 (cf.) 3 4th 5 6 (cf.) 7th 8 (cf.) 9 (cf.) I. 100 100 100 100 100 100 100 100 Acrylonitrile butadiene rubber 100 40 40 40 40 40 40 40 40 SRF-L carbon black ¹ ) 40 2.5 2.5 2.5 - - - - - Alkali salt of a higher fatty acid ² ) 2.5 1 I. 1 2 2 I. I. 1 sulfur 1 - - - 3 - 3 - - 50% aqueous lysine solution 2.5 - 2.5 - - - - 50% aqueous ornithine solution - - - 2.5 - - - Proline - - - - - - - 1.5 1.5 DBTD ') - - - - - - - - 5 ZnO - - - - - - - - 1 Stearic acid - 160 160 170 160 160 160 160 160 Vulcanization temperature (C) 160 30th 30th 25th 20th 20th 20th 20th 20th Vulcanization time (minutes) 30th 25th 66 48 112 13th 53 48 93 300% modulus (kg / cm ² ) 70 87 159 133 172 49 163 190 129 Tensile strength (kg / cm ² ) 156 840 620 650 450 1120 760 790 410 Strain (%) 590 49 54 52 63 52 57 57 57 hardness 55

'), ² ) and'): as in example 1.

Example 3

Using the compositions from the approaches listed in Table III, the polybutadiene rubber The same tests as in Example 1 were carried out. The properties of the obtained vulcanized rubber compositions are listed in Table III. The vulcanization curves obtained at 170 "C of the mass: n of experiments nos. 1 and 1 are shown in FIG. 3 shown. If vulcanization using

Sulfur and a conventional vulcanization accelerator without activator was carried out (Experiment No. 7). the phenomenon of blooming (whitening of the surface of rubber) considerably occurred, so that Such a vulcanization system is not suitable for technical operation. In contrast /, to this the vulcanization proceeded smoothly when a mixture of sulfur and those specified according to the invention Amino acids was used and the blooming phenomenon did not occur.

Table III attempt No. 3 4th 5 (cf.) 6th 7 (comp.) 8 (comp.) 1 2 (cf.) 100 100 100 100 100 100 100 100 40 40 40 40 40 40 Polybutadiene rubber 40 40 2.5 - - - - - SRF-L soot ') 2.5 2.5 1 2 2 1 1 1 Alkali salt of a higher fatty acid ² ) 1 1 - - - 1.5 - - sulfur 2.5 - - - - 1.5 - - 50% aqueous lysine solution 2.5 - 2.5 - - - - - Arginine - - - 3 - - - - Proline - - - - - - 1.5 1.5 50% aqueous ornithine solution - - - - - - 0.2 0.2 DBTD ³ ) - - - - - - - 5 TMTD ⁴ ) - - - - - - - 1 ZnO - - 170 160 160 160 160 160 Stearic acid 160 160 30th 20th 20th 20th 20th 20th Vulcanization temperature ('C) 30th 30th Vulcanization time (minutes)

continuation

300% modulus (kg / cm ² )
Tensile strength (kg / cm ² )
Strain (%)
hardness

'), ² ) and'): as in example 1.
) Tetramethylthiuram disulfide as a common vulcanization accelerator.

attempt No. } 4th 5 (cf.) 6th 7 (comp.) 8 (compare: I. 2 (cf.) 46 44 2 22nd 30th 22nd 25th 6th 141 157 6th 81 120 81 100 25th 650 750 1180 640 670 640 690 750 47 47 22nd 37 47 37 42 24

Example 4

Using the compositions from the batches listed in Table IV, a rubber from styrene / butad ^; Ericopolymer type contained, the> o same tests as in Example 1 were carried out. The properties of the vulcanized rubber obtained are Table IV

weights are shown in Table IV. The vulcanization curve obtained at 170 ^° C. for the masses from experiments nos. 1 and 2 are shown in table IV. In the case of the composition according to Experiment No. 4, in which 3,5-diiodotyrosine was used, foaming occurred and vulcanization could not be achieved. The physical properties could therefore not be determined.

Experiment no. 2 (cf.)

4 (cf.)

Styrene / butadiene copolymer 100 100 100 100

rubber

SRF-L carbon black ¹ ) 40 40 40 40

Sulfur 2 2 2 2

SOVoige aqueous lysine solution 3 - 1.5

Arginine - - 1.5 -

3,5-Diiodotyrosine - - - 3

Vulcanization temperature (C) 160 160 160 160

Vulcanization time (minutes) 20 20 20 20

300% modulus (kg / cm ² ) 45 4 43

Tensile strength (kg / cm) Ί70 7 Ί34

Elongation (%) 730 2800 690

Hardness 44 34 44 ') as in example 1.

