CA2186060A1 - Process for the preparation of vulcanisable rubber mixtures and the mixtures thus prepared - Google Patents
Process for the preparation of vulcanisable rubber mixtures and the mixtures thus preparedInfo
- Publication number
- CA2186060A1 CA2186060A1 CA 2186060 CA2186060A CA2186060A1 CA 2186060 A1 CA2186060 A1 CA 2186060A1 CA 2186060 CA2186060 CA 2186060 CA 2186060 A CA2186060 A CA 2186060A CA 2186060 A1 CA2186060 A1 CA 2186060A1
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- Canada
- Prior art keywords
- rubber
- rubber mixture
- parts
- mixture according
- silica
- 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.)
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Abstract
The invention provides a method for the preparation of vulcanisable rubber mixtures containing silicas and organosilane compounds, and these mixtures. The organosilane compounds are of the general formula: (C1-8 alkly -O) 3Si (CH2)3SCN. The mixtures when vulcanised provide mouldings and structural components for tyres having decreased abrasion.
Description
-Description The invention relates to a process for the preparation of vulcanisable rubber mixtures and to the mixtures thus prepared.
Effecting economies in fuel consumption and lowering the discharge of pollutants are nowadays receiving a growing priority as environmental awareness increases. For the tyre manufacturer, this signifies the development of tyres distin~l;she~ by a very low rolling resistance combi~ed with ~cellent wet skid resistance and good abrasion resistance.
In numerous publications and patents proposals are made for lowering the rolling resistance of a tyre and consequently the fuel consumption. In this connection decreasing the content of carbon black in the mixture and using specific carbon ~lacks are mentioned (US Patent 4,866,131, US
Patent 4,894,420). None of these proposed solutions has led, however, to a satisfactory balance between the low rolling resistance aimed for and the likewise important tyre properties such as wet skid resistance and abrasion resistance.
Only the use of highly active silica fillers in combination with the organosilane bis(triethoxysilylpropyl)-tetrasulphane (TESPT) largely in exchange for the carbon black in the rubber mixture appears here to indicate a way of rendering possible the production of a tyre having distinctly lowered rolling resistance while simultaneously maintaining or even improving the two other tyre properties mentioned above.
Effecting economies in fuel consumption and lowering the discharge of pollutants are nowadays receiving a growing priority as environmental awareness increases. For the tyre manufacturer, this signifies the development of tyres distin~l;she~ by a very low rolling resistance combi~ed with ~cellent wet skid resistance and good abrasion resistance.
In numerous publications and patents proposals are made for lowering the rolling resistance of a tyre and consequently the fuel consumption. In this connection decreasing the content of carbon black in the mixture and using specific carbon ~lacks are mentioned (US Patent 4,866,131, US
Patent 4,894,420). None of these proposed solutions has led, however, to a satisfactory balance between the low rolling resistance aimed for and the likewise important tyre properties such as wet skid resistance and abrasion resistance.
Only the use of highly active silica fillers in combination with the organosilane bis(triethoxysilylpropyl)-tetrasulphane (TESPT) largely in exchange for the carbon black in the rubber mixture appears here to indicate a way of rendering possible the production of a tyre having distinctly lowered rolling resistance while simultaneously maintaining or even improving the two other tyre properties mentioned above.
- 2 1 ~6060 On the occasion of the ACS Meeting in 1986 in New Yor~, S.
Wolff ~1] showed that in a passenger car the rolling resistance of a tyre tread based on emulsion styrene-butadiene rubber (E-SBR) is successfully distinctly lowered by the use of silica in combination with TESPT as compared with the standard mixture filled with carbon black, while wet s~id resistance and abrasion resistance are largely maintained.
A further optimisation of this system with regard to all three properties was achieved through the use of particular styrene-butadiene polymers prepared by the solution-polymerisation process (EP O 447 066 A1), partly blended with other polymers, in particular polybutadiene, and the additional use of novel types of silica (US Patent 5,227,425) as well as polymer blends specially adapted for this use (EP O 620 250 Al) using proportions of three to four different starting polymers.
It is characteristic of all these publications and patents that in order to achieve a low rolling resistance while maintaining or even improving wet skid resistance and abrasion resistance, a greater part or the entire content of the conventionally employed carbon black filler is replaced by a highly active silica. In all cases the organosilane bis(triethoxysilylpropyl)tetrasulphane (TESPT) was used as a coupler between silica and polymer in order to achieve the tyre properties required nowadays.
The present invention provides rubber mixtures vulcanisable with sulphur and comprising in addition to the conventional auxiliary substances 1. S. Wolff, 129'h Meeting of lhe Rubber Division. A nerican Chcmical Socicty, Ncw York, April 8-11, 1986 2. S . Wolff, Third Annual Meeting and C r ~ : of Tirc Science and T. ' . ' g~, The Tire Society, Akron, OhiolUSA, March 28-~9, 1984 a) from 10 to loo parts of a precipitated silica, b) from O to 100 parts of a rubber carbon black, in each case referred to 100 parts of the c) copolymer also comprised, which consists of a conjugated diene contAining an aromatic vinyl component, prepared by the solution polymerisation process, having a styrene content of between 10 and 40% and a vinyl content of between 20 and 80~, preferably from 40 to 60~, and a glass transition temperature of from O to -60C, or blends of these copolymers with other diene rubbers, with the proportion of these diene rubbers constituting ~p to 60 to 100 parts of the blends, d) and from 1 to 20 parts, preferably 5 to 10 parts, of an organosilane compound corresponding to the general formula (I) (RO)3Si(CH233SCN (I) wherein R signifies alkyl, branched or unbranched having 1 to 8 C atoms, preferably 1 to 4 C atoms, referred to 100 parts of silica.
