SK119196A3 - Curable rubber mixtures containing organosilanic compounds and silicic acid and manufacturing process thereof - Google Patents
Curable rubber mixtures containing organosilanic compounds and silicic acid and manufacturing process thereof Download PDFInfo
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- 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
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- 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
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Abstract
Description
Oblasť technikyTechnical field
Vynález sa týka spôsobu výroby vulkanizovateíných kaučukových zmesí a takto vyrobených zmesí.The invention relates to a process for the preparation of vulcanizable rubber compositions and to the compositions thus produced.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Úspory v spotrebe palív a radukovanie odvádzania škodlivín získavajú dnes so zosilňujúcim sa ekologickým uvedomením rastúcu prioritu. Pre výrobcu pneumatík to znamená, aby sa vyvíjali pneumatiky, ktoré vynikajú veími malým valivým odporom pri vynikajúcej odolnosti proti sklzu za mokra a dobrou odolnosťou proti oderu.Savings in fuel consumption and the reduction of pollutant removal are increasingly gaining priority today with increasing environmental awareness. For the tire manufacturer, this means developing tires that have very low rolling resistance with excellent wet slip resistance and good abrasion resistance.
V mnohých publikáciách a patentoch sa navrhuje znižovanie valivého odporu pneumatiky, a tým znižovanie spotreby palív. Uvádza sa pritom redukcia obsahu sadzí v zmesi, ako aj použitie špeciálnych sadzí /US patent 4,866,131, US patent 4,894,420/. Žiadny z týchto návrhov riešenia však neviedol k uspojivej rovnováhe medzi malým valivým odporom, ktorý sa má dosiahnuť, a rovnako dôležitými vlastnosťami pneumatík, ako je odolnosť proti sklzu za mokra a odolnosť proti oderu.Many publications and patents suggest reducing the rolling resistance of a tire, thereby reducing fuel consumption. There is mentioned a reduction in the soot content in the mixture as well as the use of special soot (U.S. Pat. No. 4,866,131, U.S. Pat. No. 4,894,420). However, none of these solution proposals has led to a satisfactory balance between the low rolling resistance to be achieved and equally important tire characteristics such as wet slip and abrasion resistance.
Až použitie vysokoúčinných plnív na báze .kyseliny kremičitej v kombinácii s organosilánom bis(trietoxysilylpropyl)tetrasulfán /TESPT/ v rozsiahlom /nahradení sadzí v kaučukovej zmesi sa tu zdá byť cestou, ktorá umožňuje výrobu pneumatiky so značne zníženým valivým odporom v porovnaní so štandardnou pneumatikou za súčasného zachovania aleboOnly the use of high-performance silica-based fillers in combination with organosilane bis (triethoxysilylpropyl) tetrasulfane (TESPT) in the extensive / replacement of carbon black in the rubber compound seems to be the way to produce a tire with considerably reduced rolling resistance compared to a standard tire. at the same time, or
- 2 dokonca zlepšenie obidvoch äalších horeuvedených vlastností pneumatiky.- 2 even improving the two other above-mentioned tire characteristics.
Pri príležitosti mítingu ACS 1936 v New Yorku ukázal,On the occasion of the 1936 ACS meeting in New York,
S. Wolffj[l], že je možné pomocou použitia kyseliny kremičitej v kombinácii s TESPT v jazdnej ploche osobných automobilov na báze emulzného butádiénstyrénového kaučuku /E-SBR/ výrazne znížiť valivý odpor v porovnaní so štandardnými zniesiamí plnenými sadzami pri rozsiahlom zachovaní odolnosti proti sklzu za mokra a odolnosti proti oderu.S. Wolffj [1] that it is possible by using silicic acid in combination with TESPT in the tread of passenger cars based on emulsion butadiene styrene rubber (E-SBR) to significantly reduce the rolling resistance compared to standard carbon black-filled moldings while largely maintaining slip resistance wet and abrasion resistance.
Ďalšia optimalizácia tohto systému s ohladom na všetky tri vlastnosti sa podarila pomocou použitia špeciálnych butadiénstyrénových polymérov, vyrobených polymerizáciou v roztoku /EP 0 447 066 A1/, čiastočne v zmesi s iným polymérom, najmä polybutadiénom, a pomocou dodatočného použitia nových typov kyseliny kremičitej /US patent 5»227,425/, ako aj špeciálne na toto použitie zameraných polymérových zmesí /EP 0620250/ s sčasti s tromi až štyrmi rozdielnymi východiskovými polymérmi.Further optimization of this system with respect to all three properties has been achieved through the use of special butadiene styrene polymers produced by solution polymerization (EP 0 447 066 A1), partly mixed with another polymer, in particular polybutadiene, and the additional use of new types of silicic acid. U.S. Pat. No. 5,227,425), as well as specifically targeted polymer blends (EP 0620250), with in part three to four different starting polymers.
