CA2177095A1 - Blends of organosilane compounds and their use - Google Patents
Blends of organosilane compounds and their useInfo
- Publication number
- CA2177095A1 CA2177095A1 CA002177095A CA2177095A CA2177095A1 CA 2177095 A1 CA2177095 A1 CA 2177095A1 CA 002177095 A CA002177095 A CA 002177095A CA 2177095 A CA2177095 A CA 2177095A CA 2177095 A1 CA2177095 A1 CA 2177095A1
- Authority
- CA
- Canada
- Prior art keywords
- blends
- organosilane compounds
- filler
- vulcanisable
- parts
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
-
- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention relates to blends of sulphur-containing organosilanes and alkylalkoxysilanes, their use in vulcanisable rubber mixtures and moulding compositions and the mixtures so produced.
Description
2 1 7~95 Blends of organ~silane compounds and their use The invention relates to blends of organosilane compounds, s their use in vulcanisable rubber mixtures and moulding compositions and the associated mixtures.
It is known that organosilanes in combination with pale-coloured fillers, in particular active, precipitated 10 silica, can be used in rubber mixtures (1). By partly or completely substituting carbon black filler with this combination, in particular in the tyre sector, unimagined improvements in vulcanising characteristics can now be produced. An example in this connection is the production 15 of reversion-stable rubber mixtures, which have proved advantageous in particular for heavy-duty OTR tyres with long heating times (2). In addition, the use of silica combined with bis(triethyoxy-silylpropyl)tetrasulphane leads above all to a reduction in the generation of heat in 20 tyres, especially heavy goods vehicle tyres, under stress (3). The currently most important and recent application of this system relates to reducing the rolling resistance (4) of tyres by replacing the carbon black, with the advantage of a reduction in petrol consumption.
The object of many recent applications and patents is this particularly important property, it being accompanied by a reduction in the production of hazardous substances. The following applications may be mentioned: EP-Al 0447 066, 30 EP-Al 0620 250 and US-PS S,227,425.
It is shown that the use of silica combined with bis(triethoxysilylpropyl)tetrasulphane instead of carbon black as a filler leads to a considerable reduction in 35 rolling resistance and in equally important tyre properties such as resistance to wet skidding and abrasion resistance.
; 21 7~095 It has now been found that blends of bis(trialkoxysilylalkylene)polysulphanes and alkyltrialkoxysilanes, as compared with the use of bis(trialkoxysilylpropyl)polysulphane as the only organosilane compound, leads to synergistic effects, in particular to clear improvements in the tear propagation resistance and fatigue characteristics of the rubber mixture with an otherwise almost identical set of general properties.
The invention provides blends consisting of organosilane compounds in accordance with the general formulas:
[(R)3Si(cHz)3sx]2 (I) and (R'O)3si(cH2)y~CH3 (II) in which R represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, preferably with 1-4 carbon atoms, x represents 1-4, preferably 1-3, R' represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, preferably with 1-4 carbon atoms, wherein R and R' may be identical or different, y represents 1-19, preferably 1-6 and the proportion of the compound of formula (I) in the blend is 40 to 95 wt.%, preferably 70 to 95 wt.%, and accordingly the proportion of the silane of formula (II) is 5 to 60 wt.%, preferably 5 to 30 wt.~.
Blends which consist of bis(trialkoxysilylpropyl~-tetrasulphane or -disulphane and trialkoxypropylsilane in 2 1 770q5 which the alkoxy groups are CH30- or C2H5O- are particularly preferred.
These blends are generally used in vulcanisable moulding compositions and rubber mixtures, which optionally contain pale-coloured fillers combined with carbon black, which are conventionally used in the rubber sector.
These pale-coloured fillers include oxide and silicate fillers based on naturally occurring substances such as, - for instance, clays and silica chalks or synthetic fillers such as silicas and silicates obtained by precipitation.
Synthetic fillers are preferably used according to the invention.
Accordingly, mixtures of organosilanes (I) and (II) with one or more of the pale-coloured fillers mentioned are also provided by the invention.
These contain 30 to 95 wt.~ of filler, with respect to the total amount of organosilane compound.
Silicate fillers and precipitated silicas which have reactive silanol groups at the surface and a specific surface area between 1 and 220 m2/g (ISO 5794/ID) are preferably used, in particular if the DBP index (ASTM D
2414) is determined to be 150 to 300 ml/100 g.
The reaction between filler surface and the alkoxy groups in the organosilane compounds proceeds at the appropriate temperature either completely or partly during blending with the filler (US-PS 4,297,146, US-PS 5,116,886) or else only after production of the moulding composition or rubber mixture, then completely in each case.