Preferably used are precipitated silicas having a BET
surface area (ISO 5794/lD) of between 100 and 250 m2/g, in particular when they have a C~AB surface area (ASTM D3765-92) of between 100 and 250 m2/g and a DBP number of ~etween 150 and 300 ml/100 g (ASTM D1208~.
The silicas are added both in powder form and as pellets or granules. These silicas are the types known for many years as well as the new developments described, for example, in DE-OS 44 27 137.
According to the present invention additives such as, for example, inorganic fillers other than the above-mentioned 21 8606~
.
silica and silicates can be incorporated into the rubber mixture, provided that the quantities used do not obstruct the purpose of this invention.
Examples of other inorganic fillers are carbon blacks such as SRF, GPF, FEF, HAF, ISAF, FT and MT.
If carbon black is employed, a weight ratio of silica to carbon black of at least 2:1 is used.
The total proportion of fillers is not to exceed 120 parts per 100 parts of polymer.
The production of vulcanisates from the rubber mixtures according to the invention requires simply the preparation of raw rubber mixtures by the method described below, subsequent shaping of the raw mixtures according to requirement~, followed by wlcanisation in the same ~nner as for collve~tional rubber mixtures.
For the production of the vulcanisates according to this invention - in addition to the above-mentioned rubber components, the organosilane compound and the amorphous silica and according to the intended application of the vulcanisates and the requirements placed on them - the nature and quantity of the plasticisers, the nature and quantity of the compounds constituting a vulcanisation system, such as, for example, vulcanising agents, w lcanisation activators (ZnO, stearic acid), vulcanisation accelerators and other w lcanisation auxiliaries, as well as the process for the production of the wlcanisates, are carefully selected. Petroleum-based plasticisers conventionally employed in rubber may be used as the above-mentioned plasticisers.
Sulphur compounds such as those listed below are used as vulcanising agents for the production of the vulcanisates according to the invention. These sulphur compounds include, for example, sulphur, morpholine disulphide, alkylphenol disulphide, tetramethylthiuram disulphide and ~ 1 8~060 selenium dimethyl dithiocarbamate. Of these, preferably sulphur is used. The above-mentioned sulphur compounds are used in quantities of between 0.1 and 4 parts by weight, preferably between 0.5 and 3 parts by weight, referred to 100 parts by weight of the copolymer or of mixtures thereof with polymers. If a sulphur compound is used as a vulcanising agent in the production of vulcanisates according to this invention, then preferably a w lcanisation accelerator is used in addition. The wlcanisation accelerators used include, for example, thiazole compounds such as N-cyclohexyl-2-benzothiazole sulphen~ e, N,N-diiso~lo~1-2-benzothiazole sul~hen~m; de, 2-mercapt~h~n~othiazole and dibenzothiazyl disulphide;
guanidine compounds such as, for example, diphenylguanidine, triphenylguanidine, diorthotolylguanidine;
imidazoline compounds such as, for example, 2-mercaptoimidazoline;
thiourea compounds such as, for example, diethylthiourea, dibutylthiourea, trimethylthiourea and diorthotolylthiourea;
thiuram compounds such as, for example, tetramethylthiuram monosulphide, tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabutylthiuram disulphide, pentamethylene thiuram tetrasulphide;
dithioc~rh~m~te compounds such as, for example, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate;
xanthate compounds such as, for example, zinc dibutylxanthate.
The said vulcanisation accelerators are used in a quantity of between 1 and 20 parts by weight, preferably between 0.5 and 10 parts by weight, referred to 100 parts by weight of the copolymer or of mixtures thereof with the other polymers.
me organosilane and the æilica are preferably m;~e~ or even reacted with one another prior to being incorporated into the rubber mixtures, as is described in US-PS 5,116,886 (EP-B-O 442 143).
It is not absolutely essential to modify in advance the entire quantity of the silica used by means of the organosilane correspond;ng to formula (I). It is also possible to mndify only a portion in advance and to add the r~m~;nAer without prior modification.
If c~rhon black is provided as additional filler for the rubber m;Yt~re being prepared, in another variant it is possible to add the organosilane corresponding to formula (I) completely or partly as a carbon black/organosilane mixture. This is used preferably in the fonm of a granular material cont?;n;ng from 30 to 60 wt.~ of organosilane and from 70 to 40 wt.~ of cArhon black respectively. The production of 6;~;l~r granular materials is described in DE-PS 27 47 277 (US-PS 4,128,438) and can be carried out here in a corresponding m~nner.