Všetky tieto publikácie a patenty majú spoločné to, že na dosiahnutie malého valivého odporu pri zachovaní alebo dokonca zlepšení odolnosti proti sklzu za mokra a odolnosti proti oderu sa nahrádza veíká časť, prípadne celý. obsah zvyčajne používaného sadzového plniva vysokoúčinnou kyselinou kremičitou. Vo všetkých prípadoch sa na dosiahnutie v súčasnosti vyžadovaných vlastností pneumatík : použil organosilán bis(trietoxysilylpropyl)-tetrasulfán /TESPT/ ako spojivo medzi kyselinou kremičitou a polymérom.All these publications and patents have in common that a large part or the whole is replaced to achieve a low rolling resistance while maintaining or even improving the wet slip and abrasion resistance. content of the commonly used carbon black filler with high-efficiency silicic acid. In each case, to obtain the current characteristics required of tires: used organosilane bis (triethoxysilylpropyl) -tetrasulfán / TESPT / as a link between the silica and the polymer.
1. S. Wolfíy 129th Meeting of the Rubber Division, Američan Chemical Society, New York, April 8—11, 1986.1. S. Wolfie 129 th Meeting of the Rubber Division, American Chemical Society, New York, April 8-11, 1986.
2* S. Wolff, Third Annual Meeting and Conference of Tire Science and echnology, The Tire Society, Akron, Ohio/USA, March 28-29, 19842 * S. Wolff, Third Annual Meeting and Conference of Tire Science and Technology, The Tire Society, Akron, Ohio / USA, March 28-29, 1984
- 3 Podstata vynálezu3 Summary of the Invention
Predmetom vynálezu sú sírou vulkanizovateíné kaučukové zmesi obsahujúce okrem zvyčajných pomocných prostriedkov a/ 10 až 100 dielov vyzrážanej kyseliny kremičitej, b/ 0 až 100 dielov gumárskych sadzí vzhľadom na 100 dielov taktiež c/ zahrnutých kopolymérov, skladajúcich sa z jedného konjugovaného diénu s jednou aromatickou vinylovou zložkou, vyrobených polymerizáciou v roztoku, s obsahom styrénu medzi 10 a 40 % a obsahom vinylu medzi 20 a 80 %, prednostne 40 až 60 %, a s teplotou skleného prechodu od 0 do -60 °C, alebo týchto polymérov zmiešaných s ďalšími diénovými kaučukmi, pričom podiel týchto diénových kaučukov je až do 60 dielov zo 100 dielov.nadstavenéj zmesi.The present invention relates to sulfur vulcanizable rubber compositions containing, in addition to the usual auxiliaries, (a) 10 to 100 parts of precipitated silica, (b) 0 to 100 parts of rubber soot relative to 100 parts also c) of copolymers comprised of one conjugated diene with one aromatic vinyl a component produced by solution polymerization, with a styrene content between 10 and 40% and a vinyl content between 20 and 80%, preferably 40 to 60%, and a glass transition temperature of 0 to -60 ° C, or of these polymers mixed with other diene rubbers wherein the proportion of these diene rubbers is up to 60 parts of 100 parts of the expanded composition.
d/ a 1 až 20 dielov, prednostne 5 až 10 dielov organosilánovej zlúčeniny všeobecného vzorca (I) (PO) 3Si (ch2) 3scn (I) v ktorom znamená:d / a 1 to 20 parts, preferably 5 to 10 parts, of an organosilane compound of formula (I) (PO) 3 Si (ch 2 ) 3 scn (I) wherein:
R rpzvétvený alebo nerozvetvený alkyl s 1 až 8 atómami uhlíka, prednostne s 1 až 4 atómami uhlíka, vzhíadom na 100 dielov kyseliny kremičitej,R is branched or unbranched alkyl of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, based on 100 parts of silicic acid,
Prednostne sa používajú vyzrážané kremičité kyseliny s povrchom BET /ISO 5794/1D/ medzi 100 a 250 m2/g, najmS ak vykazujú povrch CTAB /ASTM D3765-92/ medzi 100 a 250 m2/g a počet DBP medzi 150 a 300 ml/100 g /ASTM D1208/.Preferably precipitated silicas with a BET / ISO 5794 / 1D / surface area of between 100 and 250 m 2 / g are used, in particular if they exhibit a CTAB / ASTM D3765-92 / surface of between 100 and 250 m 2 / g and a DBP number between 150 and 300 ml. (100 g / ASTM D1208).
