DE2658693A1 - HAIRABLE RUBBER MASS - Google Patents

Description

The invention is concerned with a new and superior vulcanization accelerator for use in the vulcanization of a variety of rubbers such as Styrol-Butadienkautsch.uk (SBR) -, acrylonitrile-butadiene rubber (NBR) ₁ J polybutadiene rubber (BR), acrylonitrile-isoprene rubber (NIR) , Alfin rubber (AR), butadiene methyl methacrylate rubber (MBR), polyisoprene rubber (IR), acrylonitrile butadiene isoprene rubber (NBIR), carboxylated acrylonitrile butadiene rubber (CNBR), propylene oxide rubber (POR), propylene butadiene rubber (POR) ) or natural rubber (NR.) with sulfur and / or eir-e? · sulfur donor.

The rubbers listed above are now quite commonly used in the rubber industry, and so are these Rubbers are süaitliche with sulfur as the main hardening

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medium hardened. If desired, the thermal To improve the durability and aging resistance of vulcanized rubber, the use of a sulfur donor becomes Recommended as a hardness remedy. In numerous cases the sulfur donor is used in combination with sulfur.

It has been previously assumed that the use of curing accelerators and activators together with sulfur is essential in sulfur vulcanization. The vulcanization accelerator is a substance which, if used in small amounts, increase the degree of vulcanization and can reduce the time required for vulcanization temperature and time). The accelerator gives another favorable result, for example, improving the physical properties of vulcanized rubbers such as tensile strength or modulus, preventing blooming or improving aging resistance. The activators, on the other hand, are substances which, if used together with the vulcanization accelerators, enable the vulcanization process to take place. . They tend to show their activities effectively and affect the rate of vulcanization and the physical properties and aging properties of the rubber. Vulcanization with sulfur alone without an accelerator is hardly acceptable in industrial operation because the vulcanization rate is low and the vulcanized rubbers obtained have poor physical 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 are extremely unsatisfactory: .snd. For this reason it was assumed in the rubber industry that sulfur, accelerators and activators are the three essential elements in the vulcanization of rubbers.

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Typical examples of vulcanization accelerators that have heretofore been used in the art are guanidines, such as diphenylguanidine, aldehyde amines, such as condensation products of n-butyraldehyde and butylideneaniline, aldehyde ammonia, such as hexamethylenetetramine and acetaldehyde ammonia, thiazoles, such as 2-mercaptobenzothiazole, sulfenamides, such as benzothiazyl-2-diethylsulfenamide and N-cyclohexyl-2-benzothiazylsulfenamide, Thiurams, such as tetramethylthiuram disulfide and dipentamethylene thiuram hexasulfide, Dithiocarbamates, such as atrium dimethyldithiocarbamate and zinc dimethyldithiocarbamate and xanthates such as sodium isopropyl xanthate. All of these accelerators must be used in conjunction with activators, mainly zinc oxide. Some of these usual Accelerators have known or suspected toxicity, and from an environmental pollution control point of view the development of harmless accelerators with a high degree of safety is desired.

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 has practically all of its inclusion in the rubber industry. However, zinc oxide tends to be scattered as dust, and its use is unfavorable to the health of workers. The zinc oxide added as an activator remains in the finished vulcanized rubber product and dissolves out during use. Therefore, the use of zinc oxide is particularly unfavorable when vulcanized rubber products are used in medical therapy and food related applications _; For example, they can be used as bottle stoppers, nipples on feeding bottles or cover linings. It is therefore very beneficial to develop accelerators that do not share the common

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require the use of activators of the zinc oxide type.

On the other hand, it is known that if a sulfur donor as hardeners · either alone or in combination Used with sulfur, the common application of zinc oxide is essential. As a result, the same hygiene problems also arise in this case.

It has now been found that specific amino acids show very good vulcanization acceleration effects when the above rubbers with sulfur and / or a Sulfur donor can be vulcanized and surprisingly becomes completely common in the application of the amino acids The use of activators, which is essential in the case of the usual vulcanization accelerators, is avoided.

The invention relates to a vulcanizable composition (A) at least one rubber from the group of styrene-butydiene rubber (SBR), acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), acrylonitrile isoprene rubber (NIR), AIfinkaut schuk (AR), butadiene methyl methacrylate rubber (MBR), polyisoprene rubber (IR), acrylonitrile-butadiene-I soprene rubber (NBIR), carboxylated acrylonitrile butadiene rubber (CNBR), propylene oxide rubber (POR), propylene butadiene rubber (PBR) and natural rubber §TR), (B) one made up of sulfur and / or a sulfur donor Curing agent and (C) at least one compound the group of arginine, lysine, hydroxylysine, ornithine, Proline, hydroxyproline, leucine, isoleucine, histidine, tryptophan, threonine, serine, homoserine, alanine, phenylalanine, valine, Methionine, citrulline, tyrosine, asparagine, aspartic acid, glutamine, glutamic acid and salts of these amino acids.

The ".Fig. 1 to 11 show the vulcanization curves of rubber compounds used in the examples.

The different as the first component of the mass according to The rubbers used in the invention are all

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known. A styrene-butadiene rubber (SBR) is specific a synthetic rubber produced by copolymerization of Styrene and butadiene by an emulsion or solution polymerization process get vmrde. An acrylonitrile butadiene rubber (NBR) is a synthetic rubber produced mainly by emulsion copolymerization of acrylonitrile and butadiene was obtained. A polybutadiene rubber (BR) is a synthetic rubber produced by solution polymerization or emulsion polymerization of butadiene was obtained in the presence of an organometallic compound as a catalyst. An acrylonitrile isoprene rubber (NIR) is a synthetic rubber with superior oil resistance obtained by copolymerizing acrylonitrile and isoprene became. An alfin rubber is a synthetic rubber, that by solution polymerization using a Alfin catalyst is produced and it is divided into styrene / butadiene copolymers and isoprene / butadiene copolymers. A butadiene methyl methacrylate rubber (MBR) is a synthetic rubber, which is produced by copolymerization of butadiene and methyl methacrylate, optionally together with a third component such as a carboxylic acid. A polyisoprene rubber (IR) is a synthetic rubber with a chemical composition similar to that of natural rubber obtained by polymerizing isoprene has been and includes both the cis-type and the trans-type. An acrylonitrile / butadiene / isoprene rubber (NBIR) is a ternary copolymer rubber made from acrylonitrile, butadiene and isoprene is built up. A carboxylated acrylonitrile / Butadiene rubber (CNBR) is a synthetic rubber made from a ternary copolymer - butadiene, acrylonitrile and a small amount of an acidic monomer such as acrylic acid, Methacrylic acid or maleic acid. A Propylene oxide rubber (POR) and a propylene butadier /: autschuk (PBR) are relatively new rubbers. POl- is

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a copolymer of propylene oxide and allyl glycidyl ether and PBR is a block copolymer made from propylene and butadiene with thermal stability and low permanent press hardening. They can be used as rubbers with various fields of application. Natural rubber is a natural Occurring rubber, which is built up from a polymer of isoprene, and includes both natural rubbers of the cis type as well as trans-type natural rubbers, for example Gutta-percha and balata.

The various rubbers listed above can be either in solid form or in latex form as rubber components the masses can be used according to the invention. Furthermore, two or more of these rubbers can be used as a mixture can be used in a desired mixing ratio. Of these rubbers, styrene-butadiene rubber (SBR), Acrylonitrile butadiene rubber (NBR) and polybutadiene rubber (BR) are particularly preferred.

The curing agent as the second component is either sulfur alone, a sulfur donor alone, or a mixture from sulfur and sulfur donor. With Schwefeldonor one becomes Substance denotes / et, which releases sulfur in the active state at the vulcanization temperature and which therefore acts as a hardening agent can be used for rubbers.

The sulfur donors are known and include, for example, sulfur compounds such as sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol ^{disulfide, Ν, Ν 1} -dithiobis- (hexahydro-2H-azepinone-2) and phosphorus-containing polysulfides, thiazole compounds such as 2- (4 -'- morpholinedithio) -benzothiazole and thiuram polysulfide compounds, such as tetramethylthiuraradici'ilfid, activated tetrathiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N'-dimethyl-N, U ¹ -diphenylthiuramdisulfide, diphenylthiuram-disulfide, diphenylthiuram-disulfide thi, diphenylthiuram-disulfide, diphenylthiuram-disulfide, diphenylthiuram-disulfide, diphenylthiuram-disulfide,

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pentamethylene thiuram hexasulphide, Di eye lop en t am ethyl enthiuram disulphide and mixed alkylthiuram disulfides.

The third component of the masses according to the invention consists 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, stronger preferably sodium salts.

Of the amino acids specified in the context of the invention, arginine, lysine, ornithine and proline are particularly preferred.

It has been suggested that certain amino acids have superior curing effects for brominated butyl rubber (Japanese patent application 124031 / 74-), epichlorohydrin rubber (Japanese patent application 124O32 / 74-), Polybutadiene rubber with bromine at the terminals (Japanese Patent application 11407/75) and chloroprene rubber (Japanese patent application 13329/75) and that therefore without joint use of other known hardening agents} the hardening agents composed only of amino acids give completely satisfactory effects. In contrast to this, the amino acids indicated in the context of the invention show practically no significant curing effects for the rubbers used according to the invention, but rather show superior vulcanization acceleration effects for sulfur and / or sulfur donors. This thing was under the Invention discovered for the first time. In particular, the fact that the amino acids specified in the context of the invention as a curing agent, a superior vulcanization accelerating effect without joint application of an activator, such as zinc oxide, is surprising and can show off cannot be derived from previous knowledge. The present invention is also surprising from the point of view of the fact that, as follows on the basis of a comparison

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Suches occupies, for example, 3 »5-Diiodotyrosine, an amino acid outside the scope of the invention, at all no vulcanization acceleration effect despite their extreme similarity of chemical structure to tyrosine, one Amino acid in the context of the invention shows and that, as shown in the following comparative example, the in the context of Amino acids specified in the invention do not have any vulcanization acceleration effects for rubbers not listed in the context of the invention, for example butyl rubbers or Own EPDM rubbers.