, ` - 21 ~7Q95 The total amount of organosilane compound in the moulding composition or rubber mixture amounts to 0.1 to 20 wt.~, with respect to the amount of pale-coloured filler. Thus, if a pale-coloured filler with a high proportion by weight of organosilane compound is admixed, a corresponding amount of silicate filler or silica whose surface can subsequently react with the still unreacted organosilane compound has to be added to the mixture to be vulcanised.
In many cases a conventionally used carbon black as an additional filler, optionally also in a blend with organosilane compounds (I) and (II), is used. The amount of carbon black amounts to 0 to 150 parts per 100 parts of polymer.
The pale-coloured filler, in particular precipitated silica, is preferably used in this application in an amount of 10 to 250, preferably 25 to 80 parts, with respect to 100 parts of polymer, optionally with the addition of 1 to 20 parts of carbon black.
The total amount of filler should not exceed 250 parts by weight.
It is advantageous to use the filler, whether or not is has been modified with organosilane compounds (I) and (II), in granulated or pelletised form.
According to the invention, the new blends with and without additional filler are used in vulcanisable moulding compositions and rubber mixtures.
These are crosslinkable natural and synthetic elastomers with conventional accelerators and sulphur, oil-extended or not, as individual polymers or blended with other rubbers such as, for instance, natural rubbers, butadiene rubbers, isoprene rubbers, butadiene/styrene rubbers, j 21 7709~
butadiene/acrylonitrile rubbers, butyl rubbers, terpolymers made from ethylene, propylene and non-conjugated dienes.
Furthermore, the following additional rubbers may be considered for rubber mixtures with the rubbers mentioned above: carboxyl rubbers, epoxide rubbers, trans-polypentenamers, halogenated butyl rubbers, rubbers made from 2-chlorobutadiene, ethylene/vinylacetate copolymers, optionally also chemical derivatives of natural rubber and modified natural rubbers.
An SBR prepared by the solution polymerisation process, mixed with other diene rubbers with not less than 30 parts per 100 of the other rubbers, is preferably used.
Components in the wlcanisable moulding compositions and rubber mixtures are conventional auxiliary agents such as plasticisers, stabilisers, activators, pigments, antioxidants and processing agents in conventional amounts.
The mixtures are prepared using mixing units which are used in the rubber industry such as internal mixers and roll mills.
Organosilane blends according to the invention may be used in all rubber applications such as, for example, tyres, conveyor belts, sealants, V-bel~s, hoses, etc. and lead to improved tear propagation resistances and fatigue characteristics for the vulcanisate even when the total amount of blend is no greater than the amount of tetrasulphane in the comparison mixture.
`. 2~ 7~5 (lJ S. Wolff, "Silanes in Tire Compounding after ten Years Review, Third Annual meeting and Conference on Tire Science and Technology, The Tire Society, March 28-29, 1984, Akron, Ohio/USA
s (2) S. Wolff, Kautschuk und Gummi, Runststoffe" 10 (1979), pages 760 et seq., US-PS 4,517,336 10 (3J S. Wolff, R. Panenka "Present Possibilities to Reduce Heat Generation of Tire Compounds" International Rubber Conference, October 15-18, 1985, Kyoto/Japan (4J S. Wolff n The Influence of Fillers on Rolling Resistance" 129th Meeting of the Rubber Division American Chemical Society, April 8-11, 1986, New York, N.J./USA
" ` 21 77095 The following test standards are used in the examples:
Unit Standard 5 Tensile strength MPa DIN 53 504 300 ~ modulus MPa DIN 53 504 Tear propagation resistance N/mm DIN 53 507 Shore A hardness - DIN 53 505 DIN abrasion mm3 DIN 53 516 Crack growth (De Mattia) Kc ASTM D 813 In the application examples, the following chemicals are used:
First Latex Crepe Natural rubber Si 69 Bis(triethoxysilylpropyl)tetrasulphane from Degussa AG
