GB2259303A - A process for the production of vulcanizable moulding compounds and to the moulding compounds produced by this process - Google Patents
A process for the production of vulcanizable moulding compounds and to the moulding compounds produced by this process Download PDFInfo
- Publication number
- GB2259303A GB2259303A GB9217649A GB9217649A GB2259303A GB 2259303 A GB2259303 A GB 2259303A GB 9217649 A GB9217649 A GB 9217649A GB 9217649 A GB9217649 A GB 9217649A GB 2259303 A GB2259303 A GB 2259303A
- Authority
- GB
- United Kingdom
- Prior art keywords
- vulcanizable
- moulding compounds
- production
- moulding
- accelerators
- 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.)
- Granted
Links
- 239000000206 moulding compound Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 150000004659 dithiocarbamates Chemical class 0.000 claims abstract description 4
- -1 3-thiocyanatopropyl Chemical group 0.000 claims abstract description 3
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 3
- 229920001194 natural rubber Polymers 0.000 claims abstract description 3
- 150000004756 silanes Chemical class 0.000 claims abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 3
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 7
- 229960002447 thiram Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 238000010057 rubber processing Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- MNQHIZVVIZUIRN-UHFFFAOYSA-N C(COCCO)O.S(C#N)CCC[Si](OCC)(OCC)OCC Chemical compound C(COCCO)O.S(C#N)CCC[Si](OCC)(OCC)OCC MNQHIZVVIZUIRN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100449067 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cbs-2 gene Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ARZGJPVQNURLFJ-UHFFFAOYSA-N silyl thiocyanate Chemical compound [SiH3]SC#N ARZGJPVQNURLFJ-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Paper (AREA)
- Tires In General (AREA)
Abstract
In a process for the production of vulcanizable moulding compounds consisting of one or more natural or synthetic rubbers or polymers the quantity of accelerators from the class of thiurams and/or dithiocarbamates is reduced to half the quantity originally required through the use of 3-thiocyanatopropyl trialkoxy silanes.
Description
A Process for the Production of Vulcanizable Moulciing Compounds and to
the Moulding Compounds Produced by this Process This invention relates to a process for the production of vulcanizable moulding compounds and to the moulding compounds produced by this process.
For some years now, the problems presented by the formation of volatile carcinogenic N-nitrosamines during the processing, vulcanization and storage of rubber arti cles have been of increasing concern in the rubber-proces sing industry. Initial legal regulations in the Federal Republic of Germany, such as for example the 11Technische Richtlinien filr Gefahrstoffell (TRGS 552), stipulate upper limits to the content of volatile N-nitrosamines in the working environment and prescribe significant limitations to the output of factories exceeding those limits. To avoid this. the rubber-processing industry is making increasing efforts to replace N-nitrosamine-forning agents in rubber mixtures and, where this is not possible, at least to reduce the quantities required.
As has meanwhile become known from various publica tions (see, for example, R.H. Schuster, F. Nabholz, M.
Gmfinder, "Kautschuk, Gummi, Kunststoffe 211 (1990) 95; W.
Hoffmann, "Zum Problem der Herstellung N-nitrosaminfreil!r Gummiartikelll, paper presented before the DKG-Bezirksgruppe Sild- u. SUdwestdeutschland, April 1990), nitrosamines are formed at the temperatures required for the compounding, processing and vulcanization of rubber mixtures through the decomposition of, in particular. mixture constituents which release secondary amines and reaction of those amines with the NO, omnipresent in nature.
One of the main sources of amines are the vulcaniza tion accelerators from the class of sulfenamides, thiurams and dithiocarbanates now mainly used in the rubber indus try. Accordingly, efforts are naturally being made in the rubber-processing industry to replace these toxic nitros amine-forming accelerators by safer compounds or at least to reduce the quantities required without,at the same is 2 is 91 185 KV time, giving rise to serious changes in the rubber properties.
The present invention relates to a process f or the production of vulcanizable moulding compounds consisting of one or more natural or synthetic rubbers or polymers vulcanized with sulfur or sulfur donors and accelerators, fillers and other typical constituents, at least one accelerator belonging to the class of thiurams and/or dithiocarbamates being used, characterized in that, where 3- thiocyanatopropyl trialkoxy silanes corresponding to the following general formula:
(R0) 3 S i (CH2) 3 S CN (I) in which R = Cl-8 alkyl, are simultaneously used, the quantity of accelerators from the class of thiurams and/or dithiocarbanates is reduced to at least half the quantity originally used in the vulcanizable moulding compound free from organosilicon compounds.
