Highly dispersible silica for using in rubber
20 claims: 20 independent, 0 dependent
- 1Fällungskieselsäure, gekennzeichnet durch folgende physikalisch-chemische Parameter:CTAB-Oberfläche 100-160 m2/g, gemessen mit modifizierter ASTM 3765, bzw, NFT 45-007 (Kapitel 5.12.1.3);BET-Oberfläche 100-190 m2/g, gemäß ISO 5794-1/Annex D;DBP-Zahl 180-300 g/(100 g), gemessen mit modifizierter Norm DIN 53601;Searszahl V2 15-28 ml/(5 g)Feuchte 4-8 %, gemessen mit modifizierter ISO 787-2 Verhältnis Searszahl V2 zu BET-Oberfläche 0,150 bis 0,280 ml (5m2). Precipitated silica, characterized by the following physical and chemical parameters: CTAB surface area 100-160 m2/g, measured using modified ASTM 3765, or NFT 45-007 (Section 5.12.1.3);BET surface area 100-190 m2/g, to ISO 5794-1/Annex D;DBP value 180-300 g/(100 g), measured using modified standard DIN 53601;Sears value V2 15-28 ml/(5 g)Moisture level 4-8%, measured using modified ISO 787-2 Ratio of Sears value V2 to BET surface area 0.150 to 0.280 ml (5m2) . Silice précipitée, caractérisée par les paramètres physico-chimiques suivants : Surface CTAB100 à 160 m2/g, mesurée avec ASTM 3765 modifié ou NFT 45-007 (chapitre 5.12.1.3) ;Surface BET100 à 190 m2/g, selon ISO 5794-1/Annexe D ;Indice DBP180 à 300 g/(100 g), mesurée avec la norme DIN 53601 modifiée ;Nombre de Sears V215 à 28 ml/(5 g),Humidité4 à 8 %, mesurée avec ISO 787-2 modifiéRapport nombre de Sears V2 sur surface BET0,150 à 0,280 ml/(5 m2).
- 2Fällungskieselsäure nach Anspruch 1, dadurch gekennzeichnet, dass die BET-Oberfläche 100 bis 170 m2/g beträgt. Precipitated silica according to Claim 1, characterized in that the BET surface area is from 100 to 170 m2/g. Silice précipitée selon la revendication 1, caractérisée en ce que la surface BET est de 100 à 170 m2/g.
- 3Fällungskieselsäure nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die CTAB-Oberfläche 100 bis 150 m2/g beträgt. Precipitated silica according to Claim 1 or 2, characterized in that the CTAB surface area is from 100 to 150 m2/g. Silice précipitée selon la revendication 1 ou 2, caractérisée en ce que la surface CTAB est de 100 à 150 m2/g.
- 4Fällungskieselsäure nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Searszahl V2 20 bis 28 ml/(5 g) beträgt. Precipitated silica according to any of Claims 1 to 3, characterized in that the Sears value V2 is from 20 to 28 ml/(5 g). Silice précipitée selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le nombre de Sears V2 est de 20 à 28 ml/(5 g).
- 5Fällungskieselsäure nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Searszahl V2 22 bis 28 ml/ (5 g) beträgt. Precipitated silica according to any of Claims 1 to 3, characterized in that the Sears value V2 is from 22 to 28 ml/(5 g). Silice précipitée selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le nombre de Sears V2 est de 22 à 28 ml/(5 g).
- 6Fällungskieselsäure nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die DBP-Zahl 200 bis 250 g/ (100 g) beträgt. Precipitated silica according to any of Claims 1 to 5, characterized in that the DBP value is from 200 to 250 g/(100 g). Silice précipitée selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'indice DBP est de 200 à 250 g/(100 g).
- 7Fällungskieselsäure nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die DBP-Zahl 250 bis 280 g/ (100 g) beträgt. Precipitated silica according to any of Claims 1 to 5, characterized in that the DBP value is from 250 to 280 g/(100 g). Silice précipitée selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'indice DBP est de 250 à 280 g/(100 g).
- 8Fällungskieselsäure nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Verhältnis BET/CTAB 0.9 bis 1.2 beträgt. Precipitated silica according to any of Claims 1 to 7, characterized in that the BET/CTAB ratio is from 0.9 to 1.2. Silice précipitée selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le rapport BET/CTAB est de 0,9 à 1,2.
- 9Process for preparing precipitated silicas according to any of Claims 1 to 8, which comprises a) taking an aqueous solution of an alkali metal silicate or alkaline earth metal silicate and/or of an organic and/or inorganic base with an alkali value from 7 to 30 as initial charge,b) metering water glass and an acidifier simultaneously into this initial charge at from 55 to 95°C, with stirring, for from 10 to 120 minutes, in such a way that during the precipitation the AV remains constant at from 7 to 30,c) using an acidifier to acidify to a pH of from approx. 2.5 to 6, andd) filtering, washing and drying. Procédé de fabrication de silices précipitées selon l'une quelconque des revendications 1 à 8, dans lequel a) une solution aqueuse d'un silicate alcalin ou alcalino-terreux et/ou d'une base organique et/ou inorganique d'un indice alcalin de 7 à 30 est chargée initialement,b) du verre soluble et un acidifiant sont ajoutés simultanément à cette charge initiale sous agitation à une température de 55 à 95 °C pendant 10 à 120 minutes, de manière à ce que l'indice AZ reste constant entre 7 et 30 pendant la précipitation,c) on acidifie avec un acidifiant à un pH d'environ 2,5 à 6 etd) on filtre, on lave et on sèche. Verfahren zur Herstellung von Fällungskieselsäuren nach einem der Ansprüche 1 bis 8, wobei a) eine wässrige Lösung eines Alkali-oder Erdalkalisilikats und/oder einer organischen und/oder anorganischen Base mit einer Alkalizahl von 7 bis 30 vorgelegt,b) in diese Vorlage unter Rühren bei 55 bis 95 °C für 10 bis 120 min gleichzeitig Wasserglas und ein Säuerungsmittel derart zudosiert werden, dass während der Fällung die AZ-Zahl konstant zwischen 7 bis 30 bleibt,c) mit einem Säuerungsmittel auf einen pH-Wert von ca. 2.5 bis 6 angesäuert undd) filtriert, gewaschen und getrocknet wird.
- 10Process according to Claim 9, characterized in that the AV is from 15 to 25. Procédé selon la revendication 9, caractérisé en ce que l'indice AZ est compris entre 15 et 25. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die AZ-Zahl zwischen 15 und 25 liegt.
- 11Process according to either of Claims 9 and 10, characterized in that, after step a), the steps carried out comprise b') stopping the feed for from 30 to 90 minutes while maintaining the temperature, andb") then, at the same temperature, for from 10 to 120 minutes, preferably from 10 to 60 minutes, simultaneously adding water glass and an acidifier in such a way that the AV remains constant during the precipitation. Procédé selon l'une quelconque des revendications 9 ou 10, caractérisé en ce que les étapes b') arrêt de l'ajout pendant 30 à 90 minutes en maintenant la température, puisb") ajout simultané de verre soluble et d'un acidifiant à la même température pendant 10 à 120 minutes, de préférence 10 à 60 minutes, de manière à ce que l'indice AZ reste constant pendant la précipitation, sont réalisées après l'étape a). Verfahren nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, dass nach Schritt a), die Schritte b') Stoppen der Zudosierung für 30 bis 90 Minuten unter Einhaltung der Temperatur undb") anschließend bei gleicher Temperatur für 10 bis 120, bevorzugt 10 bis 60 Minuten, gleichzeitige Zugabe von Wasserglas und einem Säuerungsmittel derart, dass die AZ-Zahl während der Fällung konstant bleibt, ausgeführt werden.
- 12Process according to either of Claims 9 and 11, characterized in that during step b) and/or b') and/or b") an organic or inorganic salt is added. Procédé selon l'une quelconque des revendications 9 ou 11, caractérisé en ce qu'un ajout d'un sel organique ou inorganique a lieu pendant l'étape b) et/ou b') et/ou b"). Verfahren nach einem der Ansprüche 9 oder 11, dadurch gekennzeichnet, dass während des Schritts b) und/oder b') und/oder b") eine Zugabe eines organischen oder anorganischen Salzes erfolgt.
- 13Process according to any of Claims 9 to 12, characterized in that for the drying process use is made of a pneumatic drier, spray drier, disk drier, belt drier, rotating-tube drier, flash drier, spin flash drier, or spray tower. Procédé selon l'une quelconque des revendications 9 à 12, caractérisé en ce qu'un séchoir à écoulement, un séchoir à pulvérisation, un séchoir à étages, un séchoir à bande, un séchoir à tube rotatif, un séchoir pneumatique, un séchoir pneumatique rotatif ou une tour à buses est utilisé(e) pour le séchage. Verfahren nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, dass zur Trocknung ein Stromtrockner, Sprühtrockner, Etagentrockner, Bandtrockner, Drehrohrtrockner, Flash-Trockner, Spin-Flash-Trockner oder Düsenturm eingesetzt wird.
- 14Process according to Claims 9 to 13, characterized in that, after the drying process, a roller compactor is used for pelletizing. Procédé selon l'une quelconque des revendications 9 à 13, caractérisé en ce qu'une granulation avec un compacteur à cylindres est réalisée après le séchage. Verfahren nach den Ansprüchen 9 bis 13, dadurch gekennzeichnet, dass nach der Trocknung eine Granulation mit einem Walzenkompaktor durchgeführt wird,
- 15Fällungskieselsäuren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass ihre Oberflächen mit Organosilanen der Formel I bis III modifiziert sind:[SiR1n(OR)r(Alk)m(Ar)p]q[B] (I), SiR1n(OR)3-n(Alkyl) (II), oder SiR1n(OR)3-n(Alkenyl) (III), in denen bedeuten B: -SCN, -SH, -Cl, -NH2, -OC(O)CHCH2, -OC(O)C(CH3)CH2 (wenn q = 1) oder -Sw- (wenn q = 2), wobei B chemisch an Alk gebunden ist,R und R1: aliphatischer, olefinischer, aromatischer oder arylaromatischer Rest mit 2-30 C-Atomen, der optional mit den folgenden Gruppen substituiert sein kann: Hydroxy-, Amino-, Alkoholat-, Cyanid-, Thiocyanid-, Halogen-, Sulfonsäure-, Sulfonsäureester-, Thiol-, Benzoesäure-, Benzoesäureester-, Carbonsäure-, Carbonsäureester-, Acrylat-, Metacrylat-, Organosilanrest, wobei R und R1 eine gleiche oder verschiedene Bedeutung oder Substituierung haben können.n: 0,1 oder 2,Alk : einen zweiwertigen unverzweigten oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen,m: 0 oder 1,Ar: einen Arylrest mit 6 bis 12 C-Atomen, bevorzugt 6 C-Atomen, der mit den folgenden Gruppen substituiert sein kann: Hydroxy-, Amino-, Alkoholat-, Cyanid-, Thiocyanid-, Halogen-, Sulfonsäure-, Sulfonsäureester-, Thiol-, Benzoesäure-, Benzoesäureester-, Carbonsäure-, Carbonsäureester-, Acrylat-, Metacrylat-, Organosilanrest,p: 0 oder 1, mit der Maßgabe, dass p und n nicht gleichzeitig 0 bedeuten,q: 1 oder 2,w: eine Zahl von 2 bis 8,r: 1,2 oder 3, mit der Maßgabe, dass r + n + m + p = 4,Alkyl: einen einwertigen unverzweigten oder verzweigten gesättigten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, bevorzugt 2 bis 8 Kohlenstoffatomen,Alkenyl : einen einwertigen unverzweigten oder verzweigten ungesättigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen, bevorzugt 2 bis 8 Kohlenstoffatomen. Precipitated silicas according to any of Claims 1 to 8, characterized in that their surfaces have been modified with organosilanes of the formulae I to III: [SiR1n(OR)r(Alk)m(Ar)p]q[B] (I), SiR1n(OR)3-n(Alkyl) (II), or SiR1n(OR)3-n(Alkenyl) (III), where B is -SCN, -SH, -Cl, -NH2, -OC(O)CHCH2, -OC(O)C(CH3)CH2 (if q = 1), or -Sw- (if q = 2), B being chemically bonded to Alk,R and R1 are an aliphatic, olefinic, aromatic, or arylaromatic radical having 2-30 carbon atoms, optionally with substitution by the following groups: the hydroxyl, amino, alcoholate, cyanide, thiocyanide, halo, sulfonic acid, sulfonic ester, thiol, benzoic acid, benzoic ester, carboxylic acid, carboxylic ester, acrylate, methacrylate, or organosilane radical, where the meaning or substitution of R and R1 may be identical or different,n is 0, 1, or 2,Alk is a bivalent unbranched or branched hydrocarbon radical having from 1 to 6 carbon atoms,m is 0 or 1,Ar is an aryl radical having from 6 to 12 carbon atoms, preferably 6 carbon atoms, which may have substitution by the following groups: the hydroxyl, amino, alcoholate, cyanide, thiocyanide, halo, sulfonic acid, sulfonic ester, thiol, benzoic acid, benzoic ester, carboxylic acid, carboxylic ester, acrylate, methacrylate, or organosilane radical,p is 0 or 1, with the proviso that p and n are not simultaneously 0,q is 1 or 2,w is a number from 2 to 8,r is 1, 2, or 3, with the proviso that r + n + m + p = 4,Alkyl is a monovalent unbranched or branched saturated hydrocarbon radical having from 1 to 20 carbon atoms, preferably from 2 to 8 carbon atoms,Alkenyl is a monovalent unbranched or branched unsaturated hydrocarbon radical having from 2 to 20 carbon atoms, preferably from 2 to 8 carbon atoms. Silices précipitées selon l'une quelconque des revendications 1 à 8, caractérisées en ce que leurs surfaces sont modifiées avec des organosilanes de formules I à III : [SiR1n(OR)r(Alk)m(Ar)p]q[B] (I), SiR1n(OR)3-n(Alkyle) (II), ou SiR1n(OR)3-n(Alcényle) (III), dans lesquelles B signifie : -SCN, -SH, -Cl, -NH2, -OC(O)CHCH2,-OC(O)C(CH3)CH2 (lorsque q = 1) ou -Sw- (lorsque q = 2), B étant relié chimiquement à Alk,R et R1 signifient : radical aliphatique, oléfinique, aromatique ou arylaromatique de 2 à 30 atomes C, qui peut éventuellement être substitué avec les groupes suivants : radical hydroxy, amino, alcoolate, cyanure, thiocyanure, halogène, acide sulfonique, ester de l'acide sulfonique, thiol, acide benzoïque, ester de l'acide benzoïque, acide carboxylique, ester de l'acide carboxylique, acrylate, méthacrylate, organosilane, R et R1 pouvant avoir une signification ou une substitution identique ou différente,n signifie : 0, 1 ou 2,Alk signifie : un radical hydrocarboné bivalent ramifié ou non ramifié de 1 à 6 atomes de carbone,m signifie : 0 ou 1,Ar signifie : un radical aryle de 6 à 12 atomes C, de préférence de 6 atomes C, qui peut être substitué avec les groupes suivants : radical hydroxy, amino, alcoolate, cyanure, thiocyanure, halogène, acide sulfonique, ester de l'acide sulfonique, thiol, acide benzoïque, ester de l'acide benzoïque, acide carboxylique, ester de l'acide carboxylique, acrylate, méthacrylate, organosilane,p signifie : 0 ou 1, à condition que p et n ne signifient pas simultanément 0,q signifie : 1 ou 2,w signifie : un nombre de 2 à 8,r signifie : 1, 2 ou 3, à condition que r + n + m + p = 4,Alkyle signifie : un radical hydrocarboné monovalent saturé ramifié ou non ramifié de 1 à 20 atomes de carbone, de préférence de 2 à 8 atomes de carbone,Alcényle signifie : un radical hydrocarboné monovalent insaturé ramifié ou non ramifié de 2 à 20 atomes de carbone, de préférence de 2 à 8 atomes de carbone.