Si 69/Si 203 Blend of bis(triethoxysilylpropyl)tetrasulphane and triethoxypropylsilane (ratio by amounts) Ingraplast NS Mineral oil plasticiser Vulkanox BKF Phenolic antioxidant from Bayer AG
Vulkacit DM Dibenzothiazyl disulphide, accelerator from Bayer AG
Hexa K Hexamethylenetetramine from Degussa AG
30 P extra N Dithiocarbamate, accelerator from Bayer AG
Buna VSL 1955 S 25 Styrene/butadiene rubber based on solution polymerisation from Bayer Buna CB 24 Polybutadiene rubber from Bayer 3~ Naftolen ZD Aromatic plasticiser from Chemetal Vulkanox 4020 Colouring antioxidant based on phenylenediamine from Bayer AG
21 ~7(395 Protector G 35 Anti-ozonant wax from Fuller Vulkacit D Diphenylguanidine, accelerator from Bayer AG
Vulkacit CZ Benzothiazyl-2-cyclohexylsuphenamide accelerator from Bayer AG
Cariflex Styrene/butadiene rubber based on emulsion polymerisation from Exxon Ultrasil VN 3 GR Precipitated silica with a BET surface area of 175 m2/g from Degussa AG
10 Polywachs 6000 Silica activator Vulkacit Merkapto 2-mercaptobenzothiazol from Bayer AG
- 21 ~7~5 g ExamPle l:Comparison of Si 69 with Si 69/Si 203 and Si 69/Si 216 blends in a mixture based on NR
Forrnulation First Latex Crepe 100 100 100 100 100 Ultrasil VN 3GR 50 50 50 50 50 ZnO active ~ 2 2 2 2 2 Benzoic acid 0.8 0.8 0.8 0.8 0.8 Si69 3 - - - -Si69/Si203go:1o 3 Si69/Si203 80:20 - - 3 Si69/Si203 70:30 3 Si69/Si216 90:10 - - - - 3 I~y~ asl NS 3 3 3 3 3 Vulkanox BKF
DEG
Vulkacit DM 0.8 0.8 0.8 0.8 0.8 Hexa K 1.6 1.6 1.6 1.6 1.6 P extra N 0.3 0.3 0.3 0.3 0.3 Sulphur 2.8 2.8 2.8 2.8 2.8 - - 21 77~5 Vuic~-lisate dab: 145-C/tg5% 1 2 3 4 5 Tensile strength [MPa~ 24.8 25.4 24.7 24.9 25.0 300 % modulus [I\~lPa] 9 3 8.8 9.1 9.0 9.3 Tear propagation r~:,is~ance ~N/mm] 30 42 41 37 38 Shore A hardness 76 76 78 77 77 DIN al~ld~ion lmm3] 153 153 148 153 157 Fatigue properties De Mattia 2 mm - 4 mm [kc] 1.3 2.2 1.4 1.4 1.5 4 mm - 8 mm [kc] 7.8 19.6 13.2 14.7 13.8 8 mm - 12 mm [kc] 20.5 63.7 43.4 51.9 44.8 The compounds according to the invention show, as compared with pure Si 69, considerable improvements in tear propagation resistance and fatigue characteristics (crack propagation) with otherwise approximately the same general properties.
2 1 77~5 ;
Example 2:Comparison of Si 69 with Si 69/Si 203 blends in S-SBR/BR motor car wheel treads Fol-..uldlion Buna VSL 1955 S 25 96 96 96 Buna CB 24 30 30 30 Ultrasil VN 3 GR 80 80 80 Si 69 6.4 - -Si 69/Si203 90:10 - 6.4 Si 69/Si203 80:20 - - 6.4 ZnO RS 3 3 3 Stearic acid 2 2 2 Naftolen ZD 15 15 15 Vulkanox 4020 1.5 1.5 1.5 Protector G 35 Vulkacit D 2 2 2 Vulkacit CZ 1.7 1.7 1.7 Sulphur 1.4 1.4 1.4 ' ` - 21 77095 Vulcanisate data: 165C/tgs% 1 2 3 Tensile strength lMPa] 14.4 14.1 14.8 300% modulus [MPa] 8.4 8.2 8.0 Tear propagation resistance [N/mm]
DIN abrasion [mm3]
De Mattia (crack propagation) 2mm-4mm[kc] 0.3 0.3 0.8 4mm-8mm[kc] 1.3 1.9 2.5 8mm-12mmlkc] 2.8 4.9 5.1 MTS testing tan ~ 0C 0.490 0.482 0.494 0.139 0.138 0.143 tan ~ 60C
As in example 1, the compounds according to the invention, as compared with pure Si 69, showed much better values for tear propagation resistance and De Mattia crack propagation properties, with otherwise largely similar general properties.
2 t 1 7 j~q5 xample 3:Comparison of Si 69 with Si 69/Si 203 blends in E-SBR
~ormulation Cariflex 1509 100 100 100 Ultrasil VN 3 GR 50 50 50 ZnO RS 3 3 3 Stearic acid 2 2 2 Si 69 3 _ _ Si 69/Si 203 90:10 - 3 Si 69/ Si 203 80:20 _ _ 3 Polywachs 6000 1.5 1.5 1.5 Vulkacit DM 1.2 1.2 1.2 Vulkacit Merkapto 0,7 0,7 0.7 Sulphur 2.0 2.0 2.0 Vulcanisate data: 1 2 3 155C/t,s~
Tensile strength [MPa] 16.4 16.2 15.7 300 ~ modulus [MPa]11.3 10.9 10.3 Tear propagation resistance [N/mm] 8 12 14 Shore A hardness 75 74 73 DIN abrasion [mm3] 112 108 110 De Mattia (crack propagation) 2 mm - 4 mm [kc] 0.1 0.1 0.2 4 mm - 8 mm [kc] 0.6 0.8 1.3 8 mm - 12 mm [kc] 2.0 3.0 3.8 As in the preceding examples, the compounds according to the invention, as compared with pure Si 69, showed clear advantages in De Mattia and crack propagation resistance characteristics.
It is known that organosilanes in combination with pale-coloured fillers, in particular active, precipitated 10 silica, can be used in rubber mixtures (1). By partly or completely substituting carbon black filler with this combination, in particular in the tyre sector, unimagined improvements in vulcanising characteristics can now be produced. An example in this connection is the production 15 of reversion-stable rubber mixtures, which have proved advantageous in particular for heavy-duty OTR tyres with long heating times (2). In addition, the use of silica combined with bis(triethyoxy-silylpropyl)tetrasulphane leads above all to a reduction in the generation of heat in 20 tyres, especially heavy goods vehicle tyres, under stress (3). The currently most important and recent application of this system relates to reducing the rolling resistance (4) of tyres by replacing the carbon black, with the advantage of a reduction in petrol consumption.
The object of many recent applications and patents is this particularly important property, it being accompanied by a reduction in the production of hazardous substances. The following applications may be mentioned: EP-Al 0447 066, 30 EP-Al 0620 250 and US-PS S,227,425.
It is shown that the use of silica combined with bis(triethoxysilylpropyl)tetrasulphane instead of carbon black as a filler leads to a considerable reduction in 35 rolling resistance and in equally important tyre properties such as resistance to wet skidding and abrasion resistance.
; 21 7~095 It has now been found that blends of bis(trialkoxysilylalkylene)polysulphanes and alkyltrialkoxysilanes, as compared with the use of bis(trialkoxysilylpropyl)polysulphane as the only organosilane compound, leads to synergistic effects, in particular to clear improvements in the tear propagation resistance and fatigue characteristics of the rubber mixture with an otherwise almost identical set of general properties.
The invention provides blends consisting of organosilane compounds in accordance with the general formulas:
[(R)3Si(cHz)3sx]2 (I) and (R'O)3si(cH2)y~CH3 (II) in which R represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, preferably with 1-4 carbon atoms, x represents 1-4, preferably 1-3, R' represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, preferably with 1-4 carbon atoms, wherein R and R' may be identical or different, y represents 1-19, preferably 1-6 and the proportion of the compound of formula (I) in the blend is 40 to 95 wt.%, preferably 70 to 95 wt.%, and accordingly the proportion of the silane of formula (II) is 5 to 60 wt.%, preferably 5 to 30 wt.~.
Blends which consist of bis(trialkoxysilylpropyl~-tetrasulphane or -disulphane and trialkoxypropylsilane in 2 1 770q5 which the alkoxy groups are CH30- or C2H5O- are particularly preferred.
These blends are generally used in vulcanisable moulding compositions and rubber mixtures, which optionally contain pale-coloured fillers combined with carbon black, which are conventionally used in the rubber sector.
These pale-coloured fillers include oxide and silicate fillers based on naturally occurring substances such as, - for instance, clays and silica chalks or synthetic fillers such as silicas and silicates obtained by precipitation.
Synthetic fillers are preferably used according to the invention.
Accordingly, mixtures of organosilanes (I) and (II) with one or more of the pale-coloured fillers mentioned are also provided by the invention.
These contain 30 to 95 wt.~ of filler, with respect to the total amount of organosilane compound.
Silicate fillers and precipitated silicas which have reactive silanol groups at the surface and a specific surface area between 1 and 220 m2/g (ISO 5794/ID) are preferably used, in particular if the DBP index (ASTM D
2414) is determined to be 150 to 300 ml/100 g.
The reaction between filler surface and the alkoxy groups in the organosilane compounds proceeds at the appropriate temperature either completely or partly during blending with the filler (US-PS 4,297,146, US-PS 5,116,886) or else only after production of the moulding composition or rubber mixture, then completely in each case.
, ` - 21 ~7Q95 The total amount of organosilane compound in the moulding composition or rubber mixture amounts to 0.1 to 20 wt.~, with respect to the amount of pale-coloured filler. Thus, if a pale-coloured filler with a high proportion by weight of organosilane compound is admixed, a corresponding amount of silicate filler or silica whose surface can subsequently react with the still unreacted organosilane compound has to be added to the mixture to be vulcanised.
In many cases a conventionally used carbon black as an additional filler, optionally also in a blend with organosilane compounds (I) and (II), is used. The amount of carbon black amounts to 0 to 150 parts per 100 parts of polymer.
The pale-coloured filler, in particular precipitated silica, is preferably used in this application in an amount of 10 to 250, preferably 25 to 80 parts, with respect to 100 parts of polymer, optionally with the addition of 1 to 20 parts of carbon black.
The total amount of filler should not exceed 250 parts by weight.
It is advantageous to use the filler, whether or not is has been modified with organosilane compounds (I) and (II), in granulated or pelletised form.