Example 5

Using compositions from the approaches shown in Table V, the acrylonitrile-isoprene rubber contained as a rubber component, the same tests as in Example 1 were carried out. the Physical properties of the vulcanized rubber compositions are shown in Table V. the Vulcanization curves of the masses are shown in FIG. 5 shown.

Table V

Attempt no.
1 2 (comp.)

Acrylonitrile isoprene rubber 100 100

SRF-L carbon black ¹ ) ^ 40 40

Alkali salt of a higher fatty acid ² ) 2.5 2.5 sulfur

50% aqueous lysine solution

Vulcanization temperature (C)
Vulcanization time (minutes)
300% modulus (kg / cm ² )
Tensile strength (kg / cm ² )
Strain (%)
hardness

') and ² ) as in example 1.

Example 6

This example shows that the amino acids specified according to the invention, with the exception of those already in

V ersuc h no. 1 2 (cf) 1
2.5 1 170 170 20th 20th 46 31 120 87 830 900 60 58

Examples 1 to 5 used are superior vulcanization accelerators and the common Use of activators in sulfur vulcanization of acrylonitrile / butadiene rubber do not require.

The compositions used were prepared in accordance with the approach of Table VI A and the amino acids used are listed in Table VI B The vulcanization was carried min using an electrically heated press at 170 ° C for 30 14

The properties of the vulcanized rubber compositions are listed in Table VI B.

Table VI A

Acrylonitrile butadiene rubber SFR-RuDC) sulfur

Alkali salt of a higher fatty acid * ² ) 2 ^

Amino acid 2 ^> (1) and (2): as in example 1

Table VI B

attempt

No.

amino acids

Properties of rubbers 300% modulus tensile strength elongation (kg / cm ² ) (kg / cm ² ) (%)

hardness

1 isoleucine

2 histidine

3 hydroxyproline

4 tryptophan

5 threonine

6 serine

7 valine

8 methionine

9 tyrosine

10 alanine

11 aspartic acid

12 citrulline

13 glutamine

14 sodium glutamate

15 homosexual woman

16 without

60 54 52 48 55 48 52 42 54 53 44 58 50 54 41 21 163 151 147 163 143 143 155 134 155 136 133 146 153 162 195 115

700 650 650 730 620 690 670 740 650 630 690 620 710 680 870 1040

53 44 54 44 54 54 53 53 55 55 53 54 53 53 53 51

Example 7

The compounds of the formulations listed in Table VII, which contained styrene / butadiene rubber, were vulcanized using a sulfur dispenser as a vulcanizing agent at 160 ° C for 20 minutes The properties of the vulcanized rubber compositions are listed in Table VIl.

Table VII Attempt no. 2 (cf.) 3 (cf.) 1 100 100 100 40 40 Styrene butadiene rubber 40 3 3 SRF-L carbon black ¹ ) 3 - - TETS ² ) 6th 50% aqueous - 5 Lysine solution - _ 1 ZnO _ Stearic acid

Attempt no.

1 2 (comp.) 3 (comp.)

300% modulus (kg / cm ² )
Tensile strength (kg / cm ² )
Strain (%)
hardness

38 4

155 5

850 1520

53 40

44 187 750 53

') as in example 1.

² ) Tetraäthylthiuramdisulfid as a sulfur donor.

As can be seen from the experimental results shown above, even if the vulcanization is below If only a sulfur donor is used, the rubber obtained is very poor Properties. However, if an amino acid is also used, the result obtained is equivalent to that obtained when ZnO and stearic acid are used together as in common practice be used. As a result, the dangerous ZnO can be replaced by non-toxic amino acids.

Example 8

Using the compositions from the batches listed in Table VIII which contained natural rubber,

the same tests as in Example 1 were carried out. The properties of the vulcanized obtained Rubber compounds can be seen from Table VIII The at 160 ° C from the compounds according to the The vulcanization curves obtained in experiments nos. 1,4 and 5 are from FIG. 6 can be seen. It can be seen from FIG. 6, that the mass according to Experiment No. 4 was slow in terms of vulcanization. In case the vulcanized Rubber compositions from Experiment No. 4 were left to stand for 1 or 2 days, significant blooming occurred on and vulcanization using sulfur alone in the absence of activators and Accelerators were technically quite useless. In contrast, the vulcanization could take Use of a mixture of sulfur and the specified amino acids (experiments No. 1 to 3) smoothly in the absence of activators, such as zinc oxide,

Table VIII

are executed. Show modulus and tensile strength of the vulcanized rubber compositions obtained a great improvement and no blooming occurred.