Kremičité kyseliny sa pridávajú ako. v práškovéj forme, tak aj vo forme perál alebo granúl. Jedná.sa pritom ako o už mnoho rokov známe typy, tak aj o nové typy, aké sú popísané napríklad v DE-OS 4427137.Silicas are added as. in powder form as well as in the form of beads or granules. These are both known types for many years and new types as described, for example, in DE-OS 4427137.
Zodpovedajúc tomuto vynálezu môžu byť prímesi, ako napríklad iné anorganické plnivá ako horeuvedená kyselina kremičitá a silikáty, zapracované do kaučukovej zmesi, pokiaí použité množstvá neobmedzujú zmysel tohto vynálezu. Iné anorganické plnivá sú napríklad sadze, ako SRF, GPF, FEF, HAF, ISAF, FT a MT.According to the invention, admixtures such as other inorganic fillers such as the aforementioned silicic acid and silicates may be incorporated into the rubber composition as long as the amounts used do not limit the purpose of the invention. Other inorganic fillers are, for example, carbon black, such as SRF, GPF, FEF, HAF, ISAF, FT, and MT.
Ak sa použijú sadze, použije sa hmotnostný pomer kyseliny kremičitej k sadzám aspoň 2:1. Celkový podiel plnív by nemal prekročiť i 120 dielov ha 100 dielov polyméru.If carbon black is used, a weight ratio of silicic acid to carbon black of at least 2: 1 is used. The total proportion of fillers should not exceed 120 parts and 100 parts of polymer.
Výroba vulkanizátov z kaučukových zmesí podía vynálezu vyžaduje len výrobu zmesí surového kaučuku podía dolu popísanej metódy, následné formovanie surových zmesí podía požiadaviek a nasledujúcu vulkanizáciu' rovnakým spôsobom ako pri tradičných kaučukových zmesiach.The production of vulcanizates from the rubber blends of the present invention requires only the production of the raw rubber blends according to the method described below, the subsequent formation of the raw blends as required and the subsequent vulcanization in the same manner as traditional rubber blends.
Na výrobu vulkanizátov podía tohto vynálezu sa ·.> dodatočne k horeuvedeneji kaučukovej1 zložké, , organosilánovéj zlúčenine a amorfnej kyseline kremičitej a zodpovedajúc za-, mýšíanému využitiu vulkanizátov a na ne kladeryŕm'požiadavkám starostlivo zvolí druh a množstvo zmäkčovadiel, druh a množstvo zlúčenín, ktoré predstavujú vulkanizačný systém, ako napríklad vulkanizačné prísady, aktivátory vulkanizácie /ZnO, kyselina stearová/, urýchíovačevulkanizácie a ostatné vulkanizačné pomocné prostriedky, ako i spôsob výroby vulkanizá- .. tov. Ako hore menované zmäkčovadlá sa môžu použiť zvyčajne v kaučukoch používané zmäkčovadlá na báze ropy.For the production of the vulcanizates according to the invention, in addition to the abovementioned rubber component 1 , the organosilane compound and the amorphous silicic acid, and correspondingly to the intended use of the vulcanizates, the species, amount and amount of plasticizers, the amount and amount of plasticizers, which represent a vulcanizing system, such as vulcanizing additives, vulcanizing activators (ZnO, stearic acid), vulcanizing accelerators and other vulcanizing auxiliaries, as well as a process for producing vulcanizers. As the above-mentioned plasticizers, petroleum-based plasticizers commonly used in rubbers may be used.