According to the invention, the new blends with and without additional filler are used in vulcanisable moulding compositions and rubber mixtures.
These are crosslinkable natural and synthetic elastomers with conventional accelerators and sulphur, oil-extended or not, as individual polymers or blended with other rubbers such as, for instance, natural rubbers, butadiene rubbers, isoprene rubbers, butadiene/styrene rubbers, j 21 7709~
butadiene/acrylonitrile rubbers, butyl rubbers, terpolymers made from ethylene, propylene and non-conjugated dienes.
Furthermore, the following additional rubbers may be considered for rubber mixtures with the rubbers mentioned above: carboxyl rubbers, epoxide rubbers, trans-polypentenamers, halogenated butyl rubbers, rubbers made from 2-chlorobutadiene, ethylene/vinylacetate copolymers, optionally also chemical derivatives of natural rubber and modified natural rubbers.
An SBR prepared by the solution polymerisation process, mixed with other diene rubbers with not less than 30 parts per 100 of the other rubbers, is preferably used.
Components in the wlcanisable moulding compositions and rubber mixtures are conventional auxiliary agents such as plasticisers, stabilisers, activators, pigments, antioxidants and processing agents in conventional amounts.
The mixtures are prepared using mixing units which are used in the rubber industry such as internal mixers and roll mills.
Organosilane blends according to the invention may be used in all rubber applications such as, for example, tyres, conveyor belts, sealants, V-bel~s, hoses, etc. and lead to improved tear propagation resistances and fatigue characteristics for the vulcanisate even when the total amount of blend is no greater than the amount of tetrasulphane in the comparison mixture.
`. 2~ 7~5 (lJ S. Wolff, "Silanes in Tire Compounding after ten Years Review, Third Annual meeting and Conference on Tire Science and Technology, The Tire Society, March 28-29, 1984, Akron, Ohio/USA
s (2) S. Wolff, Kautschuk und Gummi, Runststoffe" 10 (1979), pages 760 et seq., US-PS 4,517,336 10 (3J S. Wolff, R. Panenka "Present Possibilities to Reduce Heat Generation of Tire Compounds" International Rubber Conference, October 15-18, 1985, Kyoto/Japan (4J S. Wolff n The Influence of Fillers on Rolling Resistance" 129th Meeting of the Rubber Division American Chemical Society, April 8-11, 1986, New York, N.J./USA
" ` 21 77095 The following test standards are used in the examples:
Unit Standard 5 Tensile strength MPa DIN 53 504 300 ~ modulus MPa DIN 53 504 Tear propagation resistance N/mm DIN 53 507 Shore A hardness - DIN 53 505 DIN abrasion mm3 DIN 53 516 Crack growth (De Mattia) Kc ASTM D 813 In the application examples, the following chemicals are used:
First Latex Crepe Natural rubber Si 69 Bis(triethoxysilylpropyl)tetrasulphane from Degussa AG
Si 69/Si 203 Blend of bis(triethoxysilylpropyl)tetrasulphane and triethoxypropylsilane (ratio by amounts) Ingraplast NS Mineral oil plasticiser Vulkanox BKF Phenolic antioxidant from Bayer AG
Vulkacit DM Dibenzothiazyl disulphide, accelerator from Bayer AG
Hexa K Hexamethylenetetramine from Degussa AG
30 P extra N Dithiocarbamate, accelerator from Bayer AG
Buna VSL 1955 S 25 Styrene/butadiene rubber based on solution polymerisation from Bayer Buna CB 24 Polybutadiene rubber from Bayer 3~ Naftolen ZD Aromatic plasticiser from Chemetal Vulkanox 4020 Colouring antioxidant based on phenylenediamine from Bayer AG
21 ~7(395 Protector G 35 Anti-ozonant wax from Fuller Vulkacit D Diphenylguanidine, accelerator from Bayer AG
Vulkacit CZ Benzothiazyl-2-cyclohexylsuphenamide accelerator from Bayer AG
Cariflex Styrene/butadiene rubber based on emulsion polymerisation from Exxon Ultrasil VN 3 GR Precipitated silica with a BET surface area of 175 m2/g from Degussa AG
10 Polywachs 6000 Silica activator Vulkacit Merkapto 2-mercaptobenzothiazol from Bayer AG
- 21 ~7~5 g ExamPle l:Comparison of Si 69 with Si 69/Si 203 and Si 69/Si 216 blends in a mixture based on NR
Forrnulation First Latex Crepe 100 100 100 100 100 Ultrasil VN 3GR 50 50 50 50 50 ZnO active ~ 2 2 2 2 2 Benzoic acid 0.8 0.8 0.8 0.8 0.8 Si69 3 - - - -Si69/Si203go:1o 3 Si69/Si203 80:20 - - 3 Si69/Si203 70:30 3 Si69/Si216 90:10 - - - - 3 I~y~ asl NS 3 3 3 3 3 Vulkanox BKF
DEG
Vulkacit DM 0.8 0.8 0.8 0.8 0.8 Hexa K 1.6 1.6 1.6 1.6 1.6 P extra N 0.3 0.3 0.3 0.3 0.3 Sulphur 2.8 2.8 2.8 2.8 2.8 - - 21 77~5 Vuic~-lisate dab: 145-C/tg5% 1 2 3 4 5 Tensile strength [MPa~ 24.8 25.4 24.7 24.9 25.0 300 % modulus [I\~lPa] 9 3 8.8 9.1 9.0 9.3 Tear propagation r~:,is~ance ~N/mm] 30 42 41 37 38 Shore A hardness 76 76 78 77 77 DIN al~ld~ion lmm3] 153 153 148 153 157 Fatigue properties De Mattia 2 mm - 4 mm [kc] 1.3 2.2 1.4 1.4 1.5 4 mm - 8 mm [kc] 7.8 19.6 13.2 14.7 13.8 8 mm - 12 mm [kc] 20.5 63.7 43.4 51.9 44.8 The compounds according to the invention show, as compared with pure Si 69, considerable improvements in tear propagation resistance and fatigue characteristics (crack propagation) with otherwise approximately the same general properties.
2 1 77~5 ;
Example 2:Comparison of Si 69 with Si 69/Si 203 blends in S-SBR/BR motor car wheel treads Fol-..uldlion Buna VSL 1955 S 25 96 96 96 Buna CB 24 30 30 30 Ultrasil VN 3 GR 80 80 80 Si 69 6.4 - -Si 69/Si203 90:10 - 6.4 Si 69/Si203 80:20 - - 6.4 ZnO RS 3 3 3 Stearic acid 2 2 2 Naftolen ZD 15 15 15 Vulkanox 4020 1.5 1.5 1.5 Protector G 35 Vulkacit D 2 2 2 Vulkacit CZ 1.7 1.7 1.7 Sulphur 1.4 1.4 1.4 ' ` - 21 77095 Vulcanisate data: 165C/tgs% 1 2 3 Tensile strength lMPa] 14.4 14.1 14.8 300% modulus [MPa] 8.4 8.2 8.0 Tear propagation resistance [N/mm]
DIN abrasion [mm3]
De Mattia (crack propagation) 2mm-4mm[kc] 0.3 0.3 0.8 4mm-8mm[kc] 1.3 1.9 2.5 8mm-12mmlkc] 2.8 4.9 5.1 MTS testing tan ~ 0C 0.490 0.482 0.494 0.139 0.138 0.143 tan ~ 60C
As in example 1, the compounds according to the invention, as compared with pure Si 69, showed much better values for tear propagation resistance and De Mattia crack propagation properties, with otherwise largely similar general properties.
2 t 1 7 j~q5 xample 3:Comparison of Si 69 with Si 69/Si 203 blends in E-SBR
~ormulation Cariflex 1509 100 100 100 Ultrasil VN 3 GR 50 50 50 ZnO RS 3 3 3 Stearic acid 2 2 2 Si 69 3 _ _ Si 69/Si 203 90:10 - 3 Si 69/ Si 203 80:20 _ _ 3 Polywachs 6000 1.5 1.5 1.5 Vulkacit DM 1.2 1.2 1.2 Vulkacit Merkapto 0,7 0,7 0.7 Sulphur 2.0 2.0 2.0 Vulcanisate data: 1 2 3 155C/t,s~
Tensile strength [MPa] 16.4 16.2 15.7 300 ~ modulus [MPa]11.3 10.9 10.3 Tear propagation resistance [N/mm] 8 12 14 Shore A hardness 75 74 73 DIN abrasion [mm3] 112 108 110 De Mattia (crack propagation) 2 mm - 4 mm [kc] 0.1 0.1 0.2 4 mm - 8 mm [kc] 0.6 0.8 1.3 8 mm - 12 mm [kc] 2.0 3.0 3.8 As in the preceding examples, the compounds according to the invention, as compared with pure Si 69, showed clear advantages in De Mattia and crack propagation resistance characteristics.
Claims (11)
1. Blends consisting of organosilane compounds in accordance with the general formulas [(R0)3Si(CH2)3Sx]2 (I) and (R'O)3Si(CH2)y-CH3 (II) in which R represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, x represents 1-4, R' represents an alkyl group, straight chain or branched, with 1-8 carbon atoms, wherein R and R' may be identical or different, y represents 1-19 and the proportion of the compound of formula (I) in the blend is 40 to 95 wt.%, and accordingly the proportion of the silane of formula (II) is 5 to 60 wt.%.
2. Blends according to Claim 1, characterised in that they also contain a silicate or oxide filler in an amount of 30 to 95 wt.%, with respect to the total amount of organosilane compounds.
3. Blends according to Claim 2, characterised in that the silicate filler is a precipitated silica with a specific surface area between 1 and 200 m2/g (ISO 5794/D).
4. Blends according to Claim 3, characterised in that the silica has a structure of 150 to 300 ml/100 g determined as the DBP index (ASTM
D 2414).
D 2414).
5. Blends according to Claim 1, characterised in that they also contain carbon black in an amount of 30 to 95 wt.%, with respect to the total amount of organosilane compounds.
6. Blends according to Claims 2 to 5, characterised in that the filler or carbon black has at least partly reacted at the surface with organosilane compounds (I) and (II).
7. Use of blends according to Claims 1 to 6 in vulcanisable moulding compositions and rubber mixtures.
8. Use of blends according to Claim 7 in vulcanisable rubber mixtures based on solution-SBR.
9. Use of blends according to Claim 7 in vulcanisable rubber mixtures based on emulsion-SBR.
10. Vulcanisable moulding compositions and rubber mixtures, containing 10 to 250 parts of a silicate filler and 0 to 150 parts of carbon black, with respect to 100 parts of polymer, and 0.1 to 20 parts of organosilane compounds, with respect to 100 parts of silicate filler, characterised in that they contain blends consisting of the organosilane compounds of formulas (I) and (II).
11. Vulcanisable moulding compositions and rubber mixtures according to Claim 9, characterised in that they contain blends as described in Claims 2 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19519364A DE19519364A1 (en) | 1995-05-26 | 1995-05-26 | Mixtures of organosilane compounds, their use in vulcanizable rubber mixtures and molding compositions and the associated mixtures |
| DE19519364.4 | 1995-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2177095A1 true CA2177095A1 (en) | 1996-11-27 |
Family
ID=7762940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002177095A Abandoned CA2177095A1 (en) | 1995-05-26 | 1996-05-22 | Blends of organosilane compounds and their use |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0744437B1 (en) |
| JP (1) | JPH08325278A (en) |
| KR (1) | KR100447688B1 (en) |
| CN (1) | CN1144820A (en) |
| AR (1) | AR002090A1 (en) |
| AU (1) | AU5452496A (en) |
| BR (1) | BR9602491A (en) |
| CA (1) | CA2177095A1 (en) |
| CZ (1) | CZ291869B6 (en) |
| DE (2) | DE19519364A1 (en) |
| EG (1) | EG21286A (en) |
| ES (1) | ES2208704T3 (en) |
| IL (1) | IL118405A0 (en) |
| IN (1) | IN187768B (en) |
| MX (1) | MX9601929A (en) |
| PT (1) | PT744437E (en) |
| SK (1) | SK67896A3 (en) |
| TR (1) | TR199600371A2 (en) |
| ZA (1) | ZA964206B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180710B1 (en) | 1997-07-11 | 2001-01-30 | Bridgestone Corporation | Addition of salts to improve the interaction of silica with rubber |
| US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6313210B1 (en) | 2000-07-31 | 2001-11-06 | Bridgestone Coporation | Silica-reinforced rubber compounds containing moisture stabilized polymers |
| US6342552B1 (en) | 1997-07-11 | 2002-01-29 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6369138B2 (en) | 1997-07-11 | 2002-04-09 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US6433065B1 (en) | 2000-10-13 | 2002-08-13 | Bridgestone Corporation | Silica-reinforced rubber compounded with mercaptosilanes and alkyl alkoxysilanes |
| US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US6608145B1 (en) | 2000-10-13 | 2003-08-19 | Bridgestone Corporation | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature |
| US9034962B2 (en) | 2004-04-27 | 2015-05-19 | Bridgestone Corporation | Method of producing a tire composition having improved silica reinforcement |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5914364A (en) * | 1996-03-11 | 1999-06-22 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| US5780538A (en) * | 1996-03-11 | 1998-07-14 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| JPH10152582A (en) * | 1996-11-26 | 1998-06-09 | Yokohama Rubber Co Ltd:The | Filler for reinforcing rubber and rubber composition using the same |
| CA2216062A1 (en) * | 1997-09-19 | 1999-03-19 | Bayer Inc. | Silica-containing rubber composition |
| US6573324B1 (en) | 2000-04-04 | 2003-06-03 | The Goodyear Tire & Rubber Company | Tire with component comprised of rubber composition containing pre-hydrophobated silica aggregates |
| AU2001217666A1 (en) * | 2000-11-16 | 2002-05-27 | Bridgestone Corporation | Silica-reinforced rubber compounded with an alkoxysilane and a strong organic base |
| DE102017221272A1 (en) * | 2017-11-28 | 2019-05-29 | Evonik Degussa Gmbh | Silane mixtures and process for their preparation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4119959A1 (en) * | 1991-06-18 | 1992-12-24 | Degussa | METHOD FOR PRODUCING VULCANIZABLE, RUSSELED PLASTIC AND RUBBER MIXTURES |
| DE4236218C2 (en) * | 1991-12-19 | 2001-08-16 | Degussa | Vulcanizable EPDM rubber compounds |
| JP2676125B2 (en) * | 1992-04-30 | 1997-11-12 | 世界長株式会社 | Abrasion resistant white rubber composition |
| DE4308311C2 (en) * | 1993-03-16 | 1995-04-06 | Degussa | Use of precipitated silicas with high spec. Surface for improving the transparency and brightness properties of vulcanizable, light rubber mixtures, rubber mixtures containing the precipitated silicas and their production |
-
1995
- 1995-05-26 DE DE19519364A patent/DE19519364A1/en not_active Ceased
-
1996
- 1996-04-23 DE DE59610840T patent/DE59610840D1/en not_active Expired - Fee Related
- 1996-04-23 PT PT96106332T patent/PT744437E/en unknown
- 1996-04-23 ES ES96106332T patent/ES2208704T3/en not_active Expired - Lifetime
- 1996-04-23 EP EP96106332A patent/EP0744437B1/en not_active Expired - Lifetime
- 1996-05-08 TR TR96/00371A patent/TR199600371A2/en unknown
- 1996-05-16 JP JP8122002A patent/JPH08325278A/en active Pending
- 1996-05-17 IN IN904CA1996 patent/IN187768B/en unknown
- 1996-05-20 CZ CZ19961448A patent/CZ291869B6/en not_active IP Right Cessation
- 1996-05-21 EG EG43396A patent/EG21286A/en active
- 1996-05-22 MX MX9601929A patent/MX9601929A/en not_active IP Right Cessation
- 1996-05-22 CA CA002177095A patent/CA2177095A1/en not_active Abandoned
- 1996-05-23 KR KR1019960017597A patent/KR100447688B1/en not_active IP Right Cessation
- 1996-05-23 IL IL11840596A patent/IL118405A0/en unknown
- 1996-05-23 AR ARP960102693A patent/AR002090A1/en unknown
- 1996-05-24 ZA ZA964206A patent/ZA964206B/en unknown
- 1996-05-24 AU AU54524/96A patent/AU5452496A/en not_active Abandoned
- 1996-05-27 BR BR9602491A patent/BR9602491A/en not_active IP Right Cessation
- 1996-05-27 SK SK678-96A patent/SK67896A3/en unknown
- 1996-05-27 CN CN96105301A patent/CN1144820A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6384117B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6342552B1 (en) | 1997-07-11 | 2002-01-29 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6348531B1 (en) | 1997-07-11 | 2002-02-19 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6369138B2 (en) | 1997-07-11 | 2002-04-09 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US6180710B1 (en) | 1997-07-11 | 2001-01-30 | Bridgestone Corporation | Addition of salts to improve the interaction of silica with rubber |
| US6384118B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US6790889B2 (en) | 1997-07-11 | 2004-09-14 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6313210B1 (en) | 2000-07-31 | 2001-11-06 | Bridgestone Coporation | Silica-reinforced rubber compounds containing moisture stabilized polymers |
| US6433065B1 (en) | 2000-10-13 | 2002-08-13 | Bridgestone Corporation | Silica-reinforced rubber compounded with mercaptosilanes and alkyl alkoxysilanes |
| US6608145B1 (en) | 2000-10-13 | 2003-08-19 | Bridgestone Corporation | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature |
| US9034962B2 (en) | 2004-04-27 | 2015-05-19 | Bridgestone Corporation | Method of producing a tire composition having improved silica reinforcement |
Also Published As
| Publication number | Publication date |
|---|---|
| AR002090A1 (en) | 1998-01-07 |
| TR199600371A2 (en) | 1996-12-21 |
| PT744437E (en) | 2004-04-30 |
| IL118405A0 (en) | 1996-09-12 |
| DE59610840D1 (en) | 2004-01-15 |
| DE19519364A1 (en) | 1996-11-28 |
| CN1144820A (en) | 1997-03-12 |
| EP0744437B1 (en) | 2003-12-03 |
| JPH08325278A (en) | 1996-12-10 |
| MX9601929A (en) | 1997-01-31 |
| CZ291869B6 (en) | 2003-06-18 |
| CZ144896A3 (en) | 1996-12-11 |
| EG21286A (en) | 2001-06-30 |
| ZA964206B (en) | 1996-12-04 |
| AU5452496A (en) | 1996-12-05 |
| ES2208704T3 (en) | 2004-06-16 |
| EP0744437A1 (en) | 1996-11-27 |
| SK67896A3 (en) | 1996-12-04 |
| IN187768B (en) | 2002-06-22 |
| KR960041187A (en) | 1996-12-19 |
| BR9602491A (en) | 1998-09-08 |
| KR100447688B1 (en) | 2004-11-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |