Patent Grant
9598562
The invention relates to a mercaptosilane-carbon black blend, method for producing same, and use thereof.
EP 1285926 and EP 1683801 disclose mercaptosilanes having polyether groups.
Additionally, KR 850000081 discloses silane/filler blends.
A disadvantage of the known mercaptosilane/filler blends is the poor shelf life.
It is an object of the present invention to provide blends of mercaptosilanes with carbon black that enjoy an improved shelf life.
The invention provides a mercaptosilane-carbon black blend comprising at least 20 wt. %, preferably at least 25 wt. %, more preferably at least 30 wt. %, of mercaptosilane of the general formula I
based on the mercaptosilane-carbon black blend,
The mercaptosilane-carbon black blend may comprise a mixture of different mercaptosilanes of the general formula I and/or their condensation products.
The carbon black in the mercaptosilane-carbon black blend may have a sieve residue ≦50 ppm, preferably <40 ppm, more preferably <35 ppm.
The mercaptosilanes of the general formula I may be compounds wherein R1 is an alkyl polyether group —O—(R6—O)m—R6, with R5, identical or different at each occurrence, being a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m being on average 1 to 30, and R6 consisting of at least 11 C atoms and being an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,
The mercaptosilanes of the general formula I may be compounds wherein R1 is
The mercaptosilanes of the general formula I may be compounds wherein R1 is
Preferred compounds of the formula I with R4═H may be:
Preferred compounds of the formula I with R4=CN may be:
Preferred compounds of the formula I with R4=—C(═O)—R9 and R9=branched or unbranched —C5H11, —C6H13, —C7H15, —C8H17, —C9H19, —C10H21, —C11H23, —C12H25, —C13H27, —C14H29, —C15H31, —C16H33, —C17H35 and —C6H5 (phenyl) may be:
R6 may preferably be C12 to C17, very preferably C12 to C16, exceptionally preferably C12 to C14, unsubstituted or substituted, branched or unbranched monovalent alkyl.
R6 may be a —C11H23, —C12H25, —C13H27, —C14H29, —C15H31, —C16H33 or —C17H35 alkyl group.
R6 may preferably be C11 to C35, more preferably C11 to C30, very preferably C12 to C30, exceptionally preferably C13 to C20, unsubstituted or substituted, branched or unbranched monovalent alkenyl.
R6 may preferably be C11 to C14 and/or C16 to C30, very preferably C11 to C14 and/or C16 to C25, exceptionally preferably C12 to C14 and/or C16 to C20, unsubstituted or substituted, branched or unbranched monovalent aralkyl.
R6 as alkenyl may be C11H21, —C12H23, —C13H25, —C14H27, —C15H29, —C16H31 or —C17H33.
R1 may be an alkoxylated castor oil (e.g. CAS 61791-12-6).
R1 may be an alkoxylated oleylamine (e.g. CAS 26635-93-8).
The polyether group (R5O)m may comprise random ethylene and. propylene oxide units, or may comprise polyether blocks of polyethylene oxide and polypropylene oxide.
The mercaptosilane-carbon black blend may comprise a mixture of different mercaptosilanes of the general formula I.
The mixture of different mercaptosilanes of the general formula I may have a molecular weight distribution of the polyether group.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I wherein R6 consists of different C atom chain lengths and. has a molecular weight distribution.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I with R4 being —CN or condensation products thereof.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I with R4 being (C═O)—R9 or condensation products thereof.
The polyether group (R5—O)m may preferably be:
The indices a, b and c are integers and denote the number of repeating units.
For R4 as —H, —CN or —C(═O)—R9, the group (R5—O)m may preferably comprise ethylene oxide units (CH2—CH2—O)a or propylene oxide units (CH(CH3)—CH2—O)a and/or (CH2—CH(CH3)—O)a.
For R4 as —H, —CN or —C(═O)—R9, the group (R5—O)m may preferably comprise ethylene oxide units (CH2—CH2—O)a and propylene oxide units (CH(CH3)—CH2—O)a and/or (CH2—CH(CH3)—O)a, randomly distributed or in blocks.
For R4 as —H, the alkyl polyether group (R5—O)m may preferably comprise ethylene oxide units (CH2—CH2—O)a and propylene oxide units (CH(CH3)—CH2—O)a and/or (CH2—CH(CH3)—O)a, randomly distributed or in blocks.
For R4 as —H, the group (R5—O)m may preferably comprise propylene oxide units (CH(CH3)—CH2—O)a and/or (CH2—CH(CH3)—O)a.
For R4 as —H, —CN or —C(C═O)—R9, the alkyl polyether group O—(R5—O)m—R6 may be:
The group R5 may be substituted. The group R6 may be C13—H27.