Ako vulkanizačné prísady na výrobu vulkanizátov pódia vynálezu sa používajú zlúčeniny síry, ako je áalej uvedené. K týmto zlúčeninám síry patrí napríklad síra, morfolíndisulfid, alkylfenyldisulfid, tetrametyltiuramdisulfid a seléniumdimetylditiokarbamát. Z týchto sa používa predovšetkým síra. Hore uvedené zlúčeniny síry sa používajú v množstvách 0,1 až 4 hmotnostné diely, najmá 0,5 až 3 hmotnostné diely vzhíadom na 100 hmotnostných dielov kopolyméru, prípadne jeho zmesí s polymérom. Ak sa pri výrobe vulkanizátov pódia tohto vynálezu použije ako vulkanizačná prísada sírna zlúčenina, potom je predovšetkým treba dodatočne použii urýchiovač vulkanizácie. K používaným urýchiovačom vulkanizácie patria napríklad tiazolové zlúčeniny, ako napríklad N-cyklohexyl-2-benztiazolsulfénamid, N,N-diizopropyl-2-benztiazolsulfénamid, 2-merkaptobenztiazol a dibenztiazyldisulfid; guanidínové zlúčeniny, ako napríklad difenylguanidín, trifenylguanidín, diortotolylguanidín; imidazolínové zlúčeniny, ako napríklad 2-merkaptoimidazolín; tiomočovinové zlúčeniny, ako napríklad dietyltiomočovina, dibutyltiomočovina, trimetyltiomočovina a diortotolyltiomočovina; tiurámové zlúčeniny, ako napríklad tetrametyltiuram-monosulfid, tetrametyltiuramdisulfid, tetraetyltiuram-disulfid, tetrabutyltiuram-disulfid, pentametyléntiuram-tetrasulfid; ditiokarbamátové zlúčeniny, ako napríklad dimetylditiokarbamát zinočnatý, dietylditiokarbamát žinočnatý, di-n-butylditiokarbamát zinočnatý, etylfenylditiokarbamát zinočnatý, butylfenylditiokarbamát zinočnatý, dimetylditíokarbamát sodný, dimetylditiokarbamát selénu a dimetylditiokarbamát telúru; xantogenátové zlúčeniny, ako napríklad dibutylxantogenát zinočnatý;Sulfur compounds are used as vulcanizing agents for the production of the vulcanizates according to the invention as described below. Such sulfur compounds include, for example, sulfur, morpholinedisulfide, alkylphenyl disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Of these, sulfur is mainly used. The abovementioned sulfur compounds are used in amounts of 0.1 to 4 parts by weight, in particular 0.5 to 3 parts by weight, based on 100 parts by weight of the copolymer or its mixtures with the polymer. If a sulfur compound is used as vulcanizing agent in the manufacture of the vulcanizates of the present invention, then a vulcanization accelerator is particularly required. The vulcanization accelerators used include, for example, thiazole compounds such as N-cyclohexyl-2-benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole and dibenzothiazyl disulfide; guanidine compounds such as diphenylguanidine, triphenylguanidine, diortotolylguanidine; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as diethylthiourea, dibutylthiourea, trimethylthiourea and diortotolylthiourea; thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenthiuram tetrasulfide; dithiocarbamate compounds such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate and dimethyldithiocarbamate; xanthate compounds such as zinc dibutyl xanthate;
Zlúčeniny;compounds;
ϊ'ϊ '
Vymenované urýchľovače vulkanizácie sa používajú v množstve 1 až 20 hmotnostných dielov, najmä 0,5 až 5 hmotnosťných dielov vzhľadom na 100 hmotnostných dielov kopolyméru, prípadne jeho zmesí s inými~polymérmi.Said vulcanization accelerators are used in an amount of 1 to 20 parts by weight, in particular 0.5 to 5 parts by weight, based on 100 parts by weight of the copolymer or mixtures thereof with other polymers.
Organosilán a kyselina kremičitá sa predovšetkým pred vmiešaním do vyžadovanej kaučukovej zmesi navzájom zmiešajú alebo tiež privádzajú k’ reakcii· tak, ako sa popisuje v US-PS 5,116,836 /EP-B-0442 143/.In particular, the organosilane and the silicic acid are mixed with one another or even reacted as described in US-PS 5,116,836 (EP-B-0442 143) prior to mixing into the desired rubber mixture.
Nevyžaduje sa bezpodmienečne, aby celkové použité množ^ tvo kyseliny kremičitej bolo vopred modifikované s organosilánom vzorca (I). Možné je aj to, že sa len čas£ vopred modifikuje a zvyšok sa použije bez predchádzajúcej modifikácie .It is not absolutely necessary that the total amount of silicic acid used be pretreated with the organosilane of formula (I). It is also possible that only part δ is modified in advance and the residue is used without prior modification.
