CA2010905A1 - Sulfur-vulcanizable rubber mixtures having a reduced blooming effect - Google Patents
Sulfur-vulcanizable rubber mixtures having a reduced blooming effectInfo
- Publication number
- CA2010905A1 CA2010905A1 CA 2010905 CA2010905A CA2010905A1 CA 2010905 A1 CA2010905 A1 CA 2010905A1 CA 2010905 CA2010905 CA 2010905 CA 2010905 A CA2010905 A CA 2010905A CA 2010905 A1 CA2010905 A1 CA 2010905A1
- Authority
- CA
- Canada
- Prior art keywords
- rubber
- sulfur
- weight
- rubber mixtures
- thiuram
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
SULFUR-VULCANIZABLE RUBBER MIXTURES HAVING A REDUCED
BLOOMING EFFECT
A B S T R A C T
The vulcanization of rubber of low C-C double bond content with a vulcanization system containing sulfur, thiuram accelerator and N-trichloromethyl sulfenyl benzene-sulfanilide gives vulcanizates having improved properties.
BLOOMING EFFECT
A B S T R A C T
The vulcanization of rubber of low C-C double bond content with a vulcanization system containing sulfur, thiuram accelerator and N-trichloromethyl sulfenyl benzene-sulfanilide gives vulcanizates having improved properties.
Description
SULF'UR-VULCANIZABI.E RUBBER MIXTURES H~VING A REDUCED
BLOOMING EFFECT
This invention relates to vulcanizable rubber mixtures containing sulfur as a vulcanizing agent; a thiuram c~mpound as an accelerator and a certain benzenesullanilide as an additive for reducing blooming, to a process for the pro-duction of these rubber mixtures by mixing of the compon-ents and to the use of these rubber mixtures for the pro-duction of vulcanizates.
It is known that vulcanization accelerators are sub-stances which shorten the vulcanization time or which enable vulcanization to be carried out at a relatively low temperature, cf. Ullmanns Encyclopadie der technischen Chemie, 3rd Edition, Urban & Schwarzenberg, Munchen-Berlin 1957, pages 383 et seq. Auxiliary accelerators are option-ally added to develop the full effectiveness of the vulcan-ization accelerators.
So-called "EV systems" ("EV" = efficient vulcaniza-tion) are often used for sulfur vulcanization, in which case thiuram compounds, such as tetraalkyl thiuram mono-sulfides (for example;tetramethyl thiuram monosulfide), tetraalkyl thiuram tetrasulfides (for examplejtetramethyl thiuram tetrasulfide) and, preferably, tetraalkyl thiuram disulfides (for examplej tetramethyl thiuram disulfide, hereinafter referred to as TMTD), are generally used as vulcanization accelerators. By virtue of their excellent effect, these thiuram compounds are also known as ultra-accelerators and lead in particular to high hot air resis-tance of the vulcanizates produced with them.
~hiuram compounds themselves,or the xeaction products formed therefrom during vulcanization; have a tendency towards blooming, resulting in an undesirable coating on `~-the vulcanizate. The tendency towards blooming is influ-enced inter ~li~ by the type of rubber and by the concen-Le A 26 355 tration of the thiuram compound (cf. W. Hofmann in Gummi-Asbest-Kunststoffe 9 (1986), pages 422 et ~g~.
Vulcanizates of rubber having a low conten~ of C=C
double bonds, such as EPDM, butyl rubber ana preferably nitrile rubber, of which the C-C double bonds are selec-tively hydrogenated either in part or completely, often have a low degree of crosslinking which is reflected in low modulus values and in a moderate compression set (CS) value, as measured after compression under heat, for example in hot air or in hot oil. There are limits to the extent to which the CS value can be increased by l~rger amounts of thiuram compound on account of the blooming phenomenon mentioned above.
It has now surprisingly been found that a vulcaniza-tion system containing sulfur in small guantities, thiuram accelerator and N-trichloromethyl sulfenyl benzenesulf-anilide cl3c-S---N---S02 ~
overcomes the disadvantages of the prior art.
: 25 Accordingly, the present invention relates to vulcan-izable rubber mixtures based on rubber of low c-c double bona content, cont~ining 0.2 to 1 % by weight sulfur, 1 to 3.5 % by weight thiuram accalerator and 0.1 to 3 ~ by weight and preferably 0.15 to 1% by weight N-trichloromethyl sulfenyl benzenesulfaniI~
ide, the percentages being based on the rubber to be vulcanized.
The present invention also relates to a process for the production of these rubber mixtures by mixing of the Le A 26 355 2 - . . . . .
20109~5 components and to their use for the production of vulcan-izates.
In the context of the invention, rubbers of low C-C
double bond content are those having iodine values of 2 to 35, preferably from 3 to 30 and more preferably from 5 to 25. The iodine values are generally determined by the Wijs method, i.e. by addition of iodine chloride in glacial acetic acid (DIN S3 241, Part 1). The iodine value defines the quantity of iodine in grams which is chemically bound by 100 g substance. Examples of preferred rubbers are EPDM, butyl rubber and, preferably, hydrogenated nitrile rubber.
The rubbers preferably have glass transition tempera-tures below 0-C and more especially below -10-C.
The letters "EPDM" stand for ethylene/propylene/diene terpolymers. EPDMs comprise rubbers in which the ratio by weight of ethylene to propylene residues is from 40:60 to 65:35 and which may contain from 1 to 20 C-C double bonds/
1,000 C atoms. Suitable diene monomers in the EPDM are, for example, conjugated dienes, for example isoprene and 1,3-butadiene, and unconjugated dienes containing from 5 to 25 C atoms, for example 1,4-pentadiene, 1,4-hexadiene, 1,5-hPxadiene, 2,5-dimethyl-1,5-hexadiene nd 1,4-octadiene;
cyclic dienes, for example cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene; alkylidene and alkenyl norbornenes, for example 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene, 2-isopro~enyl-5-norbornene and tricyclodienes.
The uncon~ugated dienes; 1,5-hexadiene, ethylidene norbornene and dicyclopentadiene;are preferred. The diene content of the EP~M i8 preferably from 0.5 to 10% by weight, based on EPDM.
EPDM rubbers of the type in questlon are described, for examFle, in DE-OS 2 808 709.
In the context of the invention, the term "butyl Le A 26 3S5 3 Z0~0905 rubber" encompasses isobutene copolymers of 95 to 99.5% by weight and preferably 97.5 to 99.5% by weight isobutene and 0.5 to 5% by weight and preferably 0.5 to 2.5% by weight copolymerizable diene, such as,for examplejbutadiene, di-methyl butadiene, 1,3-pentadiene, more especially isoprene.
On an industrial scale, butyl rubber is produced almost exclusively as an isobutene/isoprene copolymer by cationic solution polymerization at low temperatures; cf. for example Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Vol. 7, page 688, Intersciene Publ., New York/Lon-don/Sydney, 1965 and Winnacker-Xuchler, Chemische Technolo-gie, 4th Edition, Vol. 6, pages 550-555, Carl Hanser Verlag, Munchen-Wien 1962.
The preferred hydrogenated nitrile rubbers are based on butadiene/acrylonitrile copolymers containing from 5 to 60% by weight and preferably from 10 to 50% by weight copolymerized acrylonitrile. "Hydrogenated" in this context means that 90 to 98.5% and preferably 95 to 98% of the hydrogenatable C-C double bonds are hydrogenated. The degree of hydrogenation can be determined by IR-spectros- -copy. ' -The hydrogenation of nitrile rubber is known: US-PS
3,700,637, DE-OS 25 39 132, 30 46 008, 30 46 251, 32 27 650, 33 29 974, EP-A 111 412, FR-PS 2 540 503. Hydrogenat-ed nitrile rubber is distinguished above all by compara-tively high stability to oxidation.
The rubbers suitable for the process according to the invention generally have Mooney viscosities (DIN 53 523) of from 10 to 150 and preferably from 25 to 80 (ML 1+4)/100-C.
Preferred thiuram accelerators include the above-mentioned tetraalkyl thiuram mono- and polysulfides, the alkyl groups generally containing 1 to 4 and preferably 1 -or 2 C atoms.
- The N-trichloromethyl sulfenyl benzenesulfanilide to be used ln accordance with the invention i8 known and is ;
Le A 26 355 4 - ,.- : -, ~ .
; :0109OS
commercially available, for example, as ~ ulkalent E (a product of Bayer AG, Leverkusen).
Vulcanization auxiliaries and, as required, scti-vators, filler6, such as for example carbon blac~, pIasticizer~, antiagers andtor processing aids, may be added in the uCual quantities before vulcanization.