The average branching index of the carbon chain R6 may be 1 to 5, preferably 1.2 to 4. This average branching index is defined as the number of CH3 groups −1.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I having different R1 and R2 groups, with the R1 and R2 groups consisting of alkoxy and alkyl polyether groups.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I with different R2s.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I with different R1 and R2 groups, the R1 and R2 groups consisting of ethoxy and alkyl polyether groups, and R6 having an alkyl chain length of 13 C atoms, R5 being ethylene and m being on average 5.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I wherein R2 is identical or different at each occurrence and is an ethoxy or alkyl polyether group (R1), R6 an alkyl chain length of 13 C atoms, R5 is ethylene and m is on average 5, and R2 is different.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I wherein R1 and R2 are alkoxy and alkyl polyether groups and R6 consists of different C atom chain lengths and has a molecular weight distribution.
The mixture of different mercaptosilanes of the general formula I may comprise different mercaptosilanes of the general formula I wherein r2 is identical or different at each occurrence and is an alkoxy or alkyl polyether group (R1) and R2 in the mixture is different, R6 consists of different C atom chain lengths and has a molecular weight distribution.
The mixture of different, mercaptosilanes of the general formula I may preferably comprise
and/or hydrolysis and/or condensation products of the aforementioned compounds.
From the mercaptosilanes of the formula I it is easily possible, by adding water and optionally adding additives, to form condensation products—that is, oligosiloxanes and polysiloxanes.
These oligomeric or polymeric siloxanes of the compounds of the formula I may be used as coupling reagents for the same applications as the monomeric compounds of the formula I.
The mercaptosilane compounds may also take the form of a mixture of the oligomeric or polymeric siloxanes of mercaptosilanes of the general formula I or the form of mixtures of mercaptosilanes of the general formula I with mixtures of the oligomeric or polymeric siloxanes of mercaptosilanes of the general formula I.
The carbon black may have an STSA surface area (measured according to ASTM D 6556) of 10-150 m2/g, preferably of 15-90 m2/g. The carbon black may have an OAN number (measured according to ASTM D 2414) of 50-150 ml/100 g, preferably of 70-140 ml/100 g.
With particular preference the carbon black may have an STSA surface area of 20-70 m2/g and an OAK number of 100-135 ml/100 g.
The weight ratio of mercaptosilane of the general formula I to carbon black may be 30:70 to 80:20, preferably 40:60 to 70:30.
The invention further provides a method for producing the mercaptosilane-carbon black blend of the invention, the method being characterized in that at least 20 wt. %, preferably at least 25 wt. %, more preferably at least 30 wt. %, of mercaptosilanes of the general formula I, based on the mercaptosilane-carbon, black blend, are mixed with carbon black, the carbon black having an iron content of <9 ppm, very preferably of 0.1-6 ppm.
The method of the invention may be carried out continuously or discontinuously.
The mercaptosilane of the general formula I may be used in a weight ratio to carbon black of 30:70 to 80:20, preferably of 40:60 to 70:30.
The method of the invention may be carried out at. temperatures between 5 and 200° C., preferably between 10 and 100° C., more preferably between 15 and 60° C. In order to avoid condensation reactions it may be advantageous to carry out the reaction in a water-free environment, ideally in an inert gas atmosphere,
The method of the invention can be carried out under atmospheric pressure or reduced pressure.
The mercaptosilane-carbon black blend of the invention may be used as an adhesion promoter between inorganic materials, for example glass fibres, metals, oxidic fillers, silicas, and organic polymers, for example thermosets, thermoplastics or elastomers, and/or as crosslinking agent and surface modifier. The mercaptosilane-carbon black blend of the invention may be used as a coupling reagent in rubber mixtures, for example tyre treads.
The invention further provides a rubber mixture comprising
Rubber used may be natural rubber and/or synthetic rubbers. Preferred synthetic rubbers are described for example in W. Hofmann, Kautschuktechnologie, Genter Verlag, Stuttgart 1980. Among others they may be
In one preferred embodiment the rubbers may be sulphur-vulcanizable. For the production of car tyre treads it is possible in particular to use anionic polymerized S-SBR rubbers (solution-SBR) with a glass transition temperature of more than −50° C., and also mixtures thereof with diene rubbers. With particular preference it is possible to use S-SBR rubbers whose butadiene moieties have a vinyl fraction of more than 20 wt. %. With very particular preference it is possible to use S-SBR rubbers whose butadiene moieties have a vinyl fraction of more than 50 wt. %.
With preference it is possible to use mixtures of the aforementioned rubbers which have an S-SBR fraction of more than 50 wt. %, mere preferably more than 60 wt. %.
Fillers that may be used for the rubber mixture of the invention include the following fillers:
With preference it is possible to use amorphous silicas, produced by precipitating solutions of silicates, having BET surface areas of 20 to 400 m2/g, more preferably 100 m2/g to 250 m2/g, in amounts of 5 to 150 parts by weight, based in each case on 100 parts of rubber.
The stated fillers may be used alone or in a mixture.
The rubber mixture may comprise 5 to 150 parts by weight of filler (B) and 0.1 to 35 parts by weight, preferably 2 to 20 parts by weight, more preferably 5 to 15 parts by weight, of mercaptosilane-carbon black blend (C) of the invention, the parts by weight being based on 100 parts by weight of rubber.
The rubber mixture may further comprise silicone oil and/or alkylsilane.
The rubber mixture of the invention may comprise other known rubber assistants, such as, for example, crosslinkers, vulcanization accelerants, reaction accelerants, reaction retardants, ageing inhibitors, stabilizers, processing assistants, plasticizers, waxes or metal oxides, and also, optionally, activators, such as triethanolamine, polyethylene glycol or hexanetriol.
The rubber assistants may be used in customary amounts, which are guided by factors including the intended use. Customary amounts may be, for example, amounts of 0.1 to 50 wt. %, based on rubber.
Crosslinkers which can be used include sulphur or organic sulphur donors.
The rubber mixture of the invention may comprise further vulcanization accelerants. Suitable vulcanization accelerants that may be used include, for example, mercaptobenzothiazoles, sulphenamides, guanidines, dithiocarbamates, thioureas, thiocarbonates, and also zinc salts thereof, such as zinc dibutyldithiocarbamate, for example.
The rubber mixture of the invention may preferably further comprise
The rubber mixture of the invention may comprise (D) tetrabenzylthiuram disulphide or tetramethylthiuram disulphide at not less than 0.25 part by weight, based on 100 parts by weight of rubber, (E) diphenylguanidine at not more than 0.25 part by weight, based on 100 parts by weight of rubber, and (G) cyclohexyl or dicyclohexyl sulphenamide, with more parts by weight than (D).
With preference it is possible to use sulphenamides together with guanidines and thiurams, more preferably cyclohexyl sulphenamide or dicyclohexyl sulphenamide together with diphenylguanidine and tetrabenzylthiuram disulphide or tetramethylthiuram disulphide.
The vulcanization accelerants and sulphur can be used in amounts of 0.1 to 10 wt. %, preferably 0.1 to 5 wt. %, based on the rubber used. With particular preference it is possible to use sulphur and sulphenamides in amounts of 1 to 4 wt. %, thiurams in amounts of 0.2 to 1 wt. % and guanidines in amounts from 0 wt. % to 0.5 wt. %.
The invention further provides a method for producing the rubber mixture of the invention, this method being characterized in that the rubber or mixture of rubbers (A), the filler (B), at least one mercaptosilane-carbon black blend (C) of the invention and optionally further rubber assistants are mixed in a mixing assembly.
The blending of the rubbers with the filler, optionally rubber assistants, and the mercaptosilanes of the invention may be carried our in customary mixing assemblies, such as rolls, internal mixers and mixing extruders. Such rubber mixtures can typically be produced in internal mixers, in which case first of all, in one or more successive thermomechanical mixing stages, the rubbers, the filler, the mercaptosilanes of the invention and. the rubber assistants are incorporated by mixing at 100 to 170° C. The sequence of this addition and the time of this addition of the individual components may have decisive consequences for the mixture properties obtained. The resulting rubber mixture can usually be admixed with the crosslinking chemicals in an internal mixer or on a roll at 40 to 110° C., and processed to give what is known as the crude mixture for the subsequent, processing steps, such as shaping and vulcanization, for example.
Vulcanization of the rubber mixture of the invention may take place at temperatures of 80 to 200° C., preferably 130 to 180° C., optionally under a pressure of 10 to 200 bar.
The rubber mixture of the invention can be used for producing mouldings, as for example for producing pneumatic tyres, tyre treads, cable sheathing, hoses, drive belts, conveyor belts, roll coverings, other tyres, footwear soles, sealing elements, such as sealing rings, for example, and damping elements.
The invention additionally provides mouldings obtainable by vulcanization from the rubber mixture of the invention.
An advantage of the mercaptosilane-carbon black blends of the invention is that even in the case of a prolonged storage time, the mercaptosilane does not alter to the degree observed with the known mercapto/filler blends.
Determination of Iron Content in Mercaptosilane-carbon Black Blend
Total Iron Assay After High-pressure Ashing Using ICP-MS:
Approximately 200-300 mg of the mercaptosilane-carbon black blend, are weighed out to an accuracy of 0.1 mg into a vessel made of vitreous silica.
10 ml of HNO3 (approximately 65 wt. %, super-pure) are added and the sample is digested completely in a pressure vessel at a temperature from at least 280° C. to not more than 500° C.
Thereafter the digestion product is made up to 50 ml with water (ultra-pure) and transferred to a volumetric flask (plastic).
Digestion takes place with a duplicate determination.
Prior to each digestion, 1 ml is introduced into a test-tube and made up to 10 ml with water (ultra-pure).
Each solution is subjected to measurement in an inductively coupled plasma mass spectrometer (ICP-MS) with a calibration.
For the calibration, four reference solutions and one blank solution are produced from a standard solution, based on an NIST reference material.
Corresponding chemical blank values are subjected to measurement together with the sample solutions. An internal standard is added at the same concentration to all of the measurement solutions.
Determination of Carbon Black by Sieve Residue
The 325 mesh sieve residue is determined in accordance with ASTM D1514, in ppm.
STSA Surface Area
The STSA is determined in accordance with ASTM D 6556.
OAN Number
The OAN is determined in accordance with ASTM D 2414.
Shelf Life, Determination by GPC:
Procedure:
The acetonitrile extracts are analyzed on a GPC column. To quantify the amounts of silane, a 1-point calibration is carried out with a pure specimen of the particular silane being assayed.
Instrument Settings:
HPLC system: HPLC pump S2100 from SFD, Autosampler SIL10-AF from Shimadzu, RI detector 7515A from ERC, Controller CBM-20A from Shimadzu analysis software Class VP5 from Shimadzu
Preliminary column: MZ-gel SDplus 50 Å 5μ 50×3 mm, from MZ-Analysentechnik
Analytic column: MZ-gel SDplus 50 Å 5μ 300×8 mm, from MZ-Analysentechnik
Mobile phase: 100% methyl ethyl ketone (MEK)
Flow rate: 1.0 ml/min
Metering volume: 30 μl Analysis temperature: room temperature 20° C.
10 g of product are admixed with 180 ml of acetonitrile and stirred for 2 hours, then filtered, diluted 1:1 with methyl ethyl ketone, and injected.
The parameter evaluated is the peak area of the respective silane in the HPLC chromatogram of the RI detector (no GPC molar mass evaluation).
In the comparative examples, the reference carbon block used is N 330 (iron content: 16 ppm), and Purex HS 45 (iron content: 6 ppm) is used in the inventive examples (both commercial products from Orion Engineered Carbons). The mercaptosilane of the formula I that is used is Si 363 ((R*O)3Si(CH2)3SH with R*═C13H27(OC2H4)n and C2H5, average C2H5 content=33%, average number n=5) from Evonik Industries.
A Henschel mixer is charged with 1 kg of carbon black (a: N 330, b: Purex HS 45). At a through-flow temperature of 20° C., a rotary speed of 1500 rpm and a pressure of 40 bar, in one stage with a nozzle diameter of 0.5 mm, 462 g of mercaptosilane Si 363 are added until a final mixing temperature of 62-65° C. is reached (fill level: 45%).
The shelf life is determined by storing the mercaptosilane-carbon black blends at T=20° C. and 60% atmospheric humidity for 18 days.
The measurement for the comparative mercaptosilane-carbon black blend (a: N 330/Si 363 11 ppm Fe) after storage gives 7-1 wt. % of Si 363, relative to the theoretical value. The measurement for the inventive mercaptosilane-carbon black blend (b: Purex 45/Si 363 4 ppm Fe) after storage gives 85 wt. % of Si 363, relative to the theoretical value.
The formula used for the rubber mixtures is shown in Table 1 below. In the table, the unit phr denotes weight fractions relative to 100 parts of the crude rubber used.
The polymer VSL 5025-1 is a solution polymerized SBR copolymer from Bayer AG, having a styrene content of 25 wt. % and a butadiene content of 75 wt. %. The copolymer contains 37.5 phr of oil and has a Mooney viscosity (ML 1+4/100° C.) of 50.
The polymer Buna CB 24 is a cis-1,4-polybutadiene (neodymium type) from Bayer AG, having a cis-1,4 content of at least 96% and a Mooney viscosity of 44±5.
Ultrasil 7000 GR is a readily dispersible silica from Evonik Industries AG and has a BET surface area of 170 m2/g. Corax N330 is a carbon black from Orion Engineered Carbons with an STSA surface area of 76 in2/g.