Ak sa ako čalšle plnivo pre kaučukovú zmes·, ktorá sa má vyrobil, použijú sadze, vzniká v inom variante možnosľ použiľ organosilán vzorca (I) úplne alebo sčasti ako zmes sadze-organosilán. Táto sa potom .^využije najmä vo forme granulátu s obsahom 30 až 60 % hmotnostných organosilánu, prípadne 70 až 40 % hmotnostných sadzí. Výroba podobných granulátov je popísaná v DE-PS 27 47 277 /US-PS 4,128,438/ a tu môže byľ analogicky uskutočnená.If carbon black is used as the other filler for the rubber mixture to be produced, it is possible in another variant to use the organosilane of formula (I) wholly or partly as a carbon black-organosilane mixture. This is then used in particular in the form of a granulate containing 30 to 60% by weight of organosilane or 70 to 40% by weight of carbon black. The preparation of similar granules is described in DE-PS 27 47 277 (US-PS 4,128,438) and can be carried out analogously here.
Zmes surového kaučuku sa vyrába podľa cíalej popísanej metódy. Hore uvedené kaučukové zložky, organosilánové zlúčeniny, amorfná kyselina kremičitá a prípadne sadze, ako i prípadne zmäkčovadlo sa hnetú v hnetacom zariadení, napríklad v Banburyho miesiči, pri teplote približne 120 až 200 °C 3 až 10 minút, potom sa pridá vulkanizačná prísada, ako urýchľovač a síra alebo iná vulkanizačná sekundárna prísada a buá v Banburyho miesiči, alebo na miešacom valci pokraču-The raw rubber mixture is produced according to the method described below. The above rubber components, organosilane compounds, amorphous silicic acid and optionally carbon black, as well as optionally a plasticizer, are kneaded in a kneading apparatus, for example a Banbury mixer, at a temperature of about 120 to 200 ° C for 3 to 10 minutes, then a curing agent such as accelerator and sulfur or other vulcanizing secondary additive and either in the Banbury mixer or on the mixing cylinder.
je miešanie pri vhodnej teplote áelších 5 až 30 minút a hotová kaučuková zmes sa následne vyťahuje ako plást surového kaučuku alebo vo forme pásov.the mixture is stirred at a suitable temperature for a further 5 to 30 minutes and the finished rubber mixture is subsequently drawn out as a sheath of raw rubber or in the form of strips.
Gumársko-technická skúška vulkanizátov vyrobených zo zmesí podía vynálezu ukazuje, že sa pomocou použitia 3-tiokyanátopropyltrialkoxysilánov ako organosilánu v kombinácii s kremičitými kyselinami v butadiénstyrénových kaučukoch, vyrobených roztokovou polymerizáciou, dá dosiahnuť výrazne lepšia odolnosť proti oderu v porovnaní s použitím TESPT, pri inak rozsiahle rovnakom vzore hodnôt.The rubber-technical examination of the vulcanizates produced from the mixtures according to the invention shows that by using 3-thiocyanatopropyltrialkoxysilanes as organosilane in combination with silicas in butadiene-styrene rubbers produced by solution polymerization, a significantly better abrasion resistance can be achieved compared to other TES. the same pattern of values.
Priemyselná využiteľnosťIndustrial usability
Tieto vulk.anizáty sa používajú pri výrobe formovaných výrobkov a štruktúrových zložiek pneumatík.These vulcanizates are used in the manufacture of molded articles and structural components of tires.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Nasledujúce príklady objasňujú výhody použitých organosilánov vzorca (l)v porovnaní so štandardných silánom TESPT v polymérnom systéme podía nároku 1 a v kombinácii s kremičitými kyselinami podía nároku 2.The following examples illustrate the advantages of the used organosilanes of formula (1) compared to standard TESPT silane in the polymer system of claim 1 and in combination with the silicas of claim 2.
Skúšobné normy <na vyhodnotenieTest standards <for evaluation
V príkladoch využitia sa používajú nasledujúce názvy a skratky:The following names and abbreviations are used in the usage examples:
Buna VSL 1950 S 25 olejom nadstavovaný L-SBR firmy BayerBuna VSL 1950 With 25 oil superstructure L-SBR from Bayer
AG s obsahom vinylu 50 % a obsahom sty. rénu 25 %; teplota skleného prechodu je pri -25 °C.AG with a vinyl content of 50% and a sty. rene 25%; the glass transition temperature is at -25 ° C.
Buna VSL 1955 S 25 olejom nadstavovaný L-SBR firmy Bayer AG s obsahom vinylu 55 % a obsahom styrénu 25 %; teplota skleného prechodu je pri -20 °C.Buna VSL 1955 With 25 oil extended L-SBR from Bayer AG with a vinyl content of 55% and a styrene content of 25%; the glass transition temperature is at -20 ° C.
- 10 Príklad 1: Porovnanie.Si 264_s.Si.69 v jazdnej ploche osobného automobilu s'Ultrasil VN 3 GR ako plnivom- 10 Example 1: Comparison.Si 264_s.Si.69 in the tread of a passenger car s'Ultrasil VN 3 GR as a filler
Si 264 v Jčombinácii s Ultrasil VN 3 GR ukazuje v porovnaní š. Si 69 výrazné zlepšenia v odere pri inak rozsiahle rovnakých vlastnostiach vulkanizátu. Pri reometrickom teste spočíva výhoda Si 264 v rýchlej-Si 264 in JCombination with Ultrasil VN 3 GR shows w. Si 69 marked abrasion improvements with otherwise extensive equal vulcanizate properties. In the rheometric test, the advantage of Si 264 lies in the fast-
Kombinácia Ultrasil 3370 GP/Si 264 ukazuje zreteíné výhody v odere v porovnähí s Ultrasil 3370 GR/Si 69·The Ultrasil 3370 GP / Si 264 combination shows clear abrasion benefits over the Ultrasil 3370 GR / Si 69 ·
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Application Number | Priority Date | Filing Date | Title |
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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 |
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SK119196A3 true SK119196A3 (en) | 1997-04-09 |
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SK119196A SK119196A3 (en) | 1995-09-23 | 1996-09-18 | Curable rubber mixtures containing organosilanic compounds and silicic acid and manufacturing process thereof |
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) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19732725A1 (en) * | 1997-07-30 | 1999-02-04 | Degussa | Mixtures consisting of bis (silylorganyl) polysulfanes and silylorganylthiocyanates, their preparation and use |
BR9806096B1 (en) † | 1997-08-21 | 2009-01-13 | blocked mercaptosilane; process for the manufacture of a loaded rubber; process for the manufacture of a blocked mercaptosilane; rubber composition; and silane. | |
DE19814839A1 (en) | 1998-04-02 | 1999-10-07 | Bayer Ag | Emulsion rubber mixtures containing hydrophobic oxidic or silicate fillers and their use for the production of tires |
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 |
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 |
EP0974616A1 (en) | 1998-07-18 | 2000-01-26 | Bayer Aktiengesellschaft | Solution-polymerised rubber containing hydroxyl groups |
DE19914848A1 (en) | 1999-04-01 | 2000-10-05 | Bayer Ag | Rubber mixture, especially for production of tyre treads, contains solution-polymerised styrene-diene rubber modified with sec. hydroxyl groups not more than four carbon atoms away from side-chain ends |
DE10009909A1 (en) | 2000-03-01 | 2001-09-27 | Bayer Ag | Rubbers with polyether side groups |
DE10012407A1 (en) | 2000-03-15 | 2001-09-20 | Bayer Ag | Rubber mixtures, useful for the production of tire tread contain a polyether, a filler and optionally other processing aids and/or crosslinking agents. |
DE10037076A1 (en) | 2000-07-27 | 2002-02-07 | Bayer Ag | Polybutadienes with a reduced solution viscosity / Mooney viscosity ratio |
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 |
DE10135014A1 (en) | 2001-07-18 | 2003-01-30 | Bayer Ag | Rubber mixtures containing 1,4-butenediol (polyether) |
DE10216657A1 (en) | 2002-04-15 | 2003-10-23 | Rhein Chemie Rheinau Gmbh | Vulcanizable rubber compounds and manufacturing process |
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 |
DE602006020668D1 (en) * | 2005-09-26 | 2011-04-28 | Sumitomo Rubber Ind | Rubber composition for tires and tires made therefrom |
US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated 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 |
US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
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 |
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 |
GB9318850D0 (en) * | 1993-09-11 | 1993-10-27 | Sumitomo Rubber Ind | Rubber compositions |
GB9318849D0 (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 JP JP8250320A patent/JPH09176383A/en active Pending
- 1996-09-20 AU AU65761/96A patent/AU6576196A/en not_active Abandoned
- 1996-09-20 CA CA 2186060 patent/CA2186060A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP0764687A1 (en) | 1997-03-26 |
AU6576196A (en) | 1997-03-27 |
JPH09176383A (en) | 1997-07-08 |
MX9603304A (en) | 1997-03-29 |
PL316128A1 (en) | 1997-04-01 |
CA2186060A1 (en) | 1997-03-24 |
CN1148607A (en) | 1997-04-30 |
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