Preferred vulcanization auxiliaries, which are generally used in quantities of from 0.1 to 2, prefer-ably from 0.2 to 1, X by weight (based on rubber), include thiazole accelerators, such as 2-mercapto-benzothiazole, dibenzothiazyl disulfide, benzothiazyl-2-cyclohexyl sulfenamide (CBS), benzothiazyl-2-tert.-butyl sulfenamide (TBBS), N-morpholinothio-2-benzothia-zol (MBS), benzothiazyl-2-diisopropyl sulfenamide (DIBS), benzothiazyl-2-tert.-amyl sulfenamide (AMZ), benzothiazyl dicyclohexyl ~ulfenamide (DCBS) and morpholinothioearbonyl sulfene morpholide (OTOS).
The mast significant inorganic activators are the metal oxides, particularly zinc oxide. In some cases, magnesium oxide or calcium hydroxide may also be used. -~
Suitable processing aids are, for example, fatty acids, such as stearic acid, for example, and their zinc ~alts which may cause an advantageous effect on the properties of the resulting vulcanizates.
The components may be m;xed in standard mixing units.
Preferred mixing units are the kneaders, rolls, internal mixers,and mixing extruders typically used in the rubber industry which generally oparste at shear rates of 1 to 1~000 sec~1 and preferably 1 to 20 sec~l.
Vulcanization may be carried out at temperatures in the range from 100 to 200C and preferably at temperatures in the range from 130 to 180C, opt;onally under a pres~ure of 10 to 200 bar.
Le A 26 355 - 5 ~
The oustanding v~l~niza~e pr~per~ies arQ generally achieved withou~ post-curing, bu~ can often be improv~d by pos~-curing.
The vulsaniza~es ob~ainable in acccrdance with ~he invention are excellent material~ for drive belts and gear belts by virtue of their high resilience. In addi~ion, they show excellen~ properti0s as sealing materials of all kinds and may be used in~er alia a3 hose cores or shea~hs.
EXAMPLES
A hydrogenated acrylonitrile/butadiene copolymer having an acrylonitrile content of 33.7% by weight, a degree of hydrogenation of 96.4~, based on the C-C double bonds originally present, and a Mooney viscosity of 67 (ML
114)/l00-C was used as rubber for the following Examples.
In a laboratory kneader, l00 parts rubber were masti-cated for 0.5 minute at 50 C, after which 0.5l part sulfur, l part stearic acid, 2 parts zinc oxide, l part octylated diphenylamine (~a~Vulkanox OCD, a product of Bayer AGj, 0.4 part methyl mercaptobenzimidazole (~R~Vulkanox ZMB2, a product of Bayer AG) and 45 parts carbon black (Corax N550, a product of Degussa~Wesseling) were added and the mixture 8~æd wa8 by kneading (4.5 minutes).
After cooling of the rubber mixture to approximately l00-C on rolls, an accelerator system consisting of 2 parts tetramethyl thiuram disulfide (~R~ Vulkacit Thiuram, a product of Bayer AG), 0.5 part benzothiazyl-2-cyclohexyl sulfenamide (~R~Vulkacit CZ, a product of Bayer AG) and varying amounts (see Table l) of N-trichloromethyl 6ulfenyl benzene~ulfanilide (~Vulkalent E, a product of Bayer AG) were added.
The properties of the ~ixtures obtained are listed in the following:
Le A 26 355 - 6 -20~0905 Table 1 Mixture properties 5 Examples 1 ~ 2 3 4 5 . . _ _ . . _ _ _ . .
N-trichlorome~hyl sulfenyl - 0.5 1 1.5 0.4 benzenesulfanilide (parts) zincstearate - - - - 2 10 Scorch time Mooney scorch MS-t5/130C 18.5 20.9 17.9 16.2 21~9 (min.) Vulcameter 160C t1o (min.) 4.5 5.0 4.7 4.6 4.9 t90 (min.)12.6 12.7 11.7 12.4 12.5 FmaX (cN) 43.8 57 60 61 59 The mixtures obtained were vulcanized for 30 minutes at 160C. The vulcanizate properties were de-termined on S2 test specimens (2 mm thick) in accordance 2~ with IS0 standard 37-1977; for results, see Tsble 2.