The raw rubber mixture is prepared according to the method described below. The above-mentioned rubber components, the organosilane compound, the amorphous silica and the carbon black optionally present, as well as optionally a plasticiser, are kne~ for 3 to 10 minutes in a kneader, for example a Banbury closed mixer, at a temperature of from about 120 to 200C; a vulcanising agent such as accelerator and sulphur or another vulcanisation auxiliary is then added and mixing is continued at suitable temperatures for a further 5 to 30 minutes, either in a Banbury closed mixer or on a m; ~i ng roll, and the finished `- 21 86060 7 ~.
rubber mixture is then drawn out as rubber sheet or in the form of strips.
StAn~Ard rubber testing carried out on the vulcanisates produced from the mixtures according to the invention shows that, through the use of 3-thiocyanatopropyl-trialkoxysilanes as organosilane in combination with silicas in styrene-butadiene rubbers produced by the solution polymerisation process, a distinctly better abrasion resistance can be obtA; ne~ in cQ~p~rison with the use of TESPT with an otherwise largely identical set of values.
These vulcanisates are used for the production of mouldings and of structural components of tyres.
The examples ~elow clearly illustrate the advantages over the standard silane TESPT of the organosilane corresponding to formula (I) used in the polymer system according to the present invention.
Standard test methods for the assessment Test method Unit Tensile strength DIN 53 504 MPa Modulus 300~ DIN 53 504 MPa Stretch at break DIN 53 504 Shore hardness DIN 53 505 Impact resilience DIN 53 512 DIN abrasion DIN 53 516 mm3 MTS test DIN 53 515 The following names and abbreviations are used in the Examples of application:
Buna VSL 1950 S 25 Oil-filled L-SBR from the firm Bayer AG
having a vinyl content of 50~ and a styrene cont~nt of 25~; the glass transition temperature is -25C.
*
Buna VSL 1955 S 25 Oil-filled L-SBR from the firm Bayer AG
having a vinyl content of 55~ and a styrene content of 25~; the glass transition temperature is -20C.
*
Buna CB 24 Butadiene rubber having a proportion of 1,4 cis of at least 96~.
Naftolen ZD AFomatic oil from the firm Chemetal.
Protector G 35 Antiozonant wax from the firm Fuller.
* t rad ema rk * g Vulkanox 4020 Antioxidant from BAYER AG.
*
Vulkacit D Diphenyl~l~n;~;ne, acce~erator from BAYER AG.
*
Vul~acit CZ Benzothiazyl-2-cyclohexyl sulph~n~;de, accelerator from BAYER AG.
Ultrasil VN 3 GR Precipitated silica having an N2 surface area of 175 m2/g, a CTAB surface area of about 170 m2/g and a DBP number of 220 ml/100 g (Degussa AG).
*
Ultrasil 3370 GR Precipitated æilica according to the Patent DE P 44 27 137.9, ha~ing an N2 surface area of 170 m2/g, a CTAB surface area of 165 m2/g and a DBP number of 250 ml/100 g (Degussa AG).
20 Si 69 Bis~triethoxysilylpropyl)tetrasulphane, organosilane from Degussa AG.
Si 264 3-thiocyanat~ o~yltriethoxysilane, organosilane from Degussa AG.
* t rad emark - lO 2186060 Example 1: Comparison of Si 264 against Si 69 in the tyre tread of a passen,ger car, with ~ltrasi~*-vN 3 GR as filler Fol lAtion BUI~VSL 1950 S 25 96 96 Buna CB 24 30 30 Vltrasil*VN 3 GR 80 80 Si 69 6.4 Si 264 - 6.4 ZnO RS
Stearic ~cid 2 '2 NaftoleD~ZD 10 10 Pr~tectQ~*G 35 ~1 k~ng~ 4020 - 1.5 1.5 ~1 k~; t~D 2 2 Vulkacit~ CZ 1.7 2 ~"rh"~ 1.4 1.7 ~heometer: 165C
t~ min: S.9 3 9 t,o~ ,min: 30.0 16.8 t,~ in' 57.8 47.5 t,~- t~o~ :min: 24.2 12.9 Data on ~ulc~ni~Ate:
165 C/t9b~
T~nsile sL~uy~h tMpa~ 14.1 13.7 Mo~ c 300~ tMPa3 10.0 9.3 Shore A hardness 74 75 DIN abrasion rmm3] 97 69 Viscoelasticity data according to DIN 53 513 tan h 0C 0.437 0.424 tan ~ 60C 0.164 0.172 Si 264 in combination with ~ltrasi~ VN 3 GR shows in comparison with Si 69 distinct im~o~ - 's in abrasion where vulcAnisate properties are otherwise largely identical. In the rheometer test the advantage of Si 264 lies in the more rapid complete w lcanisation.
* trademark Example 2: Comparison of Si 264 against Si 69 in t*~e tyre tread of a passenger car, with Ultrasil 3370 GR as filler Formulation Buna*VSL 1955 S 25 96 96 Buna CB 24 30 30 Ultrasil*3370 GR 80 80 Si 69 6.4 Si 264 - 6.4 ZnO RS 3 3 Stearic acid 2 2 .
Naftolen*ZD 14 14 Protector*G 35 ~llkAnn~4020 1.5 1.5 Vulkaci~*D 2 2 VlllkAc;t CZ 1.7 2 Snlrhllr 1.4 1.7 Data on vulcAniæAte:
165C/tg5~
T~n~ile ~ ~yLh tMPa] 14.6 14.1 Modulu~ 300~ tMPa] 7.7 7.4 Stretch at break t~] 470 460 Impact resilience t%] 33 34 Shore A hardness 66 67 DIN abrasion tmm3] 111 75 ViscoelAsticity data according to DIN 53 513 E' 0C tMPa] 26.6 31.2 E" 0C lMPa] 12.2 13.3 tan ~0C 0.437 0.427 E~ 60C [MPa] 9 7 10.3 E" 60C [MPa] 1.1 1.3 -tan ~ 60C 0.116 0.123 The combination Ultrasil 3370 GR/ Si 264 e~h;b;ts distinct advantages in abrasion in comparison with Ultrasil 3370 GR/ Si 69.
* trademark
Wolff ~1] showed that in a passenger car the rolling resistance of a tyre tread based on emulsion styrene-butadiene rubber (E-SBR) is successfully distinctly lowered by the use of silica in combination with TESPT as compared with the standard mixture filled with carbon black, while wet s~id resistance and abrasion resistance are largely maintained.
A further optimisation of this system with regard to all three properties was achieved through the use of particular styrene-butadiene polymers prepared by the solution-polymerisation process (EP O 447 066 A1), partly blended with other polymers, in particular polybutadiene, and the additional use of novel types of silica (US Patent 5,227,425) as well as polymer blends specially adapted for this use (EP O 620 250 Al) using proportions of three to four different starting polymers.
It is characteristic of all these publications and patents that in order to achieve a low rolling resistance while maintaining or even improving wet skid resistance and abrasion resistance, a greater part or the entire content of the conventionally employed carbon black filler is replaced by a highly active silica. In all cases the organosilane bis(triethoxysilylpropyl)tetrasulphane (TESPT) was used as a coupler between silica and polymer in order to achieve the tyre properties required nowadays.
The present invention provides rubber mixtures vulcanisable with sulphur and comprising in addition to the conventional auxiliary substances 1. S. Wolff, 129'h Meeting of lhe Rubber Division. A nerican Chcmical Socicty, Ncw York, April 8-11, 1986 2. S . Wolff, Third Annual Meeting and C r ~ : of Tirc Science and T. ' . ' g~, The Tire Society, Akron, OhiolUSA, March 28-~9, 1984 a) from 10 to loo parts of a precipitated silica, b) from O to 100 parts of a rubber carbon black, in each case referred to 100 parts of the c) copolymer also comprised, which consists of a conjugated diene contAining an aromatic vinyl component, prepared by the solution polymerisation process, having a styrene content of between 10 and 40% and a vinyl content of between 20 and 80~, preferably from 40 to 60~, and a glass transition temperature of from O to -60C, or blends of these copolymers with other diene rubbers, with the proportion of these diene rubbers constituting ~p to 60 to 100 parts of the blends, d) and from 1 to 20 parts, preferably 5 to 10 parts, of an organosilane compound corresponding to the general formula (I) (RO)3Si(CH233SCN (I) wherein R signifies alkyl, branched or unbranched having 1 to 8 C atoms, preferably 1 to 4 C atoms, referred to 100 parts of silica.
Preferably used are precipitated silicas having a BET
surface area (ISO 5794/lD) of between 100 and 250 m2/g, in particular when they have a C~AB surface area (ASTM D3765-92) of between 100 and 250 m2/g and a DBP number of ~etween 150 and 300 ml/100 g (ASTM D1208~.
The silicas are added both in powder form and as pellets or granules. These silicas are the types known for many years as well as the new developments described, for example, in DE-OS 44 27 137.
According to the present invention additives such as, for example, inorganic fillers other than the above-mentioned 21 8606~
.
silica and silicates can be incorporated into the rubber mixture, provided that the quantities used do not obstruct the purpose of this invention.
Examples of other inorganic fillers are carbon blacks such as SRF, GPF, FEF, HAF, ISAF, FT and MT.
If carbon black is employed, a weight ratio of silica to carbon black of at least 2:1 is used.
The total proportion of fillers is not to exceed 120 parts per 100 parts of polymer.
The production of vulcanisates from the rubber mixtures according to the invention requires simply the preparation of raw rubber mixtures by the method described below, subsequent shaping of the raw mixtures according to requirement~, followed by wlcanisation in the same ~nner as for collve~tional rubber mixtures.
For the production of the vulcanisates according to this invention - in addition to the above-mentioned rubber components, the organosilane compound and the amorphous silica and according to the intended application of the vulcanisates and the requirements placed on them - the nature and quantity of the plasticisers, the nature and quantity of the compounds constituting a vulcanisation system, such as, for example, vulcanising agents, w lcanisation activators (ZnO, stearic acid), vulcanisation accelerators and other w lcanisation auxiliaries, as well as the process for the production of the wlcanisates, are carefully selected. Petroleum-based plasticisers conventionally employed in rubber may be used as the above-mentioned plasticisers.
Sulphur compounds such as those listed below are used as vulcanising agents for the production of the vulcanisates according to the invention. These sulphur compounds include, for example, sulphur, morpholine disulphide, alkylphenol disulphide, tetramethylthiuram disulphide and ~ 1 8~060 selenium dimethyl dithiocarbamate. Of these, preferably sulphur is used. The above-mentioned sulphur compounds are used in quantities of between 0.1 and 4 parts by weight, preferably between 0.5 and 3 parts by weight, referred to 100 parts by weight of the copolymer or of mixtures thereof with polymers. If a sulphur compound is used as a vulcanising agent in the production of vulcanisates according to this invention, then preferably a w lcanisation accelerator is used in addition. The wlcanisation accelerators used include, for example, thiazole compounds such as N-cyclohexyl-2-benzothiazole sulphen~ e, N,N-diiso~lo~1-2-benzothiazole sul~hen~m; de, 2-mercapt~h~n~othiazole and dibenzothiazyl disulphide;
guanidine compounds such as, for example, diphenylguanidine, triphenylguanidine, diorthotolylguanidine;
imidazoline compounds such as, for example, 2-mercaptoimidazoline;
thiourea compounds such as, for example, diethylthiourea, dibutylthiourea, trimethylthiourea and diorthotolylthiourea;
thiuram compounds such as, for example, tetramethylthiuram monosulphide, tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabutylthiuram disulphide, pentamethylene thiuram tetrasulphide;
dithioc~rh~m~te compounds such as, for example, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate;
xanthate compounds such as, for example, zinc dibutylxanthate.
The said vulcanisation accelerators are used in a quantity of between 1 and 20 parts by weight, preferably between 0.5 and 10 parts by weight, referred to 100 parts by weight of the copolymer or of mixtures thereof with the other polymers.
me organosilane and the æilica are preferably m;~e~ or even reacted with one another prior to being incorporated into the rubber mixtures, as is described in US-PS 5,116,886 (EP-B-O 442 143).
It is not absolutely essential to modify in advance the entire quantity of the silica used by means of the organosilane correspond;ng to formula (I). It is also possible to mndify only a portion in advance and to add the r~m~;nAer without prior modification.
If c~rhon black is provided as additional filler for the rubber m;Yt~re being prepared, in another variant it is possible to add the organosilane corresponding to formula (I) completely or partly as a carbon black/organosilane mixture. This is used preferably in the fonm of a granular material cont?;n;ng from 30 to 60 wt.~ of organosilane and from 70 to 40 wt.~ of cArhon black respectively. The production of 6;~;l~r granular materials is described in DE-PS 27 47 277 (US-PS 4,128,438) and can be carried out here in a corresponding m~nner.
The raw rubber mixture is prepared according to the method described below. The above-mentioned rubber components, the organosilane compound, the amorphous silica and the carbon black optionally present, as well as optionally a plasticiser, are kne~ for 3 to 10 minutes in a kneader, for example a Banbury closed mixer, at a temperature of from about 120 to 200C; a vulcanising agent such as accelerator and sulphur or another vulcanisation auxiliary is then added and mixing is continued at suitable temperatures for a further 5 to 30 minutes, either in a Banbury closed mixer or on a m; ~i ng roll, and the finished `- 21 86060 7 ~.
rubber mixture is then drawn out as rubber sheet or in the form of strips.
StAn~Ard rubber testing carried out on the vulcanisates produced from the mixtures according to the invention shows that, through the use of 3-thiocyanatopropyl-trialkoxysilanes as organosilane in combination with silicas in styrene-butadiene rubbers produced by the solution polymerisation process, a distinctly better abrasion resistance can be obtA; ne~ in cQ~p~rison with the use of TESPT with an otherwise largely identical set of values.
These vulcanisates are used for the production of mouldings and of structural components of tyres.
The examples ~elow clearly illustrate the advantages over the standard silane TESPT of the organosilane corresponding to formula (I) used in the polymer system according to the present invention.
Standard test methods for the assessment Test method Unit Tensile strength DIN 53 504 MPa Modulus 300~ DIN 53 504 MPa Stretch at break DIN 53 504 Shore hardness DIN 53 505 Impact resilience DIN 53 512 DIN abrasion DIN 53 516 mm3 MTS test DIN 53 515 The following names and abbreviations are used in the Examples of application:
Buna VSL 1950 S 25 Oil-filled L-SBR from the firm Bayer AG
having a vinyl content of 50~ and a styrene cont~nt of 25~; the glass transition temperature is -25C.
*
Buna VSL 1955 S 25 Oil-filled L-SBR from the firm Bayer AG
having a vinyl content of 55~ and a styrene content of 25~; the glass transition temperature is -20C.
*
Buna CB 24 Butadiene rubber having a proportion of 1,4 cis of at least 96~.
Naftolen ZD AFomatic oil from the firm Chemetal.
Protector G 35 Antiozonant wax from the firm Fuller.
* t rad ema rk * g Vulkanox 4020 Antioxidant from BAYER AG.
*
Vulkacit D Diphenyl~l~n;~;ne, acce~erator from BAYER AG.