In experiment no. 5, in which sulfur is combined with 3,5-diiodotyrosine, which is not among the amino acids according to the present invention, the rate of vulcanization increased to a greater extent than in the case of the application of sulfur alone and the properties of the vulcanized Rubbers were deteriorated. This is clear from the test results shown in Table VIII and the vulcanization curves shown in FIG. Furthermore, that obtained in Experiment No. 5 showed vulcanized rubber had the same bloom as the vulcanized rubber of Experiment No. 4.

Search no.

4 (cf.)

5 (cf.)

Natural rubber 100 SRF-L, carbon black ¹ ) 40 sulfur 3 50% aqueous lysine solution 1.57 Histidine 3.43 Tyrosine - Glutamic acid - Arginine - 3,5-diiodlyrosine - Vulcanization temperature (C) 160 Vulcanization time (minutes) 30th 300% modulus (kg / cm ² ) 33 Tensile strength (kg / cm ² ) 162 Strain (%) 680 Mars 42 ') lsi the same as') from Example I.

100

40

1.45

1.78
1.78

160 30th

34 178 690 42

100

160
30th

28
128
640
36

100

40

2.5 160 30

12 68 610

27

Example 9

Using compositions of the approaches listed in Table IX, which are an acrylonitrile-biladiene-isoprcn-Kaiitschuk contained as a kaulschtik component, the same tests as in Example 1 were carried out. The properties of the vulcanized obtained Rubbers are shown in Table IX and the vulcanization temperatures of the compositions obtained at 16 (TC The tests No. 1, 2 and 3 are shown in FIG. 7 shown. It is clear from the values obtained that the the same results as in Example I were obtained.

Table IX

Vcpsucli no I 2

.1 (cf.)

Acrylnilril-Uulailicn-Isoprciikaulsdnik

SKF-I .. KuU ¹ )

KHl 100 KKI search no.

I 2. '(Cf.)

4 (1

40

40

Sulfur 2 1 2

507 aqueous lysine solution 3 - -

50% aqueous - 3

Ornithine solution

Vulcanization temperature (C) 160 160 160

Vulcanization 7cit (minutes) 20 20 20

300% modulus (kg / cnv) 155 153 23

Tensile strength (kg / cnr) 155 208 80

Elongation ("/") 3 (H) 430 470

Märte 67 65 56) as in example I.

Hi-ι s |) ic-l IO

I inier application of the im den in lalu'lle X

listed salts auiuefülen masses, you · one

26 58 17th III Experiment no. 693 18th Alkali salt of a higher one Attempt no. Versucn-INr 2 3 (Verg |.) 2, ') I 12 at 160 "C as in MVcrgl.) Table XII. carboxylated acrylonite-butadiene rubber as chewing 1 2 3 (comp.) Fatty acid") I 2 I. Crowds from the KX) tscbuk component contained were the same 50% aqueous lysine solution Polyisoprcnkiiutschuk 100 KK) 2.5 2.5 G. 9 listed. 40 Experiments as carried out in Example I. These properties Arginine SRF-L, soot ') 40 40 2.5 160 IW) 3 tf * n of fulfilling vulknniiierlpn Kniitcphiilf micc ^ n Carboxylated acrylonitrile- 100 100 100 ^r> Threonine Sulfur 3 3 2.1 - 20 20 I. result from Table X and the ί obtained at 160 ° C Butadiene rubber Vulcanization temperature (C) Alkaline / a higher I I 2.5 - - 27 21 .5 Vulcanization curves of the masses from the tests SRF-L, carbon black ¹ ) 40 40 40 Vulcanization time (minutes) I'ellic acid- ') 2.5 2.9 - Iftl 157 KK) ■ - Nos. I and 3 are from FIG. 8 can be seen. Sulfur 2 2 2 300% modulus (kg / cm- ¹ ) 5 ()% aqueous lysine solution 2.1 2 ,! - 150 160 750 7'JO 40 - Table X Tensile strength (kg / cm ') Isoleucine 2, ') 160 20th 20th 40 3X 3 - Strain (%) Tryptophan - 2.9 20th 99 10 I. - hardness Leucine 132 199 27 ') and ") as in Example I. (ilulamin 220 540 1790 l, fi - Example 11 (ilutaniiiisiiure. 490 60 51 - - Using the approaches according to 2> Arginine 66 - IW) Table Xl listed masses, the polyisoprene rubber VulkiinisiilionslemperaUir (() IW) iW) - 20th contained chuk as a rubber component Vulkanisalions / eil (Mhniieii) 20 20 Properties of the vulcanized rubber obtained 13th the same experiments as in Example I carried out. the 3IK)% - Moilul (kg / cm ') 2' »21 masses are given in Table Xl and the 1.7 SO Table Xl Tensile strength (kg / cm ') 173 160 obtained vulcanization curves of the 1.7 740 Elongationf%) 7W) 830 Try No. I uiiviö are in F IW) 28 lliirte 40 40 20th ¹ I mill I as in example I. I ') i. I) c ι s ρ i ι .1 \ 154 Example I. i
II Inter application of the in the Ansat / en \ m \ lahellc 100 100 XIO the preserved volcanic i XIl .iiifgcfi'ihrtcn masses containing a butadiene methyl 40 40 .U) Safe rubbers result from the I meiliai'rylalkuulschuk as Kiiiilschiikkompcnenle developed 3 3 I I stopped, the same attempts were made 2.1 2.1 executed. The Kigcnscliaflcn - 2, '»

