SE190886C1

SE190886C1 -

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Publication number: SE190886C1
Authority: SE
Publication date: 1964-01-01

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Uppfinnare: E Wagner och H Westlinning Prioritetbegard frail den 15 december 1953 (Forbundsrepubliken Tyskland) Foreliggande uppfinning hanfor sig till ett forfarande fOr framstallning av vulkbara blandningar pa basis av elastomerer. Inventors: E. Wagner and H. Westlinning Priority Required from December 15, 1953 (Federal Republic of Germany) The present invention relates to a process for the preparation of vulcanizable mixtures based on elastomers.

De t ãr kant att de till Mr vulkningen avsedda gummiblandningarna satta finfiirdelade, i gasfas framstallda metall- eller metalloidoxider, isynnerhet kiseldiokid, var for sig eller flera tillsammans, eventuellt Liven med andra fyllmedel, och pa detta satt astadkomma en forstarkning, dvs. en forbattring av de gummitekniska egenskaperna. De forsffirkande egenskaperna hos en sadan, exempelvis genom sonderdelning av kiseltetraklorid i angf as utvunnen kiselsyra aro de pa annat satt framstallda fyllmedlen vida overlagsna i flera avseenden. Emellertid ar en sadan kiselsyra behaftad med vissa nackdelar, vilka framforallt ge sig till kanna i den kraftiga krympningen (Verstrammung) av blandningama och den darigenom fOrsvarade inarbetningsmojligheten. Man kan heller icke alltid genom tillblandning av andra fyllmedel helt undvika sadana svarigheter. It is clear that the rubber mixtures intended for Mr vulkningen put finely divided, gas-produced metal or metalloid oxides, in particular silicon dioxide, separately or several together, possibly Liven with other fillers, and in this way achieve a reinforcement, ie. an improvement of the rubber technical properties. The fortifying properties of such, for example by probing silicon tetrachloride in the form of recovered silicic acid, the fillers produced in other ways are far superior in several respects. However, such silicic acid suffers from certain disadvantages, which are mainly manifested in the sharp shrinkage (Verstrammung) of the mixtures and the possibility of incorporation thereby defended. Nor can such similarities be completely avoided by mixing other fillers.

Det har nu befunnits, att vid anvandning av fyllmedel pa basis av metall- eller metalloidoxider, som framstallts i gasfas pa sa satt, att blandningar av minst tva metall- ochjeller metalloidoxider, som i homogen blandning med syre och brannbara gaser, ledas till en brannare och omsattas i en lag% det icke blott är mojligt undvika dessa svarigheter, utan att det aven är indjligt uppna ovantade fordelar vid fyllmedlets anvandning. It has now been found that when using fillers based on metal or metalloid oxides produced in the gas phase in such a way that mixtures of at least two metal and / or metalloid oxides, which in homogeneous mixture with oxygen and combustible gases, are led to a burner and is transposed into a law% it is not only possible to avoid these responsibilities, but also to earn the above advantages in the use of the filler.

I enlighet harmed astadkommes enligt foreliggande uppfinning ett forfarande for framstallning av vulkbara blandningar pa basis av elastomerer genom inarbetning av hogdispersa oxider som forstarkande fylImedel, vilka oxider erhallits genom omsattning av flyktiga metall- eller metalloidfOreningar i gasfas, vilket forfarande i huvudsak kannetecknas av att man som forstarkande fyllmedel anvander en blandoxid, erhallen fran en Dupl. kl. 39 b: 5/07 blandning av fasta oxider bildande, flyktiga metall- och/eller metalloidfbreningar med syre och brannbara gaser genom homogen hopblandning, tillforsel till en brannare och omsattningi en Som flyktiga foreningar valjer man med fordel halogenider, isynnerhet klorider, exempelvis av kisel, aluminium, titan, zirkonium, jam, krom m. fl. En blandning av minst tva sadana foreningar, t. ex. kiseltetraklorid och aluminiumklorid i angform, blandas fOr framstallningen av det nya fyllmedlet intimt med syre och brannbara gaser, och denna gasblandning ledes genom en brannare till en laga, i vilken foreningarna omsattas till de motsvarande oxiderna. Det har visat sig, att man med avseende pa omsattningens likformiga forlopp, som ju med hansyn till spjalkningen av de oxidbildande fOreningarna forlOper endotermt, uppnar de gynnsammaste resultaten, om blandningens syrehalt installes sá att syret ar tillrackligt for forbranningen av den brannbara gasen och f Or oxidbildningen, dvs. att Fagan kan brinna av sig sjalv utan yttre tillforsel av luft eller syrehaltiga gaser. Syret installes salunda med fordel i den for reaktionen avsedda gasblandningen pa &Mani; satt, att det fOreligger i den for fullstandig forbranning och oxidation av de ifragavarande foreningarna stokiometriska mangden. Accordingly, the present invention provides a process for preparing vulcanizable mixtures based on elastomers by incorporating highly dispersed oxides as reinforcing fillers, which oxides are obtained by reacting volatile metal or metalloid compounds in gas phase, which process is mainly characterized by reinforcing fillers use a mixed oxide, obtained from a Dupl. at 39 b: 5/07 mixture of solid oxides forming volatile metal and / or metalloid compounds with oxygen and combustible gases by homogeneous mixing, supply to a burner and turnover. , aluminum, titanium, zirconium, jam, chromium, etc. A mixture of at least two such associations, e.g. silicon tetrachloride and aluminum chloride in angular form, are mixed intimately with oxygen and combustible gases for the preparation of the new filler, and this gas mixture is passed through a burner to a layer in which the compounds are converted to the corresponding oxides. It has been found that with regard to the uniform course of the reaction, which, in view of the cleavage of the oxide-forming compounds, proceeds endothermically, the most favorable results are obtained if the oxygen content of the mixture is installed so that the oxygen is sufficient for combustion of the combustible gas. oxide formation, i.e. that the phage can burn on its own without an external supply of air or oxygen-containing gases. The acid is thus advantageously installed in the gas mixture intended for the reaction on &Mani; provided that it is present in the for complete combustion and oxidation of the compounds in question the stoichiometric amount.

Som brannbar gas kan man exempelvis anvanda koloxid, vid vars forbranning till koldimdd alstras den varmemangd, som erfordras for spjalkningen av de flyktiga metall- eller metalloidforeningarna i den tillforda angblandningen. As a combustible gas, it is possible, for example, to use carbon monoxide, in the case of which combustion to carbon fumes produces the heat quantity required for the cleavage of the volatile metal or metalloid compounds in the supplied steam mixture.

Urnsattningen gar sardeles hastigt, om man valjer branngaser, som reagera med syre under vattenbildning, dvs. omman som branngas anvander vate, vatehaltiga eller vateavgivande gaser eller gasblandningar, t. ex. metan eller lysgas. Till fOljd av vattenblldningen sonderdelas di de 2--- — ' flyktiga oxidbildande fOreningarna p. samma satt som vid en- hydrolys. Den hastiga omsattningen, som blir foljden av detta spjalkningssatt, medlar sarskilda fordelar genom att oxiderna erhallas i utomordentligt finfordelat tillstand och med likformig kornstorlek, alldenstund en utflockning eller selektiv reaktion mellan de latt sOnderdelbara kloriderna praktiskt taget ej kan intrada. A.ven om man som branngaser valjer sadana som reagera med syre under vattenbildning, skall syrgasmangden foretradesvis installas sá att den atminstone är tillracklig for vattenbildningen, dvs. man installer den brannbara gasen och syrgasen i den homogena, till Fagan ledda blandningen i stokio-, metriskt ftirhallande med avseende pa vattenbildningen. The precipitation is extremely fast, if you choose fire gases, which react with oxygen during water formation, ie. omman as fire gas uses hydrogen, hydrogen-containing or hydrogen-releasing gases or gas mixtures, e.g. methane or light gas. Due to the water mixture, the 2 --- - 'volatile oxide-forming compounds are divided in the same way as in hydrolysis. The rapid reaction which results from this cleavage is given particular advantages in that the oxides are obtained in an extremely finely divided state and with a uniform grain size, while a flocculation or selective reaction between the readily decomposable chlorides can practically not occur. A. even if fire gases are selected as those which react with oxygen during water formation, the amount of oxygen should preferably be installed so that it is at least sufficient for the water formation, ie. the combustible gas and the oxygen gas are installed in the homogeneous, Fagan-led mixture in the stoichio-, metric relation with respect to the water formation.

FOr oxidernas anvandning som fyllmedel spelar bl. a. kornstorleken en avgorande roll, vilken vid forfarandet enligt uppfinningen kan paverkas pa sb. satt, att de oxidbildande foreningarna vid reaktionen i gasblandningen anvandas i storsta mojliga utspadning. Genom att andra den tillmatade mangden av de oxidbildande fOreningarna till den for forbranningen avsedda gasblandningen kan man salunda reglera kornstorleken hos de bildade oxiderna. Darvid kommer givetvis oxidproduktionen att bli mindre, vilket begransar nyttan av denna atgard. For att vid konstant oxidproduktion kunna erhalla en mera finfordelad produkt, kan man emellertid leda de syreavgivande komponenterna, t. ex. luften i gasblandningen, i en med avseende pa vattenbildningen overstoldometrisk mangd till lagan. For the use of oxides as fillers, e.g. a. the grain size plays a decisive role, which in the process according to the invention can be affected by sb. that the oxide-forming compounds in the reaction in the gas mixture are used in the greatest possible dilution. By changing the amount of the oxide-forming compounds fed to the gas mixture intended for combustion, it is thus possible to control the grain size of the oxides formed. Thereby, of course, the oxide production will be less, which limits the benefit of this action. However, in order to be able to obtain a more finely divided product with constant oxide production, one can conduct the oxygen-releasing components, e.g. the air in the gas mixture, in an amount overstoldometric to the law with respect to water formation.

For att erhalla en sá aktiv yta som mojligt hos de fasta reaktionsprodukterna, vilka forst utfalla som aerosol, och for att i storsta mopiga utstrackning motverka bildningen av gitterstOrningsstallen och fOrhindra bildningen av aktiva centra i primarpartiklarna, skall lagans temperatur genom installning av branngasen hallos sh lag som mbjligt vid fullstandig omsattning. Man arbetar Odor med fordel med lagtemperaturer av c:a 900-1200° C. Den onskade lagtemperaturen kan dessutom uppratthallas genom att man till lagan satter utspadande inertgaser, t. ex. kvave, varvid samtidigt en minskning av de bildade oxidernas kornstorlek astadkommes till foljd av branngasens utspadning. In order to obtain as active an area as possible in the solid reaction products, which first precipitate as aerosol, and in order to counteract the formation of the lattice tower to the greatest extent and to prevent the formation of active centers in the primary particles, the temperature of the gas must be as possible at full turnover. Odor is used to advantage with layer temperatures of about 900-1200 ° C. The desired layer temperature can also be maintained by adding diluting inert gases to the layer, e.g. nitrogen, whereby at the same time a reduction in the grain size of the formed oxides is effected as a result of the dilution of the fire gas.

For att man skall kunna bibehalla den aktiva Ytan hos de bildade oxidpartiklarna är det av storsta vikt, att partiklarnas uppehallstid i lagan blir sa kort som mojligt. Man anvander darfor lampligen korta lagor, som uppvisa stor lagvolym vid liten flamhojd. Sadana lagor alstras exempelvis i en s. k. duschbrannare, vid vilken ett flertal smâ lagor forenas till en enda stor och fOrhallandevis kort Det namndes ovan, att vid forfarandet for framstallningen av de nya fyllmedlen den for forbranningen erforderliga syrgasen tillfordes Nan Over reaktionsblandningen och att denna darfor ej behbvde tillforas nagon syrgas utifran. In order to be able to maintain the active surface of the formed oxide particles, it is of the utmost importance that the residence time of the particles in the layer is as short as possible. It is therefore appropriate to use short layers, which have a large layer volume at a small flame height. Such layers are generated, for example, in a so-called shower burner, in which a plurality of small layers are combined into a single large and relatively short one. needed to be supplied with some oxygen from outside.

FOr att man skall kunna uppna en homogen och likformig fordelning av de olika reaktionskompo- nenterna i praktiskt taget hela lagans volym, är det icke heller onskvart att det alstras nagon turbulens eller virvelbildning i eller i narheten av lagan. Darfor skall den gas- eller angformiga utgangsblandningen pa vagen till lagan foras under laminar stromning i den utstrackning som overhuvudtaget dr mi5jlig. In order to be able to achieve a homogeneous and uniform distribution of the various reactants in practically the entire volume of the law, it is also not unreasonable that any turbulence or vortex formation is generated in or near the law. Therefore, the gaseous or vaporous exit mixture on the road to the layer should be carried under laminar flow to the extent possible.

Utstromningshastigheten hos den av minst tva metall- eller metalloidforeningar, syre och en brannbar gas bestaende homogena utgangsblandningen skall vid brannaroppningen utgora en multipel av blandningens tandhastighet. For att undvika att en alltfOr tidig utskiljning omkring brannarkanten av fasta reaktionsprodukter in-trader i blandningen, som redan i reaktionsbenagen sammansattning ledes till brannarmynningen, Mlles denna vid framstallningen av fyllmedlet enligt uppfinningen fri fran branngasblandningen genom att man inleder en spolgas, t. ex. luft eller vate, som i tunna skikt strommar forbi brannarmynningen, eller ocksa med mekaniska hjalpmedel. The outflow rate of the homogeneous starting mixture of at least two metal or metalloid compounds, oxygen and a combustible gas must be a multiple of the tooth velocity of the mixture at the time of fire. In order to avoid a premature precipitation around the edge of the fire of solid reaction products entering the mixture, which is already led to the burner orifice in the reactant composition, this is obtained during the preparation of the filler according to the invention free from the flue gas mixture by initiating a purge gas, e.g. air or cotton wool, which flows in thin layers past the mouth of the fire, or also with mechanical aids.

Vid anvandning av halogenidblandningar, som omsattas med stokiometriska mangder vattenbildande gaser i intim blandning, bildas jamte de fasta oxiderna framfbrallt saltsyra, fran vilken oxiderna maste skiljas. Sasom namts tidigare, erhallas oxiderna forst i form av en aerosol, for vars utfallning fran de gasformiga reaktionsprodukterna man kan anvanda i och for sig kanda anordningar sasom filter eller eventuellt elektrofilter, men i all synnerhet cykloner. For att man skall kunna bibehalla de gynnsamma egenskaperna hos de bildade oxidpartiklarna med avseende pa finhet och ytstruktur har det visat sig utomordentligt fordelaktigt att lata koagulationen forsigga i narvaro av de pa ett tidigare stadium koagularade partiklarna, vilka i viss man kunna tjana som ympmedel eller kondensationskarnor for de annu icke koagulerade mangderna. Man hailer darfOr reaktionsprodukterna i svavande tillstand under en lang stracka, varvid koagulationen kan beframjas ytterligare genom att man hailer partiklarna i kraftig rorelse i forhallande till varandra. For detta andamal uppvirvlas den aerosolhaltiga gasstrommen i rymliga kamrar eller ledes genom langa, lampligen upprepade ganger krokta ror, sá att man far till stand en turbulent stromning och de svavande partiklarna kvarstanna nagra sekunder i koagulationsrummet fore avskiljningen i cyklonen. When halide mixtures are used, which are reacted with stoichiometric amounts of water-forming gases in intimate mixture, the solid oxides form hydrochloric acid, from which the oxides must be separated. As mentioned earlier, the oxides are first obtained in the form of an aerosol, for the precipitation of which from the gaseous reaction products one can use per se known devices such as filters or possibly electrostatic precipitators, but in particular cyclones. In order to be able to maintain the favorable properties of the formed oxide particles with respect to fineness and surface structure, it has proved extremely advantageous to allow the coagulation to proceed in the presence of the particles coagulated at an earlier stage, which can in some cases serve as inoculants or condensation nuclei. for the not yet coagulated amounts. The reaction products are therefore hailed in a floating state for a long distance, whereby the coagulation can be further promoted by hailing the particles in vigorous motion in relation to each other. For this purpose, the aerosol-containing gas stream is swirled in spacious chambers or passed through long, suitably repeatedly curved tubes, so that a turbulent flow is effected and the sulfur particles remain for a few seconds in the coagulation chamber before separation in the cyclone.

De fasta reaktionsprodukterna, som besta av minst tva oxider och uppvisa speciella egenskaper, som fyilmedel, skilja sig i flera avseenden Iran sa.dana fyllmedel, som endast besta av enkla fysikaliska blandningar av motsvarande oxider. Som senare skall visas i exemplen, aro de icke endast blandningar av motsvarande oxider, utan aven de fyllmedel, som besta av en enhetlig oxid, vida Overlagsna med avseende pa bearbetbarheten i gummiblandningar och pa grund av det selektiva inflytandet pa de gummitekniska egenskaperna. The solid reaction products, which consist of at least two oxides and exhibit special properties, as fillers, differ in several respects from Iran such fillers, which consist only of simple physical mixtures of corresponding oxides. As will be shown later in the examples, they are not only mixtures of corresponding oxides, but also the fillers which consist of a uniform oxide, far superior to the processability of rubber compounds and due to the selective influence on the rubber technical properties.

Det ror sig darvid uppenbarligen om en speciell — —3 materialklass, vars struktur endast kan erhallas genom den enligt uppfinningen foreslagna om- sattningen mellan blandningar av minst tva oxidbildande fOreningar i homogen blandning med de brannbara och syrehaltiga gasema. Dessa reaktionsbetingelser utgora uppenbarligen en garanti for att vid anvandningen av blandningar av oxidbildande fereningar, vilkas formaga att reagera med syre eller vatten är olika, ingen som heist utflockning eller selektiv reaktion intrader. Fyllmedlets karaktar kan varieras genom lampligt val av de metaller eller metalloider, av vilka fyllmedlet bestar. Det kan besta saval av en komplex oxid som ett fOrstadium till en forening. Aven en egentlig foreningsbildning kan redan ha intratt eller atminstone ha borjat. Genom omsdttming av en blandning av kiseltetraklorid och aluminiumklorid pa angivet satt kan man salunda exempelvis framstalla ett fyllmedel, som till sin kemiska natur representerar ett forstadium till ett aluminiumsilikat och som ifraga om sina egenskaper patagligt skiljer sig Iran en enkel blandning av de bada namnda oxiderna. This is obviously a special class of material, the structure of which can only be obtained by the reaction proposed according to the invention between mixtures of at least two oxide-forming compounds in a homogeneous mixture with the combustible and oxygen-containing gases. These reaction conditions obviously provide a guarantee that in the use of mixtures of oxide-forming compounds, which are capable of reacting with oxygen or water, no one such as heist flocculation or selective reaction occurs. The character of the filler can be varied by appropriate choice of the metals or metalloids of which the filler consists. It can consist of a complex oxide as a precursor to a compound. Even an actual association formation may have already taken place or at least begun. By reacting a mixture of silicon tetrachloride and aluminum chloride in the manner indicated, it is thus possible, for example, to produce a filler which, by its chemical nature, represents a precursor to an aluminum silicate and which, in view of its properties, differs from Iran in a simple mixture of the two oxides.

For kombinationen av de oxidbildande amnena fOreligger ett flertal mojligheter saval med hansyn till arten som mangden av de oxidbildande amnena. Jamte det redan anforda exemplet pa omsattningen av en blandning av kisel- och aluminiumhalogenider kan man aven anvanda blandningar av kisel- och titanforeningar, isynnerhet halogenider, som overforts till oxider och anvandas som fyllmedel, varvid man allt efter behov kan lagga huvudvikten vid kiselkomponenten eller aluminium- resp. titankomponenten. Aven kiselfria fyllmedel, t. ex. sadana bestaende av titandiwdd och aluminiumdicodd eller av zirkoniumoxid och aluminiumoxid, slutligen aven av dessa oxidkombinationer och en annan oxid sasom kromoxid, jarnoxid, vanadinoxid, kunna utvinnas enligt det nya forfarandet. For the combination of the oxide-forming substances, there are a number of possibilities with the view of the species as well as the amount of the oxide-forming substances. In addition to the example already given of the reaction of a mixture of silicon and aluminum halides, it is also possible to use mixtures of silicon and titanium compounds, in particular halides, which are converted to oxides and used as fillers, whereby the main weight may be added to the silicon component or aluminum. - resp. the titanium components. Also silicon-free fillers, e.g. such consisting of titanium dioxide and alumina or of zirconia and alumina, finally also of these oxide combinations and another oxide such as chromium oxide, iron oxide, vanadium oxide, can be recovered according to the new process.