*
Vul~acit CZ Benzothiazyl-2-cyclohexyl sulph~n~;de, accelerator from BAYER AG.
Ultrasil VN 3 GR Precipitated silica having an N2 surface area of 175 m2/g, a CTAB surface area of about 170 m2/g and a DBP number of 220 ml/100 g (Degussa AG).
*
Ultrasil 3370 GR Precipitated æilica according to the Patent DE P 44 27 137.9, ha~ing an N2 surface area of 170 m2/g, a CTAB surface area of 165 m2/g and a DBP number of 250 ml/100 g (Degussa AG).
20 Si 69 Bis~triethoxysilylpropyl)tetrasulphane, organosilane from Degussa AG.
Si 264 3-thiocyanat~ o~yltriethoxysilane, organosilane from Degussa AG.
* t rad emark - lO 2186060 Example 1: Comparison of Si 264 against Si 69 in the tyre tread of a passen,ger car, with ~ltrasi~*-vN 3 GR as filler Fol lAtion BUI~VSL 1950 S 25 96 96 Buna CB 24 30 30 Vltrasil*VN 3 GR 80 80 Si 69 6.4 Si 264 - 6.4 ZnO RS
Stearic ~cid 2 '2 NaftoleD~ZD 10 10 Pr~tectQ~*G 35 ~1 k~ng~ 4020 - 1.5 1.5 ~1 k~; t~D 2 2 Vulkacit~ CZ 1.7 2 ~"rh"~ 1.4 1.7 ~heometer: 165C
t~ min: S.9 3 9 t,o~ ,min: 30.0 16.8 t,~ in' 57.8 47.5 t,~- t~o~ :min: 24.2 12.9 Data on ~ulc~ni~Ate:
165 C/t9b~
T~nsile sL~uy~h tMpa~ 14.1 13.7 Mo~ c 300~ tMPa3 10.0 9.3 Shore A hardness 74 75 DIN abrasion rmm3] 97 69 Viscoelasticity data according to DIN 53 513 tan h 0C 0.437 0.424 tan ~ 60C 0.164 0.172 Si 264 in combination with ~ltrasi~ VN 3 GR shows in comparison with Si 69 distinct im~o~ - 's in abrasion where vulcAnisate properties are otherwise largely identical. In the rheometer test the advantage of Si 264 lies in the more rapid complete w lcanisation.
* trademark Example 2: Comparison of Si 264 against Si 69 in t*~e tyre tread of a passenger car, with Ultrasil 3370 GR as filler Formulation Buna*VSL 1955 S 25 96 96 Buna CB 24 30 30 Ultrasil*3370 GR 80 80 Si 69 6.4 Si 264 - 6.4 ZnO RS 3 3 Stearic acid 2 2 .
Naftolen*ZD 14 14 Protector*G 35 ~llkAnn~4020 1.5 1.5 Vulkaci~*D 2 2 VlllkAc;t CZ 1.7 2 Snlrhllr 1.4 1.7 Data on vulcAniæAte:
165C/tg5~
T~n~ile ~ ~yLh tMPa] 14.6 14.1 Modulu~ 300~ tMPa] 7.7 7.4 Stretch at break t~] 470 460 Impact resilience t%] 33 34 Shore A hardness 66 67 DIN abrasion tmm3] 111 75 ViscoelAsticity data according to DIN 53 513 E' 0C tMPa] 26.6 31.2 E" 0C lMPa] 12.2 13.3 tan ~0C 0.437 0.427 E~ 60C [MPa] 9 7 10.3 E" 60C [MPa] 1.1 1.3 -tan ~ 60C 0.116 0.123 The combination Ultrasil 3370 GR/ Si 264 e~h;b;ts distinct advantages in abrasion in comparison with Ultrasil 3370 GR/ Si 69.
* trademark
Claims (16)
1. A rubber mixture, vulcanisable with sulphur, comprising:
(a) from 10 to 100 parts of a precipitated silica relative to 100 parts of a copolymer consisting of a conjugated diene containing an aromatic vinyl component, prepared by the solution polymerisation process, having a styrene content of between 10 and 40% and a vinyl content of between 20 and 80%, and a glass transition temperature of from 0 to -60°C, or a blend of said copolymer with at least one other diene rubber, with the proportion of said other diene rubber constituting up to 60 to 100 parts of the blend, and from 1 to 20 parts, of an organosilane compound corresponding to the general formula (I) (RO)3Si(CH2)3SCN (I) wherein R signifies alkyl, branched or unbranched, having 1 to 8 C atoms, relative to 100 parts of silica.
(a) from 10 to 100 parts of a precipitated silica relative to 100 parts of a copolymer consisting of a conjugated diene containing an aromatic vinyl component, prepared by the solution polymerisation process, having a styrene content of between 10 and 40% and a vinyl content of between 20 and 80%, and a glass transition temperature of from 0 to -60°C, or a blend of said copolymer with at least one other diene rubber, with the proportion of said other diene rubber constituting up to 60 to 100 parts of the blend, and from 1 to 20 parts, of an organosilane compound corresponding to the general formula (I) (RO)3Si(CH2)3SCN (I) wherein R signifies alkyl, branched or unbranched, having 1 to 8 C atoms, relative to 100 parts of silica.
2. The rubber mixture according to claim 1, further comprising:
(b) up to 100 parts of a rubber carbon black relative to the copolymer.
(b) up to 100 parts of a rubber carbon black relative to the copolymer.
3. The rubber mixture according to claim 2, wherein said vinyl content is from 40 to 60%, said organosilane compound constitutes from 5 to 10 parts, and R has 1 to 4 C
atoms.
atoms.
4. The rubber mixture according to claim 2, comprising as diene rubbers polyisoprene, natural rubber, a polybutadiene having a proportion of 1,4 cis bonds of > 90%
or a mixture thereof.
or a mixture thereof.
5. The rubber mixture according to any one of claims 1 to 4, comprising a silica having a specific surface area of between 100 and 250 m2/g, a CTAB surface areas of between 100 and 250 m2/g and a DBP number of between 150 and 300 ml/100 g, as powder or in a form low in dust.
6. The rubber mixture according to claim 5, comprising 40 to 80 parts of the silica.
7. The rubber mixture according to any one of claims 2 to 4 and 6, wherein the weight ration of the silica to the carbon black, when present, is at least 2:1.
8. The rubber mixture according to claim 7, wherein the total amount of fillers is at most 120 parts per 100 parts of the copolymer.
9. The rubber mixture according to any one of claims 1 to 4, 6 and 8, wherein the silica, prior to being incorporated into the rubber mixture, is mixed or reacted with the organosilane corresponding to formula (I).
10. The rubber mixture according claim 9, comprising a granular mixture of said organosilane and carbon black.
11. The rubber mixture according to claim 10, wherein said granular mixture comprises from 30 to 60% of the organosilane and from 70 to 40% of the carbon black.
12. The rubber mixture according to any one of claims 1 to 4, 6, 8, 10 and 11, comprising at least one auxiliary agent.
13. A method for the preparation of the rubber mixture according to any one of claims 1 to 4, 6, 8, 10 and 11, characterised in that the rubber component(s), the organosilane compound, the silica and the carbon black, when present, are kneaded for 3 to 10 minutes in a kneader, at a temperature of from 120 to 200°C; a vulcanising agent is then added and mixing is continued at suitable temperatures for a further 5 to 30 minutes, and the finished rubber mixture is then drawn as rubber sheet or in the form of strips.
14. The method of claim 13, wherein kneading is effected in the presence of a plasticiser and in a Banbury closed mixer, wherein the vulcanising agent is an accelerator and sulphur or a vulcanisation auxiliary, and wherein the mixing is effected in a Banbury closed mixer or on a mixing roll.
15. The use of the rubber mixture according to any one of claims 1 to 4, 6, 8, 10 and 11 for production of mouldings and of structural components of tyres having a decreased abrasion.
16. Mouldings and structural components for tyres having a decreased abrasion prepared from the rubber mixture of any one of claims 1 to 4, 6, 8, 10 and 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19535394 | 1995-09-23 | ||
| DE19544469A DE19544469A1 (en) | 1995-09-23 | 1995-11-29 | Vulcanizable rubber compounds containing organosilane compounds and silica and process for producing them |
| DE19544469.8 | 1995-11-29 | ||
| DE19535394.3 | 1995-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2186060A1 true CA2186060A1 (en) | 1997-03-24 |
Family
ID=26018864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2186060 Abandoned CA2186060A1 (en) | 1995-09-23 | 1996-09-20 | Process for the preparation of vulcanisable rubber mixtures and the mixtures thus prepared |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0764687A1 (en) |
| JP (1) | JPH09176383A (en) |
| CN (1) | CN1148607A (en) |
| AU (1) | AU6576196A (en) |
| CA (1) | CA2186060A1 (en) |
| MX (1) | MX9603304A (en) |
| PL (1) | PL316128A1 (en) |
| SK (1) | SK119196A3 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936112A (en) * | 1997-07-30 | 1999-08-10 | Degussa Aktiengesellschaft | Mixtures consisting of bis (silylorganyl) polysulfans and silyorganylthiocyanates, their production, and use |
| US6252008B1 (en) | 1998-07-18 | 2001-06-26 | Bayer Aktiengesellschaft | Solution rubbers containing hydroxyl groups |
| US6313211B1 (en) | 1998-04-02 | 2001-11-06 | Bayer Aktiengesellschaft | Emulsion rubber mixtures containing hydrophobic-rendered oxide or silicate type fillers and their use for producing tires |
| US6521684B2 (en) | 2000-03-15 | 2003-02-18 | Bayer Aktiengesellschaft | Polyether-containing rubber mixtures |
| US6521698B2 (en) | 2000-03-01 | 2003-02-18 | Bayer Aktiengesellschaft | Rubbers with polyether side groups |
| US6576731B2 (en) | 2000-07-27 | 2003-06-10 | Bayer Aktiengesellschaft | Polybutadienes with a reduced solution viscosity/mooney viscosity ratio |
| US6699937B1 (en) | 1999-04-01 | 2004-03-02 | Bayer Aktiengesellschaft | Rubber compositions containing hydroxyl groups |
| US6815484B2 (en) | 2001-07-18 | 2004-11-09 | Bayer Aktiengesellschaft | Rubber mixtures containing 1,4-butenediol (polyether) |
| US7160956B2 (en) | 2002-04-15 | 2007-01-09 | Rhein Chehie Rheinau Gmbh | Vulcanizable rubber compounds and process for their production |
| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0958298B2 (en) † | 1997-08-21 | 2008-10-22 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents for filled rubbers |
| US6221196B1 (en) | 1998-04-08 | 2001-04-24 | Firma Carl Freudenberg | Method for improving the adhesion of an elastomeric, polymeric material to a support element |
| DE19815758C2 (en) * | 1998-04-08 | 2001-08-16 | Freudenberg Carl Fa | Process for improving the connection of an elastomeric, polymeric rubber to a support element |
| US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
| US6635700B2 (en) | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
| JP4138729B2 (en) * | 2004-11-01 | 2008-08-27 | 住友ゴム工業株式会社 | Rubber composition and tire comprising the same |
| EP1770122B1 (en) * | 2005-09-26 | 2011-03-16 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and tire using the same |
| EP2311889A1 (en) | 2009-10-16 | 2011-04-20 | LANXESS Deutschland GmbH | Neodym-catalysed polybutadiene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4004781A1 (en) * | 1990-02-16 | 1991-08-22 | Degussa | Modifying surface of natural or synthetic oxidic or silicate fillers - using organo:silicon cpds. useful in vulcanisable natural rubber mixts. to improve rubber properties |
| GB9318849D0 (en) * | 1993-09-11 | 1993-10-27 | Sumitomo Rubber Ind | Rubber compositions |
| GB9318850D0 (en) * | 1993-09-11 | 1993-10-27 | Sumitomo Rubber Ind | Rubber compositions |
| DE4400996C2 (en) * | 1994-01-14 | 1997-04-24 | Uniroyal Englebert Gmbh | Tire tread |
-
1996
- 1996-08-09 MX MX9603304A patent/MX9603304A/en unknown
- 1996-08-20 EP EP96113278A patent/EP0764687A1/en not_active Withdrawn
- 1996-09-17 CN CN 96113102 patent/CN1148607A/en active Pending
- 1996-09-18 PL PL31612896A patent/PL316128A1/en unknown
- 1996-09-18 SK SK119196A patent/SK119196A3/en unknown
- 1996-09-20 CA CA 2186060 patent/CA2186060A1/en not_active Abandoned
- 1996-09-20 JP JP8250320A patent/JPH09176383A/en active Pending
- 1996-09-20 AU AU65761/96A patent/AU6576196A/en not_active Abandoned
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936112A (en) * | 1997-07-30 | 1999-08-10 | Degussa Aktiengesellschaft | Mixtures consisting of bis (silylorganyl) polysulfans and silyorganylthiocyanates, their production, and use |
| US6313211B1 (en) | 1998-04-02 | 2001-11-06 | Bayer Aktiengesellschaft | Emulsion rubber mixtures containing hydrophobic-rendered oxide or silicate type fillers and their use for producing tires |
| US6252008B1 (en) | 1998-07-18 | 2001-06-26 | Bayer Aktiengesellschaft | Solution rubbers containing hydroxyl groups |
| US6319994B2 (en) | 1998-07-18 | 2001-11-20 | Bayer Aktiengesellschaft | Solution rubbers containing hydroxyl groups |
| US6699937B1 (en) | 1999-04-01 | 2004-03-02 | Bayer Aktiengesellschaft | Rubber compositions containing hydroxyl groups |
| US6521698B2 (en) | 2000-03-01 | 2003-02-18 | Bayer Aktiengesellschaft | Rubbers with polyether side groups |
| US6521684B2 (en) | 2000-03-15 | 2003-02-18 | Bayer Aktiengesellschaft | Polyether-containing rubber mixtures |
| US6576731B2 (en) | 2000-07-27 | 2003-06-10 | Bayer Aktiengesellschaft | Polybutadienes with a reduced solution viscosity/mooney viscosity ratio |
| US6815484B2 (en) | 2001-07-18 | 2004-11-09 | Bayer Aktiengesellschaft | Rubber mixtures containing 1,4-butenediol (polyether) |
| US7160956B2 (en) | 2002-04-15 | 2007-01-09 | Rhein Chehie Rheinau Gmbh | Vulcanizable rubber compounds and process for their production |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8067491B2 (en) | 2006-12-28 | 2011-11-29 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US8188174B2 (en) | 2006-12-28 | 2012-05-29 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US8383850B2 (en) | 2006-12-28 | 2013-02-26 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US8501849B2 (en) | 2006-12-28 | 2013-08-06 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
| US8669389B2 (en) | 2006-12-28 | 2014-03-11 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making the uses in rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6576196A (en) | 1997-03-27 |
| SK119196A3 (en) | 1997-04-09 |
| EP0764687A1 (en) | 1997-03-26 |
| CN1148607A (en) | 1997-04-30 |
| PL316128A1 (en) | 1997-04-01 |
| JPH09176383A (en) | 1997-07-08 |
| MX9603304A (en) | 1997-03-29 |
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