Table XU Experiment no. 2 3 (cf.) I. 100 100 100 Methyl methacrylate butadiene 40 40 rubber*) 40 2 2 SRF-L, carbon black ¹ ) 2 2.5 2.5 sulfur 2.5 Alkali salt of a higher one - - Fatty acid-') 2.5 50% aqueous ornithine 2.5 - solution - 160 160 Methionine 160 20th 20th Vulcanization temperature (C) 20th 139 125 Vulcanization time (minutes) 149 194 167 300% modulus (kg / cm- ') 198 460 450 Tensile strength (kg / cm ¹ ) 390 70 67 Strain (%) 67 hardness

Vcisiich no.
I 1

3 <compare)

l'ropylene oxide
SKI-L, cult ¹ )

100
40

100
40

KX)
40

*) Solid rubber, obtained through complete drying at room temperature from a latex made from methyl methacrylut-Buladiene rubber with a total retention rate of 40%.

¹ I and Ί as in example I.

Ii e i s ρ i c I IJ

Using the masses given in the batches listed in Table XIII, the l'ropylenoxydkaulschiik as rubber components were the same experiments as in Example I executed. The properties of the vulcanized rubber compositions obtained are shown in Table XIII and the viilcanization curves obtained at 160 "C the masses from experiments no. 2 and i are shown in FIG. 10ge. .-igt.

Table XIII

20th

Experiment no. I.

3 (veri> l.)

Sulfur 1.5 1.5 1.5

50% aqueous lysine solution 3 - -

50% aqueous ornithine - 3 solution

Vulcanization temperature (C) 160 160

Vulcanization time (minutes) 30 30

300% modulus (kg / cm ³ ) 50 43

Tensile strength (kg / cnr) 24 71

Elongation (%) 420 500 1080

Hardness 48 46 ') as in the example

example

Rubber stocks were prepared according to the approaches shown in Table XIVA and under the conditions set out in Table XIVA using those set out in Table XIVB Amino acids not used in Example 13 were vulcanized. The properties of the vulcanized rubber compounds are shown in Table XIV B.

Table XIVA

l'ropyleno.x id rubber *) SKF-L, carbon black ¹ ) Sulfur Λ: Potash salt of a higher fatty acid ') Amino acid (see table XIV H) Vulcanization temperature (C) Vulcanization time (min)

*) as in example

') and') as in example

Experiment no. U Ill 100 KX) 40 40 1.5 1.5 2.5 2.5 - 2.5 160 160 10 30th

Table XIVB V'iTsia h-Nr \ miiios.iiire

Leucine

Proline
Arginine
CiIuI. imin
1> raisin
Valine
Isoleucine iiieMsL'hallen the vulcanized rubber compounds i (HI \, module / upleslitihcit Dehnung Harte

(kg / cm ') (kg / cm') ("■ ..)