Naftolen ZD from Chemetall is used as aromatic oil; Vulkanox 4020 is 6PPD from Bayer AG, and Protektor G3108 is an ozone protection wax from Paramelt B.V. Vulkacit D (DPG) and Vulkacit CZ (CBS) are commercial products of Bayer AG, Perkacit TBzTD (Tetrabenzylthiuram disulphide) is a product from Flexsys N.V.
The rubber mixture is produced in three stages in an internal mixer in accordance with Table 2.
The general method for producing rubber mixtures and vulcanizates thereof is described in “Rubber Technology Handbook”, W. Hofmann, Hanser Verlag 1994.
Technical rubber testing takes place in accordance with the test methods specified in Table 3.
Table 4 reports the technical rubber data for crude mixture and vulcanizate.
It is found that only in the case of the inventive rubber mixture is it possible to achieve the values of the in situ mixture (reference rubber mixture I). Reference rubber mixture II, which contains a carbon black with an iron fraction greater than 9 ppm, exhibits marked disadvantages in viscosity and in the dynamic data, corresponding to a significantly poorer rolling resistance.
The formula used for the rubber mixtures is given in Table 5 below. The unit phr denotes weight fractions relative to 100 parts of the crude rubber used.
The silane-carbon black blend X 50-S (Si 69 on N 330) used for the reference rubber mixtures is available commercially from Evonik Industries.
The polymer VSL 5025-1 is a solution polymerized SBR copolymer from Bayer AG, having a styrene content of 25 wt. % and a butadiene content of 75 wt. %. The copolymer contains 37.5 phr of oil and has a Mooney viscosity (ML 1+4/100° C.) of 50.
The polymer Buna CB 24 is a cis-1,4-polybutadiene (neodymium type) from Bayer AG, having a cis-1,4 content of at least 96% and a Mooney viscosity of 44±5.
Ultrasil 7000 GR is a readily dispersible silica from Evonik Industries AG and has a BET surface area of 170 m2/g.
Naftolen ZD from Chemetall is used as aromatic oil; Vulkanox 4020 is 6PPD from Bayer AG, and Protektor G3108 is an ozone protection wax from Paramelt B.V. Vulkacit D (DPG) and Vulkacit CZ (CBS) are commercial products of Bayer AG. Perkacit TBzTD (Tetrabenzylthiuram disulphide) is a product from Flexsys N.V.
The rubber mixture is produced in three stages in an internal mixer in accordance with Table 2.
The general method for producing rubber mixtures and vulcanizates thereof is described in “Rubber Technology Handbook”, W. Hofmann, Hanser Verlag 1994.
Technical rubber testing takes place in accordance with the test methods specified in Table 3.
Table 6 reports the technical rubber data for crude mixture and vulcanizate.
In comparison to the reference rubber mixture III, the inventive rubber mixture comprising the mercaptosilane-carbon black blend, as per Example 1b exhibits better tensile strength, greater elongation at break, lower DIN abrasion (corresponding to reduced wear), a significantly higher tear propagation resistance, a very low tanδ at 60° C. (corresponding to a level reduced by 20% relative to the X50-S reference), which is an indicator of a significantly improved rolling resistance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2012 205 642 | Apr 2012 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2013/054847 | 3/11/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2013/149790 | 10/10/2013 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6849754 | Deschler | Feb 2005 | B2 |
| 7323582 | Deschler et al. | Jan 2008 | B2 |
| 8013178 | Klockmann et al. | Sep 2011 | B2 |
| 20030229166 | Krafczyk et al. | Dec 2003 | A1 |
| 20080319128 | Korth | Dec 2008 | A1 |
| 20110217229 | Inomata | Sep 2011 | A1 |
| 20120270974 | Steinhauser et al. | Oct 2012 | A1 |
| 20140206809 | Miyazaki | Jul 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 102009023915 | Dec 2010 | DE |
| 1285926 | Feb 2003 | EP |
| 1367059 | Dec 2003 | EP |
| 1683801 | Jul 2006 | EP |
| 62-181346 | Aug 1987 | JP |
| 850000081 | Feb 1985 | KR |
| Entry |
|---|
| Notification of Transmittal of International Preliminary Report on Patentability (Forms PCT/IB/326, 373, and 237) , for Application No. PCT/EP2013/054847 dated Oct. 7,2014. |
| Notification of Transmittal of International Preliminary Report on Patentability (Forms PCT/IB/338, 373 and 237), for Application No. PCT/EP2013/054847 dated Oct. 7, 2014. |
| Number | Date | Country | |
|---|---|---|---|
| 20150175782 A1 | Jun 2015 | US |