- 16Fällungskieselsäuren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass ihre Oberflächen mit Siliciumorganischen Verbindungen der Zusammensetzung SiR24-nXn (mit n = 1, 2,3, 4), [SiR2xXyO]x (mit 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; 3 ≤ z ≤ 10, mit x + y = 2), [SiR2XXyN]z (mit 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; 3 ≤ z ≤ 10, mit x + y = 2), SiR2nXmOSiR2oXp (mit 0 ≤ n ≤ 3; 0 ≤ m ≤ 3; 0 ≤ o ≤3; 0 ≤ p ≤ 3, mit n + m = 3, o + p = 3), SiR2oXmNSiR2oXp (mit 0 ≤ n ≤ 3; 0 ≤ m ≤ 3; 0 ≤ o ≤3; 0 ≤ p ≤ 3, mit n + m = 3, o + p = 3), und/oder SiR2nXm[SiR2xXyO]zSiR2oXp (mit 0 ≤ n ≤ 3; 0 ≤ m ≤ 3; 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; o ≤ 3; 0 ≤ p ≤ 3; 1 ≤ z ≤ 10000, mit n + m = 3, x + y = 2, o + p = 3) wobei bedeuten R2:substituierte und/oder unsubstituierte Alkyl-und/oder Arylreste mit 1-20 Kohlenstoffatomen und/oder Alkoxy-und/oder Alkenyl-und/oder Alkinyl- -Gruppen und/oder schwefelhaltige GruppenX: Silanol-, Amino-, Thiol-, Halogen-, Alkoxy-, Alkenyl-und/oder Wasserstoff-Rest, modifiziert sind. Precipitated silicas according to any of Claims 1 to 8, characterized in that their surfaces have been modified with organosilicon compounds whose composition is SiR24-nXn (where n = 1, 2, 3, 4), [SiR2xXyO]x (where 0 ≤ x ≤ 2;0 ≤ y ≤ 2;3 ≤ z ≤ 10, where x + y = 2), [SiR2xXyN]z (where 0 ≤ x ≤ 2;0 ≤ y ≤ 2;3 ≤ z ≤ 10, where x + y = 2), SiR2nXmOSiR2oXp (where 0 ≤ n ≤ 3;0 ≤ m ≤ 3;0 ≤ o ≤ 3;0 ≤ p ≤ 3, where n + m = 3, o + p = 3), SiR2oXmNSiR2oXp (where 0 ≤ n ≤ 3;0 ≤ m ≤ 3;0 ≤ o ≤ 3;0 ≤ p ≤ 3, where n + m = 3, o + p = 3), and/or SiR2nXm[SiR2xXyO]zSiR2oXp (where 0 ≤ n ≤ 3;0 ≤ m ≤ 3;0 ≤ x ≤ 2;0 ≤ y ≤ 2;o ≤ 3;0 ≤ p ≤ 3;1 ≤ z ≤ 10 000, where n + m = 3, x + y = 2, o + p = 3) where R2 is alkyl and/or aryl radicals, substituted and/or unsubstituted, having 1-20 carbon atoms, and/or is alkoxy and/or alkenyl and/or alkynyl groups, and/or is sulfur-containing groups,X is a silanol, amino, thiol, halogen, alkoxy, alkenyl and/or hydrogen radical. Silices précipitées selon l'une quelconque des revendications 1 à 8, caractérisées en ce que leurs surfaces sont modifiées avec des composés organiques de silicium de composition SiR24-nXn (avec n = 1, 2, 3, 4), [SiR2xXyO]x (avec 0 ≤ x ≤ 2 ;0 ≤ y ≤ 2 ;3 ≤ z ≤ 10, avec x + y = 2), [SiR2xXyN]z (avec 0 ≤ x ≤ 2 ;0 ≤ y ≤ 2 ;3 ≤ z ≤ 10, avec x + y = 2), SiR2nXmOSiR2oXp (avec 0 ≤ n ≤ 3 ;0 ≤ m ≤ 3 ;0 ≤ o ≤ 3 ;0 ≤ p ≤ 3, avec n + m = 3, o + p = 3), SiR2oXmNSiR2oXp (avec 0 ≤ n ≤ 3 ;0 ≤ m ≤ 3 ;0 ≤ o ≤ 3 ;0 ≤ p ≤ 3, avec n + m = 3, o + p = 3), et/ou SiR2nXm[SiR2xXyO]zSiR2oXp (avec 0 ≤ n ≤ 3 ;0 ≤ m ≤ 3 ;0 ≤ x ≤ 2 ;0 ≤ y ≤ 2 ;o ≤ 3 ;0 ≤ p ≤ 3 ;1 ≤ z ≤ 10 000, avec n + m = 3, x + y = 2 ;o + p = 3), R2 signifiant : radicaux alkyle et/ou aryle substitués et/ou non substitués de 1 à 20 atomes de carbone et/ou groupes alcoxy et/ou alcényle et/ou alcynyle et/ou groupes contenant du soufre,X signifiant : radical silanol, amino, thiol, halogène, alcoxy, alcényle et/ou hydrogène.
- 17Process for preparing the silicas according to Claim 15 or 16, characterized in that the precipitated silicas are modified with organosilanes in mixtures of from 0.5 to 50 parts, based on 100 parts of precipitated silica, in particular from 1 to 15 parts, based on 100 parts of precipitated silica, where the reaction between precipitated silica and organosilane is carried out during the preparation of the mixture (in situ) or externally via spray application and subsequent heat-conditioning of the mixture, via mixing of the organosilane and the silica suspension with subsequent drying and heat-conditioning. Procédé de fabrication des silices selon la revendication 15 ou 16, caractérisé en ce que les silices précipitées sont modifiées avec des organosilanes dans des mélanges de 0,5 à 50 parties, par rapport à 100 parties de silice précipitée, notamment 1 à 15 parties, par rapport à 100 parties de silice précipitée, la réaction entre la silice précipitée et l'organosilane étant réalisée pendant la fabrication du mélange (in situ) ou en dehors par pulvérisation, puis recuit du mélange, par mélange de l'organosilane et de la suspension de silice avec séchage et recuit ultérieurs. Verfahren zur Herstellung der Kieselsäuren gemäß Anspruch 15 oder 16, dadurch gekennzeichnet, dass man die Fällungskieselsäuren mit Organosilanen in Mischungen von 0.5 bis 50 Teilen, bezogen auf 100 Teile Fällungskieselsäure, insbesondere 1 bis 15 Teile, bezogen auf 100 Teile Fällungskieselsäure modifiziert, wobei die Reaktion zwischen Fällungskieselsäure und Organosilan während der Mischungsherstellung (in situ) oder außerhalb durch Aufsprühen und anschließendes Tempern der Mischung, durch Mischen des Organosilans und der Kieselsäuresuspension mit anschließender Trocknung und Temperung durchgeführt wird.
- 18Use of silicas according to any of Claims 1 to 17 in elastomer mixtures, in vulcanizable rubber mixtures, and/or in other vulcanizates, such as pneumatic tires, tire treads, cable sheathing, hoses, drive belts, conveyor belts, V-belts, roller coverings, tires, shoe soles, gaskets, and damping elements. Utilisation de silices selon l'une quelconque des revendications 1 à 17 dans des mélanges d'élastomères, des mélanges de caoutchoucs vulcanisables et/ou d'autres vulcanisats, tels que des pneumatiques, des surfaces de roulement de pneus, des gainages de câbles, des tuyaux, des courroies d'entraînement, des bandes transporteuses, des courroies trapézoïdales, des revêtements de cylindres, des pneus, des semelles de chaussures, des joints et des éléments d'amortissement. Verwendung von Kieselsäuren gemäß einem der Ansprüche 1 bis 17 in Elastomerenmischungen, vulkanisierbaren Kautschukmischungen und/oder sonstigen Vulkanisaten, wie Luftreifen, Reifenlaufflächen, Kabelmänteln, Schläuchen, Treibriemen, Förderbändern, Keilriemen, Walzenbelägen, Reifen, Schuhsohlen, Dichtungen und Dämpfungselementen.
- 19Use of silicas according to any of Claims 1 to 17 in battery separators, as antiblocking agent, as matting agent in inks and paints, as carrier for agricultural products and for feeds, in coatings, in printing inks, in fire-extinguisher powders, in plastics, in the non-impact printing sector, in paper pulp, or in the personal care sector. Utilisation de silices selon l'une quelconque des revendications 1 à 17 dans des plaques d'interconnexion de batteries, en tant qu'agent anti-adhérent, en tant qu'agent matifiant dans les peintures et les laques, en tant que support de produits agraires et de produits alimentaires, dans des revêtements, dans des encres d'impression, dans des poudres d'extinction des incendies, dans des plastiques, dans le domaine de l'impression sans impact, dans les pâtes à papier, dans le domaine de l'hygiène personnelle. Verwendung von Kieselsäuren nach einem der Ansprüche 1 bis 17 in Batterieseparatoren, als Anti-Blocking-Mittel, als Mattierungsmittel in Farben und Lacken, als Träger von Agrarprodukten und Nahrungsmitteln, in Beschichtungen, in Druckfarben, in Feuerlöschpulvern, in Kunststoffen, im Bereich Non impact printing, in Papiermasse, im Bereich Personal care.
- 20Mélanges de caoutchoucs vulcanisables et vulcanisats, qui contiennent la silice précipitée selon la revendication 1 présentant les paramètres physico-chimiques suivants :Surface CTAB100 à 160 m2/g,Surface BET100 à 190 m2/g,Indice DBP180 à 300 g/(100 g),Nombre de Sears V215 à 28 ml/(5 g),Humidité4 à 8 %, en tant que charge. Vulcanizable rubber mixtures and vulcanizates comprising, as filler, the precipitated silica according to Claim 1, with the following physical and chemical parameters: CTAB surface area100-160 m2/gBET surface area100-190 m2/gDBP value180-300 g/(100 g)Sears value V215-28 ml/(5 g)Moisture level4-8%. Vulkanisierbare Kautschukmischungen und Vulkanisate, die die Fällungskieselsäure gemäß Anspruch 1 mit folgenden physikalisch-chemischen Parametern CTAB-Oberfläche100-160 m2/gBET-Oberfläche100-190 m2/gDBP-Zahl180-300 g/(100 g)Searszahl V215-28 ml/(5 g)Feuchte4-8 %. als Füllstoff enthalten.
Independent claims20
176 paragraphs, as filed
The present invention relates to highly disperse precipitated silicas which have an extremely high reinforcement of rubber vulcanizates and advantages in the vulcanization time, a process for their production and their use as a filler for rubber mixtures.