Table 2 Vulcanizate properties Example 1 2 3 4 5 ~ ;
Tensile strength (MPa) 29 28 28 28 29 ~ -~
~ Elon~ation at break (%)5Z0500 490 470 500 ; ~odulus S10O (MPa)3.43.83.94.03.6 Shore A hardneas 72 73 73 73 72 30 Compression set according7053 55 57 54 to DIN 53 517, te~t speci-men 2, 70 h/100C (X) Ditto after post-curing for 54 35 ~8 42 33 6 hours at 140C (%) Le A 26 355 - 7 -
BLOOMING EFFECT
This invention relates to vulcanizable rubber mixtures containing sulfur as a vulcanizing agent; a thiuram c~mpound as an accelerator and a certain benzenesullanilide as an additive for reducing blooming, to a process for the pro-duction of these rubber mixtures by mixing of the compon-ents and to the use of these rubber mixtures for the pro-duction of vulcanizates.
It is known that vulcanization accelerators are sub-stances which shorten the vulcanization time or which enable vulcanization to be carried out at a relatively low temperature, cf. Ullmanns Encyclopadie der technischen Chemie, 3rd Edition, Urban & Schwarzenberg, Munchen-Berlin 1957, pages 383 et seq. Auxiliary accelerators are option-ally added to develop the full effectiveness of the vulcan-ization accelerators.
So-called "EV systems" ("EV" = efficient vulcaniza-tion) are often used for sulfur vulcanization, in which case thiuram compounds, such as tetraalkyl thiuram mono-sulfides (for example;tetramethyl thiuram monosulfide), tetraalkyl thiuram tetrasulfides (for examplejtetramethyl thiuram tetrasulfide) and, preferably, tetraalkyl thiuram disulfides (for examplej tetramethyl thiuram disulfide, hereinafter referred to as TMTD), are generally used as vulcanization accelerators. By virtue of their excellent effect, these thiuram compounds are also known as ultra-accelerators and lead in particular to high hot air resis-tance of the vulcanizates produced with them.
~hiuram compounds themselves,or the xeaction products formed therefrom during vulcanization; have a tendency towards blooming, resulting in an undesirable coating on `~-the vulcanizate. The tendency towards blooming is influ-enced inter ~li~ by the type of rubber and by the concen-Le A 26 355 tration of the thiuram compound (cf. W. Hofmann in Gummi-Asbest-Kunststoffe 9 (1986), pages 422 et ~g~.
Vulcanizates of rubber having a low conten~ of C=C
double bonds, such as EPDM, butyl rubber ana preferably nitrile rubber, of which the C-C double bonds are selec-tively hydrogenated either in part or completely, often have a low degree of crosslinking which is reflected in low modulus values and in a moderate compression set (CS) value, as measured after compression under heat, for example in hot air or in hot oil. There are limits to the extent to which the CS value can be increased by l~rger amounts of thiuram compound on account of the blooming phenomenon mentioned above.
It has now surprisingly been found that a vulcaniza-tion system containing sulfur in small guantities, thiuram accelerator and N-trichloromethyl sulfenyl benzenesulf-anilide cl3c-S---N---S02 ~
overcomes the disadvantages of the prior art.
: 25 Accordingly, the present invention relates to vulcan-izable rubber mixtures based on rubber of low c-c double bona content, cont~ining 0.2 to 1 % by weight sulfur, 1 to 3.5 % by weight thiuram accalerator and 0.1 to 3 ~ by weight and preferably 0.15 to 1% by weight N-trichloromethyl sulfenyl benzenesulfaniI~
ide, the percentages being based on the rubber to be vulcanized.
The present invention also relates to a process for the production of these rubber mixtures by mixing of the Le A 26 355 2 - . . . . .
20109~5 components and to their use for the production of vulcan-izates.
In the context of the invention, rubbers of low C-C
double bond content are those having iodine values of 2 to 35, preferably from 3 to 30 and more preferably from 5 to 25. The iodine values are generally determined by the Wijs method, i.e. by addition of iodine chloride in glacial acetic acid (DIN S3 241, Part 1). The iodine value defines the quantity of iodine in grams which is chemically bound by 100 g substance. Examples of preferred rubbers are EPDM, butyl rubber and, preferably, hydrogenated nitrile rubber.
The rubbers preferably have glass transition tempera-tures below 0-C and more especially below -10-C.
The letters "EPDM" stand for ethylene/propylene/diene terpolymers. EPDMs comprise rubbers in which the ratio by weight of ethylene to propylene residues is from 40:60 to 65:35 and which may contain from 1 to 20 C-C double bonds/
1,000 C atoms. Suitable diene monomers in the EPDM are, for example, conjugated dienes, for example isoprene and 1,3-butadiene, and unconjugated dienes containing from 5 to 25 C atoms, for example 1,4-pentadiene, 1,4-hexadiene, 1,5-hPxadiene, 2,5-dimethyl-1,5-hexadiene nd 1,4-octadiene;
cyclic dienes, for example cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene; alkylidene and alkenyl norbornenes, for example 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene, 2-isopro~enyl-5-norbornene and tricyclodienes.
The uncon~ugated dienes; 1,5-hexadiene, ethylidene norbornene and dicyclopentadiene;are preferred. The diene content of the EP~M i8 preferably from 0.5 to 10% by weight, based on EPDM.
EPDM rubbers of the type in questlon are described, for examFle, in DE-OS 2 808 709.
In the context of the invention, the term "butyl Le A 26 3S5 3 Z0~0905 rubber" encompasses isobutene copolymers of 95 to 99.5% by weight and preferably 97.5 to 99.5% by weight isobutene and 0.5 to 5% by weight and preferably 0.5 to 2.5% by weight copolymerizable diene, such as,for examplejbutadiene, di-methyl butadiene, 1,3-pentadiene, more especially isoprene.
On an industrial scale, butyl rubber is produced almost exclusively as an isobutene/isoprene copolymer by cationic solution polymerization at low temperatures; cf. for example Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Vol. 7, page 688, Intersciene Publ., New York/Lon-don/Sydney, 1965 and Winnacker-Xuchler, Chemische Technolo-gie, 4th Edition, Vol. 6, pages 550-555, Carl Hanser Verlag, Munchen-Wien 1962.
The preferred hydrogenated nitrile rubbers are based on butadiene/acrylonitrile copolymers containing from 5 to 60% by weight and preferably from 10 to 50% by weight copolymerized acrylonitrile. "Hydrogenated" in this context means that 90 to 98.5% and preferably 95 to 98% of the hydrogenatable C-C double bonds are hydrogenated. The degree of hydrogenation can be determined by IR-spectros- -copy. ' -The hydrogenation of nitrile rubber is known: US-PS
3,700,637, DE-OS 25 39 132, 30 46 008, 30 46 251, 32 27 650, 33 29 974, EP-A 111 412, FR-PS 2 540 503. Hydrogenat-ed nitrile rubber is distinguished above all by compara-tively high stability to oxidation.
The rubbers suitable for the process according to the invention generally have Mooney viscosities (DIN 53 523) of from 10 to 150 and preferably from 25 to 80 (ML 1+4)/100-C.
Preferred thiuram accelerators include the above-mentioned tetraalkyl thiuram mono- and polysulfides, the alkyl groups generally containing 1 to 4 and preferably 1 -or 2 C atoms.
- The N-trichloromethyl sulfenyl benzenesulfanilide to be used ln accordance with the invention i8 known and is ;
Le A 26 355 4 - ,.- : -, ~ .
; :0109OS
commercially available, for example, as ~ ulkalent E (a product of Bayer AG, Leverkusen).
Vulcanization auxiliaries and, as required, scti-vators, filler6, such as for example carbon blac~, pIasticizer~, antiagers andtor processing aids, may be added in the uCual quantities before vulcanization.
Preferred vulcanization auxiliaries, which are generally used in quantities of from 0.1 to 2, prefer-ably from 0.2 to 1, X by weight (based on rubber), include thiazole accelerators, such as 2-mercapto-benzothiazole, dibenzothiazyl disulfide, benzothiazyl-2-cyclohexyl sulfenamide (CBS), benzothiazyl-2-tert.-butyl sulfenamide (TBBS), N-morpholinothio-2-benzothia-zol (MBS), benzothiazyl-2-diisopropyl sulfenamide (DIBS), benzothiazyl-2-tert.-amyl sulfenamide (AMZ), benzothiazyl dicyclohexyl ~ulfenamide (DCBS) and morpholinothioearbonyl sulfene morpholide (OTOS).