The vulcanization of the composition according to the invention can

at temperatures, e.g. 140 to 180 ° C, and pressures,

ο
for example 100 to 230 kg / cm, which are usually used for the various rubbers 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 up to 10 parts by weight per 100 parts by weight of the total rubber content. The content of sulfur and / or sulfur donor as hardening agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per part by weight of the total amino acid content.

It is possible to use the usual compounding chemicals, such as reinforcing agents, processing aids, pigments, To incorporate plasticizers, plasticizers and antioxidants into the curable compositions according to the invention. Desired The usual vulcanization accelerators can also be used can also be used.

The rubber compositions according to the invention have utility in various fields of application where common rubbers are used. For example, can them as bicycle and. Motor vehicle tires, window frames, Shoe soles, belts, hoses, pressure rollers and oil seals can be used. Since the vulcanization

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Amino acids used more quickly are non-toxic and do not contain activators, such as zinc oxide, which are harmful to health are, require, the masses according to the invention can be used in a favorable manner as nipples on feeding bottles, stoppers for associated with drug therapy and food Articles, tubes for milk and milking machines, tapes and hoses for food manufacture or transportation and linings can be used for caps of beer and juice bottles.

The following examples and comparative examples illustrate the present invention. Designate in each example the numerical values in the tables are the parts by weight of the components.

The rubber compounds were produced according to the following procedures stipulated by ASTM:

ASTM D15-68a Part B 17 ASTM D15-68a Part B 19

ASTM D15-68a Part B 22

for NR and IR

for SBR, BR, PBR, MBR and POR

for NBR, NIR, NBIR and CNBR

The vulcanization curves of the masses were determined using an oscillating disk rheotaeter (TSS type) manufactured.

Tensile strength, elongation and modulus of the vulcanized Rubbers were prepared in accordance with JIS K-6301 using a Draft measuring device of the Schopper type with a withdrawal speed of 500 mm / min.

The determination of the hardness was made according to JIS K-6301 carried out using a JIS-A type hardness tester .

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example 1

Compositions containing SBR as a rubber component, were prepared according to the approaches listed in Table I. The haters were vulcanized under the specified conditions using a steam press. The properties of the vulcanized rubbers obtained are shown in Table I.

Λ the cure curves obtained at 170 ° G of the compounds of Experiment Nos. 1, 2, 9, ₅ 10 and 11 are shown in Fig.. The digits on the curves correspond to the experimental digits.

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1 2
(Cf. - Tabel ) 100 - 4th I. 5 - 6th - 3 - 7th
(Cf. 2 - 8th
) 9 10 11
(Comp.) (Comp.) (Comp.) 100 100 Experiment no. 100 100 - 40 2.5 100 100 - 100 - 100 - 100 100 40 40 Styrene-butadiene rubber 40 40 - 2.5 - 40 40 - 40 40 - 40 40 - 2.5 SRF-L-Russ ^ 2.5 2.5 - 1 2.5 2.5 2.5 - - - - - 1 1 TE- 58A ^ ' 1 1 1 1 2 1 1 - - sulfur 2.5 2.5 1.5 - - 50% aqueous lysine solution - - - - - - 50% aqueous ornithine solution - 2.5 1.5 - - - Arginine - - - - Proline

3,5 diriodotyrosine

ZnO
Stearic acid

Vulcanization ^{temperature (0} C) 160 160

Vulcanization time (minutes) 30 30

300 module (kg / cm ² ) 50 6

Tensile strength (kg / cm ² ) 153 13

Elongation (%) 670 1360

Hardness 55 40

160 170 160 160 160 160

30 30 20 20 20 20

51 58 63 4 53 34

173 195 211 6 192 165

670 700 640 1360 860 860

55 52 56 38 38 49

160 20

22nd

153

940

44

co cn co cn

Footnotes:

(1) JSR SBW 1502 ^, a product of Japan Synthetic Rubber Co., Ltd.

(2) Low structure semi-reinforcing furnace carbon black, added as a reinforcing agent.

(3) Higher fatty acid alkali salts from Technical Processing Company, U.S.A., added as a rolling mill sverb it ser er.

(4-) Dibenzothiazyl disulfide as a common vulcanization accelerator.