Det anfOrdes ovan, att en vasentlig fOrdel med de nya fyllmedlen jamfort med de materiellt enhetliga, pa liknande satt utvunna fyllmedlen är, att de nya fyllmedlen under bibehallande av hog aktivitet och de darav foljande, for gummiblandningarna gynnsamma egenskaperna, kunna inarbetas vasentligt lattare, dvs. visa bearbetningsegenskaper, som endast kunna uppnas hos i ovrigt mindre aktiva fyllmedel. It was stated above that a significant advantage of the new fillers compared to the materially uniform, similarly recovered fillers is that the new fillers, while maintaining high activity and the consequent properties favorable for the rubber mixtures, can be incorporated substantially more easily, ie. . show processing properties, which can only be achieved with otherwise less active fillers.

En annan fordel hos det fyllmedel, som i enlighet med foreliggande uppfinning kommer till anvandning vid framstallning av de vulkbara blandningarna är att man vid deras anvanclning for vulkning av gummi behOver anvanda mindre mangder svavel och vulkningsacceleratorer an vid anvandning av enhetliga wider. Genom val av de lampliga mangderna och bestandsdelarna i det nya fyllmedlet kan man exempelvis hos gummi uppna samma egenskaper vid betydligt lagre fyllnadsgrad a.n vid fyllning med storre mangder kiseldioxid enbart eller i mekanisk blandning med exempelvis aluminiumoxid. Another advantage of the filler which, in accordance with the present invention, is used in the preparation of the vulcanizable mixtures is that in their use for vulcanization of rubber smaller amounts of sulfur and vulcanization accelerators need to be used than in the use of uniform wides. By choosing the suitable amounts and constituents of the new filler, the same properties can be achieved with rubber, for example, at a much lower degree of filling, for example when filling with larger amounts of silica alone or in mechanical mixing with, for example, alumina.

Sarskilt lampliga ha sidana fyllmedel visat sig vara, som utvunnits genom omSattning av 'en blandning av kiseltetraklorid och aluminiumklorid, t. ex. i mangder av 0,5-30 °,/o. Pa liknande satt ha aven titanoxidhaltiga fyllmedel bestatt provet i praktiken, vilka aven kunna erhallas om man omsatter angformiga blandningar av kiseltetraklorid tillsammans med vate och syre i stokiometriskt fbrhallande i en laga, varvid kloridblandningens halt av titantetraklorid exempelvis kan variera mellan 5 och 35 %. Naturligtvis kan man aven anvanda det omvanda mangdfdrhallandet, namligen blandningar av aluminiumklorid eller titantetraklorid sinsemellan eller med mindre mangder kiseltetraklorid, for framstallningen av de uppfunna fyllmedlen, om en motsvarande modifiering av egenskaperna visar sig onskvard. Particularly suitable side-fillers have been found to be obtained by reacting a mixture of silicon tetrachloride and aluminum chloride, e.g. in amounts of 0.5-30 °, / o. Similarly, titanium oxide-containing fillers have also passed the test in practice, which can also be obtained by reacting angular mixtures of silicon tetrachloride together with hydrogen and oxygen in a stoichiometric ratio in a layer, whereby the chloride mixture content of titanium tetrachloride can vary between 5 and 35%. Of course, it is also possible to use the converted ratio, namely mixtures of aluminum chloride or titanium tetrachloride among themselves or with smaller amounts of silicon tetrachloride, for the preparation of the invented fillers, if a corresponding modification of the properties turns out to be undesirable.

Exempel 1. I detta exempel visas en jamfOrelse mellan tva gummiblandningar I och II, som var och en innehaller 40 delar fyllmedel och 100 delar ragummi. Fyllmecllet i blandningen I bestar av kiseldioxid, som utvunnits genom termisk soliderdelning av kiseltetraklorid i gasfas, och som ar enhetligt uppbyggd. I blandningen II har ett fyllmedel enligt uppfinningen utvunnits genom omsattning av en blandning av kiseltetraklorid och aluminiumtetraklorid med en halt av 10 % aluminiumoxid och. 90 % kiseldioxid. Vid vulkningen uppnas fOr de hada blandningarna foljande varden: I II Defohardhet 1800 67 Dragbrottgrans kpfcm2. 314 313 Modul 300 kplcm2 70 6 Brottoj ning % 670 68 StOtelasticitet % 62 Shorehardhet 656 Rivhallfasthet kp/em 37 Av exemplet framgar, att man vid anvandning av det uppfunna fyllmedlet uppnar en myeket iinskvard mjukning av gummiblandningen under kraftigt reducerad defohardhet, varigenom bearbetbarheten forbdttras och kraftbehovet vid framstallningen av den for vulkningen avsedda blandningen vasentligt minskas. Trots detta amo vardena pa dragbrottgransen, brottojningen och rivhallfastheten praktiskt taget oforandrade, medan stotelasticiteten erfarit en pataglig hojning. Vulkaten utveckla darfOr mindre varme vid dynamisk pakanning, vilket kan vara av vasentlig fordel f Or manga andamal. Aven minskningen av shorehardheten verkar i samma riktning. Example 1. This example shows a comparison between two rubber compounds I and II, each containing 40 parts of filler and 100 parts of rag rubber. The filler in mixture I consists of silica, which is extracted by thermal solid decomposition of silica tetrachloride in the gas phase, and which is uniformly composed. In the mixture II, a filler according to the invention has been recovered by reacting a mixture of silicon tetrachloride and aluminum tetrachloride with a content of 10% alumina and. 90% silica. During vulcanization, the following values are obtained for the had mixtures: I II Defohardhet 1800 67 Dragbrottgrans kpfcm2. 314 313 Module 300 kplcm2 70 6 Breaking% 670 68 Shock elasticity% 62 Shore hardness 656 Tear resistance kp / em 37 the power requirement in the preparation of the mixture intended for vulcanization is substantially reduced. Despite this, the values of the tensile strength, the breaking elongation and the tear hall strength are practically unchanged, while the impact elasticity has experienced a sudden increase. Vulcates therefore develop less heat during dynamic packing, which can be of significant benefit to many purposes. The reduction in shore hardness also works in the same direction.

Exempel 2. For att visa det olikartade forhallandet gentemot ett vulkat, vid vilket en blandning av kiseldioxid och aluminiumoxid anvandes som fyllmedel, mattes vardena pa tva blandningar med en jamfort med exemplet 1 avvikande sammansattning. En blandning III framstalldes med ett fyllmedel enligt uppfinningen, bestaende av 90 % kiseldioxid och 10 % aluminiumoxid, medan man som fyllmedel vid en annan blandning IV anvande en blandning av separat ur gasfas:utvunnen, finfordelad kiseldi- — — oxid och finfordelad aluminiumoxid. Fyllnadsgraden utgjorde 40 delar fyllmedel pa 100 delar gummi. Blandningarnas sammansattning och de erhallna gummitekniska vardena hos vulkaten framga av foljande uppstallning: Blandning III IV Gummi 100 100 Fyllmedel enl. uppf. Blandning Si02 + A1203 Stearinsyra 1,0 1,0 Ozokerit 2,7 2,7 Zinkoxid 5,0 5,0 Accelerator Vulkasit (Toluylen-bisguanidin) 2,3,0 Svavel 4,0 4,8 Defohardhet 71 Defoelasticitet 15,2 25,8 Dragbrottgrans kplemz 274 284 Modul 300 kplcm2 67 79 Brottojning % 644 652 Stotelasticitet % 59 48 Shorehardhet 58 69 Rivhallfasthet kp/cm 32 31 Aven har visa resultaten en vasentlig nedgang i defohardheten vid anvandning av de uppfunna fyllmedlen jamfort med de i blandningen IV anvanda rena blandningarna av samma oxider i samma mangdforhallande. Vidare erholls aven har en kraftig nedgang i shorehardheten och en vasentlig Okning av elasticiteten, som aterigen ger mera elastiska vulkat, vid vilkas dynamiska pakanning varmeutvecklingen hailer sig mom laga granser. Papekas bor liven det mindre behovet av acceleratorer och svavel i blandningen III. Example 2. To show the different ratio to a volcano, in which a mixture of silica and alumina was used as filler, the values of two mixtures were measured with a composition different from Example 1. A mixture III was prepared with a filler according to the invention, consisting of 90% silica and 10% alumina, while as a filler in another mixture IV a mixture of separately from gas phase was used: recovered, finely divided silica and finely divided alumina. The degree of filling was 40 parts filler per 100 parts rubber. The composition of the mixtures and the obtained rubber technical values of the volcanoes are shown in the following table: Mixture III IV Rubber 100 100 Fillers acc. opg. Mixture SiO2 + Al2 O3 Stearic acid 1.0 1.0 Ozokerite 2.7 2.7 Zinc oxide 5.0 5.0 Accelerator Vulkasite (Toluylene-bisguanidine) 2.3.0 Sulfur 4.0 4.8 Defo hardness 71 Defoelasticity 15.2 25.8 Traction breakage spruce kplemz 274 284 Module 300 kplcm2 67 79 Gross elongation% 644 652 Shock elasticity% 59 48 Shore hardness 58 69 Tear resistance kp / cm 32 31 use the pure mixtures of the same oxides in the same ratio. Furthermore, recovered aven has a sharp decrease in shore hardness and a significant increase in elasticity, which in turn gives more elastic vulvae, at the dynamic packing of which heat development accelerates to the right limits. Papekas live the less need for accelerators and sulfur in mixture III.

Pa analogt satt som visades for gummi, aro de nya fyllmedlen aven mycket lampliga for inarbetning i elastomer och andra plaster, isynnerhet sadana som i likhet med gummi kunna forstarkas. In an analogous manner as shown for rubber, the new fillers are also very suitable for incorporation into elastomers and other plastics, especially those which, like rubber, can be reinforced.

Claims

Patent claim:

A process for the preparation of vulcanizable mixtures based on elastomers by incorporating highly dispersed oxides as reinforcing fillers, which oxides are obtained by reacting volatile metal or metalloid compounds in the gas phase, characterized in that as reinforcing. filler is used a mixed oxide, obtained from a mixture of solid oxides forming volatile metal and / or metalloid compounds with oxygen and combustible gases by homogeneous mixing, which mixing may have been carried out using inert gases as diluent, supply to a burner and reaction in a lap ..

Process according to claim 1, characterized in that in stoichiometrically proportionally composed, homogeneous mixtures of metal or metallodi compounds, oxygen and combustible gases are brought to reaction.

Process according to claims 1 and 2, characterized in that combustible gases during water formation, e.g. vate or methane, and oxygen mixed homogeneously with the mixture of volatile metal and / or metalloid compounds and then brought to reaction in the law.

Process according to Claims 1 to 3, characterized in that mixtures of silicon tetraloride and aluminum chloride, in particular those with 0.5-30% of aluminum chloride, are brought to react.

Process according to claims 1-3, characterized in that mixtures of silicon tetrachloride and titanium tetrachloride, preferably with 5-35% titanium tetrachloride, are reacted.

Process according to claims 1-3, characterized in that mixtures of aluminum chloride and titanium tetrachloride are used.

7. A method according to claims 1-6, characterized in that the homogeneous gaseous and / or vaporous starting mixture is immediately pre- and in the layer kept under laminar flow.

8. A process according to claims 1-7, characterized in that the finely divided, solid reaction products before complete conversion of the aerosol to gel form are kept for a few seconds in the floating state and only then separated in cyclones, filters and the like. Request publications: Patents Iran Sweden 173 420; France 597 727; Great Britain 535 214; Germany 736 411.