The mast significant inorganic activators are the metal oxides, particularly zinc oxide. In some cases, magnesium oxide or calcium hydroxide may also be used. -~
Suitable processing aids are, for example, fatty acids, such as stearic acid, for example, and their zinc ~alts which may cause an advantageous effect on the properties of the resulting vulcanizates.
The components may be m;xed in standard mixing units.
Preferred mixing units are the kneaders, rolls, internal mixers,and mixing extruders typically used in the rubber industry which generally oparste at shear rates of 1 to 1~000 sec~1 and preferably 1 to 20 sec~l.
Vulcanization may be carried out at temperatures in the range from 100 to 200C and preferably at temperatures in the range from 130 to 180C, opt;onally under a pres~ure of 10 to 200 bar.
Le A 26 355 - 5 ~
The oustanding v~l~niza~e pr~per~ies arQ generally achieved withou~ post-curing, bu~ can often be improv~d by pos~-curing.
The vulsaniza~es ob~ainable in acccrdance with ~he invention are excellent material~ for drive belts and gear belts by virtue of their high resilience. In addi~ion, they show excellen~ properti0s as sealing materials of all kinds and may be used in~er alia a3 hose cores or shea~hs.
EXAMPLES
A hydrogenated acrylonitrile/butadiene copolymer having an acrylonitrile content of 33.7% by weight, a degree of hydrogenation of 96.4~, based on the C-C double bonds originally present, and a Mooney viscosity of 67 (ML
114)/l00-C was used as rubber for the following Examples.
In a laboratory kneader, l00 parts rubber were masti-cated for 0.5 minute at 50 C, after which 0.5l part sulfur, l part stearic acid, 2 parts zinc oxide, l part octylated diphenylamine (~a~Vulkanox OCD, a product of Bayer AGj, 0.4 part methyl mercaptobenzimidazole (~R~Vulkanox ZMB2, a product of Bayer AG) and 45 parts carbon black (Corax N550, a product of Degussa~Wesseling) were added and the mixture 8~æd wa8 by kneading (4.5 minutes).
After cooling of the rubber mixture to approximately l00-C on rolls, an accelerator system consisting of 2 parts tetramethyl thiuram disulfide (~R~ Vulkacit Thiuram, a product of Bayer AG), 0.5 part benzothiazyl-2-cyclohexyl sulfenamide (~R~Vulkacit CZ, a product of Bayer AG) and varying amounts (see Table l) of N-trichloromethyl 6ulfenyl benzene~ulfanilide (~Vulkalent E, a product of Bayer AG) were added.
The properties of the ~ixtures obtained are listed in the following:
Le A 26 355 - 6 -20~0905 Table 1 Mixture properties 5 Examples 1 ~ 2 3 4 5 . . _ _ . . _ _ _ . .
N-trichlorome~hyl sulfenyl - 0.5 1 1.5 0.4 benzenesulfanilide (parts) zincstearate - - - - 2 10 Scorch time Mooney scorch MS-t5/130C 18.5 20.9 17.9 16.2 21~9 (min.) Vulcameter 160C t1o (min.) 4.5 5.0 4.7 4.6 4.9 t90 (min.)12.6 12.7 11.7 12.4 12.5 FmaX (cN) 43.8 57 60 61 59 The mixtures obtained were vulcanized for 30 minutes at 160C. The vulcanizate properties were de-termined on S2 test specimens (2 mm thick) in accordance 2~ with IS0 standard 37-1977; for results, see Tsble 2.
Table 2 Vulcanizate properties Example 1 2 3 4 5 ~ ;
Tensile strength (MPa) 29 28 28 28 29 ~ -~
~ Elon~ation at break (%)5Z0500 490 470 500 ; ~odulus S10O (MPa)3.43.83.94.03.6 Shore A hardneas 72 73 73 73 72 30 Compression set according7053 55 57 54 to DIN 53 517, te~t speci-men 2, 70 h/100C (X) Ditto after post-curing for 54 35 ~8 42 33 6 hours at 140C (%) Le A 26 355 - 7 -
Claims (4)
1. Vulcanizable rubber mixtures based on rubber of low C=C double bond content, containing 0.2 to 1 % by weight sulfur, 1 to 3.5 % by weight thiuram accelerator and 0.1 to 3 % by weight N-trichloromethyl sulfenyl benzene sulfanilide, the percentages being based on the rubber to be vulcanized.