The use of precipitated silica in elastomer compounds such as tire tread compounds has been known for a long time (<patcit id="pcit0001" dnum="EP0501227A"><text>EP 0 501 227</text></patcit>). High demands are placed on the use of silica as a reinforcing filler in rubber mixtures, such as those used in the production of air-filled tires and technical rubber articles. They should be easily and readily incorporable and dispersible in the rubber and, in conjunction with a coupling agent, preferably a bifunctional organosilicon compound, should form a chemical bond with the rubber which leads to the desired high level of reinforcement of the rubber mixture. The reinforcement property can be determined in particular by high static stress values and a low abrasion value. The particle size, surface morphology, surface activity and the binding capacity of the coupling agent are of particular importance for the reinforcing properties of the silica.
It is known that the properties of a silica are largely determined by its manufacturing process. In particular, the conditions of the precipitation are responsible for the properties. The person skilled in the art is familiar with production processes for silicas with the most varied of precipitation conditions. Thus, precipitations at constant pH in the<patcit id="pcit0002" dnum="EP0937755A"><text>EP 0 937 755</text></patcit> described. Silicic acids, which were precipitated with a constant excess of cations, were used in the<patcit id="pcit0003" dnum="DE10124298"><text>DE 101 24 298</text></patcit> disclosed. In the<patcit id="pcit0004" dnum="DE10112441A1"><text>DE 10112 441 A1</text></patcit>, the<patcit id="pcit0005" dnum="EP0754650A"><text>EP 0 754 650</text></patcit>, the<patcit id="pcit0006" dnum="EP0755899A"><text>EP0 755 899</text></patcit> and the<patcit id="pcit0007" dnum="US4001379A"><text>U.S. 4001 379</text></patcit> precipitations at constant alkali number (AZ number) were described.
Silicic acids that have been precipitated at a constant AZ number are used as carrier materials, matting agents for paints, as battery separators, in toothpastes or as flocculation aids. Silicic acids that are suitable for applications in elastomers or rubber mixtures and that have been precipitated at a constant AZ number are not yet known.
As a rule, silicas for rubber applications are produced by a process in which the precipitation takes place at temperatures between 60 and 95 °C and a pH between 7 and 10, see e.g. B.<patcit id="pcit0008" dnum="EP0901986A1"><text>EP 0 901 986 A1</text></patcit>.
The aim of the present invention is to provide new, easily dispersible precipitated silicas which can be incorporated into elastomer mixtures and improve their properties.
Surprisingly, it has now been shown that new silicas can be obtained by precipitation at a constant AZ number, which can be incorporated particularly well into elastomer mixtures and improve their properties.
The subject of the present invention are therefore easily dispersible precipitated silicas characterized by:<tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="130mm" /><tbody><row><entry>CTAB surface</entry><entry>100 - 160 m<sup>2</sup>/g with preferred ranges of 100 - 150 m<sup>2</sup>/g, 100-135 m<sup>2</sup>/g and 100-120 m<sup>2</sup>/G,</entry></row><row><entry>BET surface</entry><entry>100 -190m<sup>2</sup>/g with the preferred range of 100 -170 m<sup>2</sup>/g, 100-160 m<sup>2</sup>/g, 100-140m<sup>2</sup>/g and 110-135 m<sup>2</sup>/G,</entry></row><row><entry>DBP number</entry><entry>180 - 300 g/(100 g), preferred range 200 - 280 g/(100 g),</entry></row><row><entry>Sears number V<sub>2</sub></entry><entry>15 - 28 ml/(5 g) with the preferred range of 20 - 28 ml/(5 g), 22 - 28 ml/(5 g) and especially 25 - 28 ml/(5 g),</entry></row><row><entry>humidity</entry><entry>4-8%.</entry></row></tbody></tgroup></table></tables>
Furthermore, the precipitated silicas according to the invention can preferably have one or more of the following physicochemical parameters:<tables id="tabl0002" num="0002"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="44mm" /><colspec colnum="2" colname="col2" colwidth="122mm" /><tbody><row><entry>Ratio Sears number V<sub>2</sub> to BET surface</entry><entry>0.140 - 0.280ml/(5m<sup>2</sup>), with the preferred ranges 0.150 - 0.280 ml/(5 m<sup>2</sup>), 0.170 - 0.280 mol/(5 m<sup>2</sup>), 0.180 - 0.280ml/(5m<sup>2</sup>) and particularly preferably 0.190 - 0.280 ml/(5 m<sup>2</sup>) and 0.190 - 0.250 ml/(5 m<sup>2</sup>),</entry></row><row><entry>Ratio BET to CTAB</entry><entry>0.9 -1.2, preferably 1 - 1.15,</entry></row><row><entry>primary particle diameter</entry><entry>10 - 80nm.</entry></row></tbody></tgroup></table></tables>
The primary particle diameter can e.g. B. be determined by means of the image evaluation of transmission electron spectroscopy (TEM) (<nplcit id="ncit0001" npl-type="b"><text>R H. Lange, J. Bloedorn: "The electron microscope, TEM + SEM" Thieme Verlag, Stuttgart, New York (1981</text></nplcit>)).
In a first preferred embodiment, the precipitated silicas according to the invention have a DBP number of 200-250 g/(100 g) and in a second preferred embodiment a DBP number of 250-280 g/(100 g).
In addition to a high absolute number of silanol groups (Sears number V<sub>2</sub>), a greatly increased ratio of the Sears number V compared to prior art precipitated silicas<sub>2</sub> to the BET surface. i.e. the precipitated silicas according to the invention have a very high number of silanol groups, in particular in relation to the total surface area.
In addition to the increased number of silanol groups, the precipitated silicas according to the invention are distinguished by low microporosity, ie a very low BET to CTAB ratio.
The combination of the mentioned features, in particular the high Sears number V<sub>2</sub>/ BET ratio mean that the precipitated silicas according to the invention are outstandingly suitable as reinforcing fillers for elastomers. The precipitated silicas according to the invention are notable for increased rubber activity, exhibit very good dispersion behavior and a shorter vulcanization time.
Another object of the present invention is a method according to claims 9 to 14
The template can be about 20, 30, 40, 50, 60, 70, 80 or 90% of the final volume of the precipitation. The basic compounds provided are selected in particular from the group of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal silicates. Water glass and/or caustic soda are preferably used.
The constant alkali number in the initial charge and during step b) is in the range from 7 to 30, preferably from 10 to 30, particularly preferably from 15 to 25, and the AZ number is very particularly preferably at a value between 18 and 22 held.
Optionally, the dosing can be interrupted during step b), in which case the steps<ul id="ul0001" list-style="none" compact="compact"><li>b ') stopping the addition for 30 to 90 minutes while maintaining the temperature and</li><li>b") then simultaneously metering in water glass and an acidifier at the same temperature for 10 to 120, preferably 10 to 60 minutes in such a way that the AZ number remains constant during the precipitation,</li></ul>to be executed.
Furthermore, an additional addition of organic or inorganic salts can optionally take place during steps a) and/or b) and/or b') and/or b"). This can be in solution or as a solid, in each case continuously over the addition time of the water glass and the acidulant or as a batch addition It is also possible to dissolve the salts in one or both components and then add them at the same time.
Alkali metal or alkaline earth metal salts are preferably used as inorganic salts. In particular, all combinations of the following ions can be used: Li<sup>+</sup>, N / A<sup>+</sup>, K<sup>+</sup>, Rb<sup>+</sup>, be<sup>2+</sup>, mg<sup>2+</sup>, approx<sup>2+</sup> sir<sup>2+</sup>, ba<sup>2+</sup>, H<sup>+</sup>, F<sup>-</sup>, cl<sup>-</sup>, brother<sup>-</sup>, I<sup>-</sup>, SO<sub>3</sub><sup>2-</sup>, SO<sub>4</sub><sup>2-</sup>, HSO<sub>4</sub><sup>-</sup> , PO<sub>3</sub><sup>3-</sup>, PO<sub>4</sub><sup>3-</sup>, NO<sub>3</sub><sup>-</sup>, NO<sub>2</sub><sup>-</sup>, CO<sub>3</sub><sup>2-</sup>, HCO<sub>3</sub><sup>-</sup>, OH<sup>-</sup>, TiO<sub>3</sub><sup>2-</sup>, ZrO<sub>3</sub><sup>2-</sup>, ZrO<sub>4</sub><sup>4-</sup>, AlO<sub>2</sub><sup>-</sup>, Al<sub>2</sub>O<sub>4</sub><sup>2-</sup>, BO<sub>4</sub><sup>3-</sup>.
The salts of formic, acetic and propionic acid are suitable as organic salts. The alkali metal or alkaline earth metal ions mentioned may be mentioned as the cation. The concentration of these salts in the addition solution can be 0.01 to 5 mol/l. The preferred inorganic salt is Na<sub>2</sub>SO<sub>4</sub> used.
In addition to water glass (sodium silicate solution), other silicates such as potassium or calcium silicate can also be used. In addition to sulfuric acid, other acidifying agents such as HCl, HNO<sub>3</sub>, H<sub>3</sub>PO<sub>4</sub> or CO<sub>2</sub> be used.
In step d), the precipitated silica is first filtered and then washed with water and dried. The silica is washed until the sodium sulfate content is <4% by weight. The sodium sulfate content can be measured by methods known to those skilled in the art, such as e.g. B. in the<patcit id="pcit0009" dnum="EP0754650A1"><text>EP 0 754 650 A1</text></patcit> described, take place.
The person skilled in the art is familiar with the filtration and long- or short-term drying of the silicas according to the invention and can, for. B. can be read in the documents mentioned above.
The silica according to the precipitation is preferably dried in a stream dryer, spray dryer, layer dryer, belt dryer, rotary tube dryer, flash dryer, spin-flash dryer or nozzle tower. These drying variants include operation with an atomizer, a single or two-component nozzle or an integrated fluidized bed. After drying, grinding and/or granulation can optionally be carried out using a roller compactor. After the drying step or the grinding or the granulation, the precipitated silica according to the invention preferably has a particle shape with an average diameter of more than 15 μm, in particular more than 80 μm, particularly preferably more than 200 μm (determined according to ISO 2591-1, December 1988). The precipitated silicas according to the invention are particularly preferably in the form of a powder with a mean diameter of more than 15 μm or in the form of essentially round particles with a mean diameter of more than 80 μm (micro beads) or in the form of granules with a mean diameter of ≧1 mm.
A further object of the present invention is the use of the precipitated silica according to the invention for the production of elastomer mixtures, vulcanizable rubber mixtures and/or other vulcanizates.
Another subject of the invention are elastomer mixtures, vulcanizable rubber mixtures and / or other vulcanizate containing the silica according to the invention, such as molded articles such as pneumatic tires, tire treads, cable jackets, hoses, drive belts, conveyor belts, roller coverings, tires, shoe soles, sealing rings and damping elements.
Furthermore, the silicas according to the invention can be used in all areas of application in which silicas are usually used, such as. B. in battery separators, as an anti-blocking agent, as a matting agent in paints and varnishes, as a carrier of agricultural products and foodstuffs, in coatings, in printing inks, in fire extinguishing powders, in plastics, in non-impact printing, in paper pulp, in the personnel sector care and special applications.
When used in the field of non-impact printing, e.g. B. in the inkjet process, the use of silicas according to the invention in<ul id="ul0002" list-style="dash" compact="compact"><li>printing inks to thicken or to prevent spattering and offsetting,</li><li>Paper as a filler, coating pigment, blueprint paper, thermal paper, thermal sublimation to prevent printing inks from bleeding through, improving the basic image calmness and contrast, improving dot sharpness and color brilliance.</li></ul>
When used in the field of personal care, the use of the silicas according to the invention as a filler or thickener, e.g. B. to understand in the field of pharmacy or personal care.
The silica according to the invention can optionally be modified with silanes or organosilanes of the formulas I to III [SiR<sup>1</sup><sub>n</sub>(OR)<sub>right</sub>(Alcohol)<sub>m</sub>(Are)<sub>p</sub>]<sub>q</sub>[B] (I), SiR<sup>1</sup><sub>n</sub>(OR)<sub>3-n</sub>(alkyl) (II), or SiR<sup>1</sup><sub>n</sub>(OR)<sub>3-n</sub>(alkenyl) (III), in which mean<dl id="dl0001"><dt>B:</dt><dd>-SCN, -SH, -Cl, -NH<sub>2</sub>, -OC(O)CHCH<sub>2</sub>, -OC(O)C(CH<sub>3</sub>)CH<sub>2</sub> (when q = 1) or -S<sub>w</sub>- (when q = 2), where B is chemically bonded to Alk,</dd><dt>R and R<sup>1</sup>:</dt><dd>Aliphatic, olefinic, aromatic or arylaromatic radical with 2 - 30 carbon atoms, which can optionally be substituted with the following groups: hydroxy, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol, benzoic acid, benzoic acid ester, carboxylic acid, carboxylic acid ester, acrylate, methacrylate, organosilane radical, where R and R<sup>1</sup> may have the same or different meaning or substitution.</dd><dt>n:</dt><dd>0, 1 or 2,</dd><dt>Alcohol:</dt><dd>a divalent unbranched or branched hydrocarbon radical having 1 to 6 carbon atoms,</dd><dt>m:</dt><dd>0 or 1,</dd><dt>Are:</dt><dd>an aryl radical having 6 to 12 carbon atoms, preferably 6 carbon atoms, which can be substituted by the following groups: hydroxy, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol -, benzoic acid, benzoic acid ester, carboxylic acid, carboxylic acid ester, organosilane radical.</dd><dt>p:</dt><dd>0 or 1, with the proviso that p and n do not mean 0 at the same time,</dd><dt>q:</dt><dd>1 or 2,</dd><dt>w:</dt><dd>a number from 2 to 8,</dd><dt>r:</dt><dd>1, 2 or 3, with the proviso that r + n + m + p = 4,</dd><dt>alkyl:</dt><dd>a monovalent unbranched or branched saturated hydrocarbon radical having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms,</dd><dt>alkenyl:</dt><dd>a monovalent unbranched or branched unsaturated hydrocarbon radical having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.</dd></dl>
The silica according to the invention can also contain organosilicon compounds of the composition SiR<sup>2</sup><sub>4-n</sub>X<sub>n</sub> (with n = 1, 2, 3, 4), [SiR<sup>2</sup><sub>x</sub>X<sub>y</sub>O]<sub>e.g</sub> (with 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; 3 ≤ z ≤ 10, with x + y = 2), [SiR<sup>2</sup><sub>x</sub>X<sub>y</sub>N]<sub>e.g</sub> (with 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; 3 ≤ z ≤ 10, with x + y = 2), SiR<sup>2</sup><sub>n</sub>X<sub>m</sub>OSiR<sup>2</sup><sub>O</sub>X<sub>p</sub>(with 0≤ n ≤3; 0≤ m ≤ 3; 0≤ o ≤ 3; 0≤ p ≤ 3, with n+m=3, o+p=3), SiR<sup>2</sup><sub>n</sub>X<sub>m</sub>NSiR<sup>2</sup><sub>O</sub>X<sub>p</sub>(with 0≤n≤3; 0≤m≤3; 0≤o≤3; 0≤p≤3, with n+m=3, o+p=3), SiR<sup>2</sup><sub>n</sub>X<sub>m</sub>[SiR<sup>2</sup><sub>x</sub>X<sub>y</sub>O]<sub>e.g</sub>SiR<sup>2</sup><sub>O</sub>X<sub>p</sub> (with 0 ≤ n ≤ 3; 0 ≤ m ≤3; 0 ≤ x ≤ 2; 0 ≤ y ≤ 2; 0 ≤ 0 ≤ 3; 0 ≤ p ≤ 3; 1 ≤ z ≤ 10000, with n + m = 3 , x + y = 2, o + p = 3). These compounds can be linear, cyclic, and branched silane, silazane, and siloxane compounds. At R<sup>2</sup> can be substituted and/or unsubstituted alkyl and/or aryl radicals with 1-20 carbon atoms, which can be substituted with functional groups such as the hydroxy group, the amino group, polyethers such as ethylene oxide and/or propylene oxide and halide groups such as fluoride. R<sup>2</sup> may also contain groups such as alkoxy, alkenyl, alkynyl and aryl groups and groups containing sulfur. X can be reactive groups such as silanol, amino, thiol, halogen, alkoxy, alkenyl and a hydrogen radical.
Linear polysiloxanes of the composition SiR are preferred<sup>2</sup><sub>n</sub>X<sub>m</sub>[SiR<sup>2</sup><sub>x</sub>X<sub>y</sub>O]<sub>e.g</sub>SiR<sup>2</sup><sub>O</sub>X<sub>p</sub> (with 0≤n≤3; 0≤m≤3; 0≤x≤2; 0≤y≤2; 0≤o≤3;0≤p≤3;1≤z≤10000, with n+m=3 ; x + y = 2; o + p = 3) where R<sup>2</sup> is preferably represented by methyl.
Polysiloxanes of the composition SiR are particularly preferred<sup>2</sup><sub>n</sub>X<sub>m</sub>[SiR<sup>2</sup>xX<sub>y</sub>O]<sub>e.g</sub>SiR<sup>2</sup><sub>O</sub>X<sub>p</sub> (with 0≤n≤3; 0≤m≤1; 0≤x≤2;0≤y≤2; 0≤o≤3;0≤p≤1; 1≤z≤1000, with n+m=3 , x + y = 2, o + p = 3) where R<sup>2</sup> is preferably represented by methyl.
The optionally granulated, ungranulated, ground and/or unground precipitated silica can be modified with one or more of the organosilanes mentioned in mixtures of 0.5 to 50 parts, based on 100 parts of precipitated silica, in particular 1 to 15 parts, based on 100 parts of precipitated silica, wherein the reaction between precipitated silica and organosilane during the preparation of the mixture (in situ) or outside by spraying and subsequent tempering of the mixture, by mixing the organosilane and the silica suspension with subsequent drying and tempering (for example according to<patcit id="pcit0010" dnum="DE3437473"><text>UK 3437473</text></patcit> and<patcit id="pcit0011" dnum="DE19609619"><text>EN19609619</text></patcit>) or according to the method described in<patcit id="pcit0012" dnum="DE19609619"><text>EN19609619</text></patcit> or<patcit id="pcit0013" dnum="DE4004781C"><text>DE-PS 4004781</text></patcit> can be carried out.
In principle, all bifunctional silanes are suitable as organosilicon compounds, which on the one hand can bring about a coupling to the filler containing silanol groups and on the other hand a coupling to the polymer. Customary amounts of the organosilicon compounds used are 1 to 10% by weight, based on the total amount of precipitated silica.
Examples of these organosilicon compounds are: bis(3-triethoxysilylpropyl)tetrasulfane, bis(3-triethoxysilylpropyl)disulfane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane. Other organosilicon compounds are in<patcit id="pcit0014" dnum="WO9909036A"><text>WO 99/09036</text></patcit>, <patcit id="pcit0015" dnum="EP1108231A"><text>EP 1108231</text></patcit>, <patcit id="pcit0016" dnum="DE10137809"><text>UK 10137809</text></patcit>, <patcit id="pcit0017" dnum="DE10163945"><text>UK 10163945</text></patcit>, <patcit id="pcit0018" dnum="DE10223658"><text>UK 10223658</text></patcit> described.
In a preferred embodiment of the invention, bis(triethoxysilylpropyl)tetrasulfane can be used as the silane.
The silica according to the invention can be mixed into elastomer mixtures, tires or vulcanizable rubber mixtures as a reinforcing filler in amounts of 5 to 200 parts, based on 100 parts of rubber, as a powder, spherical product or granules both with and without silane modification.
Rubber and elastomer mixtures are to be regarded as equivalent for the purposes of the present invention.
The silanol groups on the silicic acid surface act as possible chemical reaction partners with a coupling agent in caoutchouc or rubber mixtures. This is, for example, a bifunctional silane such as bis(3-triethoxysilylpropyl)tetrasulfane, which enables the silicic acid to bond to the rubber matrix. With the highest possible number of silanol groups, there is a high probability of coupling between the silica and the coupling agent and thus a high probability of the silica binding to the rubber matrix, which ultimately leads to a higher reinforcement potential. The Sears number V<sub>2</sub> is a measure for describing the number of silanol groups in the silica, while the BET surface area of a silica describes its specific surface area, which has a major influence on the processing behavior and other technical rubber properties of a compound.
However, stating the absolute number of silanol groups alone is not sufficient to adequately characterize a precipitated silica, since precipitated silicas with a high surface area generally have a higher absolute number of silanol groups than precipitated silicas with a low surface area. The quotient of the Sears number V is therefore important<sub>2</sub>/BET. In this way, the amplification potential generated by the silanol groups per specific surface unit introduced can be represented.
In addition to mixtures which contain exclusively the silicas according to the invention, with and without the organosilanes mentioned, as fillers, the elastomer or rubber mixtures can also be filled with one or more more or less reinforcing fillers.
The following materials can be used as additional fillers:<ul id="ul0003" list-style="dash" compact="compact"><li>Carbon blacks: The carbon blacks to be used here are produced by the lamp black, furnace or gas black process and have BET surface areas of 20 to 200 m<sup>2</sup>/g, such as B. SAF, ISAF, HSAF, HAF, FEF or GPF carbon blacks. If appropriate, the carbon blacks can also contain heteroatoms such as, for example, silicon.</li><li>highly dispersed pyrogenic. Silicic acids, produced for example by flame hydrolysis of silicon halides. If appropriate, the silicic acids can also be present as mixed oxides with other metal oxides, such as Al, Mg,</li></ul>
Ca, Ba, Zn and titanium oxides are present.<ul id="ul0004" list-style="dash" compact="compact"><li>other commercial silicas</li><li>Synthetic silicates such as aluminum silicate, alkaline earth silicates such as magnesium silicate or calcium silicate, with BET surface areas of 20 to 400 m<sup>2</sup>/ g and primary particle diameters from 10 to 400 nm</li><li>Synthetic or natural aluminum oxides and hydroxides</li><li>Natural silicates such as kaolin other naturally occurring silicon dioxide compounds</li><li>Glass fiber and glass fiber products (mats, strands) or glass microspheres</li><li>Starch and modified types of starch</li><li>Natural fillers, such as clays and silica chalk</li></ul>
Here too, as with the dosage of the organosilanes, the blending ratio depends on the properties to be achieved in the finished rubber compound. A ratio of 5-95% between the silicas according to the invention and the other fillers mentioned above (also as a mixture) is conceivable and is also realized within this framework
In a particularly preferred embodiment, 10 to 150 parts by weight of silica, consisting entirely or partially of the silica according to the invention, optionally together with 0 to 100 parts by weight of carbon black, and 1 to 10 parts by weight of an organosilicon compound, each based on 100 parts by weight of rubber, are used to produce the mixtures.
In addition to the silicas according to the invention, the organosilanes and other fillers, the elastomers form another important component of the rubber mixture. Mention should be made here of elastomers, natural and synthetic, oil-extended or not, as a single polymer or blended with other rubbers, such as natural rubbers, polybutadiene (BR), polyisoprene (IR), styrene/butadiene copolymers with styrene contents of 1 to 60, preferably 2 to 50% by weight (SBR), in particular produced by means of the solution polymerization process, butyl rubbers, isobutylene/isoprene copolymers (IIR), Butadiene/acrylonitrile copolymers with acrylonitrile contents of 5 to 60, preferably 10 to 50% by weight (NBR), partially or fully hydrogenated NBR rubber (HNBR), ethylene/propylene/diene copolymers (EPDM), and mixtures of these rubbers .
The following additional rubbers are also suitable for rubber mixtures with the rubbers mentioned: carboxyl rubbers, epoxy rubbers, transpolypentenamer, halogenated butyl rubbers, rubbers made from 2-chlorobutadiene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, optionally also chemical derivatives of natural rubber and modified natural rubbers.
Preferred synthetic rubbers are described, for example, by W. Hofmann, "Rubber Technology", Genter Verlag, Stuttgart 1980.
Anionically polymerized L-SBR rubbers (solution SBR) with a glass transition temperature above −50° C. and mixtures thereof with diene rubbers are of particular interest for the production of the tires according to the invention.
The silicas according to the invention, with or without silane, can be used in all rubber applications, such as molded bodies, tires, tire treads, conveyor belts, conveyor belts, seals, drive belts, hoses, shoe soles, cable sheaths, roller coverings, damping elements, etc.
This silica is incorporated and the mixtures containing this silica are prepared in the manner customary in the rubber industry in an internal mixer or roll mill, preferably at 80-200.degree. The silicic acids can be administered or used in the form of a powder, a spherical product or granules. Here, too, the silicas according to the invention do not differ from the known light-colored fillers.
The rubber vulcanizates according to the invention can contain other rubber auxiliaries in the usual dosages, such as reaction accelerators, aging inhibitors, heat stabilizers, light stabilizers, ozone protection agents, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators such as triethanolamine , polyethylene glycol, hexanetriol. These compounds are well known in the rubber industry.
The rubber auxiliaries can be used in known amounts, which depend, inter alia, on the intended use. Typical amounts are, for example, amounts from 0.1 to 50% by weight, based on the rubber used. Sulfur or sulphur-donating substances can be used as crosslinking agents. The rubber mixtures according to the invention can also contain vulcanization accelerators. Examples of suitable main accelerators are mercaptobenzothiazoles, sulfenamides, thiurams, dithiocarbamates in amounts of 0.5 to 3% by weight. Examples of co-accelerators are guanidienes, thioureas and thiocarbonates in amounts of 0.5 to 5% by weight. Sulfur can usually be used in amounts of 0.1 to 10% by weight, preferably 1 to 3% by weight, based on the rubber used.
The silicas according to the invention can be used in rubbers which can be crosslinked with accelerators and/or sulfur, but also peroxide.
The rubber mixtures according to the invention can be vulcanized at temperatures of 100 to 200° C., preferably 130 to 180° C., optionally under a pressure of 10 to 200 bar. The blending of the rubbers with the filler, any rubber auxiliaries and the organosilicon compound can be carried out in known mixing units, such as rollers, internal mixers and mixing extruders.
The rubber mixtures according to the invention are suitable for the production of moldings, for example for the production of pneumatic tires, tire treads for summer, winter and all-season tires, car tires, tires for commercial vehicles, motorcycle tires, tire sub-components, cable sheaths, hoses, drive belts, conveyor belts, roller coverings, shoe soles, sealing rings and cushioning elements.
The silicas according to the invention have the advantage that they give the rubber vulcanizates greater reinforcement and thus improved abrasion resistance due to the higher rubber activity compared to an identical rubber mixture containing previously known silicas. In addition, they show very good dispersions and also advantages in the vulcanization time.
The rubber mixtures according to the invention are particularly suitable for the production of car tire treads with low rolling resistance or good suitability for winter use. Furthermore, the silicas according to the invention, without the addition of organosilicon compounds, in a blend with a typical tread carbon black are also suitable for improving the cut & chip behavior of construction, agricultural machinery and pit tires (for definition and further explanations see "New insights into the tear mechanism" and References herein presented at Tire Tech 2003 in Hamburg by Dr. W. Niedermeier).
The reaction conditions and the physical/chemical data of the precipitated silicas according to the invention are determined using the following methods:
<u>Determination of the moisture content of silica</u>
According to this method, based on ISO 787-2, the volatile fractions (hereinafter referred to as moisture for the sake of simplicity) of silica are determined after drying at 105° C. for 2 hours. This drying loss generally consists predominantly of water moisture.
execution
10 g of the powdered, spherical or granular silica are weighed out to an accuracy of 0.1 mg (initial weight E) into a dry weighing glass with a ground-glass lid (diameter 8 cm, height 3 cm). With the lid open, the sample is dried in a drying cabinet at 105 ± 2 °C for 2 h. The weighing glass is then closed and cooled to room temperature in a desiccator cabinet using silica gel as a desiccant. The weight A is determined gravimetrically.
The moisture content is determined in % according to ((E in g - A in g) * 100%) / (E in g).
<u>Determination of the modified Sears number of silicas</u>
The modified Sears number (hereinafter Sears number V<sub>2</sub> called) as a measure of the number of free hydroxy groups.
The method of determination is based on the following chemical reactions, with "Si"-OH symbolizing a silanol group of silica: "Si"-OH + NaCl → "Si"-ONa + HCl HCl + KOH → KCl + H<sub>2</sub>O.
execution
10.00 g of a powdered, spherical or granular silica with a moisture content of 5±1% are comminuted for 60 seconds using an IKA universal mill M 20 (550 W; 20,000 rpm). If necessary, the moisture content of the starting substance must be adjusted by drying at 105 °C in a drying cabinet or evenly moistening, and the comminution repeated. 2.50 g of the silica treated in this way are weighed into a 250 ml titration vessel at room temperature and treated with 60.0 ml of methanol p. A shifted. After the sample has been completely wetted, 40.0 ml of deionized water are added and dispersion is carried out using an Ultra Turrax T 25 stirrer (KV-18G stirrer shaft, 18 mm diameter) for 30 seconds at a speed of 18,000 rpm. The sample particles adhering to the edge of the vessel and the stirrer are rinsed into the suspension with 100 ml of deionized water and heated to 25° C. in a thermostated water bath.
The pH meter (Knick, type: 766 pH meter Calimatic with temperature sensor) and the pH electrode (combination electrode from Schott, type N7680) are calibrated at room temperature using buffer solutions (pH 7.00 and 9.00). The initial pH value of the suspension is first measured at 25 °C with the pH meter, then depending on the result, the pH value is adjusted with potassium hydroxide solution (0.1 mol/l) or hydrochloric acid solution (0.1 mol/l). 6.00 set. The consumption of KOH and HCl solution in ml up to pH 6.00 corresponds to V<sub>1</sub>'.
Then 20.0 ml of sodium chloride solution (250.00 g NaCl pa made up to 11 with deionized water) are metered in. The titration is then continued with 0.1 mol/l KOH up to a pH value of 9.00. The consumption of KOH solution in ml up to pH 9.00 corresponds to V<sub>2</sub>'.
Then the volumes V<sub>1</sub>', or v<sub>2</sub>' first normalized to the theoretical weight of 1 g and expanded by 5, from which V<sub>1</sub> and the Sears number V<sub>2</sub> in units of ml/(5 g).
<u>Determination of the BET surface area</u>
The specific nitrogen surface area (referred to below as the BET surface area) of the pulverulent, spherical or granular silica is determined in accordance with ISO 5794-1/Annex D using an AREA meter (Ströhlein, JUWE).
<u>Determination of the CTAB surface area</u>
The method is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the "outer" surface of the silica, which is also referred to as the "rubber-effective surface", based on ASTM 3765 or NFT 45-007 (Chapter 5.12.1.3). CTAB is adsorbed in aqueous solution with stirring and ultrasonic treatment. Excess, non-adsorbed CTAB is determined by back-titration with NDSS (dioctyl sodium sulfosuccinate solution, "Aerosol OT" solution) using a titroprocessor, the end point being given by the maximum turbidity of the solution and being determined using a phototrode. The temperature during all performed operations is 23-25 °C to prevent CTAB from crystallizing out. The back titration is based on the following reaction equation: (C<sub>20</sub>H<sub>37</sub>O<sub>4</sub>)SO<sub>3</sub>Na + BrN(CH<sub>3</sub>)<sub>3</sub>(C<sub>16</sub>H<sub>33</sub>) → (C<sub>20</sub>H<sub>37</sub>O<sub>4</sub>)SO<sub>3</sub>N(CH<sub>3</sub>)<sub>3</sub>(C<sub>16</sub>H<sub>33</sub>) + NaBr NDSS CTAB
Devices
<ul id="ul0005" list-style="none" compact="compact"><li>Titroprocessor METTLER Toledo type DL 55 and titroprocessor METTLER Toledo type DL 70, each equipped with: pH electrode, make Mettler, type DG 111 and phototrode, make Mettler, type DP 550</li><li>100 ml titration beaker made of polypropylene</li><li>Titration glass vessel, 150 ml with lid</li><li>Pressure filtration device, 100 ml capacity</li><li>Membrane filter made of cellulose nitrate, pore size 0.1 µm, 47 mm Ø, e.g. B. Whatman (Order No. 7181-004)</li></ul>
reagents
The solutions of CTAB (0.015 mol/l in deionized water) and NDSS (0.00423 mol/l in deionized water) are obtained ready for use (Kraft, Duisburg: order no. 6056.4700 CTAB solution 0.015 mol/l; order no 6057.4700 NDSS solution 0.00423 mol/l) stored at 25 °C and used within one month.
execution
blind titration
The consumption of NDSS solution for the titration of 5 ml CTAB solution must be checked once a day before each series of measurements. For this purpose, the phototrode is set to 1000 ± 20 mV (corresponding to a transparency of 100%) before the start of the titration.
Exactly 5.00 ml of CTAB solution are pipetted into a titration beaker and 50.0 ml of deionized water are added. With stirring, the titration with NDSS solution is carried out according to the measuring method familiar to the person skilled in the art with the Titroprocessor DL 55 up to the maximum turbidity of the solution. One determines the consumption V<sub>1</sub> of NDSS solution in ml. Each titration must be carried out as a triple determination.
adsorption
10.0 g of the powdery, spherical or granulated silica with a moisture content of 5 ± 2% (if necessary, the moisture content is adjusted by drying at 105 °C in a drying cabinet or evenly moistening) are ground with a mill (Krups, model KM 75, article no . 2030-70) crushed for 30 seconds. Exactly 500.0 mg of the comminuted sample is transferred to a 150 ml titration vessel with magnetic stirring rods and exactly 100.0 ml CTAB solution is added. The titration vessel is closed with a lid and stirred with a magnetic stirrer for 15 minutes. Hydrophobic silicas are stirred with an Ultra Turrax T 25 stirrer (KV-18G stirrer shaft, 18 mm diameter) at 18,000 rpm for a maximum of 1 minute until wetting is complete. The titration vessel is screwed to the Titroprocessor DL 70 and the pH of the suspension is adjusted to a value of 9 ± 0.05 with KOH (0.1 mol/l). The suspension in the titration vessel is sonicated for 4 minutes in an ultrasonic bath (Bandelin, Sonorex RK 106 S, 35 kHz) at 25.degree. This is followed by immediate pressure filtration through a membrane filter at a nitrogen pressure of 1.2 bar. The forerun of 5 ml is discarded.
titration
5.00 ml of the remaining filtrate are pipetted into a 100 ml titration beaker and made up to 50.00 ml with deionized water. The titration beaker is screwed onto the Titroprocessor DL 55 and the titration with NDSS solution is carried out while stirring until maximum turbidity is reached. One determines the consumption V<sub>II</sub> of NDSS solution in ml. Each turbidity must be carried out as a triple determination.
calculation
With the help of the measured values<ul id="ul0006" list-style="none" compact="compact"><li>V<sub>I</sub> = Consumption of NDSS solution in ml in the titration of the blank</li><li>V<sub>II</sub> = consumption of NDSS solution in ml when using the filtrate</li></ul>surrendered:<maths id="math0001" num=""><math display="block"><msub><mi mathvariant="normal">V</mi><mi mathvariant="normal">I</mi></msub><mo>/</mo><msub><mi mathvariant="normal">V</mi><mi>II</mi></msub><mo>=</mo><mi>amount of substance</mi><mspace width="1ex" /><mi>CTAB</mi><mspace width="1ex" /><mi>the</mi><mspace width="1ex" /><mi>blank test</mi><mo>/</mo><mi>still</mi><mspace width="1ex" /><mi>existing</mi><mspace width="1ex" /><mi>amount of substance</mi><mspace width="1ex" /><mi>CTAB</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi>the</mi><mspace width="1ex" /><mi>filtrate sample</mi><mi mathvariant="normal">.</mi></math><img file="EP1585704B2_D0001.tif" /></maths>
From this follows for the amount of substance N adsorbed on CTAB in g:<maths id="math0002" num=""><math display="block"><mi mathvariant="normal">N</mi><mo>=</mo><mfenced separators=""><mfenced separators=""><msub><mi mathvariant="normal">V</mi><mi mathvariant="normal">l</mi></msub><mo>−</mo><msub><mi mathvariant="normal">V</mi><mi mathvariant="normal">n</mi></msub></mfenced><mo>*</mo><mn>5.5</mn><mi mathvariant="normal">G</mi><mo>*</mo><mn>5</mn><mi>ml</mi></mfenced><mo>/</mo><mfenced separators=""><msub><mi mathvariant="normal">V</mi><mi mathvariant="normal">l</mi></msub><mo>*</mo><mn>100</mn><mi>ml</mi></mfenced><mo>.</mo></math><img file="EP1585704B2_D0002.tif" /></maths>
Since only 5 ml of 100 ml filtrate was titrated, 0.5 g silica of a defined moisture content was used and the space requirement of 1 g CTAB 578435 * 10<sup>-3</sup> m<sup>2</sup> is, it follows: CTAB surface area (not water corrected) in m<sup>2</sup>/g = (N * 20 * 578,435 m<sup>2</sup>/g) / (0.5 g) and CTAB surface area (not water corrected) in m<sup>2</sup>/g = ((v<sub>I</sub> - V<sub>II</sub>) * 636.2785 m<sup>2</sup>/g) / v<sub>I</sub>.
The CTAB surface area is referenced to the anhydrous silica, so the following correction is made.<maths id="math0003" num=""><math display="block"><mtable columnalign="left"><mtr><mtd><mi>CTAB</mi><mo>−</mo><mi>surface</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><msup><mi mathvariant="normal">m</mi><mn>2</mn></msup><mi>/G</mi><mo>=</mo><mfenced separators=""><mi>CTAB</mi><mo>−</mo><mi>surface</mi><mspace width="1ex" /><mfenced separators=""><mi>not</mi><mspace width="1ex" /><mi>water corrected</mi></mfenced><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><msup><mi mathvariant="normal">m</mi><mn>2</mn></msup><mo>/</mo><mi mathvariant="normal">G</mi><mo>*</mo><mn>100</mn><mi>%</mi></mfenced><mo>/</mo></mtd></mtr><mtr><mtd><mfenced separators=""><mn>100</mn><mi>%</mi><mo>−</mo><mi>humidity</mi><mspace width="1ex" /><mi>in</mi><mi>%</mi></mfenced></mtd></mtr></mtable></math><img file="EP1585704B2_D0003.tif" /></maths>
<u>Determination of DBP uptake</u>
The DBP uptake (DBP number), which is a measure of the absorbency of the precipitated silica, is determined as follows based on the DIN 53601 standard:
execution
12.50 g powdered or spherical silica with 0 - 10% moisture content (if necessary, the moisture content is adjusted by drying at 105 °C in a drying cabinet) are placed in the kneading chamber (item number 279061) of the Brabender absorptometer "E" (without damping the output filter of the torque transducer). In the case of granules, the screen fraction from 3.15 to 1 mm (stainless steel screens from Retsch) (by gently pressing the granules through the 3.15 mm pore size sieve with a plastic spatula). Dibutyl phthalate is added dropwise at room temperature through the "Dosimat Brabender T 90/50" at a rate of 4 ml/min to the mixture with constant mixing (rotational speed of the kneader blades 125 rpm). Mixing in takes place with only a small amount of power and is tracked using the digital display. Towards the end of the determination, the mixture becomes pasty, which is indicated by a steep increase in the power requirement. With a display of 600 digits (torque of 0.6 Nm), both the kneader and the DBP dosing are switched off by an electrical contact. The synchronous motor for the DBP supply is linked to a digital counter so that the consumption of DBP can be read in ml.
Evaluation
The DBP uptake is expressed in g/(100 g) and is calculated from the measured DBP consumption using the following formula. The density of DBP is typically 1,047 g/ml at 20 °C.<maths id="math0004" num=""><math display="block"><mi>DBP</mi><mo>−</mo><mi>recording</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi mathvariant="normal">G</mi><mo>/</mo><mfenced separators=""><mn>100</mn><mspace width="1ex" /><mi mathvariant="normal">G</mi></mfenced><mo>=</mo><mfenced separators=""><mfenced separators=""><mi>consumption</mi><mspace width="1ex" /><mi>at</mi><mspace width="1ex" /><mi>DBP</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi>ml</mi></mfenced><mo>*</mo><mfenced separators=""><mi>density</mi><mspace width="1ex" /><mi>of</mi><mspace width="1ex" /><mi>DBP</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi mathvariant="normal">G</mi><mo>/</mo><mi>ml</mi></mfenced><mo>*</mo><mn>100</mn></mfenced><mo>/</mo><mfenced separators=""><mn>12.5</mn><mi mathvariant="normal">G</mi></mfenced><mo>.</mo></math><img file="EP1585704B2_D0004.tif" /></maths>
The DBP uptake is defined for the anhydrous, dried silica. When using moist precipitated silica, the value must be corrected using the correction table below. The correction value corresponding to the water content is added to the experimentally determined DBP value; e.g. For example, a water content of 5.8% would mean an allowance of 33 g/(100 g) for DBP uptake.
Correction table for dibutyl phthalate uptake -anhydrous-
<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="9mm" /><colspec colnum="3" colname="col3" colwidth="9mm" /><colspec colnum="4" colname="col4" colwidth="9mm" /><colspec colnum="5" colname="col5" colwidth="9mm" /><colspec colnum="6" colname="col6" colwidth="9mm" /><thead><row rowsep="0"><entry valign="middle" /><entry namest="col2" nameend="col6" align="left" valign="top"><b>.% Water</b></entry></row><row valign="middle"><entry rowsep="0"><b>% Water</b></entry><entry colsep="0">.0</entry><entry colsep="0">.2</entry><entry colsep="0">.4</entry><entry colsep="0">.6</entry><entry>.8</entry></row></thead><tbody valign="middle"><row><entry rowsep="0">0</entry><entry>0</entry><entry>2</entry><entry>4</entry><entry>5</entry><entry>7</entry></row><row><entry rowsep="0">1</entry><entry>9</entry><entry>10</entry><entry>12</entry><entry>13</entry><entry>15</entry></row><row><entry rowsep="0">2</entry><entry>16</entry><entry>18</entry><entry>19</entry><entry>20</entry><entry>22</entry></row><row><entry rowsep="0">3</entry><entry>23</entry><entry>24</entry><entry>26</entry><entry>27</entry><entry>28</entry></row><row><entry>4</entry><entry>28</entry><entry>29</entry><entry>29</entry><entry>30</entry><entry>31</entry></row></tbody></tgroup><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="9mm" /><colspec colnum="3" colname="col3" colwidth="9mm" /><colspec colnum="4" colname="col4" colwidth="9mm" /><colspec colnum="5" colname="col5" colwidth="9mm" /><colspec colnum="6" colname="col6" colwidth="9mm" /><thead valign="middle"><row rowsep="0"><entry /><entry namest="col2" nameend="col6" align="left"><b>.%Water</b></entry></row></thead><tbody valign="middle"><row><entry rowsep="0">5</entry><entry>31</entry><entry>32</entry><entry>32</entry><entry>33</entry><entry>33</entry></row><row><entry rowsep="0">6</entry><entry>34</entry><entry>34</entry><entry>35</entry><entry>35</entry><entry>36</entry></row><row><entry rowsep="0">7</entry><entry>36</entry><entry>37</entry><entry>38</entry><entry>38</entry><entry>39</entry></row><row><entry rowsep="0">8</entry><entry>39</entry><entry>40</entry><entry>40</entry><entry>41</entry><entry>41</entry></row><row><entry rowsep="0">9</entry><entry>42</entry><entry>43</entry><entry>43</entry><entry>44</entry><entry>44</entry></row><row><entry>10</entry><entry>45</entry><entry>45</entry><entry>46</entry><entry>46</entry><entry>47</entry></row></tbody></tgroup></table></tables>
<u>pH determination</u>
The method based on DIN EN ISO 787-9 is used to determine the pH value of an aqueous suspension of silicic acids at 20 °C. For this purpose, an aqueous suspension of the sample to be examined is prepared. After briefly shaking the suspension, its pH is determined using a previously calibrated pH meter.
execution
Before carrying out the pH measurement, the pH measuring device (Knick, type: 766 pH meter Calimatic with temperature sensor) and the pH electrode (combination electrode from Schott, type N7680) are to be cleaned daily using the buffer solutions at 20° to calibrate C. The calibration function should be chosen so that the two buffer solutions used include the expected pH value of the sample (buffer solutions with pH 4.00 and 7.00, pH 7.00 and pH 9.00 and, if necessary, pH 7.00 and 12.00). When using granules, first 20.0 g of silica are comminuted in a mill (Krups, model KM 75, item no. 2030-70) for 20 s.
5.00 g powdered or spherical silica with a moisture content of 5 ± 1% (if necessary, the moisture content is adjusted by drying at 105 °C in a drying cabinet or by moistening evenly before possible crushing) are placed on a precision balance to within 0.01 g in a previously tared wide-necked glass bottle weighed in. 95.0 ml deionized water is added to the sample. The suspension in the closed vessel is then shaken at room temperature for a period of 5 minutes using a shaking machine (Gerhardt, model LS10, 55 W, level 7). The pH value is measured directly after shaking. To do this, the electrode is first rinsed with deionized water, then with part of the suspension and then immersed in the suspension. After adding a magnet fish to the suspension, the pH is measured at a constant stirring speed with slight vortex formation of the suspension. If the pH meter shows a constant value, the pH value is read on the display.
When using hydrophobic silicic acid, the procedure is analogous, but then 5.00 g of the possibly crushed sample with a moisture content of 5 ± 1% is weighed on a precision balance to within 0.01 g into a previously tared wide-necked glass bottle. 50.0 ml methanol p. A. and 50.0 ml deionized water are added and then the suspension is shaken in the sealed vessel for a period of 5 minutes using a shaking machine (from Gerhardt, model LS10, 55 W, setting 7) at room temperature. The pH value is also measured with stirring, but after exactly 5 minutes.
<u>Determination of the solids content of filter cake</u>
According to this method, the solids content of filter cakes is determined by removing the volatile components at 105 °C.
execution
100.00 g of the filter cake are weighed out (initial weight E) into a dry, tared porcelain dish (diameter 20 cm). If necessary, the filter cake is broken up with a spatula to loose chunks of a maximum of 1 cm<sup>3</sup> to obtain. The sample is dried at 105 ± 2 °C in a drying cabinet to constant weight. The sample is then cooled to room temperature in a desiccator cabinet with silica gel as a drying agent. The weight A is determined gravimetrically.
The solids content is determined in % according to 100% - (((E in g - A in g) * 100%) / (E in g)).
<u>Determination of electrical conductivity</u>
The electrical conductivity (conductivity) of silicic acids is determined in aqueous suspension.
execution
When using granules, first 20.0 g of silica are comminuted in a mill (Krups, model KM 75, item no. 2030-70) for 20 s. 4.00 g powdered or spherical silica with 5 ± 1% moisture content (if necessary, the moisture content is adjusted by drying at 105 ° C in a drying cabinet or uniform moistening before possible comminution) are suspended in 50.0 ml deionized water and heated to 100 ° C for 1 min . The sample, measured at 20 °C, is filled up to exactly 100 ml and homogenized by shaking.
The measuring cell of the conductivity meter LF 530 (from WTW) is rinsed with a small amount of sample before the measuring cell LTA01 is immersed in the suspension. The value shown on the display corresponds to the conductivity at 20 °C, since the external temperature sensor TFK 530 carries out automatic temperature compensation. This temperature coefficient and the cell constant k must be checked before each series of measurements.
A 0.01 mol/l potassium chloride solution is used as the calibration solution (conductivity at 20 °C = 1278 µS/cm).
<u>Determination of the solids content of precipitation suspensions</u>
The solids content of the precipitation suspension is determined gravimetrically after the sample has been filtered.
execution
100.0 ml of the homogenized precipitation suspension (V<sub>suspension</sub>) are measured at room temperature using a measuring cylinder. The sample is suction filtered through a round filter (TYPE 572, Schleicher & Schuell) in a porcelain suction filter, but not sucked dry, in order to prevent the formation of cracks in the filter cake. The filter cake is then washed with 100.0 ml of deionized water. The washed filter cake is completely suction filtered, transferred to a tared porcelain dish and dried at 105±2° C. in a drying cabinet to constant weight. The weight of the dried silica (m<sub>sample</sub>) is determined. The solids content is determined according to:<maths id="math0005" num=""><math display="block"><mi>solids content</mi><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi mathvariant="normal">G</mi><mo>/</mo><mi mathvariant="normal">l</mi><mo>=</mo><mfenced separators=""><msub><mi mathvariant="normal">m</mi><mi>sample</mi></msub><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi mathvariant="normal">G</mi></mfenced><mo>/</mo><mfenced separators=""><msub><mi mathvariant="normal">V</mi><mi>suspension</mi></msub><mspace width="1ex" /><mi>in</mi><mspace width="1ex" /><mi mathvariant="normal">l</mi></mfenced><mo>.</mo></math><img file="EP1585704B2_D0005.tif" /></maths>
<u>Determination of the alkali number</u>
The determination of the alkali number (AZ) is the consumption of hydrochloric acid in ml (with a sample volume of 50 ml, 50 ml distilled water and a hydrochloric acid concentration of 0.5 mol/l used) in a direct potentiometric titration of alkaline solutions or suspensions up to a pH of 8.30. This is used to determine the free alkali content of the solution or suspension.
execution
The pH device (Knick, type: 766 pH meter Calimatic with temperature sensor) and the pH electrode (combination measuring chain from Schott, type N7680) are measured using two buffer solutions (pH = 7.00 and pH = 10.00) at room temperature calibrated. The combination electrode is immersed in the measurement solution or suspension, which is at a temperature of 40 °C and consists of 50.0 ml sample and 50.0 ml deionized water. Hydrochloric acid solution with a concentration of 0.5 mol/l is then added dropwise until a constant pH of 8.30 is established. Due to the fact that the equilibrium between the silicic acid and the free alkali content is only established slowly, a waiting time of 15 minutes is required before the acid consumption can finally be read off. With the selected amounts of substance and concentrations, the hydrochloric acid consumption read off in ml corresponds directly to the alkali number, which is specified without dimensions.
The following examples are intended to explain the invention in more detail without restricting its scope.
Example 1 Production of the silicas
Example 1.1
In a reactor made of stainless steel with a propeller stirring system and jacketed heating, 1550 liters of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
Then, while stirring vigorously at 92 °C for 80 minutes, 5,505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. Then the addition of water glass is stopped and the sulfuric acid is continued until a pH of 5.0 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 21% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 18% and a pH of 4.0 is then dried in a nozzle tower while metering in ammonia.
The micro bead product obtained has a BET surface area of 123 m<sup>2</sup>/g and a CTAB surface area of 119 m<sup>2</sup>/g on.
Example 1.2
In a reactor made of stainless steel with a propeller stirring system and jacketed heating, 1550 liters of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
Then, while stirring vigorously at 88.5 °C for 80 minutes, 5.505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. The addition of water glass is then stopped and the sulfuric acid is continued until a pH of 4.5 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 19% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 17% and a pH of 3.0 is then dried in a nozzle tower while metering in ammonia.
The micro bead product obtained has a BET surface area of 168 m<sup>2</sup>/g and a CTAB surface area of 148 m<sup>2</sup>/g on.
Example 1.3
In a reactor made of stainless steel with a propeller stirring system and jacketed heating, 1550 liters of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
Then, while stirring vigorously at 93 °C for 80 minutes, 5,505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. Then the addition of water glass is stopped and the. Sulfuric acid continued until a pH of 5.0 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 21% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 18% and a pH value of 4.0 is then spray-dried and roller-granulated with the addition of ammonia.
The granular product obtained has a BET surface area of 126 m<sup>2</sup>/g and a CTAB surface area of 118 m<sup>2</sup>/g on.
Example 1.4
In a reactor made of stainless steel with a propeller stirring system and jacketed heating, 1550 liters of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
Then, while stirring vigorously at 92 °C for 100 minutes, 5,505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. Then the addition of water glass is stopped and the sulfuric acid is continued until a pH of 5.0 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 22% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 19% and a pH of 3.8 is then spray-dried with metered ammonia and roller-granulated.
The granular product obtained has a BET surface area of 130 m<sup>2</sup>/g and a CTAB surface area of 113 m<sup>2</sup>/g on.
Example 1.5
In a reactor made of stainless steel with a propeller stirring system and jacketed heating, 1550 liters of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
5.505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. Then the addition of water glass is stopped and the sulfuric acid is continued until a pH of 5.0 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 21% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 19% and a pH of 4.0 is then dried in a nozzle tower while metering in ammonia.
The micro bead product obtained has a BET surface area of 110 m<sup>2</sup>/g and a CTAB surface area of 108 m<sup>2</sup>/g on.
Example 1.6
In a reactor made of stainless steel with a propeller stirring system and double-walled heating, 1550 l of water and 141.4 kg of water glass (density 1,348 kg/l, 27.0% SiO<sub>2</sub>, 8.05% Na<sub>2</sub>O) submitted.
5.505 kg/min of the above-mentioned water glass and approx. 0.65 kg/min of sulfuric acid (density 1.83 kg/l, 96% H<sub>2</sub>SO<sub>4</sub>) added. This metering of sulfuric acid is regulated in such a way that an AZ number of 20 prevails in the reaction medium. Then the addition of water glass is stopped and the sulfuric acid is continued until a pH of 5.0 (measured at room temperature) is reached.
The suspension obtained is filtered with a membrane filter press and washed with water. The filter cake with a solids content of 22% is liquefied with aqueous sulfuric acid and a shearing unit. The silicic acid feed with a solids content of 20% and a pH of 3.0 is then dried in a nozzle tower while metering in ammonia.
The micro bead product obtained has a BET surface area of 143 m<sup>2</sup>/g and a CTAB surface area of 131 m<sup>2</sup>/g on.
Further physico-chemical data of the above-mentioned silicas are summarized in the table below.<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="9"><colspec colnum="1" colname="col1" colwidth="31mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="16mm" /><colspec colnum="5" colname="col5" colwidth="18mm" /><colspec colnum="6" colname="col6" colwidth="10mm" /><colspec colnum="7" colname="col7" colwidth="24mm" align="center" /><colspec colnum="8" colname="col8" colwidth="21mm" /><colspec colnum="9" colname="col9" colwidth="21mm" /><thead valign="top"><row><entry><b>Silicic acid from example no.</b></entry><entry><b>BET</b></entry><entry><b>CTAB</b></entry><entry><b>DBP</b></entry><entry><b>humidity</b></entry><entry><b>pH</b></entry><entry><b>conductivity</b></entry><entry><b>Sears number V<sub>2</sub></b></entry><entry><b>Sears number V<sub>2</sub>/BET</b></entry></row><row><entry /><entry align="center">[m<sup>2</sup>/G]</entry><entry align="center">[m<sup>2</sup>/G]</entry><entry align="center">[g/(100g)]</entry><entry align="center">[%]</entry><entry align="center">[-]</entry><entry>[µS/cm]</entry><entry align="center">[ml/(5g)]</entry><entry align="center">[ml/(5m<sup>2</sup>)]</entry></row></thead><tbody valign="middle"><row><entry>1.1</entry><entry align="center">123</entry><entry align="center">119</entry><entry align="center">272</entry><entry align="center">4.8</entry><entry align="center">5.6</entry><entry>610</entry><entry align="center">24</entry><entry align="center">0.195</entry></row><row><entry>1.2</entry><entry align="center">168</entry><entry align="center">148</entry><entry align="center">265</entry><entry align="center">5.5</entry><entry align="center">6.0</entry><entry>700</entry><entry align="center">26</entry><entry align="center">0.155</entry></row><row><entry>1.3</entry><entry align="center">126</entry><entry align="center">118</entry><entry align="center">207</entry><entry align="center">5.1</entry><entry align="center">5.1</entry><entry>810</entry><entry align="center">22</entry><entry align="center">0.175</entry></row><row><entry>1.4</entry><entry align="center">130</entry><entry align="center">113</entry><entry align="center">204</entry><entry align="center">5.2</entry><entry align="center">6.2</entry><entry>720</entry><entry align="center">22</entry><entry align="center">0.169</entry></row><row><entry>1.5</entry><entry align="center">110</entry><entry align="center">108</entry><entry align="center">271</entry><entry align="center">5.1</entry><entry align="center">5.5</entry><entry>930</entry><entry align="center">25</entry><entry align="center">0.227</entry></row><row><entry>1.6</entry><entry align="center">143</entry><entry align="center">131</entry><entry align="center">258</entry><entry align="center">4.8</entry><entry align="center">5.7</entry><entry>580</entry><entry align="center">26</entry><entry align="center">0.182</entry></row></tbody></tgroup></table></tables>
example 2
Example 2.1
The inventive precipitated silica 1.1 and 1.3 from example 1 were examined in an emulsion SBR rubber mixture. The silica Ultrasil VN2 GR from Degussa AG with a CTAB surface area of 125 m was used as the state of the art and as a reference<sup>2</sup>/g selected.
The formulation used for the rubber mixtures is given in Table 2.1 below. The unit phr means parts by weight, based on 100 parts of the raw rubber used.<tables id="tabl0005" num="0005"><table frame="all"><title><b>Table 2.1</b></title><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="14mm" align="center" /><colspec colnum="4" colname="col4" colwidth="14mm" align="center" /><thead valign="top"><row><entry><b>1. Step</b></entry><entry><b>reference</b></entry><entry><b>A</b></entry><entry><b>B</b></entry></row></thead><tbody valign="middle"><row><entry>Buna SBR 1712</entry><entry>137.5</entry><entry>137.5</entry><entry>137.5</entry></row><row><entry>Ultrasil VN2 GR</entry><entry>50</entry><entry>---</entry><entry>---</entry></row><row><entry>Silicic acid according to Example 1.1</entry><entry>---</entry><entry>50</entry><entry>---</entry></row><row><entry>Silicic acid according to Example 1.3</entry><entry>---</entry><entry>---</entry><entry>50</entry></row><row><entry>X50-S</entry><entry>3</entry><entry>3</entry><entry>3</entry></row><row><entry>ZnO</entry><entry>3</entry><entry>2</entry><entry>3</entry></row><row><entry>stearic acid</entry><entry>1</entry><entry>1</entry><entry>1</entry></row><row><entry>Vulkanox 4020</entry><entry>2</entry><entry>2</entry><entry>2</entry></row><row><entry>Protector G 3108</entry><entry>1.5</entry><entry>1.5</entry><entry>1.5</entry></row></tbody></tgroup><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="14mm" align="center" /><colspec colnum="4" colname="col4" colwidth="14mm" align="center" /><thead><row><entry valign="top"><b>2. Step</b></entry><entry valign="middle" /><entry valign="middle" /><entry valign="middle" /></row></thead><tbody valign="middle"><row><entry>Batch level 1</entry><entry /><entry /><entry /></row></tbody></tgroup><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="14mm" align="center" /><colspec colnum="4" colname="col4" colwidth="14mm" align="center" /><thead><row><entry valign="top"><b>3. Step</b></entry><entry valign="middle" /><entry valign="middle" /><entry valign="middle" /></row></thead><tbody valign="middle"><row><entry>Batch level 2</entry><entry /><entry /><entry /></row><row><entry>Vulkacit D/C</entry><entry>1.5</entry><entry>1.5</entry><entry>1.5</entry></row><row><entry>Vulkacit CZ/EG</entry><entry>1.5</entry><entry>1.5</entry><entry>1.5</entry></row><row><entry>sulfur</entry><entry>2.2</entry><entry>2.2</entry><entry>2.2</entry></row></tbody></tgroup></table></tables>
The Buna 1712 polymer is an emulsion-polymerized SBR copolymer from Buna DOW Leuna with a styrene content of 23.5% by weight and an oil content of 37.5 phr. X50-S is a 50/50 blend of Si 69 [bis(3-triethoxysilylpropyl)tetrasulphane] and carbon black available from Degussa AG. Vulkanox 4020 is 6PPD from Bayer AG and Protektor G 3108 is an anti-ozone wax from HB-Fuller GmbH. Vulkacit D/C (DPG) and Vulkacit CZ/EG (CBS) are commercial products from Bayer AG.
The rubber mixtures are produced in an internal mixer in accordance with the mixing specifications in Table 2.2. Table 2.3 summarizes the rubber testing methods used. The mixtures are vulcanized at 160° C. for 18 minutes. Table 2.4 shows the results of the rubber test.<tables id="tabl0006" num="0006"><table frame="all"><title><b>Table 2.2</b></title><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><b>step 1</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Mixing unit Werner & Pfleiderer 1.5N type</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>45 at least<sup>-1</sup></entry></row><row rowsep="0"><entry>friction</entry><entry>1:1.11</entry></row><row rowsep="0"><entry>stamp printing</entry><entry>5.5 bars</entry></row><row rowsep="0"><entry>void volume</entry><entry>1.61</entry></row><row rowsep="0"><entry>fill level</entry><entry>0.73</entry></row><row><entry>flow temp.</entry><entry>90 °C</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>0 up to 1 min</entry><entry>polymer</entry></row><row rowsep="0"><entry>1 up to 2 minutes</entry><entry>Components 1st stage</entry></row><row rowsep="0"><entry>2 at least</entry><entry>Clean</entry></row><row rowsep="0"><entry>2 up to 3 min</entry><entry>Mix, air</entry></row><row rowsep="0"><entry>3 up to 4 minutes</entry><entry>Mix with 70 min<sup>-1</sup>, airing</entry></row><row rowsep="0"><entry>4 up to 5 minutes</entry><entry>Mix with 75 min<sup>-1</sup>, exit</entry></row><row><entry>storage</entry><entry>24 h at room temperature</entry></row><row><entry namest="col1" nameend="col2" align="left" /></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="center"><b>Level 2</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Mixing unit as in level 1 except for:</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>70 at least<sup>-1</sup></entry></row><row><entry>fill level</entry><entry>0.71</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>0 up to 1 min</entry><entry>Plasticize batch stage 1</entry></row><row rowsep="0"><entry>1 up to 3 min</entry><entry>Batch temperature 150 °C through</entry></row><row rowsep="0"><entry /><entry>maintain speed variation</entry></row><row rowsep="0"><entry>3 at least</entry><entry>exit</entry></row><row><entry>storage</entry><entry>4 h at room temperature</entry></row><row><entry namest="col1" nameend="col2" align="left" /></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><b>level 3</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Mixing unit as in step 1 up to</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>40 at least<sup>-1</sup></entry></row><row rowsep="0"><entry>flow temp.</entry><entry>50 °C</entry></row><row><entry>fill level</entry><entry>0.69</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody><row rowsep="0" valign="middle"><entry>0 up to 2 minutes</entry><entry>Batch level 2, ingredients level 3</entry></row><row><entry rowsep="0">2 at least</entry><entry rowsep="0" valign="middle">extend and form fur on the laboratory mixing mill (diameter 200 mm, length 450 mm, flow temperature 50 °C)</entry></row><row><entry rowsep="0" /><entry rowsep="0" valign="middle">Homogenize:</entry></row><row><entry rowsep="0" /><entry rowsep="0" valign="middle">Cut 3* right, 3* left; 3* plunge at wide nip (3.5mm).</entry></row><row><entry /><entry valign="middle">and 3* with a narrow roller gap (1 mm): remove the fur</entry></row></tbody></tgroup></table></tables><tables id="tabl0007" num="0007"><table frame="all"><title><b>Table 23</b></title><tgroup cols="3" colsep="0"><colspec colnum="1" colname="col1" colwidth="24mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="39mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left">physical testing</entry><entry>Standard/Conditions</entry></row><row><entry namest="col1" nameend="col2" rowsep="0" align="left">Vulcameter test, 160 °C</entry><entry rowsep="0">DIN 53529/3, ISO 6502</entry></row><row><entry /><entry namest="col2" nameend="col3" align="left">Torque difference Dmax- Dmin [dNm]</entry></row></thead><tbody><row rowsep="0"><entry /><entry>t10% and t90% [min]</entry><entry /></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Tensile test on the ring, 23 °C</entry><entry>DIN 53504, ISO 37</entry></row><row rowsep="0"><entry /><entry namest="col2" nameend="col3" align="left">Stress values 100% and 500% [Mpa]</entry></row><row rowsep="0"><entry /><entry namest="col2" nameend="col3" align="left">Amplification factor: voltage value 500%/100% [-]</entry></row><row rowsep="0"><entry /><entry namest="col2" nameend="col3" align="left">Elongation at break [%]</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Shore A hardness, 23 °C [-]</entry><entry>DIN 53 505</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Ball Rebound [%], 0°C and 60°C</entry><entry>DIN EN ISO 8307,</entry></row><row><entry namest="col1" nameend="col2" rowsep="0" align="left" /><entry rowsep="0">Steel ball 19mm, 28g</entry></row><row><entry namest="col1" nameend="col2" align="left">Dispersion coefficient [%]</entry><entry>see text</entry></row></tbody></tgroup></table></tables>
The dispersion coefficient was determined by means of the surface topography including medial correction (A. Wehmeier, "Filler Dispersion Analysis by Topography Measurements" Technical Report TR 820, Degussa AG, Advanced Fillers and Pigments Division). The dispersion coefficient determined in this way correlates directly with a coefficient of determination of >0.95 with the light-optically determined dispersion coefficient, e.g. B. is determined by the German Institute for Rubber Technology eV, Hanover/Germany (H. Geisler, "Determination of the mixing quality", presented at the DIK workshop, November 27-28, 1997, Hanover/Germany).<tables id="tabl0008" num="0008"><table frame="all"><title><b>Table 2.4</b></title><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="46mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="12mm" align="center" /><colspec colnum="4" colname="col4" colwidth="12mm" align="center" /><thead valign="top"><row><entry><b>raw mix data</b></entry><entry><b>reference</b></entry><entry><b>A</b></entry><entry><b>B</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>Dmax-Dmin</entry><entry>11.5</entry><entry>11.8</entry><entry>11.6</entry></row><row rowsep="0"><entry>t10%</entry><entry>4.9</entry><entry>4.6</entry><entry>4.6</entry></row><row><entry>t90%</entry><entry>9.8</entry><entry>9.6</entry><entry>9.5</entry></row></tbody></tgroup><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="46mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="12mm" align="center" /><colspec colnum="4" colname="col4" colwidth="12mm" align="center" /><thead valign="middle"><row><entry><b>vulcanizate data</b></entry><entry /><entry /><entry /></row></thead><tbody valign="middle"><row><entry rowsep="0">Voltage value 100%</entry><entry rowsep="0">1.0</entry><entry rowsep="0">1.0</entry><entry rowsep="0">1.0</entry></row><row><entry rowsep="0">voltage value 500%</entry><entry rowsep="0">9.1</entry><entry rowsep="0">9.9</entry><entry rowsep="0">10.3</entry></row><row><entry rowsep="0">Voltage value 500%/100%</entry><entry rowsep="0">9.1</entry><entry rowsep="0">9.9</entry><entry rowsep="0">10.3</entry></row><row><entry>elongation at break</entry><entry>530</entry><entry>500</entry><entry>520</entry></row><row><entry>Shore A hardness</entry><entry>51</entry><entry>51</entry><entry>51</entry></row><row><entry>Ball rebound 0°C</entry><entry>22.1</entry><entry>21.2</entry><entry>21.3</entry></row><row><entry>Ball rebound 60°C</entry><entry>71.0</entry><entry>70.4</entry><entry>70.3</entry></row><row><entry>dispersion coefficient</entry><entry>98</entry><entry>99</entry><entry>97</entry></row></tbody></tgroup></table></tables>
As can be seen from the data in Table 2.4, mixtures A and B with the silicas according to the invention show a faster vulcanization time t90% than the reference mixture. In addition to the faster vulcanization, advantages can be seen in particular in a higher voltage value of 500% and the increased amplification factor. The ball rebound at 0 and 60 °C are comparable, so that no losses in the hysteresis behavior of the compounds are to be expected. The dispersion of the silicas according to the invention is very good.
Example 2.2
The inventive precipitated silica 1.2 from Example 1 was examined in an SSBR/BR rubber mixture. The silica Ultrasil 3370 GR from Degussa AG with a CTAB surface area of 160 m<sup>2</sup>/g selected. The mixture used represents a model recipe for a car tread compound.
The formulation used for the rubber mixtures is given in Table 2.5 below. The unit phr means parts by weight, based on 100 parts of the raw rubber used.<tables id="tabl0009" num="0009"><table frame="all"><title><b>Table 2.5</b></title><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="12mm" align="center" /><thead valign="top"><row><entry><b>1. Step</b></entry><entry><b>reference</b></entry><entry><b>C</b></entry></row></thead><tbody valign="middle"><row><entry>Buna VSL 5025-1</entry><entry>96</entry><entry>96</entry></row><row><entry>Buna CB 24</entry><entry>30</entry><entry>30</entry></row><row><entry>Ultrasil 3370 GR</entry><entry>80</entry><entry>---</entry></row><row><entry>Silicic acid according to Example 1.2</entry><entry>---</entry><entry>80</entry></row><row><entry>X50-S</entry><entry>12.8</entry><entry>12.8</entry></row><row><entry>ZnO</entry><entry>2</entry><entry>2</entry></row><row><entry>stearic acid</entry><entry>2</entry><entry>2</entry></row><row><entry>Naftolen ZD</entry><entry>10</entry><entry>10</entry></row><row><entry>Vulkanox 4020</entry><entry>1.5</entry><entry>1.5</entry></row><row><entry>Protector G 3108</entry><entry>1</entry><entry>1</entry></row></tbody></tgroup><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><thead><row><entry valign="top"><b>2. Step</b></entry><entry valign="middle" /><entry valign="middle" /></row></thead><tbody valign="middle"><row><entry>Batch level 1</entry><entry /><entry /></row><row><entry namest="col1" nameend="col3" align="left" /></row></tbody></tgroup><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><thead><row><entry valign="top"><b>3. Step</b></entry><entry valign="middle" /><entry valign="middle" /></row></thead><tbody valign="middle"><row><entry>Batch level 2</entry><entry /><entry /></row><row><entry>Vulkacit D/C</entry><entry>2.0</entry><entry>2.0</entry></row><row><entry>Vulkacit CZ/EG</entry><entry>1.5</entry><entry>1.5</entry></row><row><entry>Percazite TBZTD</entry><entry>0.2</entry><entry>0.2</entry></row><row><entry>sulfur</entry><entry>1.5</entry><entry>1.5</entry></row></tbody></tgroup></table></tables>
The polymer VSL 5025-1 is a solution-polymerized SBR copolymer from Bayer AG with a styrene content of 25% by weight and a butadiene content of 75% by weight. The copolymer contains 37.5 phr oil and has a Mooney viscosity (ML 1+4/100 °C) of 50 ± 4. The polymer Buna CB 24 is a cis-1,4-polybutadiene (neodymium type) from Bayer AG with a cis-1,4 content of at least 97% and a Mooney viscosity of 44 ± 5. X50-S is a 50/50 blend of Si 69 [bis(3-triethoxysilylpropyl)tetrasulphane] and carbon black available from Degussa AG. Naftolen ZD from Chemetall is used as the aromatic oil. Vulkanox 4020 is 6PPD from Bayer AG and Protektor G 3108 is an anti-ozone wax from HB-Fuller GmbH. Vulkacit D/C (DPG) and Vulkacit CZ/EG (CBS) are commercial products from Bayer AG. Perkazit TBZTD is available from Akzo Chemie GmbH.
The rubber mixtures are produced in an internal mixer in accordance with the mixing specifications in Table 2.6. In addition to the rubber testing methods shown in Table 2.3, the methods summarized in Table 2.7 were used. The mixtures are vulcanized at 165° C. for 15 minutes. Table 2.8 shows the results of the rubber test.<tables id="tabl0010" num="0010"><table frame="all"><title><b>Table 2.6</b></title><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="center"><b>step 1</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Mixing unit Werner & Pfleiderer 1.5N type</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>70 at least<sup>-1</sup></entry></row><row rowsep="0"><entry>friction</entry><entry>1:1.11</entry></row><row rowsep="0"><entry>stamp printing</entry><entry>5.5 bars</entry></row><row rowsep="0"><entry>void volume</entry><entry>1.61</entry></row><row rowsep="0"><entry>fill level</entry><entry>0.73</entry></row><row><entry>flow temp.</entry><entry>70 °C</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>0 up to 1 min</entry><entry>Buna VSL 5025-1 + Buna CB 24</entry></row><row rowsep="0"><entry>1 up to 3 min</entry><entry>1/2 filler, X50-S</entry></row><row rowsep="0"><entry>3 up to 4 minutes</entry><entry>1/2 filler, remaining ingredients stage 1</entry></row><row rowsep="0"><entry>4 at least</entry><entry>Clean</entry></row><row rowsep="0"><entry>4 up to 5 minutes</entry><entry>Mix and exit</entry></row><row><entry>storage</entry><entry>24 h at room temperature</entry></row><row><entry /><entry /></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><b>Level 2</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Mixing unit as in level 1 except for:</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>80 at least<sup>-1</sup></entry></row><row rowsep="0"><entry>flow temp.</entry><entry>80 °C</entry></row><row><entry>fill level</entry><entry>0.70</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody><row rowsep="0"><entry>0 up to 2 minutes</entry><entry>Plasticize batch stage 1</entry></row><row rowsep="0"><entry>2 up to 5 minutes</entry><entry>Batch temperature 150 °C through</entry></row><row><entry rowsep="0" /><entry rowsep="0">maintain speed variation</entry></row><row rowsep="0"><entry>5 at least</entry><entry>exit</entry></row><row><entry>storage</entry><entry>4 h at room temperature</entry></row><row><entry namest="col1" nameend="col2" align="left" /></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><b>level 3</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>settings</b></entry></row></thead><tbody><row><entry namest="col1" nameend="col2" align="left">Mixing unit as in step 1 up to</entry></row><row rowsep="0"><entry>rotation speed</entry><entry>40 at least<sup>-1</sup></entry></row><row rowsep="0"><entry>flow temp.</entry><entry>50 °C</entry></row><row><entry>fill level</entry><entry>0.69</entry></row></tbody></tgroup><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="33mm" /><colspec colnum="2" colname="col2" colwidth="133mm" colsep="1" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col2" align="left"><b>mixing process</b></entry></row></thead><tbody><row rowsep="0"><entry>0 up to 2 minutes</entry><entry>Batch level 2, ingredients level 3</entry></row><row><entry rowsep="0">2 at least</entry><entry rowsep="0">extend and form fur on the laboratory mixing mill (diameter 200 mm, length 450 mm, flow temperature 50 °C)</entry></row><row><entry rowsep="0" /><entry rowsep="0">Homogenize:</entry></row><row><entry rowsep="0" /><entry rowsep="0">Cut 3* left, 3* right</entry></row><row><entry rowsep="0" /><entry rowsep="0">5* with a narrow roller gap (1 mm) and</entry></row><row><entry /><entry>5* fall at a wide roller gap (3.5 mm) and pull off the fur</entry></row></tbody></tgroup></table></tables><tables id="tabl0011" num="0011"><table frame="all"><title><b>Table 2.7</b></title><tgroup cols="3" colsep="0"><colspec colnum="1" colname="col1" colwidth="32mm" /><colspec colnum="2" colname="col2" colwidth="34mm" /><colspec colnum="3" colname="col3" colwidth="37mm" colsep="1" /><tbody><row rowsep="0"><entry namest="col1" nameend="col2" align="left">physical testing</entry><entry>Standard/Conditions</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">Vulcameter test, 165 °C</entry><entry>DIN 53529/3, ISO 6502</entry></row><row rowsep="0"><entry /><entry namest="col2" nameend="col3" align="left">Torque difference Dmax- Dmin [dNm]</entry></row><row><entry /><entry namest="col2" nameend="col3" align="left">t10% and t90% [min]</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" align="left">viscoelastic properties,</entry><entry>DIN 53 513, ISO 2856</entry></row><row rowsep="0"><entry namest="col1" nameend="col3" align="left">0 and 60 °C, 16 Hz, 50 N preload and 25 N amplitude load</entry></row><row rowsep="0"><entry namest="col1" nameend="col3" align="left">Recording of measured values after 2 minutes of testing, i.e. 2 minutes of conditioning</entry></row><row rowsep="0"><entry /><entry namest="col2" nameend="col3" align="left">Complex modulus E* [Mpa]</entry></row><row><entry /><entry namest="col2" nameend="col3" align="left">Loss factor tan δ [-]</entry></row></tbody></tgroup></table></tables><tables id="tabl0012" num="0012"><table frame="all"><title><b>Table 2.8</b></title><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="46mm" /><colspec colnum="2" colname="col2" colwidth="19mm" align="center" /><colspec colnum="3" colname="col3" colwidth="14mm" align="center" /><thead valign="middle"><row><entry><b>raw mix data</b></entry><entry><b>reference</b></entry><entry><b>C</b></entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>Dmax-Dmin</entry><entry>18.6</entry><entry>18.5</entry></row><row rowsep="0"><entry>t10%</entry><entry>1.5</entry><entry>1.5</entry></row><row><entry>t90%</entry><entry>6.3</entry><entry>6.1</entry></row><row><entry><b>vulcanizate data</b></entry><entry /><entry /></row><row rowsep="0"><entry>Voltage value 100%</entry><entry>2.8</entry><entry>2.8</entry></row><row rowsep="0"><entry>voltage value 300%</entry><entry>13.4</entry><entry>14.7</entry></row><row rowsep="0"><entry>Voltage value 300%/100%</entry><entry>4.8</entry><entry>5.3</entry></row><row><entry>elongation at break</entry><entry>370</entry><entry>330</entry></row><row><entry>Shore A hardness</entry><entry>66</entry><entry>66</entry></row><row rowsep="0"><entry>Ball rebound 0°C</entry><entry>15.3</entry><entry>15.2</entry></row><row><entry>Ball rebound 60°C</entry><entry>61.4</entry><entry>61.6</entry></row><row rowsep="0"><entry>E* (0 °C)</entry><entry>23.4</entry><entry>31.8</entry></row><row rowsep="0"><entry>E* (60 °C)</entry><entry>8.8</entry><entry>9.0</entry></row><row rowsep="0"><entry>tan δ (0 °C)</entry><entry>0.360</entry><entry>0.441</entry></row><row><entry>tan δ (60 °C)</entry><entry>0.129</entry><entry>0.110</entry></row><row><entry>dispersion coefficient</entry><entry>95</entry><entry>99</entry></row></tbody></tgroup></table></tables>
As can be seen from the data in Table 2.8, the advantages found in example 2.1 in the vulcanization kinetics and an increased reinforcement for the mixture C with the silica according to the invention are confirmed. There are also advantages in the hysteresis behavior of mixture C. The loss factor tan δ (0°C) is increased, which indicates improved wet skid behavior, and the tan δ (60°C) is lower, which speaks for reduced rolling resistance. Furthermore, the quality of dispersion of the silicas according to the invention is exceptionally high, resulting in advantages in road abrasion.
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Numbers
- Publication
- 1585704
- Publication, DOCDB
- 1585704
- Publication, EPODOC
- EP1585704
- Application
- 47007018
- Application, DOCDB
- 04700701
- Application, EPODOC
- EP20040700701
Titles4
- German
- HÖCHSTDISPERGIERBARE SILICAS FÜR GUMMIANWENDUNGEN
- English
- HIGHLY DISPERSIBLE SILICA FOR USING IN RUBBER
- French
- SILICES HAUTEMENT DISPERSIBLES DESTINEES ETRE UTILISEES DANS DES CAOUTCHOUCS
- French
- SILICES HAUTEMENT DISPERSIBLES DESTINEES ETRE UTILISEES DANS DES CAOUTCHOUCS
Classification
- CPC, 11
- B82Y30/00
- C01B33/193
- C01B33/12
- C01P2004/64
- C01P2006/12
- C01P2006/19
- C01P2006/82
- C01P2006/90
- C08K3/36
- C01B33/143
- C07F7/0832
- IPC, 3
- B82Y30 00
- C01B33 193
- C08K3 36
Designated states27
- Contracting states, 27
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Hungary
- Ireland
- Italy
- Liechtenstein
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Portugal
- Romania
- Sweden
and 3 moreShow fewer
- Slovenia
- Slovakia
- Türkiye