The invention also relates to the vulcanizates obtained by this process.
The accelerators in question include inter alia tetramethyl thiuram disulfide (TMTD), tetramethyl thiuram monosulf ide (TMTM), zinc-Ndimethyl dithiocarbamate (MDMC), zinc-N-diethyl dithiocarbamate (ZDEC), zinc-N-ethyl phenyl dithiocarbanate (ZEPC).
In the prior art, these accelerators are used in quantities of 0.2 to 10 phr (parts per hundred parts rubber).
The reduction preferably amounts to 20 to 50% of the original quantity and, in some cases, is even 100% (see Example 2).
It has been found that it is possible in accordance with the invention to reduce the quantity of the incriminated accelerators without having to accept reductions in the 3 91 185 KV range of customary rubber properties.
The moulding compounds are produced and vulcanized by known methods.
The other typical constituents, such as plasticizers, stabilizers, activators, pigments, antiagers and processing aids, are also known.
The moulding compounds generally contain the known light silicate fillers (for example clays, kaolins, precipitated and pyrogenic silicas, silicates, etc.) having BET surfaces of 1 to 1,000 M2 /g and preferably 5 to 300 M2/g, with the hydroxyl groups of which the trialkoxysilyl groups of the compounds according to the invention react with elimination of an alcohol, which leads to a chemical bond between filler and silane. However, the known carbon blacks are also used as fillers.
The thiocyanatosilane corresponding to general formula (I) is added to the vulcanizable moulding compound generally in quantities of 0.1 to 20 parts by weight and preferably in quantities of 0.1 to 10 parts by weight, based on 100 parts rubber or polymer, either directly or in a form in which it is already bound to the filler.
In addition to the reduction in the quantity of accelerator obtained in accordance with the invention, the use of the organosilicon compound corresponding to formula (I) also leads to a reduction in the viscosity of the vulcanizable moulding compounds and hence to an improvement in their processability.
Suitable rubbers and polymers for the process according to the invention are, in particular, rubbers low in double bonds, such as EPDM and EVA, but also NBR, NR and SBR.
The following Examples illustrate the advantages of the compounds according to the invention over the prior art and show that it is possible to manage without at least a large part of toxic nitrosamine-forming accelerators and 4 91 185 KV still to achieve at least the customary rubber properties.
Test Standands for Evaluation Test Method Unit Mooney viscosity DIN 53 523/524 MPa Tensile strength DIN 53 504 MPa Modulus DIN 53 504 MPa Shore hardness DIN 53 505 compression set ASTM D 395 The names and abbreviations used in the Examples have the following meanings:
Keltan 578 N 765 N 660 Ultrasil VN 3 Suprex Clay 20 Omya chalk Sunpar 150 Si 264 DEG CBS T= Rhenocure CUT ZDBC -3.
EPDM manufactured by DSM Furnace black, surface 34 m2/g Furnace black, surface 36 M2/g Precipitated silica, BET surface 175 M2/g Sodium silicate Calcium carbonate Paraffinic plasticizer 3-Thiocyanatopropyl triethoxy silane Diethylene glycol Benzothiazy1-2-cyclohexyl sulfenamide Tetramethyl thiuram disulfide Copper dialkyl dithiophosphate Zinc dibutyl dithiocarbamate 91 185 KV Example 1 Reduction of TMTD by using Si 264 in an EPDM cable sheath mixture 1 2 Keltan 578 100 100 Ultrasil VN 3 25 25 Omya chalk 50 50 Suprex Clay 125 125 ZnO RS 5 5 Stearic acid 2 2 Sunpar 150 30 30 DEG 2 2 Si 264 - 2 CBS 2 2 TMTD 1 0.5 Rhenocure CUT 2.5 2.5 Sulfur 1.5 1.5 Rheometer: 160C D.ax - Dmin (Nm) 10.63 t902 - t10z 4.0 Mooney viscosity ML 4 (100C) (MU) 78 11.27 3.3 58 Vulcanizate data: 160C, t95% Tensile strength MPa 10.3 11.1 Modulus 300% MPa 3.2 6.0 Shore hardness 74 78 compression set 22h/70C % 26.3 19.4 70h/10O.C % 73.2 67.5 This Example shows that, despite the 50% reduction in the quantity of thiuram, the state of the art (mixture 1) can at least be equalled and, in some cases, even surpassed by the use of Si 264 (mixture 2).' 6 91 185 KV Example 2 Replacement of T= by Si 264 in an EPDM hydraulic hose cover 1 2 Keltan 578 100 100 765 75 75 660 100 100 Suprex Clay 90 90 ZnO RS 5 5 Stearic acid 1 1 Sunpar 150 100 100 Si 264 - 1 MBT 1.5 1.5 WBC 0.8 0.8 T= 0.7 - Rhenocure CUT 0.7 0.7 Sulfur 4 4 Rheometer: 160&C Dm. - Dmi. (Nm) 9.93 13.05 Vulcanizate data: 1609C, tgsz Tensile strength MPa 10.1 10.8 Modulus 100% MPa 7.5 9.6 Shore hardness 86 86 Storage in ASTM oil 2 (70 h/160OC) Tensile strength MPa 3.4 4.3 Modulus 100% MPa 2.9 4.3 Elongation at break % 110 110 In Example 2, the TMTD can be omitted altogether through the use of Si 264 without any deterioration in the rubber porperties.