It is clear from those listed in Table I. Experimental results that if SBR with a mixture of Sulfur and the amino acids specified according to the invention is vulcanized, the vulcanized rubber obtained has good properties. The vulcanization curve 1 of Fig. 1 clearly shows that the course of vulcanization to was very satisfactory at this point. If on the other hand vulcanization was carried out using only sulfur, those obtained had vulcanized ones Rubbers had very poor properties (Trials Nos. 2 and 7) and the rate of vulcanization was very high slowly (see vulcanization curve 2 in Fig. 1). Test No. 11 and vulcanization curve 11 of FIG. 1 show that 3,5-Diiodotyrosine, one not listed according to the invention Amino acid, no vulcanization accelerating effect at all shows. If- vulcanization using a mixture of sulfur and a vulcanization accelerator and an activator, which is the case with current technical practice in the art (Experiment No. 11), the properties of the vulcanized rubber and the vulcanization curve were 10, respectively satisfactory. If, however, the vulcanization using of sulfur and a vulcanization accelerator in the absence of an activator (Experiment No. 9)

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the rate of vulcanization was very slow, how through. Vulcanization curve 9 is shown and the process is not technically useful. The specified according to the invention Amino acids are far superior to the usual vulcanization accelerators in that they are superior to one Show vulcanization acceleration effect in the absence of activators.

Example 2

Using the masses according to the approaches listed in Table II, which contain NBR as a rubber component, the same tests as in Example 1 were carried out. The physical properties of the obtained vulcanized rubbers are shown in Table II. The vulcanization curves of the compounds obtained at 160 ° C of Trials Nos. 1, 2, 8 and 9 are in Pig. 2 shown. It can be seen from Table II and FIG. 2 that, with regard to NBE, the same test results as in Case can be obtained from SBR.

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O to OO

Experiment no.

Acrylonitrile Butadiene Rubber (NBR) " ¹ ^

■ SEjT-L-Eus

Sulfur 50% aqueous lysine solution 50% aqueous ornithine solution Proline

Table II _ 3 '' 0 100 _ 4th _ 5 2 6th CVJ _ 7th 1 8th 1 ) 9 1 _ ) 1 2 ' 40 3 (Cf.] 3 (Cf. (Cf. (Cf. 2.5 100 100 100 100 100 100 100 100 1 40 40 40 40 40 40. 40 40 2.5 - - - - - 2.5 2.5 1 1 1 2.5

2.5

1.5

ZnO stearic acid

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

Vulcanization temperature ( ⁰ G) 160 160 160 170 160 160 160 160 160 Vulcanization time (minutes) 30 30 30 25 20 20 20 2o 20

70 25th 66 48 112 13th 53 48 93 2658693 156 87 159 133 172 49 163 190 129 590 840 620 650 450 1120 760 790 410 55 49 54 52 ■ 63 52 57 57

Footnotes :

(1) Polysarkrynac 34-50 ^, NBR from Polysar Ltd.

(2), (3) and (4): as in example 1

Example 3

Using the hates from those listed in Table III The same tests as in Example 1 were carried out for batches containing BR. The properties of the vulcanized rubbers obtained are shown in Table III listed. The vulcanization curves obtained at 170 ° C of the masses of Runs Nos. 1 and 1 are shown in FIG. In the case of vulcanization using sulfur and a customary vulcanization accelerator was carried out without activator (experiment ITr. 7) Appearance of efflorescence (whitening of the surface of the Rubber), 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 were used Amino acids was used and the blooming phenomenon did not occur.

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1 2 - Tabel O 100 - ' III 2 - 5 2 - ■ 6th 1 7th 1 - 8th 1 - Experiment no. (Cf. - 3 40 '- ••• 4 - (Cf.) - 1.5 (Cf.) - (Cf.) - 100 100 2.5 2.5 100 MS 100 1.5 100 100 Polybutadiene rubber (BR) ^ / 40 40 1 100 40 40 40 40. SRF-L-Russ ^ 2.5 2.5 40 - - - - TE-58A ⁽⁵⁾ 1 1 -. sulfur 2.5 50% 8ge aqueous lysine solution 2.5 Arginine mm Proline

° 5 "J0% aqueous ornithine solution

Z ^Zn0

° stearic acid

4S.

1.5

0.2

1.5

5
1

Vulcanization ^{temperature (0} C) Vulcanization time (minutes)

160 160 30th 30th 25th 6th 100 25th 690 750 42 24

160
20th

160
20th

160
20th

160
20th

300% modulus (kg / cm ² ) tensile strength (kg / cm) elongation (%) hardness

46 44 2 22nd 30th 141 157 6th 81 120 650 750 1180 640 670 47 47 22nd 37 47

640.

to cn co

Footnotes:

(1) JSR BREAD ³ ', product of Japan Synthetic Rubber Co., Ltd. (2), (3), W'- as in example Λ

(5) Tetramethylthiuram disulfide as a common vulcanization accelerator.

Example 4

Using the compositions from the batches listed in Table IV, which contained an alfine rubber (AR) as the rubber component, the same tests as in Example 1 were carried out. The properties of the vulcanized rubbers obtained are shown in Table IV. The vulcanization curve obtained at 170 ° C. for the compositions from tests Nos. Λ and 2 are shown in Table IV. In the case of the mass after the attempt by Mr. 4- using 3,5-diQOdtyrosine, foaming occurred and vulcanization could not be achieved. The physical properties could therefore not be determined.

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/ J.

Tabel Attempt no. 1 - 20th IV _ 3 4th
(Cf.) _ 3 Alfin rubber (AS) ^ ^{1 )} 100 - 45 2
(Cf.) - 100 100 - 160 SRF-L-Russ ^ 40 Vulcanization temperature
(° C) 160 170 100 - 40 40 20th sulfur 2 Vulcanization time
(Minutes) 730 40 160 2 2 - 50% aqueous lysine
solution 3 300% modulus (kg / cm ² ) 44 2 20th 1.5 - Arginine Tensile strength (kg / cm) 4th 1.5 - 3,5-Di j ο dtyrοsin Strain (%) 7th - - hardness 2800 160 1 The snoten: 34 20th 43 134 690 44

(1) JSR AL 3778 ^ (styrene / butadiene type) product of Japan Synthetic Rubber Co ,, Ltd.

(2) V / ie in example 1.

Example 5

Using compositions from the approaches shown in Table V, the. Acrylonitrile-I soprene rubber (NIR) as Containing rubber component, the same tests as in Example .1 were carried out. The physical properties of the vulcanized rubbers are shown in Table V. The vulcanization curves of the masses are in Fig. 5 shown.

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Table V

Experiment no. 1 (cf.)

Acrylonitrile isoprene rubber

(NIR) (i) 100 100

SHF-L-Russ ^ 40 40

Te-58A ^ 2.5 2.5

Sulfur 1 1

50% aqueous lysine solution 2.5

Vulcanization ^{temperature (0} C) 170 170

Vulcanization time (minutes) 20 20

300% modulus (kg / cm ² ) tensile strength (kg / cm) elongation
hardness

46 31 120 87 830 900 60 58

Footnotes:

(1) Polysar Krynac 833% acrylonitrile / isoprene rubber der Polysar Ltd.

(2) and (3) 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 the Examples 1 to 5 used, are superior vulcanization accelerators and the joint use of Activators in the sulfur vulcanization of NBR are not require.

The masses used were prepared according to the approach in Table VIA and the amino acids used are listed in Table VIB. The vulcanization was

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using an electrically heated press 170 ° C carried out for 30 minutes. The properties of the vulcanized rubbers are listed in Table VIB.

Table VIA

Acrylonitrile butadiene rubber

(NBR) (1) 100

SEF-L-Russ ^ 40

Sulfur 1

Te-58A ^ 2.5

Amino acid 2.5

Footnotes:

(1), (2) and (3): as in example 1

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at·

Table VIB

Ver amino acids (kg / cm properties Example 7 the rubbers hardness search
No. 60 Qdul Zugfe-
² ) sturdiness
(kg / cO strain 53 1 Isoleucine 54 163 700 44 2 Histidine 52 151 , 650 54 3 Hydroxyproline 48 147 650 44 4th Trypto 55 163 730 54 5 Threonine 48 143 620 54 6th Serine 52 143 690 53 7th Valine 42 155 670 53 8th Methionine 54 134 740 55 9 Tyrosine 53 155 650 55 10 Alanine 44 136 630 53 11 Aspartic acid 58 133 690 54 12th Citrulline 50 146 620 53 13th Glutamine 54 153 710 53 14th Natri umglut amat 41 162 680 53 15th Homoser 21 195 870 51 16 without 115 1040

The compounds of the formulations listed in Table VII, which contained SBR, were prepared using a sulfur donor as a hardener at 160 ° G for 20 minutes vulcanized. The properties of the vulcanized rubbers are listed in Table VII.

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' η ■

Table VII

Attempt no. 1 - 2
(Cf.) - 4th 3
(Cf.) - 5 Styrene butadiene rubber
C ΟΤ3Ό * \ V Iy 100 - 100 - 5 100 1 SHF-L-Russ ^ 40 38 40 - 1520 40 44 • 3 155 3 40 3 187 50% aqueous lysine solution 6th 850 750 ZnO 53 53 Stearic acid 500% modulus (kg / cm ² ) Tensile strength (kg / cm) Strain (%) hardness

Footnotes :

(2) and (2): as in example 1

(3) Tetraethylthiuram disulfide as a sulfur donor.

As can be seen from the test results shown above if σ ο _ö

zexgt, himself / the vulcanization is carried out using only a sulfur donor obtained Rubber has 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 will. As a result, the dangerous ZnO can be replaced by non-toxic amino acids.

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Example 8

Using the compositions from the batches listed in Table VIII, which contained natural rubber (NR), the same tests as in Example Λ were carried out. The properties of the vulcanized rubbers obtained are shown in Table VIII. The vulcanization curves obtained at 160 ° C. from the Hassen soaked in the experiments Fr. 1, 4 and 5 can be seen from FIG. It can be seen from FIG. 6 that the mass according to experiment No. 4- was slow in terms of vulcanization. If the vulcanized rubbers of Run No. 4 were allowed to stand for 1 or 2 days, there was considerable blooming and vulcanization using sulfur alone in the absence of activators and accelerators was technically quite useless. In contrast, vulcanization using a mixture of sulfur and the specified amino acids (Run Nos. 1 to 3) could be carried out smoothly in the absence of activators such as zinc oxide. The modulus and tensile strength of the vulcanized rubbers obtained showed great improvement and no blooming occurred.

In experiment no.5i in which sulfur together with 3,5-Dijοdtyrοsin, which does not fall under the amino acids according to the present invention was used the rate of vulcanization decreases to a greater extent than in the case of the use of sulfur alone and the Properties of the vulcanized rubber were damaged. This is clear from the information given in Table VIII test results shown and the vulcanization curves shown in FIG. 6. Furthermore, it showed on trial No. 5, vulcanized rubber obtained the same blooming as the vulcanized rubber of Trial No. 4-.

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Tabel VIII 3 4th
(Cf.) - 5
(Cf.) - Experiment no. 1 2 100 100 - 100 - Natural rubber "(RSSI) 100 100 40 40 - 40 - SRF-L, Russ ^ 40 40 3 3 - 3 - sulfur 3 3 1.45 - 2.5 50% aqueous lysine
solution 1.57 2.70 "- 160 160 Histidine 3, ^ 3 - - 30th 30th Tyro sin - 0.20 1.78 28 12th Glutamic acid - 3.30 1.78 128 68 Arginine - - - 640 610 3,5-Dij odtyro sin - - 160 36 27 Vulkani s ation st emp er a- 160 160 30th Vulcanization time
(Minutes) 30th 30th 34 300% ^ module. (kg / cm ² ) 33 33 178 Tensile strength (kg / cm) 162 147 690 Strain (%) 680 650 42 hardness 42 40

Footnote:

(1) is the same as (2) of Example 1.

Example 9

Using compositions of the formulations listed in Table IX, an acrylonitrile-butadiene-isoprene rubber (KBIR) as a rubber component, the same tests as in Example 1 were carried out. The properties of the

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The vulcanized rubbers obtained are shown in Table IX and the vulcanization curves obtained at 160 ° C the masses from Experiment Nos. -1, 2 and 3 are shown in FIG. It is clear from the values obtained, that the same results in terms of NEIR as in the case of SBE according to Example 1 were obtained.

Table IX - 2 « 3 3
(Cf.) - Experiment no. 1 160 100 160 100 160 Acrylonitrile butadiene
Isoprene rubber
(NBIR) (1) 100 20th 40 20th 40 20th SRF-L, Russ ^ 40 155 2 153 2 23 sulfur 2 155 208 80 50% aqueous lysine
solution 3 300 430 970 50% aqueous orni-
thin solution 67 65 56 Vulkani sation st eaip era-
tur (oc) Vulcanization time
(Minutes) 300% module (kg / eta ² ) Tensile strength (kg / cm) Strain (%) hardness

Footnotes:

(1) Mpol DN-120T ^ ·, a product of Nippon Zeon Co., Ltd.

(2) as in example 1.

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Example 10

Using the masses listed in Table X, which are carboxylated! Containing acrylonitrile butadiene rubber (CKBR) as the rubber component, the same tests were carried out as in Example 1 executed. The properties of the vulcanized rubbers obtained are shown in Table X and those at 160.degree The vulcanization curves obtained for the masses from experiments nos. 1 and 3 can be seen from FIG.

Table X

1 2 (Cf.) Carboxylated acrylonitrile Butadiene rubber (CNBR) (1) 100 100 100 SRF-L, Russ ^ 40 40 40 sulfur
f "Ύ \ 2 2 2 TE-58A ^ ^; 2.5 2.5 2.5 50% aqueous lysine solution 2.5 2.1 - Arginine 2.5 - - Threonine - 2.9 - Vulcanization temperature (° C) ic-. 160 160 Vulcanization time (minutes) 20th 20th 20th 300% modulus (kg / cnO 132 99 10 Tensile strength (kg / cm) 220 199 27 Strain (%) 490 540 1790 hardness 66 60 51 Footnotes:

(1) Nipöl 1072, a product of Nippon Zeon Co., Ltd.

(2) and (3) as in example 1.

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Example 11

Using the masses listed in Table XI, the polyisoprene rubber (IR) as Rubber components contained, the same tests were carried out as carried out in Example 1. The properties of the vulcanized rubbers obtained are shown in Table XI and the vulcanization curves of the masses obtained at 160 ° C. from the experiments ITr. 1 and 6 are in Fig. 9 listed.

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Tabel XI 40 3 4th 5 (compare) _ Attempt no. 1 2 3 100 100 100 100 - Polyisoprene rubber
(IR) (1) 100 100 1 40 40 40 40 SRF-L, carbon black ^ ^; 40 ,1 3 3 3 3 sulfur 3 - 1 1 1 1 TE-58A ^ ' 1 2.1 2.1 1.6 50% aqueous lysine
solution 2.1 2 - _ - Isoleucine 2.9

Tryptophan

Leucine

Glutamine

Glutamic acid

Arginine

2.9

2.9

2.9

1.7 1.7

Vulcanization temp erature ( ⁰ C)

Vulcanization time (minutes)

160 160 160 160 160 160 20th 20th 20th 20th 20th 20th 29 21 27 21 19th 13th 173 160 161 157 154- 80 760 830 750 790 810 740 40 40 40 38 36 28

300% modulus (kg / cm ² ) tensile strength (kg / cm) elongation (%)
Hardness 40

ffnotes: -, '

(1) Kuraprene IR-10 ^, a product of Kuraray Co., Ltd.

(2) and (3) as in example 1.

Example 12

• Using the masses listed in the batches of Table XII, which make a butadiene methyl methacrylate rubber (MBR) as a rubber component

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the same experiments as in Example 1 carried out. The properties of the vulcanized rubbers obtained result from Table XII.

Tabel Experiment no. XII 1 2 3
(Cf.) Methyl methacrylate butadiene
rubber (MBR) (1) 100 100 100 SRF-L, Russ * - ² ) 40 40 40 sulfur 2 2 2 TE-58A ^t5; 2.5 2.5 2.5 50% aqueous ornithine
solution Methionine - 2.5 - Vulcanization temperature (C) 160 160 160 Vulcanization time (minutes) 20th 20th 20th 300% modulus (kg / cm ² ) 149 139 125 Tensile strength (kg / cm) 198 194 167 Strain (%) 390 460 450 hardness 67 70 67

ffnotes:

(1) Solid rubber obtained by drying completely at room temperature from Croslene 2H-3 ^ (latex from Methyl methacrylate butadiene rubber with a total solid content of 40%, product of Takeda Chemical Co., Ltd.j

(2) and (3) as in example 1.

Example 13

Using the masses given in the formulations listed in Table XIII, the POR as rubber components

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the same tests as in Example 1 were carried out. The properties of the vulcanized obtained Rubbers can be seen from Table XIII and the vulcanization curves of the masses obtained at 160 ° C. from the Experiment Nos. 2 and 3 are shown in FIG.

Table XIII

Experiment no. 1 - 2 3 3
(Cf.) Propylene oxide (POR) ( ^Λ ) 100 160 100 160 100 SRP-L, Russ ^ 40 30th 40 30th 40 sulfur 1.5 50 1.5 43 1.5 50% aqueous lysine solution 3 24 - 71 - 50% aqueous ornithine
solution 420 500 - Vulcanization ^{temperature (0} C) 48 46 160 Vulcanization time (minutes) 30th 300% modulus (kg / cm ² ) 4th Tensile strength (kg / cm) 5 Strain (%) 1080 hardness 28 Footnotes:

(1) Parel 58, a propylene oxide rubber from Hercules Powder Co., Inc., U.S.A.

(2) as in example 1.

Example 14

Rubber stocks were prepared according to the approaches shown in Table XIVA and tested under the conditions in Conditions listed in Table XIVA using the

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amino acids shown in Table XIVB which were not used in Example 13, vulcanized. The own Properties of the vulcanized rubbers result from Table XIVB.

Tabel Experiment no. XIVA 12th /1)
Propylene oxide rubber ^v '
SEF-L, Sweet ^
sulfur
TE- 5SA ^ )
Amino acid (from Table XIVB
visible) 1-11 100
40
1.5
2.5 Vulcanization temperature (C)
Vulcanization time (minutes) - 100
40
1.5
2.5
2.5 160
30th 160
30th

! Footnotes:

(1) as in example 13

(2) and (3) as in example 1.

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Table XIVB Properties of the
Rubbers Zugfe
sturdiness
) (kg / ciO vulcanized Hardness Try-lYr » Amino acid 300? * -
Module ρ
(kg / cm ] 120 strain 36 20th 72 1240 48 1 Leucine 47 76 470 44 2 Proline 35 74 580 34 3 Arginine 14th 111 1240 38 4th Glutamine 14th 100 1380 36 5 Tyrosine 16 69 1250 32 6th Valine 11 90 1240 41 7th Isoleucine 25th 99 820 40 8th Methionine 27 88 910 42 9 Phenylalanine 29 840 10 Homo serine

3.5-

(Comparison) tyrosine

12 (comparison) without

1170 1110

28

28

■ Example 15

Using the masses obtained from the masses according to Table XV which contained PBR as a rubber component, the same tests as in Example 1 were carried out. The properties of vulcanized rubbers result from Table XV. The ones obtained at 160 ° G Vulcanization curves of the compounds of tests No. 1 and 6 (comparison) are in Pig. 11 shown.

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Table XV

Experiment no.

O CD CX)

Propylen-Butadienkaut schule ^ 'SIiF-L, river sulfur 50% aqueous ornithine solution 50% aqueous lysine solution arginine glutamine paste ¹ histidine

Vulcanization temperature (° C) Vulcanization time (minutes)

1 2 3 4th 5 6th
(Cf.) 100 100 100 100 100 100 40 40 40 40 40 40 1.5 1.5 1.5 1.5 1.5 1.5 3 - 2 _ 2.1 _

0.9

160
30th

160
30th

160 30

160 30

160 30

300% modulus (kg / cm ² ) tensile strength (kg / cm) elongation (%) hardness

Footnotes: (1) Propylene-butadiene block copolymer from Maruzen Petrochemical Co., Ltd.

(2) as in example 1

(3) Glutamine with 25% water content

60 61 52 18th 68 10 116 149 146 160 142 102 490 540 580 1110 500 1410 58 58 57 50 58 48

CO »CD CO

Comparative example 1

This comparative example shows that the amino acids specified in the context of the invention are not the same Vulcanization acceleration effects for other rubbers, as they are indicated according to the invention show.

Masses from the batches listed in Table XVI _; containing either a butyl rubber or an EPDM rubber as a rubber component, were prepared according to the method of ASTM-D15-68a, Part B 21 and then heated to 170 ° C. for 30 minutes. It was found that while a vulcanized rubber of good quality is obtained with the vulcanization system according to test No. 6, as it is commonly used in industrial operations, mixtures of sulfur and the amino acids did not initiate vulcanization.

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Table XVI

Attempt no. 12 3 100 4th - 5 _ 5 - Since there is no vulcanization
followed, these could own
properties not determined
will 6th - 5 Butyl rubber ¹ ^ ' 100 100 40 40 40 - - - - - 1 EPDM ca ut s chuk ^ ^; 2.5 2.5 5 100 - 100 100 42
660 SRP-L, Russ ^ 111 40 40 40 53 TE-58A ^^ 2.5 - 5 5 5 5 sulfur 2.5 1 1 1 50% aqueous lysine
solution _ _ _ 5 50% watery orni-
thin solution - - - 5 Arginine - - - ZnO Stearic acid 300% modulus (kg / cm ² )
tensile strenght
(kg / cm2)
Strain (%) hardness

Footnotes:

(1) Polysar Butyl 40

-R

^y , butyl rubber from Polysar Ltd. Mitsui Petrochemical product

(2) Mitsui EPT 4045, Co, Ltd.

(3) and (4) have the same meaning as (2) and (3) in example 1

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Claims (3)

Claims 1. Curable rubber composition, consisting essentially of (A) at least one of the rubbers styrene-butadiene rubber, Acrylonitrile butadiene rubber, polybutadiene rubber, acrylonitrile isoprene rubber, Alfin rubber, butadiene methyl methacrylate rubber, Polyisoprene rubber, acrylonitrile butadiene isoprene rubber, carboxylated acrylonitrile butadiene rubber, Propylene oxide rubber, propylene butadiene rubber and natural rubber, (B) at least one of the hardening agents sulfur and / or Sulfur donors and (C) at least one compound that does not require an activator as a vulcanization accelerator, namely arginine, Lysine, hydroxylysine, ornithine, proline, hydroxyproline, leucine, isoleucine, histidine, tryptophan, threonine, serine, homoserine, Alanine, phenylalanine, valine, methionine, citrulline, tyrosine, asparagine, aspartic acid, glutamine, glutamic acid and / or Salts of these amino acids. 2. Composition according to claim 1, characterized in that the compound used as a vulcanization accelerator consists of at least one of the compounds arginine, lysine, ornithine, proline and salts of these amino acids. 3. Mass according to claim 1 or 2, characterized in that that the rubber is made from styrene-butadiene rubber, acrylonitrile-butadiene rubber or a polybutadiene rubber. 4-. Compounds according to claims 1 to 3, characterized in that the tightness of the compound (C) is 0.1 to 30 parts by weight per 100 parts by weight of rubber and the amount of the curing agent is 0.1 to 20 parts by weight per part by weight of the Compound (C) is. ORiGlMAL IiSJSPECTEO 70982671049