120

Tl

76

74

III

100

1240 36 470 18th 580 44 1240 34 1,180 38 1250 36 1240 12th

Versiicli no. amino acid

ίμΐΊΐΜ'ΙιΐιΓίοιι the wilkanisierlcn K; ui! st

.'IHl -ΜικΙιιΙ / iiplcslijikeil ΙΚΊυκιημ lliirli ·

Ikp / ain Ikp / inn Cl

8th Methionine 25th 90 X20 41 9 l'hem! alanin 27 99 910 40 IO Homoser 2 ⁽ l 88 X40 42 Il 3.5-I) i.j (hold> raisin (l IX 1170 2X (Comparison) 12th without 4th K 1110 2X (Veruleich)

nι ■ ^^ | ιι ^

I inter application of materials obtained from ilen masses gemab ¹ Table XV, the Propvlcr butadiene kiiiilsclink as Kaulschukkomponente enthi'Ilen, the same experiments as in lieispiel I ausgeführi. The groups of milkanisierien kaiilschiikniassen are given in Table XV. The dilution curves of the compounds of experiments No. I and h (comparison) obtained for IhO (comparison) are shown in Ig. 11.

I dragonfly XV

l'rop> len-IUJtadienkaiilsehuk

SKII. RuIV)

Sehwelel

^ς Ο ige watery. Ornithine solution

50 ¹ ■ aqueous solution of vsin

Arginine

(ilutaniinpasle ι

I listidin

V ulkiinis.ition temperature ( <ι

V Lilkani> ations / eit (minute length

'IKi module (kg / uii)
/ uglyness (kg / em I
I) -jh η u ng ( ¹ I.
I la rl:

ι «ι ·: in licr.picl 1

ί (ilut.imin mil 25 \ ^. issiTEL-liH

\ er

) <\ Ί.τμΙ.)

KK) ΙΟΙ) loo ΙΟΙ) 100 KK) 40 40 4 (1 40 40 40 1.5 1.5 1.5 1.5 1.5 1.5 .1 τ 2.1 _

K) O 160 - 0.9 IW) K) O M) M) K) O 160 M) M) (-1 >: .1 (1 M) 10 Wi 14 ') 146 18th 68 102 116 54Π 5S0 K) (I. 142 1410 490 5 X s "7 1110 5 (K) 4λ 58 50 58

Comparative example I.

This comparative example / cig; that the in the frame the I.rfindiing specified amino acids not the same VulkanisaHonsbeschlcunigungsT.ffekle for others Rubber compounds than they are according to the invention are. 7cigcn.

Masses from those listed in Table XVI Salting, which either a Fiunlkaulschuk or an Ethy'en / Prop.lcri Tcrpoi.nicrkauischiik as Contained Kaiitschiikkornnonente were advocated Method of AST MDl 5-fi8a. Part Ii 2i liergcstclli and then aul 17 (1 (for 30 min crliit / t. Is was found, dal !, while a vulcanized Good quality rubber mi! the Viilkanisalinnss \ stem gcmäH experiment no. 6 as it is usually done in technical operation is applied. Mixtures of sulfur and the amino acids VuikaiiiSiiiiiMi üiciii initiate.

23 24

Table XVI

Attempt no.

12 3 4

Butyl rubber 100 100

Ethylene / propylene terpolymer rubber - - 100 100 100 100

SRV-I., Carbon black ¹ ) 40 40 40 40 40 40

Alkaline salt of a higher fatty acid ² ) 2.5 2.5 5 5 5 5

Sulfur 1 1

50% aqueous lysine solution 2.5

50% aqueous ornithine solution - 2.5

Arginine

Stearic acid

100 100 100 40 40 40 5 5 5 1 1 1 5 _ 5

Tensile strength (kg / cm ² ) can ^{not be} determined I ₉₃

Elongation (%) 660

Hardness 53

¹ I and ² ) have the same meanings as ') and ■') in Example 1.

In addition 6 sheets of drawings

Claims (1)

Claim; In the heat vulcanizable mass, consisting of (A) at least one rubber selected from styrene-butadiene, acrylonitrile-butadiene, polybutadiene, Acrylonitrile-isoprene, alfine, butadiene-methyl-methacrylate, polyisoprene, acrylonitrile-butadiene-isoprene, carboxylated acrylonitrile-butadiene, propylene oxide, propylene-butadiene rubber and / or natural rubber, (B) 0.1 to 20 parts by weight per part by weight of the compound (C) sulfur and / or usual Sulfur donors as vulcanizing agents and (C) 0.1 to 30 parts by weight per 100 parts by weight of rubber, at least one compound from arginine, lysine, hydroxylysine, ornithine, proline, hydroxyproline, leucine, isoleucine. Histidine, tryptophan, serine, homoserine, alanine, phenylalanine, valine, methionine, citrulline, Tyrosine, asparagine, aspartic acid, glutamine, glutamic acid and / or salts of these amino acids as vulcanization accelerators that do not require an activator.