2. Rubber mixtures as claimed in claim 1, containing 0.1%
to 1% by weight N-trichloromethyl sulfenyl benzenesulfan-ilide, based on the rubber to be vulcanized.
to 1% by weight N-trichloromethyl sulfenyl benzenesulfan-ilide, based on the rubber to be vulcanized.
3. A process for the production of the rubber mixtures claimed in claims 1 and 2 by mixing of the components.
4. The use of the rubber mixtures claimed in claims 1 and 2 for the production of vulcanizates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893906188 DE3906188A1 (en) | 1989-02-28 | 1989-02-28 | SULFUR-VOLCANIZABLE RUBBER MATERIALS WITH REDUCED FLOW-OUT EFFECT |
| DEP3906188.4 | 1989-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010905A1 true CA2010905A1 (en) | 1990-08-31 |
Family
ID=6375091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2010905 Abandoned CA2010905A1 (en) | 1989-02-28 | 1990-02-26 | Sulfur-vulcanizable rubber mixtures having a reduced blooming effect |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0386499A1 (en) |
| JP (1) | JPH02248442A (en) |
| CA (1) | CA2010905A1 (en) |
| DE (1) | DE3906188A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103562294A (en) * | 2011-06-01 | 2014-02-05 | 株式会社普利司通 | Anti-vibration rubber composition and anti-vibration rubber |
| CN104204062A (en) * | 2012-01-30 | 2014-12-10 | 株式会社普利司通 | Anti-vibration rubber composition, crosslinked anti-vibration rubber composition, and anti-vibration rubber |
| CN104640919A (en) * | 2012-09-20 | 2015-05-20 | 株式会社普利司通 | Method for manufacturing rubber composition |
| CN104797647A (en) * | 2012-11-22 | 2015-07-22 | 株式会社普利司通 | Antivibration rubber composition, and antivibration rubber |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4031566A1 (en) * | 1990-10-05 | 1992-04-09 | Bayer Ag | SULFUR-VOLCANIZABLE RUBBER MATERIALS WITH IMPROVED VULCANIZATION LEVEL |
| US5416167A (en) * | 1990-10-05 | 1995-05-16 | Bayer Aktiengesellschaft | Vulcanizable rubber compositions containing salts of partial carboxylic acid esters |
| JP3477849B2 (en) | 1994-09-30 | 2003-12-10 | 日本ゼオン株式会社 | Rubber composition comprising a nitrile group-containing highly saturated copolymer rubber and an ethylene-based saturated copolymer rubber |
| US5651995A (en) * | 1994-09-30 | 1997-07-29 | Nippon Zeon Co., Ltd. | Highly saturated nitrile rubber, process for producing same, vulcanizable rubber composition, aqueous emulsion and adhesive composition |
| CA2413636A1 (en) * | 2002-12-05 | 2004-06-05 | Bayer Inc. | Adhesive compositions |
| JP6112755B2 (en) * | 2011-04-26 | 2017-04-12 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
| JP5790236B2 (en) * | 2011-07-21 | 2015-10-07 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
| JP5893937B2 (en) * | 2012-01-30 | 2016-03-23 | 株式会社ブリヂストン | Anti-vibration rubber composition, crosslinked anti-vibration rubber composition and anti-vibration rubber |
| JP5893938B2 (en) * | 2012-01-30 | 2016-03-23 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
| JP2015101693A (en) * | 2013-11-27 | 2015-06-04 | 三菱電線工業株式会社 | Rubber composition and seal member |
| JP5957159B1 (en) * | 2016-03-23 | 2016-07-27 | 三菱電線工業株式会社 | Rubber composition and seal member |
| JP7240326B2 (en) | 2017-11-30 | 2023-03-15 | 株式会社ブリヂストン | RUBBER COMPOSITION, RUBBER COMPOSITION FOR TIRE AND TIRE |
| JP2024050070A (en) * | 2022-09-29 | 2024-04-10 | 住友理工株式会社 | Industrial Hose |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE758927A (en) * | 1969-11-15 | 1971-05-13 | Bayer Ag | NEW VULCANIZATION DELAYERS BASED ON SUBSTITUTE SULFONAMIDES |
| DE2225189A1 (en) * | 1971-05-28 | 1972-12-07 | Universal Oil Prod Co | Vulcanizable diene rubber compound |
-
1989
- 1989-02-28 DE DE19893906188 patent/DE3906188A1/en not_active Withdrawn
-
1990