7 91 185 KV
Claims (2)
1. A process for the production of vulcanizable moulding compounds consisting of one or more natural or synthetic rubbers or polymers vulcanized with sulfur or sulfur donors and accelerators, fillers and other typical constituents, at least one accelerator belonging to the class of thiurams and/or dithiocarbamates being used, characterized in that, where 3-thiocyanatopropyl trialkoxy silanes corresponding to the following general formula:
(R0) 3 S' (CH2) 3 S CN (I) in which R = Cl-, alkyl, are simultaneously used, the quantity of accelerators from the class of thiurams and/or dithiocarbamates is reduced to at least half the quantity originally used in the vulcanizable moulding compound free from organosilicon compounds.
2. Vulcanizable moulding compounds produced by the process claimed in claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4128203A DE4128203C1 (en) | 1991-08-26 | 1991-08-26 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9217649D0 GB9217649D0 (en) | 1992-09-30 |
| GB2259303A true GB2259303A (en) | 1993-03-10 |
| GB2259303B GB2259303B (en) | 1994-07-20 |
Family
ID=6439104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9217649A Expired - Fee Related GB2259303B (en) | 1991-08-26 | 1992-08-19 | Vulcanizable moulding composition |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH05214171A (en) |
| KR (1) | KR960003827B1 (en) |
| CN (1) | CN1067701C (en) |
| DE (1) | DE4128203C1 (en) |
| FR (1) | FR2680795B1 (en) |
| GB (1) | GB2259303B (en) |
| IT (1) | IT1256945B (en) |
| TW (1) | TW203070B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
| US7446137B2 (en) * | 2001-10-29 | 2008-11-04 | Dow Corning Toray Silicone Co., Ltd. | Thermosetting resin and thiocyanato-containing organohydrocarbonoxysilane |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19505650A1 (en) * | 1995-02-18 | 1996-08-22 | Freudenberg Carl Fa | Prevent or reduce the formation of amines and N-nitrosamines in the manufacture and use of elastomers |
| AU6022500A (en) * | 1999-07-23 | 2001-02-13 | Degussa A.G. | Rubber composition for extrusion molding and for molding with mold and use thereof |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | 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 |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic 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 |
| 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 |
| US7968633B2 (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 |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1355265A (en) * | 1970-07-18 | 1974-06-05 | Degussa | Sulphur-containing organo-organo-oxysilanes and use thereof |
| EP0442143A1 (en) * | 1990-02-16 | 1991-08-21 | Degussa Ag | Method of preparing fillers which are modified by organosilicon compounds, the products thus obtained and their use |
| EP0468140A2 (en) * | 1990-07-25 | 1992-01-29 | Degussa Aktiengesellschaft | With organosilicium-compound chemically modified carbon blacks, method for their preparation and their use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2819638C3 (en) * | 1978-05-05 | 1986-11-13 | Degussa Ag, 6000 Frankfurt | Vulcanizable halogen rubber compounds |
| DE3305373C2 (en) * | 1983-02-17 | 1985-07-11 | Degussa Ag, 6000 Frankfurt | Elastic molding compound, method of manufacturing and deforming and use of the same |
| JPS63199253A (en) * | 1987-02-13 | 1988-08-17 | Shin Etsu Chem Co Ltd | Rubber composition |
-
1991
- 1991-08-26 DE DE4128203A patent/DE4128203C1/de not_active Expired - Fee Related
-
1992
- 1992-06-30 FR FR9208032A patent/FR2680795B1/en not_active Expired - Fee Related
- 1992-08-11 TW TW081106326A patent/TW203070B/zh active
- 1992-08-19 GB GB9217649A patent/GB2259303B/en not_active Expired - Fee Related
- 1992-08-24 JP JP4223954A patent/JPH05214171A/en active Pending
- 1992-08-25 KR KR1019920015253A patent/KR960003827B1/en not_active IP Right Cessation
- 1992-08-25 CN CN92109579A patent/CN1067701C/en not_active Expired - Fee Related
- 1992-08-26 IT ITTO920713A patent/IT1256945B/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1355265A (en) * | 1970-07-18 | 1974-06-05 | Degussa | Sulphur-containing organo-organo-oxysilanes and use thereof |
| EP0442143A1 (en) * | 1990-02-16 | 1991-08-21 | Degussa Ag | Method of preparing fillers which are modified by organosilicon compounds, the products thus obtained and their use |
| EP0468140A2 (en) * | 1990-07-25 | 1992-01-29 | Degussa Aktiengesellschaft | With organosilicium-compound chemically modified carbon blacks, method for their preparation and their use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
| US7446137B2 (en) * | 2001-10-29 | 2008-11-04 | Dow Corning Toray Silicone Co., Ltd. | Thermosetting resin and thiocyanato-containing organohydrocarbonoxysilane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1069748A (en) | 1993-03-10 |
| JPH05214171A (en) | 1993-08-24 |
| TW203070B (en) | 1993-04-01 |
| CN1067701C (en) | 2001-06-27 |
| DE4128203C1 (en) | 1993-05-13 |
| FR2680795A1 (en) | 1993-03-05 |
| FR2680795B1 (en) | 2002-01-25 |
| KR930004332A (en) | 1993-03-22 |
| GB2259303B (en) | 1994-07-20 |
| IT1256945B (en) | 1995-12-27 |
| ITTO920713A1 (en) | 1994-02-26 |
| ITTO920713A0 (en) | 1992-08-26 |
| KR960003827B1 (en) | 1996-03-22 |
| GB9217649D0 (en) | 1992-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4222915A (en) | Vulcanizable halorubber mixtures | |
| Hewitt | Compounding precipitated silica in elastomers: theory and practice | |
| CA1161185A (en) | Vulcanizable rubber mixture containing an organosilane | |
| US8097674B2 (en) | Amino alkoxy-modified silsesquioxanes in silica-filled rubber with low volatile organic chemical evolution | |
| US5401789A (en) | Process for the production of plastic and rubber compositions filled with carbon black | |
| JP4755411B2 (en) | Rubber mixture, process for its production and use thereof | |
| US4229333A (en) | Cross-linkable rubber mixtures containing silicate fillers and process for cross-linking | |
| GB2259303A (en) | A process for the production of vulcanizable moulding compounds and to the moulding compounds produced by this process | |
| KR101125514B1 (en) | Carbon black | |
| CN1250779A (en) | Thiosilicane | |
| GB2038341A (en) | Rubber mixtures giving reversion-free vulcanisates | |
| CA1252937A (en) | Vulcanizable filled halo rubber with isothiuronium | |
| US5939493A (en) | Pneumatic tire | |
| EP3622015B1 (en) | Rubber compositions containing sulphur-containing organosilicon compounds | |
| US11739198B2 (en) | Sulfur-crosslinkable rubber mixture vulcanizate and vehicle tyre | |
| US6251976B1 (en) | Rubber mixtures containing trimethylopropane distillation residues | |
| US11414441B2 (en) | Silane, rubber mixture containing the silane, vehicle tire comprising the rubber mixture in at least one component, and process for producing the silane | |
| US20250034367A1 (en) | Sulphur-crosslinkable rubber mixture, vulcanisate of the rubber mixture, and vehicle tyre | |
| JPH10251449A (en) | Rubber composition | |
| US9593234B2 (en) | Rubber composition having intramolecular double bond | |
| JP2010196030A (en) | Rubber composition | |
| RU2812013C2 (en) | Silane, rubber mixture containing silane and vehicle tire which contains rubber mixture in at least one component, and also method for producing silane | |
| EP0864604A2 (en) | Rubber composition | |
| KR840001599B1 (en) | Hardening method of rubber mixture | |
| US20240239990A1 (en) | Organosilyl polysulfides, and rubber mixtures containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20070819 |