- 1990-02-15 EP EP90102918A patent/EP0386499A1/en not_active Withdrawn
- 1990-02-22 JP JP3988690A patent/JPH02248442A/en active Pending
- 1990-02-26 CA CA 2010905 patent/CA2010905A1/en not_active Abandoned
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103562294A (en) * | 2011-06-01 | 2014-02-05 | 株式会社普利司通 | Anti-vibration rubber composition and anti-vibration rubber |
| CN103562294B (en) * | 2011-06-01 | 2015-09-30 | 株式会社普利司通 | vibration damping rubber composition and vibration-proof rubber |
| US9725524B2 (en) | 2011-06-01 | 2017-08-08 | Bridgestone Corporation | Anti-vibration rubber composition and anti-vibration rubber |
| CN104204062A (en) * | 2012-01-30 | 2014-12-10 | 株式会社普利司通 | Anti-vibration rubber composition, crosslinked anti-vibration rubber composition, and anti-vibration rubber |
| US9238730B2 (en) | 2012-01-30 | 2016-01-19 | Bridgestone Corporation | Anti-vibration rubber composition, crosslinked anti-vibration rubber composition, and anti-vibration rubber |
| CN104204062B (en) * | 2012-01-30 | 2016-06-01 | 株式会社普利司通 | Vibration damping rubber composition, crosslinked vibration damping rubber composition and vibration-proof rubber |
| CN104640919A (en) * | 2012-09-20 | 2015-05-20 | 株式会社普利司通 | Method for manufacturing rubber composition |
| CN104640919B (en) * | 2012-09-20 | 2016-06-08 | 株式会社普利司通 | The manufacture method of rubber composition |
| CN104797647A (en) * | 2012-11-22 | 2015-07-22 | 株式会社普利司通 | Antivibration rubber composition, and antivibration rubber |
| US9416257B2 (en) | 2012-11-22 | 2016-08-16 | Bridgestone Corporation | Antivibration rubber composition, and antivibration rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02248442A (en) | 1990-10-04 |
| DE3906188A1 (en) | 1990-08-30 |
| EP0386499A1 (en) | 1990-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2010905A1 (en) | Sulfur-vulcanizable rubber mixtures having a reduced blooming effect | |
| KR960016618B1 (en) | Elastomeric composition having increased ozone resistance | |
| US7256231B2 (en) | Silica-reinforced rubber compounded with blocked mercaptosilanes and alkyl alkoxysilanes | |
| EP1731560B1 (en) | Rubber composition for tread | |
| JPS5836009B2 (en) | vulcanizable rubber mixture | |
| US5939493A (en) | Pneumatic tire | |
| JP2609369B2 (en) | Tire side surface composition | |
| KR950006137B1 (en) | Elastomeric composition and process for the production thereof | |
| CA1291284C (en) | Elastomeric composition having improved cut growth resistance | |
| US4814384A (en) | Tire having tread composition comprised of EPDM/unsaturated rubber blend | |
| JP4415459B2 (en) | Rubber composition | |
| EP0112109B1 (en) | Sulphur-vulcanisable polymer compositions | |
| CA2037793A1 (en) | Rubber composition | |
| KR100706415B1 (en) | Pyrimidine derivatives as hardness stabilizers | |
| KR20040074995A (en) | Preventing discoloration in an elastomer rubber | |
| JP3150732B2 (en) | Sulfur vulcanizable rubber composition with improved degree of crosslinking | |
| EP1879955B1 (en) | Rubber composition containing metal salts of organic acids, method of curing, cured compositions, and article | |
| JP2000309665A (en) | Rubber composition | |
| US4386181A (en) | Heat-aging-resistant rubber composition | |
| CA2053981A1 (en) | Use of maleic acid semi-esters and fumaric acid semi-esters and their salts for reducing nitrosamine formations in sulphur vulcanization | |
| KR940002279B1 (en) | Cured rubber blend and process for the production thereof | |
| JPH02169641A (en) | Chloroprene rubber composition | |
| JPH0434570B2 (en) | ||
| EP0864604A2 (en) | Rubber composition | |
| US5416167A (en) | Vulcanizable rubber compositions containing salts of partial carboxylic acid esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |