Biopolymers, biooligomers, oxidic or silicate Filler modified by silanes, method for its production and use
Abstract
A silane modified biopolymeric, bio-oligomeric, oxide or silicate filler (I) is prepared by reaction of a biopolymeric, bio-oligomeric, oxide or silicate filler with at least one silane in a condensed gas. <??>An Independent claim is included for rubber mixtures comprising the silane modified filler (I) and optionally containing precipitated silicic acid, carbon black and/or other rubber additives.

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32 claims: 32 independent, 0 dependent
- 1Silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler obtainable by reacting at least one biopolymer, bio-oligomeric, oxidic or siliceous filler in a compressed gas with at least one silane. Silanmodifizierter biopolymerer, biooligomerer, oxidischer oder silikatischer Füllstoff erhältlich, indem man mindestens einen biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoff in einem verdichteten Gas mit mindestens einem Silan umsetzt.
- 2Silane-modified biopolymer, biooligomeric, oxidic or siliceous filler according to claim 1, characterized in that this contains between 0.1 and 50.0 wt .-% silane. Silanmodifizierter biopolymerer, biooligomerer, oxidischer oder silikatischer Füllstoff nach Anspruch 1, dadurch gekennzeichnet, daß dieser zwischen 0,1 und 50,0 Gew.-% Silan enthält.
- 3Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 1, characterized in that at least one biopolymer, biooligomeric, oxidic or siliceous filler in a compressed gas is reacted with at least one silane. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 1, dadurch gekennzeichnet, daß man mindestens ein biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoff in einem verdichteten Gas mit mindestens einem Silan umsetzt.
- 4Process for the preparation of a silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the pressure during the modification reaction is between 1 and 500 bar. Verfahren zur Herstellung eines silanmodifizierten biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der Druck während der Modifizierungsreaktion zwischen 1 und 500 bar beträgt.
- 5Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the temperature is between 0 and 300 ° C. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß die Temperatur zwischen 0 und 300°C beträgt.
- 6Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the silanes used in the compressed gas are undissolved, partially or completely dissolved. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß die verwendeten Silane in dem verdichteten Gas ungelöst, teilweise oder auch vollständig gelöst sind.
- 7Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the pressure during the treatment is kept constant at different pressure levels for periods of 5 to 720 minutes and during this time the filler is immersed in, flows through or is stirred in the compressed gas. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der Druck während der Behandlung auf unterschiedlichen Druckniveaus für Zeiträume von 5 - 720 min konstant gehalten wird und der Füllstoff während dieser Zeit in dem verdichteten Gas eintaucht, von diesem durchflossen oder in diesem gerührt wird.
- 8Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the biopolymers, biooligomers, oxidic or siliceous filler and the silane are continuously circulated with a suitable stirring unit. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der biopolymere, biooligomere, oxidische oder silikatische Füllstoff und das Silan kontinuierlich mit einem geeigneten Rühraggregat umgewälzt werden.
- 9Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that Stirrer, blade stirrer, bar stirrer, perforated bar stirrer, crossbar stirrer, anchor stirrer, grid stirrer, blade roller, propeller stirrer, screw stirrer, turbine stirrer, disc stirrer, planetary stirrer, impeller mixer or impeller stirrer are used as stirrer. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß als Rühraggregat Hubrührer, Blattrührer, Balkenrührer, Lochbalkenrührer, Kreuzbalkenrührer, Ankerrührer, Gitterrührer, Schaufelwalze, Propellerrührer, Schneckenrührer, Turbinenrührer, Scheibenrührer, Planetenrührer, Kreiselmischer oder Impellerrührer verwendet werden.
- 10Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the biopolymers, biooligomers, oxidic or siliceous filler and the silane are first mixed, respectively brought into contact and then mixed with the gas present in the compressed state. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der biopolymere, biooligomere, oxidische oder silikatische Füllstoff und das Silan zuerst durchmischt, beziehungsweise in Kontakt gebracht und dann mit dem im verdichteten Zustand vorliegenden Gas gemischt werden.
- 11Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the biopolymers, bio-oligomers, oxidic or siliceous filler are first mixed with the gas present in the compressed state, or brought into contact and only then mixed with the silane. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der biopolymere, biooligomere, oxidische oder silikatische Füllstoff erst mit dem im verdichteten Zustand vorliegenden Gas durchmischt, beziehungsweise in Kontakt gebracht und erst dann mit dem Silan gemischt wird.
- 12Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the silane, first mixed with the present in the compressed state gas, or brought into contact and only then mixed with the corresponding biopolymer, bio-oligomeric, oxidic or siliceous filler. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß das Silan, erst mit dem im verdichteten Zustand vorliegenden Gas durchmischt, beziehungsweise in Kontakt gebracht und erst dann mit dem entsprechenden biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoff gemischt wird.
- 13Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the manufacturing process following the surface modification of the silane-modified biopolymer, bio-oligomeric, oxide or siliceous filler comprises an evacuation or depressurization step with separation of the compressed gas from the final product. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der Herstellungsprozess im Anschluß an die Oberflächenmodifizierung des silanmodifizierten biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoffs eine Evakuierungs- oder Druckentspannungsstufe mit Abtrennung des verdichteten Gases vom Endprodukt umfasst.
- 14Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the evacuation or depressurization step is performed in less than 10 minutes. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß die Evakuierungs- oder Druckentspannungsstufe in weniger als 10 min durchgeführt wird.
- 15Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the evacuation or depressurization step is carried out in a time between 10 minutes and 180 minutes. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß die Evakuierungs- oder Entspannungsstufe in einer Zeit zwischen 10 min und 180 min durchgeführt wird.
- 16Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the evacuation or expansion stage is carried out at temperatures between 1 and 300 ° C. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß die Evakuierungs- oder Entspannungsstufe bei Temperaturen zwischen 1 und 300°C durchgeführt wird.
- 17Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as silane an organosilicon compound of the general formula (I)ZASx-AZ used in the x is a number from 1 to 12, Z is SiX1X2X3 is and X1, X2, X3 each independently of one another can mean hydrogen (-H), Halogen or hydroxy (-OH), an alkyl, Alkenyl acid substituent or a substituted alkyl or alkenyl acid substituent, a linear or branched hydrocarbon chain with 1-6 carbon atoms, a cycloalkane radical of 5-12 carbon atoms, a benzyl radical or a halogen- or alkyl-substituted phenyl radical, Alkoxy groups with linear or branched hydrocarbon chains with (C1-6) Atoms, a cycloalkoxy group with (C5-12) Atoms, a halogen- or alkyl-substituted phenoxy group or a benzyloxy group, A (C1-C16) is branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent hydrocarbon group. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als Silan eine Organosiliziumverbindung der allgemeinen Formel (I)Z-A-Sx-A-Z verwendet, in der x eine Zahl von 1 bis 12 ist, Z gleich SiX1X2X3 ist und X1, X2, X3 jeweils unabhängig voneinander bedeuten können Wasserstoff (-H), Halogen oder Hydroxy (-OH), ein Alkyl-, Alkenylsäuresubstituent oder ein substituierter Alkyl-, beziehungsweise Alkenylsäuresubstituent, eine lineare oder verzweigte Kohlenwasserstoffkette mit 1-6 Kohlenstoffatomen, ein Cycloalkanrest mit 5-12 Kohlenstoffatomen, ein Benzylrest oder ein halogen- oder alkylsubstituierter Phenylrest, Alkoxygruppen mit linearen oder verzweigten Kohlenwasserstoffketten mit (C1-6) Atomen, eine Cycloalkoxygruppe mit (C5-12)-Atomen, eine halogen- oder alkylsubstituierte Phenoxygruppe oder eine Benzyloxygruppe, A eine (C1-C16) verzweigte oder unverzweigte, gesättigte oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische/aromatische zweibindige Kohlenwasserstoffgruppe ist.
- 18Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 17, characterized in that the silane of formula (I) [(EtO)3Yourself2)3]2S, [(EtO)3Yourself2)3]2S2, [(EtO)3Yourself2)3]2S3, [(EtO)3Yourself2)3]2S4, [(EtO)3Yourself2)3]2S5, [(EtO)3Yourself2)3]2S6, [(EtO)3Yourself2)3]2S7, [(EtO)3Yourself2)3]2S8th, [(EtO)3Yourself2)3]2S9, [(EtO)3Yourself2)3]2S10, [(EtO)3Yourself2)3]2S11, [(EtO)3Yourself2)3]2S12, [(EtO)3Yourself2)3]2S13, [(EtO)3Yourself2)3]2S14 is. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 17, dadurch gekennzeichnet, daß das Silan der Formel (I) [(EtO)3Si(CH2)3]2S, [(EtO)3Si(CH2)3]2S2, [(EtO)3Si(CH2)3]2S3, [(EtO)3Si(CH2)3]2S4, [(EtO)3Si(CH2)3]2S5, [(EtO)3Si(CH2)3]2S6, [(EtO)3Si(CH2)3]2S7, [(EtO)3Si(CH2)3]2S8, [(EtO)3Si(CH2)3]2S9, [(EtO)3Si(CH2)3]2S10, [(EtO)3Si(CH2)3]2S11, [(EtO)3Si(CH2)3]2S12, [(EtO)3Si(CH2)3]2S13, [(EtO)3Si(CH2)3]2S14 ist.
- 19Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as silane an organosilicon compound of the general formula (II)X1X2X3Si-AS-SiR1R2R3 used in the X1, X2, X3 and A independently of one another have the same meaning as in formula (I), R1, R2, R3 are each independent of each other and, (C1-C16) Alkyl, (C1-C16) Alkoxy, (C1-C16) Haloalkyl, aryl, (C7-C16) Aralkyl, H, halogen or X1X2X3Si-AS- mean. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als Silan eine Organosiliziumverbindung der allgemeinen Formel (II)X1X2X3Si-A-S-SiR1R2R3 verwendet, in der X1, X2, X3 und A unabhängig voneinander dieselbe Bedeutung wie in Formel (I) haben, R1, R2, R3 jeweils unabhängig voneinander sind und, (C1-C16) Alkyl, (C1-C16) Alkoxy, (C1-C16) Haloalkyl, Aryl, (C7-C16) Aralkyl, H, Halogen oder X1X2X3Si-A-S- bedeuten.
- 20Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as silane an organosilicon compound of the general formula (III)X1X2X3Si-Alk used in the X1, X2, X3 each independently have the same meaning as in formula (I) and Alk is a straight, branched or cyclic (C1-C18) Alkyl, (C1-C5) Alkoxy, halogen, hydroxy, nitrile, thiol, (C1-C4) Haloalkyl, -NO2, (C1-C8th) Thioalkyl, -NH2, - NHR1, -NO1R2, Alkenyl, allyl, vinyl, aryl or (C7-C16) Aralkyl is. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als Silan eine Organosiliziumverbindung der allgemeinen Formel (III)X1X2X3Si-Alk verwendet, in der X1, X2, X3 jeweils unabhängig voneinander dieselbe Bedeutung wie in Formel (I) haben und Alk ein geradkettiges, verzweigtes oder zyklisches (C1-C18)Alkyl, (C1-C5) Alkoxy, Halogen, Hydroxy, Nitril, Thiol, (C1-C4) Haloalkyl, -NO2, (C1-C8) Thioalkyl, -NH2, - NHR1, -NR1R2, Alkenyl, Allyl-, Vinyl-, Aryl oder (C7-C16) Aralkyl ist.
- 21Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 20, characterized in that the silane of the formula (III) (MeO)3-Yourself2)3-H (EtO)3-Yourself2)3-H, (MeO)3-Si-C (CH3)3, (EtO)3-Si-C (CH3)3, (MeO)3-Yourself2)8th-H, (EtO)3-Yourself2)8th-H, (MeO)3-Yourself2)16-H, (EtO)3-Yourself2)16-H, Me3Si-OMe, Me3Si-OEt, Me3Si-Cl, Et3Si-Cl, (MeO)3Si-CH = CH2, (EtO)3Si-CH = CH2, (Me3Si)2NC (O) -H or (Me3Si)2NH corresponds. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 20, dadurch gekennzeichnet, daß das Silan der Formel (III) (MeO)3-Si-(CH2)3-H (EtO)3-Si-(CH2)3-H, (MeO)3-Si-C(CH3)3, (EtO)3-Si-C(CH3)3, (MeO)3-Si-(CH2)8-H, (EtO)3-Si-(CH2)8-H, (MeO)3-Si-(CH2)16-H, (EtO)3-Si-(CH2)16-H, Me3Si-OMe, Me3Si-OEt, Me3Si-Cl, Et3Si-Cl, (MeO)3Si-CH=CH2, (EtO)3Si-CH=CH2, (Me3Si)2N-C(O)-H oder (Me3Si)2N-H entspricht.
- 22Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as silane, an organosilicon compound of the general formula (IV) or (V)[[(ROC (= O))p-(G)j]k-ys]r-G- (SiX1X2X3)s[(X1X2X3Si)q-G]a- [Y [SG-SiX1X2X3]b]c used in the Y a polyvalent species (Q)zD (= E), where:p is 0 to 5, r is 1 to 3, z is 0 to 2;q is 0 to 6, a is 0 to 7, b is 1 to 3, j is 0 to 1, but if p = 1, it may often be 0, c is 1 to 6, preferably 1 to 4, t 0 to 5, s is 1 to 3, k is 1 to 2, provided that(1) if (D) is a carbon, sulfur or sulfonyl, then a + b = 2 and k = 1,(2) if (D) is a phosphorus atom, it holds that a + b = 3 as long as c ≥ 1 and b = 1, where a = c + 1,(3) if (D) is a phosphorus atom, then k = 2, Y is a polyvalent species (Q)zD (= E), preferably - C (= NR) -, -SC (= NR) -, -SC (= O) -, (-NR) C (= O) -, (-NR) C (= S) -, - OC (= O) -, -OC (= S) -, -C (= O) -, -SC (= S) -, -C (= S) -, -S (= O) -, - S (= O)2-, -OS (= O)2-, (-NR) S (= O)2-, -SS (= O) -, -OS (= O) -, (NR) S (= O) -, -SS (= O)2-, (-S)2P (= O) -, - (- S) P (= O) -, -P (= O) (-)2, (-S)2P (= S) -, - (- S) P (= S) -, -P (= S) (-)2, (-NO)2P (= O) -, (-NR) (-S) P (= O) -, (-O) (-NR) P (= O) -, (-O) (-S) P (= O) -, (-O)2P (= O) -;- (- O) P (= O) -, - (- NR) P (= O) -, (-NR)2P (= S) -, (-NR) (-S) P (= S) -, (-O) (-NR) P (= S) -, (-O) (-S) P (= S) -, (-O)2P (= S) -, - (- O) P (= S) -, or - (- NR) P (= S) -, in each of these groups, the atom (D) is doubly linked to the heteroatom (E), which in turn is linked to the sulfur atom (S) linked to the silicon atom (Si) by a group (G), R1 independently of one another H, a straight, cyclic or branched alkyl chain, optionally alkyl chains which contain unsaturated moieties such as double bonds (alkenes), triple bonds (alkynes) or else alkylaromatics (aralkyl) or aromatics and which have the same meanings in equation (II), G independently of the other substituents, hydrogen, a straight, cyclic or branched alkyl chain with (C1-C18), optionally the alkyl chains may contain an unsaturated fraction, such as double bonds (alkenes), triple bonds (alkynes) or else alkylaromatics (aralkyl) or aromatics, when p = 0 in formula, G is preferably hydrogen (H), G does not correspond to the structure of an α, β-unsaturated fragment which is linked to the Y fragment in such a way that an α, β-unsaturated thiocarbonyl fragment is formed, X1, X2 and X3 each independently have the meaning as in formula (I). Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als Silan eine Organosiliziumverbindung der allgemeinen Formel (IV) oder (V)[[(ROC(=O))p-(G)j]k-Y-S]r-G-(SiX1X2X3)s[(X1X2X3Si)q-G]a-[Y-[S-G-SiX1X2X3]b]c verwendet, in der Y eine polyvalente Spezies (Q)zD(=E) darstellt, wobei folgendes gilt: p ist 0 bis 5, r ist 1 bis 3, z ist 0 bis 2;q ist 0 bis 6, a ist 0 bis 7, b ist 1 bis 3, j ist 0 bis 1, aber es kann, wenn p = 1 auch häufig 0 sein, c ist 1 bis 6, bevorzugt 1 bis 4, t ist 0 bis 5, s ist 1 bis 3, k ist 1 bis 2, unter der Vorraussetzung, daß (1) falls (D) ein Kohlenstoff, Schwefel oder Sulfonyl ist, gilt, daß a + b = 2 und k = 1,(2) falls (D) ein Phosphoratom ist, gilt, daß a + b = 3 solange c ≥ 1 und b = 1, wobei a = c + 1,(3) falls (D) ein Phosphoratom ist, gilt, daß k = 2, ist, Y eine polyvalente Spezies (Q)zD(=E) darstellt, bevorzugt - C(=NR)-, -SC(=NR)-, -SC(=O)-, (-NR)C(=O)-, (-NR)C(=S)-, - OC(=O)-, -OC(=S)-, -C(=O)-, -SC(=S)-, -C(=S)-, -S(=O)-, - S(=O)2-, -OS(=O)2-, (-NR)S(=O)2-, -SS(=O)-, -OS(=O)-, (NR)S(=O)-, -SS(=O)2-, (-S)2P(=O)-, -(-S)P(=O)-, -P(=O) (-)2, (-S)2P(=S)-, -(-S)P(=S)-, -P(=S)(-)2, (-NR)2P(=O)-, (-NR) (-S)P(=O)-, (-O) (-NR)P(=O)-, (-O) (-S)P(=O)-, (-O)2P(=O)-;-(-O)P(=O)-, -(-NR)P(=O)-, (-NR)2P(=S)-, (-NR) (-S)P(=S)-, (-O) (-NR)P(=S)-, (-O) (-S)P(=S)-, (-O)2P(=S)-, -(-O)P(=S)-, oder -(-NR)P(=S)-, in jeder dieser Gruppen ist das Atom (D) doppelt mit dem Heteroatom (E) verbunden, das wiederum mit dem Schwefelatom (S) verbunden ist, welches mittels einer Gruppe (G) mit dem Siliziumatom (Si) verknüpft ist, R1 unabhängig voneinander H, eine gerade, zyklische oder verzweigte Alkylkette bedeuten, gegebenenfalls Alkylketten die ungesättigte Anteile wie Doppelbindungen (Alkene), Dreifachbindungen (Alkine) oder auch Alkylaromaten (Aralkyl) oder Aromaten beinhalten und die die gleichen Bedeutungen in Gleichung (II) aufweisen, G unabhängig von den übrigen Substituenten, Wasserstoff, eine gerade, zyklische oder verzweigte Alkylkette mit (C1-C18) bedeuten, gegebenenfalls können die Alkylketten einen ungesättigten Anteil, wie Doppelbindungen (Alkene), Dreifachbindungen (Alkine) oder auch Alkylaromaten (Aralkyl) oder Aromaten beinhalten, wenn p = 0 in Formel ist, ist G vorzugsweise Wasserstoff (H), G entspricht nicht der Struktur eines α, β-ungesättigten Fragments, welches mit dem Y -Fragment in der Weise verbunden ist, daß ein α, β-ungesättigtes Thiocarbonylfragment entsteht, X1, X2 und X3 jeweils unabhängig voneinander die Bedeutung wie in Formel (I) besitzen.
- 23Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as silane an organosilicon compound of the general formula (VI)X1X2X3Si-A-Sub used, where X1, X2, X3 and A, each independently, have the meaning according to formula (I) and have -SH, -Cl, -Br, -I, -NH2, -NH (A-SiX1X2X3), -N (A-SiX1X2X3)2, - NH-CH2-CH2NH2, NH-CH2-CH2-NH-CH2-CH2NH2, NHEt, NEt2, NH (C4H9), OC (O) -C Me = CH2, O-CH2- (CH-O-CH2) or -SCN is. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als Silan eine Organosiliziumverbindung der allgemeinen Formel (VI)X1X2X3Si-A-Sub verwendet, wobei X1, X2, X3 und A, jeweils unabhängig voneinander, die Bedeutung gemäß Formel (I) haben und Sub -SH, -Cl, -Br, -I, -NH2, -NH(A-SiX1X2X3), -N(A-SiX1X2X3)2, - NH-CH2-CH2-NH2, NH-CH2-CH2-NH-CH2-CH2-NH2, NHEt, NEt2, NH(C4H9), O-C(O)-CMe=CH2, O-CH2- (CH-O-CH2) oder -SCN ist.
- 24Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or silicalite filler according to claim 23, characterized in that the silane of the formula (VI) (MeO)3Yourself2)3-SH, (EtO)3Yourself2)3-SH, (C3H7O)3Yourself2)3-SH, (MeO)3Yourself2)3-Cl, (EtO)3Yourself2)3-Cl, (C3H7O)3Yourself2)3-Cl, [(MeO)3Yourself2)3-]2NH, [(EtO)3Yourself2)3-]2NH, [(C3H7O)3Yourself2)3-]2NH, (MeO)3Yourself2)3NH2, (EtO)3Yourself2)3NH2, (C3H7O)3Yourself2)3NH2, (MeO)3Yourself2)3-NH- (CH2)2NH2, (EtO)3Yourself2)3-NH- (CH2)2NH2, (C3H7O)3Yourself2)3-NH- (CH2)2NH2, (MeO)3Yourself2)3-OC (O) -CMe = CH2, (EtO)3Yourself2)3-OC (O) -CMe = CH2, (C3H7O)3Yourself2)3-OC (O) -CMe = CH2, (MeO)3Yourself2)3-O-CH2- (CH-O-CH2), (EtO)3Yourself2)3-O-CH2- (CH-O-CH2), (C3H7O)3Yourself2)3-O-CH2- (CH-O-CH2), MeO)3Yourself2)3-SCN, (EtO)3Yourself2)3-SCN or (C3H7O)3Yourself2)3-SCN corresponds. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikalitischem Füllstoff nach Anspruch 23, dadurch gekennzeichnet, daß das Silan der Formel (VI) (MeO)3Si-(CH2)3-SH, (EtO)3Si-(CH2)3-SH, (C3H7O)3Si-(CH2)3-SH, (MeO)3Si-(CH2)3-Cl, (EtO)3Si-(CH2)3-Cl, (C3H7O)3Si-(CH2)3-Cl, [(MeO)3Si-(CH2)3-]2NH, [(EtO)3Si-(CH2)3-]2NH, [(C3H7O)3Si-(CH2)3-]2NH, (MeO)3Si-(CH2)3-NH2, (EtO)3Si-(CH2)3-NH2, (C3H7O)3Si-(CH2)3-NH2, (MeO)3Si-(CH2)3-NH-(CH2)2-NH2, (EtO)3Si-(CH2)3-NH-(CH2)2-NH2, (C3H7O)3Si-(CH2)3-NH-(CH2)2-NH2, (MeO)3Si-(CH2)3-O-C(O)-CMe=CH2, (EtO)3Si-(CH2)3-O-C(O)-CMe=CH2, (C3H7O)3Si-(CH2)3-O-C(O)-CMe=CH2, (MeO)3Si-(CH2)3-O-CH2-(CH-O-CH2), (EtO)3Si-(CH2)3-O-CH2-(CH-O-CH2), (C3H7O)3Si-(CH2)3-O-CH2-(CH-O-CH2), MeO)3Si-(CH2)3-SCN, (EtO)3Si-(CH2)3-SCN oder (C3H7O)3Si-(CH2)3-SCN entspricht.
- 25Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that one uses oligomers or cooligomers of the silanes of the formulas I-VI. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man Oligomere oder Cooligomere der Silane der Formeln I-VI verwendet.
- 26Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that the biopolymers, biooligomers, oxidic or siliceous filler is a natural and / or synthetic filler. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß der biopolymere, biooligomere, oxidische oder silikatische Füllstoff ein natürlicher und/oder synthetischer Füllstoff ist.
- 27Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that one or more substances from the group of kaolin, kieselguhr, mica, diatomaceous earth, clay, talc, wollastonite, silicates, inter alia in the form of glass fibers or glass fabrics, zeolites, aluminum oxide, aluminum hydroxide or trihydrate, as biopolymer, bio-oligomeric, oxidic or siliceous filler, Aluminum silicates, silicates, precipitated or pyrogenic silicic acids with BET surface areas (measured with gaseous nitrogen) from 1 to 1000 m2/ g, zinc oxide, boric oxide, magnesium oxide, natural or modified starch, cellulose, amylose, amylopectin, cellulose acetate, maltose, cellobiose, lactose, sucrose, raffinose, glycogen, pectin, chitin, natural or modified proteins or transition metal oxides. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß man als biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoff einen oder mehrere Stoffe aus der Gruppe Kaolin, Kieselgur, Mica, Diatomeenerden, Clay, Talkum, Wollastonit, Silikate unter anderem in Form von Glasfasern oder Glasgeweben, Zeolithe, Aluminiumoxid, Aluminiumhydroxid oder -trihydrat, Aluminiumsilikate, Silikate, gefällte oder pyrogene Kieselsäuren mit BET-Oberflächen (gemessen mit gasförmigem Stickstoff) von 1 bis 1000 m2/g, Zinkoxid, Boroxid, Magnesiumoxid, natürliche oder modifizierte Stärke, Cellulose, Amylose, Amylopectin, Celluloseacetat, Maltose, Cellobiose, Lactose, Saccharose, Raffinose, Glycogen, Pektinstoffe, Chitin, natürliche oder modifizierte Proteine oder Übergangsmetalloxide verwendet.
- 28Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 3, characterized in that as compressed gas carbon dioxide, helium, nitrogen, dinitrogen monoxide, sulfur hexafluoride, gaseous alkanes having 1 to 5 carbon atoms, gaseous alkenes having 2 to 4 carbon atoms, gaseous alkynes, gaseous dienes, gaseous fluorocarbons, chlorine and / or chlorofluorocarbons or their substitutes or ammonia, as well as mixtures of these substances. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 3, dadurch gekennzeichnet, daß als verdichtetes Gas Kohlendioxid, Helium, Stickstoff, Distickstoffmonoxid, Schwefelhexafluorid, gasförmige Alkane mit 1 bis 5 C-Atomen, gasförmige Alkene mit 2 bis 4 C-Atomen, gasförmige Alkine, gasförmige Diene, gasförmige Fluorkohlenwasserstoffe, Chlor und/oder Fluorchlorkohlenwasserstoffe oder deren Ersatzstoffe oder Ammoniak, sowie Gemische dieser Stoffe verwendet werden.
- 29Process for the preparation of silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 28, characterized in that the compressed gas is carbon dioxide. Verfahren zur Herstellung von silanmodifiziertem biopolymerem, biooligomerem, oxidischem oder silikatischem Füllstoff nach Anspruch 28, dadurch gekennzeichnet, daß das verdichtete Gas Kohlendioxid ist.
- 30Kautschukmischungen, dadurch gekennzeichnet, daß sie Kautschuk, den erfindungsgemäßen silanmodifizierten biopolymeren, biooligomeren, oxidischen oder silikatischen Füllstoff nach Anspruch 1, gegebenenfalls gefällte Kieselsäure und/oder Ruß und/oder weitere Kautschukhilfsmittel enthalten. Rubber compounds, characterized in that they contain rubber, the inventive silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler according to claim 1, optionally precipitated silica and / or carbon black and / or further rubber auxiliaries.
- 31Use of the rubber mixtures according to claim 30 for the production of moldings. Verwendung der Kautschukmischungen nach Anspruch 30 zur Herstellung von Formkörpern.
- 32Use of the rubber mixtures according to claim 30 for the production of pneumatic tires for passenger cars and trucks, tire treads for passenger cars and trucks, tire components for passenger cars and trucks, cable jackets, hoses, drive belts, conveyor belts, roller coverings, bicycle and motorcycle tires and their parts, shoe soles, Sealing rings, profiles and damping elements. Verwendung der Kautschukmischungen nach Anspruch 30 zur Herstellung von Luftreifen für Personen- und Lastkraftwagen, Reifenlaufflächen für Personen- und Lastkraftwagen, Reifenbestanteilen für Personen- und Lastkraftwagen, Kabelmänteln, Schläuchen, Treibriemen, Förderbändern, Walzenbelägen, Fahrrad- und Motorradreifen und deren Bestanteilen, Schuhsolen, Dichtungsringen, Profilen und Dämpfungselementen.
Independent claims32
122 paragraphs, as filed
The invention relates to a silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler, a process for its preparation and its use.
It is known to treat oxide or silicate compounds with organosilicon compounds in order to strengthen the bond between inorganic filler and the organic polymer used in filler-reinforced elastomers by this treatment and thus to improve the properties of the fillers in the polymers.
It is known from DE 2141159, DE 2212239 and US Pat. No. 3,978,103 that sulfur-containing organosilicon compounds, such as bis (3-triethoxysilylpropyl) tetrasulfane or 3-mercaptopropyltriethoxysilane, are used as silane coupling agent or reinforcing additive in oxide-filled rubber mixtures, inter alia for running surfaces and other parts of car tires ,
The use of mercaptosilanes in rubber compounds for tire treads is known from FR-A 152.094.859.
In order to address the significant processing problems, like pre-scorch, Scorch and plasticity behavior, to bypass mercaptosilanes is used as a coupling agent for tire parts mostly polysulfidic organosilanes, for example bis (3-triethoxysilylpropyl) tetrasulfane or bis (3-triethoxysilylpropyl) disulfane (DE 2542534, DE2405758, DE19541404, DE19734295) a compromise for silicic acid-filled vulcanizates in terms of vulcanization safety, represent simple production and amplification performance.
The introduction of the corresponding additives, especially the organosilanes and the unmodified fillers in the unvulcanized polymer mixtures can be done in different ways.
The in-situ process involves a common mixing of fillers, such as carbon black and silica, organosilanes and polymer.
The ex situ method involves modification of the filler with the appropriate organosilane or a mixture of different organosilanes before the filler is mixed with the polymer.
It is known that by dissolving the organosilicon compound in an organic solvent and then treating fillers, eg, clays, the filler surface can be modified (US Pat. No. 3,227,675).
The liquid dosage (US Pat. No. 3,997,356) or the dosage of the active filler via a preformed physical mixture of organosilane and filler plays a particularly important role today (DE 3314742, US Pat. No. 4,076,550). Disadvantages of these mixtures which have not been pretreated by heat treatment are the storage stability and thus the property stability of the products.
US Pat. No. 4,151,154 describes oxidic siliceous fillers whose surface is subjected to treatment with two different types of organosilicon compounds. The oxide particles are treated so that they show a greater affinity for water and can also be distributed more easily in aqueous systems.
From US-PS-35,67,680 the modification of water-suspended kaolin with various silanes is known. However, the described organosilicon compounds are water-soluble in the amounts necessary for the modification, so that in this case the treatment of the filler can take place from an aqueous solution.
US Pat. No. 4,044,037 describes aryl polysulfides and mineral fillers treated with these compounds, which are used in rubber mixtures. The preparation is carried out in an aqueous / alcoholic formulation containing 99.9 to 80 wt .-% alcohol.
Furthermore, EP-PS 01 26 871 discloses a process in which the surface of silicate fillers is modified by means of an aqueous emulsion of water-insoluble organosilicon compounds.
The known with silane ex-situ modified fillers have the disadvantage that the dynamic rubber properties are not the same or better but tend to be worse than in the in-situ mixed with each other fillers and silanes. In the case of fillers with a large, specific surface or a high surface structure, the impregnation is not homogeneous, but rather is usually limited to a thin surface layer and therefore unsatisfactory.
The known methods for modifying fillers for rubber and plastic applications with surface-active silanes or mixtures thereof are based on the use of water, organic solvents or the direct spraying of the organosilicon compound on the surface of the filler with a subsequent annealing reaction. The water-insoluble, rubber-typical silanes can only be converted into hydrocarbon-based solvents, which are mostly hazardous to health and highly flammable.
The object of the present invention is a silane-modified biopolymer, bio-oligomers, produce oxidic or siliceous filler, which has an improved coverage of the surface with the corresponding rubber-reactive silanes and therefore has comparable dynamic properties in rubber, as known, In situ produced silane filler mixtures and improved dynamic properties as known, ex situ produced silane filler blends, in rubber.
Another object of the present invention is to provide a method of modifying biopolymer, bio-oligomeric, oxidic or siliceous silane fillers wherein the modifying reaction is not conducted in water or organic solvent.
The invention provides a silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler obtainable by reacting at least one biopolymer, bio-oligomeric, oxidic or siliceous filler in a compressed gas with at least one silane. The silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler can have a BET surface area between 0.5 m<sup>2</sup>/ g and 500 m<sup>2</sup>/ g, preferably between 5 and 250 m<sup>2</sup>/ g, have.
The silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler may contain between 0.1 and 50.0% by weight, preferably between 1.0 and 25.0% by weight, more preferably between 1.0 and 9.0% by weight. -%, containing silane.
The silane may be chemically and / or physically linked to the surface of the fillers.
Another object of the invention is a process for the preparation of a silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler, which is characterized by reacting at least one biopolymer, bio-oligomeric, oxidic or siliceous filler in a compressed gas with at least one silane.
Silane can be an organosilicon compound of the general formula (I)<maths id="math0001" num="(I)"><math display="block"><mrow><msub><mrow><mtext>ZAS</mtext></mrow><mrow><mtext>x</mtext></mrow></msub><mtext>-AZ</mtext></mrow></math><img file="EP1256604A2_D0001.tif" /></maths> use in the x is a number from 1 to 12, preferably 1 to 8, particularly preferably 2 to 6, Z is SiX<sup>1</sup>X<sup>2</sup>X<sup>3</sup> is and X<sup>1</sup>, X<sup>2</sup>, X<sup>3</sup> each independently of one another can mean hydrogen (-H), Halogen or hydroxy (-OH), an alkyl substituent, preferably methyl or ethyl, alkenyl acid substituent, for example, acetoxy-R- (C = O) O-, or a substituted alkyl, or alkenyl acid, substituent, for example, oximato-R<sup>1</sup><sub>2</sub>C = NO-, a linear or branched hydrocarbon chain with 1-6 carbon atoms, a cycloalkane radical of 5-12 carbon atoms, a benzyl radical or a halogen- or alkyl-substituted phenyl radical, Alkoxy groups, preferably (C<sub>1</sub>-C<sub>4</sub>) Alkoxy, more preferably methoxy or ethoxy, with linear or branched hydrocarbon chains with (C<sub>1-6</sub>) Atoms, a cycloalkoxy group with (C<sub>5-12</sub>) Atoms, a halogen- or alkyl-substituted phenoxy group or a benzyloxy group, A (C<sub>1</sub>-C<sub>16</sub>), preferably (C<sub>1</sub>-C<sub>4</sub>), branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent hydrocarbon group.
A can be linear or branched and contain saturated as well as unsaturated bonds. A can be provided with various substituents, such as -CN, halogens, for example -Cl, -Br or -F, -OH, alkoxides -OR<sup>1</sup> or -O- (C = O) -R<sup>1</sup>, As A can preferably CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH (CH<sub>3</sub>), CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH (CH<sub>3</sub>), CH<sub>2</sub>CH (CH<sub>3</sub>) CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH (CH<sub>3</sub>) CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH (CH<sub>3</sub>) CH<sub>2</sub>, CH (CH<sub>3</sub>) CH<sub>2</sub>CH (CH<sub>3</sub>) or CH<sub>2</sub>CH (CH<sub>3</sub>) CH (CH<sub>3</sub>) be used.
As the silane of the general formula (I), for example, the following compounds can be used:<ul id="ul0001" list-style="none" compact="compact"><li>[(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>2</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>3</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>4</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>5</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>6</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>7</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>8th</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>9</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>10</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>11</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>12</sub>, [(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>2</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>3</sub>, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>4</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>5</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>6</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>7</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>8th</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>9</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>10</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>11</sub>, [(EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>12</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>2</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>3</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>4</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>5</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>6</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>7</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>8th</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>9</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>10</sub>, [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>11</sub> or [(C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>12</sub>,</li></ul>
As silane, compounds described in DE 198 44 607 can be used.
Silane can be an organosilicon compound of the general formula (II)<maths id="math0002" num="(II)"><math display="block"><mrow><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><msup><mrow><mtext>Si-AS-SiR</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>R</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>R</mtext></mrow><mrow><mtext>3</mtext></mrow></msup></mrow></math><img file="EP1256604A2_D0002.tif" /></maths> use in the X<sup>1</sup>, X<sup>2</sup>, X<sup>3</sup> and A independently of one another have the same meaning as in formula (I), R<sup>1</sup>, R<sup>2</sup>, R<sup>3</sup> are each independent of each other and (C<sub>1</sub>-C<sub>16</sub>) Alkyl, preferably (C<sub>1</sub>-C<sub>4</sub>) Alkyl, more preferably methyl and ethyl, (C<sub>1</sub>-C<sub>16</sub>) Alkoxy, preferably (C<sub>1</sub>-C<sub>4</sub>) Alkoxy, more preferably methoxy and ethoxy, (C<sub>1</sub>-C<sub>16</sub>) Haloalkyl, aryl, (C<sub>7</sub>-C<sub>16</sub>) Aralkyl, H, halogen or X<sup>1</sup>X<sup>2</sup>X<sup>3</sup>Si-AS- mean.
As the silane of the general formula (II), for example, the following compounds can be used:<ul id="ul0002" list-style="none" compact="compact"><li>(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S-Si (CH<sub>3</sub>)<sub>3</sub>, [(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>2</sub>Yourself<sub>3</sub>)<sub>2</sub>, [(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>3</sub>Yourself<sub>3</sub>), [(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>2</sub>Si (OEt)<sub>2</sub>, [(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>4</sub>Si, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S-Si (OEt)<sub>3</sub>, (MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S-Si (C<sub>2</sub>H<sub>5</sub>)<sub>3</sub>, [(MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>2</sub>Si (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>, [(MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>3</sub>Yourself<sub>3</sub>), [MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>2</sub>Si (OMe)<sub>2</sub>, [(MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S]<sub>4</sub>Si, (MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-S-Si (OMe)<sub>3</sub>, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>2</sub>-CH (CH<sub>3</sub>) -S-Si (CH<sub>3</sub>)<sub>3</sub>, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>2</sub>-CH (CH<sub>3</sub>) -S-Si (C<sub>2</sub>H<sub>5</sub>)<sub>3</sub>, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>2</sub>-CH (CH<sub>3</sub>) -S-Si (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> or (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>2</sub>(pC<sub>6</sub>H<sub>4</sub>) - S-Si (CH<sub>3</sub>)<sub>3</sub>,</li></ul>
Silane can be an organosilicon compound of the general formula (III)<maths id="math0003" num="(III)"><math display="block"><mrow><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><mtext>Si-Alk</mtext></mrow></math><img file="EP1256604A2_D0003.tif" /></maths> use in the X<sup>1</sup>, X<sup>2</sup>, X<sup>3</sup> each independently have the same meaning as in formula (I) and Alk is a straight, branched or cyclic (C<sub>1</sub>-C<sub>18</sub>) Alkyl, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl or tert-butyl, (C<sub>1</sub>-C<sub>5</sub>) Alkoxy, for example methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy or pentoxy, Halogen, for example fluorine, chlorine, bromine or iodine, hydroxy, thiol, nitrile, (C<sub>1</sub>-C<sub>4</sub>) Haloalkyl, -NO<sub>2</sub>, (C<sub>1</sub>-C<sub>8th</sub>) Thioalkyl, -NH<sub>2</sub>, -NHR<sup>1</sup>, -NO<sup>1</sup>R<sup>2</sup>, Alkenyl, allyl, vinyl, aryl or (C<sub>7</sub>-C<sub>16</sub>) Aralkyl is.
The term alkenyl may include the vinyl group and straight-chain, branched or cyclic fragments which may contain one or more carbon double bonds.
The term cyclic alkyl or alkenyl fragments may be monocyclic as well as bicyclic or polycyclic structures, as well as cyclic structures provided with alkyl substituents, for example norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, ethylcyclohexyl, ethylcyclohexenyl or cyclohexylcyclohexyl groups are to be summarized.
Aryl may be taken to mean phenyls, biphenyls or other benzoic compounds which may be combined with (C<sub>1</sub>-C<sub>3</sub>) Alkyl, (C<sub>1</sub>-C<sub>3</sub>) Alkoxy, halogen, hydroxy or with heteroatoms, such as NR<sup>1</sup>R<sup>2</sup>OR<sup>1</sup>, PR<sup>1</sup>R<sup>2</sup>R<sup>3</sup>, SH or SR<sup>1</sup> are substituted.
Aralkyls may be the aryls identified above that have a (C<sub>1</sub>-C<sub>6</sub>) Alkyl chain, which in turn with (C<sub>1</sub>-C<sub>3</sub>) Alkyl, (C<sub>1</sub>-C<sub>3</sub>) Alkoxy- or halogen-substituted, with the corresponding silicon atom or sulfur atom or are connected to both. If the aryl group has a heteroatom, such as O or S, the (C<sub>1</sub>-C<sub>6</sub>) Alkyl chain also have a compound via the heteroatom with the silicon atom and / or the sulfur atom.
As the silane of the general formula (III), for example, the following compounds can be used:<ul id="ul0003" list-style="none" compact="compact"><li>(EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-H, (MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>3</sub>-H, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>8th</sub>-H, (MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>8th</sub>-H, (EtO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>16</sub>-H, (MeO)<sub>3</sub>-Yourself<sub>2</sub>)<sub>16</sub>-H, (Me)<sub>3</sub>Si (OMe), ((Et)<sub>3</sub>Si (OMe), (C<sub>3</sub>H<sub>7</sub>)<sub>3</sub>Si (OMe), (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>Si (OMe), (Me)<sub>3</sub>Si (OEt), ((Et)<sub>3</sub>Si (OEt), (C<sub>3</sub>H<sub>7</sub>)<sub>3</sub>Si (OEt), (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>Si (OEt), (Me)<sub>3</sub>Si (OC<sub>3</sub>H<sub>7</sub>), ((Et)<sub>3</sub>Si (OC<sub>3</sub>H<sub>7</sub>), (C<sub>3</sub>H<sub>7</sub>)<sub>3</sub>Si (OC<sub>3</sub>H<sub>7</sub>), (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>Si (OC<sub>3</sub>H<sub>7</sub>), (Me)<sub>3</sub>SiCl, ((Et)<sub>3</sub>SiCl, (C<sub>3</sub>H<sub>7</sub>)<sub>3</sub>SiCl, (C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>SiCl, Cl<sub>3</sub>-Yourself<sub>2</sub>-CH = CH<sub>2</sub>, (MeO)<sub>3</sub>-Yourself<sub>2</sub>-CH = CH<sub>2</sub>, (EtO)<sub>3</sub>-Yourself<sub>2</sub>-CH = CH<sub>2</sub>, Cl<sub>3</sub>-Si-CH = CH<sub>2</sub>, (MeO)<sub>3</sub>-Si-CH = CH<sub>2</sub>, or (EtO)<sub>3</sub>-Si-CH = CH<sub>2</sub>,</li></ul>
Silane can be an organosilicon compound of general formula (IV) or (V)<maths id="math0004" num="(IV)"><math display="block"><mrow><msub><mrow><mtext>[[(ROC (= O))</mtext></mrow><mrow><mtext>p</mtext></mrow></msub><msub><mrow><mtext>-(G)</mtext></mrow><mrow><mtext>j</mtext></mrow></msub><msub><mrow><mtext>]</mtext></mrow><mrow><mtext>k</mtext></mrow></msub><msub><mrow><mtext>-ys]</mtext></mrow><mrow><mtext>r</mtext></mrow></msub><msup><mrow><mtext>-G- (SiX</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><msub><mrow><mtext>)</mtext></mrow><mrow><mtext>s</mtext></mrow></msub></mrow></math><img file="EP1256604A2_D0004.tif" /></maths><maths id="math0005" num="(V)"><math display="block"><mrow><msup><mrow><mtext>[(X</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><msub><mrow><mtext>Si)</mtext></mrow><mrow><mtext>q</mtext></mrow></msub><msub><mrow><mtext>-G]</mtext></mrow><mrow><mtext>a</mtext></mrow></msub><msup><mrow><mtext>- [Y [SG-SiX</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><msub><mrow><mtext>]</mtext></mrow><mrow><mtext>b</mtext></mrow></msub><msub><mrow><mtext>]</mtext></mrow><mrow><mtext>c</mtext></mrow></msub></mrow></math><img file="EP1256604A2_D0005.tif" /></maths> use, in the Y a polyvalent species (Q)<sub>z</sub>D (= E), where:<ul id="ul0004" list-style="none" compact="compact"><li>p is 0 to 5, r is 1 to 3, z is 0 to 2, q is 0 to 6, a is 0 to 7, b is 1 to 3, j is 0 to 1, but if p = 1 also frequently 0, c is 1 to 6, preferably 1 to 4, t is 0 to 5, s is 1 to 3, k is 1 to 2, with the proviso that<ul id="ul0005" list-style="none" compact="compact"><li>(1) if (D) is a carbon, sulfur or sulfonyl, then a + b = 2 and k = 1,</li><li>(2) if (D) is a phosphorus atom, it holds that a + b = 3 as long as c ≥ 1 and b = 1, where a = c + 1,</li><li>(3) if (D) is a phosphorus atom, then k = 2, Y is a polyvalent species (Q)<sub>z</sub>D (= E), preferably - C (= NR) -, -SC (= NR) -, -SC (= O) -, (-NR) C (= O) -, (-NR) C (= S) -, - OC (= O) -, -OC (= S) -, -C (= O) -, -SC (= S) -, -C (= S) -, -S (= O) -, - S (= O)<sub>2</sub>-, -OS (= O)<sub>2</sub>-, (-NR) S (= O)<sub>2</sub>-, -SS (= O) -, -OS (= O) -, (NR) S (= O) -, -SS (= O)<sub>2</sub>-, (-S)<sub>2</sub>P (= O) -, - (- S) P (= O) -, -P (= O) (-)<sub>2</sub>, (-S)<sub>2</sub>P (= S) -, - (- S) P (= S) -, -P (= S) (-)<sub>2</sub>, (-NO)<sub>2</sub>P (= O) -, (-NR) (-S) P (= O) -, (-O) (-NR) P (= O) -, (-O) (-S) P (= O) -, (-O)<sub>2</sub>P (= O) -, - (- O) P (= O) -, - (- NR) P (= O) -, (-NR)<sub>2</sub>P (= S) -, (-NR) (-S) P (= S) -, (-O) (-NR) P (= S) -, (-O) (-S) P (= S) -, (-O)<sub>2</sub>P (= S) -, - (- O) P (= S) -, or - (-NR) P (= S) -,</li></ul> in each of these groups, the atom (D) is doubly linked to the heteroatom (E), which in turn is linked to the sulfur atom (S) linked to the silicon atom (Si) by a group (G), R<sup>1</sup> independent of each other H, a straight, cyclic or branched alkyl chain, preferably (C<sub>1</sub>-C<sub>18</sub>) Alkyl, more preferably (C<sub>1</sub>-C<sub>4</sub>) Alkyl, optionally alkyl chains which contain unsaturated moieties such as double bonds (alkenes), triple bonds (alkynes) or else alkylaromatics (aralkyl) or aromatics and which have the same meanings as in formula (II), G independently of the other substituents, hydrogen, a straight, cyclic or branched alkyl chain with (C<sub>1</sub>-C<sub>18</sub>), optionally the alkyl chains can contain an unsaturated fraction, such as double bonds (alkenes), triple bonds (alkynes) or else alkylaromatics (aralkyl) or aromatics, when p = 0 in formula (IV), G is preferably hydrogen (H), G does not correspond to the structure of an α, β-unsaturated fragment linked to the Y fragment in such a way as to give an α, β-unsaturated thiocarbonyl fragment, X<sup>1</sup>, X<sup>2</sup> and X<sup>3</sup> each independently have the meaning as in formula (I).</li></ul>
An index p of 0 to 2 is preferred, where X<sup>1</sup>X<sup>2</sup> or X<sup>3</sup> an RO, for example, is RC (= O) O-. Particularly preferred is a fragment with p = 0, X.<sup>1</sup>, X<sup>2</sup> for example X<sup>3</sup> = Ethoxy and with G = alkyl skeleton or substituted alkyl skeleton with C<sub>3</sub> to C<sub>12</sub>, There can be at least one X not equal to -R<sup>1</sup> his.
In (Q)<sub>z</sub>D (= E) may be Q oxygen, sulfur or (-NR-), D may be carbon, sulfur, phosphorus or sulfonyl, E may be oxygen, sulfur or (= NR<sup>1</sup>) his.
Preferred examples of the function (-YS-) in the formulas (IV) and (V) are:<ul id="ul0006" list-style="none" compact="compact"><li>Thiocarboxylate ester -C (= O) -S-, dithiocarboxylate -C (= S) -S-, thiocarbonate ester -OC (= O) -S-, dithiocarbonate ester -SC (= O) -S- and -OC (= S) -S-, trithiocarbonate ester -SC (= S) -S-, dithiocarbamate ester -NC (= S) -S-, thiosulfonate ester -S (= O)<sub>2</sub>-S-, thiosulphate ester -OS (= O)<sub>2</sub>-S-, thiosulfamate ester (-N-) S (= O)<sub>2</sub>-S-, thiosulfinate ester -CS (= O) -S-, thiosulfite ester -OS (= O) -S-, thiosulfate ester NS (= O) -S-, thiophosphate ester P (= O) (O-)<sub>2</sub>(S-), dithiophosphate ester P (= O) (O-) (S-)<sub>2</sub> or P (= S) (O-)<sub>2</sub>(S-), trithiophosphate ester P (= O) (S-)<sub>3</sub> or P (= S) (O-) (S-)<sub>2</sub>, Tetrathiophosphate ester P (= S) (S-)<sub>3</sub>, Thiophosphate ester -P (= O) (- N -) (S-), dithiophosphamate ester -P (= S) (- N -) (S-, thiophosphoramidate ester (-N-) P (= O) (O -) ( S-), dithiophosphoramidate ester (-N-) P (= O) (S-)<sub>2</sub> or (-N-) P (= S) (O -) (S-) or trithiophosphoramidate ester (-N-) P (= S) (S-)<sub>2</sub>,</li></ul>
As the silane of the general formula (IV) or (V), for example, the following compounds can be used:<ul id="ul0007" list-style="none" compact="compact"><li>2-triethoxysilyl-1-ethyl thioacetate, 2-trimethoxysilyl-1-ethyl thioacetate, 2- (methyldimethoxysilyl) -1-ethyl thioacetate, 3-trimethoxysilyl-1-propyl, triethoxysilylmethyl thioacetate, trimethoxysilylmethyl thioacetate, triisopropoxysilylmethyl thioacetate, methyldiethoxysilylmethyl thioacetate, methyldimethoxysilylmethyl thioacetate, methyldiisopropoxysilylmethyl thioacetate, dimethylethoxysilylmethyl thioacetate, dimethylmethoxysilylmethyl thioacetate, dimethylisopropoxysilylmethyl thioacetate, 2-triisopropoxysilyl-1-ethyl thioacetate, 2- (methyldiethoxysilyl) -1-ethylthioacetate, 2- (methyldiisopropoxysilyl) -1-ethylthioacetate, 2- (dimethylethoxysilyl) -1-ethyl thioacetate, 2- (dimethylmethoxysilyl) -1-ethyl thioacetate, 2- (dimethylisopropoxysilyl) -1-ethyl thioacetate, 3-triethoxysilyl-1-propyl thioacetate, 3-triisopropoxysilyl-1-propyl thioacetate, 3-methyldiethoxysilyl-1-propyl thioacetate, 3-methyldimethoxysilyl-1-propyl thioacetate, 3-methyldiisopropoxysilyl-1-propyl thioacetate, 1- (2-triethoxysilyl-1-ethyl) -4-thioacetylcyclohexan, 1- (2-triethoxysilyl-1-ethyl) -3-thioacetylcyclohexan, 2-triethoxysilyl-5-thioacetylnorbomen, 2-triethoxysilyl-4-thioacetylnorbomen, 2- (2-triethoxysilyl-1-ethyl) -5-thioacetylnorbomen, 2- (2-triethoxysilyl-1-ethyl) -4-thioacetylnorbomen, 1- (1-oxo-2-thia-5-triethoxysilylphenyl) benzoic acid, 6-triethoxysilyl-1-hexyl thioacetate, 1-triethoxysilyl-5-hexyl thioacetate, 8-triethoxysilyl-1-octyl thioacetate, 1-triethoxysilyl-7-octyl thioacetate, 6-triethoxysilyl-1-hexyl thioacetate, 1-triethoxysilyl-5-octyl thioacetate, 8-trimethoxysilyl-1-octylt hioacetat, 1-trimethoxysilyl-7-octyl thioacetate, 10-triethoxysilyl-1-decyl thioacetate, 1-triethoxysilyl-9-decyl thioacetate, 1-triethoxysilyl-2-butyl thioacetate, 1-triethoxysilyl-3-butyl thioacetate, 1-triethoxysilyl-3-methyl-2-butyl thioacetate, 1-triethoxysilyl-3-methyl-3-butyl thioacetate, 3-trimethoxysilyl-1-propyl thiooctoate, 3-triethoxysilyl-1-propyl thiopalmitate, 3-triethoxysilyl-1-propyl thiooctoate, 3-triethoxysilyl-1-propyl thiobenzoate, 3-triethoxysilyl-1-propylthio-2-ethylhexanoate, 3 -Methyldiacetoxysilyl-1-propyl thioacetate, 3-triacetoxysilyl-1-propylthioacetate, 2-methyldiacetoxysilyl-1-ethyl thioacetate, 2-triacetoxysilyl-1-ethyl thioacetate, 1 -Methyldiacetoxysilyl-1-ethylthioacetate or 1 -triacetoxysilyl-1-ethylthioacetate.</li></ul>
Silane can be an organosilicon compound of the general formula (VI)<maths id="math0006" num="(VI)"><math display="block"><mrow><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>1</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>2</mtext></mrow></msup><msup><mrow><mtext>X</mtext></mrow><mrow><mtext>3</mtext></mrow></msup><mtext>Si-A-Sub</mtext></mrow></math><img file="EP1256604A2_D0006.tif" /></maths> use, where X<sup>1</sup>, X<sup>2</sup>, X<sup>3</sup> and A, each independently, have the meaning according to formula (I) and have -SH, -Cl, -Br, -I, -NH<sub>2</sub>, -NH (A-SiX<sup>1</sup>X<sup>2</sup>X<sup>3</sup>), -N (A-SiX<sup>1</sup>X<sup>2</sup>X<sup>3</sup>)<sub>2</sub>, -NH-CH<sub>2</sub>-CH<sub>2</sub>NH<sub>2</sub>, NH-CH<sub>2</sub>-CH<sub>2</sub>-NH-CH<sub>2</sub>-CH<sub>2</sub>NH<sub>2</sub>, NHEt, NEt<sub>2</sub>, NH (C<sub>4</sub>H<sub>9</sub>), OC (O) -C Me = CH<sub>2</sub>, O-CH<sub>2</sub>- (CH<u>-O-</u>CH<sub>2</sub>) (DS Glymo) or -SCN.
As the silane of the general formula (VI), for example, the following compounds can be used:<ul id="ul0008" list-style="none" compact="compact"><li>(MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-Cl, (MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SH, (MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>NH<sub>2</sub>, (MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SCN, (MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-OC (O) CMe = CH<sub>2</sub>, (MeO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-O-CH<sub>2</sub>- (CH<u>-O-</u>CH<sub>2</sub>), (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-Cl, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>NH<sub>2</sub>, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SH, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SCN, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-OC (O) CMe = CH<sub>2</sub>, (EtO)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-O-CH<sub>2</sub>- (CH<u>-O-</u>CH<sub>2</sub>), (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-Cl, (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SH, (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-SCN, (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-OC (O) CMe = CH<sub>2</sub>, or (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3 <</sub>> NH<sub>2</sub>, (C<sub>3</sub>H<sub>7</sub>O)<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>-O-CH<sub>2</sub>- (CH<u>-O-</u>CH<sub>2</sub>)</li></ul>
As silane it is possible to use oligomers of the organosilicon compounds of the general formula (I) - (VI). The oligomers can be prepared by oligomerization or co-oligomerization.
Oligomeric silanes are described, for example, in EP 652 245 B1, EP 0 700 951 B1, EP 0 978 525 A2 and DE 199 29 021 A1.
As silane compounds for modifying fillers it is also possible to use mixtures of silanes, for example mixtures of the silanes of the general formula I-VI or mixtures of the oligomeric or polymeric siloxanes of silanes of the general formula I-VI or mixtures of silanes of the general formula I-VI Mixtures of the oligomeric or polymeric siloxanes of silanes of the general formula I-VI.
As a biopolymer, bio-oligomeric, oxidic or siliceous filler, a natural and / or synthetic filler can be used.
The biopolymer, bio-oligomeric, oxide or siliceous filler may be -OH or -O-acetate, for example -OC (O) -CH<sub>3</sub>Contain surface groups capable of reacting with the reactive groups of the silanes used, preferably their alkoxy groups.
The biopolymer, bio-oligomeric, oxidic or siliceous filler may be compatible with the rubbers and have the fineness and reinforcing effect in the polymer matrix necessary for this use.
As the biopolymer or bio-oligomeric filler, natural or modified starch, cellulose, amylose, amylopectin, cellulose acetate, maltose, cellobiose, lactose, sucrose, raffinose, glycogen, pectin, chitin or natural or modified proteins may be used.
Silicate, for example kaolin, mica, diatomaceous earth, diatomaceous earth, talc, wollastonite or clay or silicates, inter alia in the form of glass fibers or glass fabrics, can be used as the natural, siliceous filler.
As oxidic fillers, almost all kinds of oxides, for example, alumina, aluminum hydroxide or trihydrate, zinc oxide, boron oxides, magnesium oxides, or transition metal oxides such as titanium dioxide can be used.
Furthermore, aluminum silicates, silicates, zeolites, precipitated or pyrogenic silicas having BET surface areas (measured with gaseous nitrogen) of from 1 to 1000 m can be used as the oxidic or siliceous filler<sup>2</sup>/ g, preferably up to 300 m<sup>2</sup>/ g.
For example, the precipitated silicas marketed by Degussa-Hüls AG under the trade name Ultrasil (Ultrasil 7000 GR, Ultrasil VN 3, Ultrasil VN 3 GR, Ultrasil VN 2 and Ultrasil VN 2 GR) and those of PPG Industries Inc. distributed silicic acids of the Hisil series (Hi-Sil® 195G, Hi-Sil® 190G, Hi-Sil® 170G, Hi-Sil® 255G, Hi-Sil® EZ, Hi-Sil® 243LD, Hi-Sil® 233, Hi- Sil® 315) and the products of the Zeosil series marketed by Rhodia, for example Zeosil 115 Gr, Zeosil 125 Gr, Zeosil 145 Gr, Zeosil 165 Gr, Zeosil 175 Gr, Zeosil 195 Gr, Zeosil 215 Gr. The same applies to silicas of other manufacturers which have similar properties, for example product characteristics, or have analytical data such as the abovementioned silicic acids.
As the compressed gas, compounds which are gaseous under normal temperature and pressure conditions and suitable as a carrier fluid for the silanes can be used. For example, carbon dioxide, Helium, Nitrogen, nitrous oxide, Sulfur hexafluoride, gaseous alkanes having 1 to 5 C atoms (methane, Ethan, Propane, n-butane, isobutane, Neopentane) gaseous alkenes having 2 to 4 C atoms (ethylene, propylene, Butene) gaseous alkynes (acetylene, Propyne and butyne-1), gaseous dienes (propadiene), gaseous fluorocarbons, Chloro- and / or chlorofluorocarbons (Freons, CKC, HCFC) or their substitutes or ammonia used under current legislation, and mixtures of these substances are used.
Preferably, carbon dioxide can be used as the compressed gas because it is non-toxic, non-combustible, less reactive and inexpensive. In addition, the required supercritical conditions can be easily achieved, because the critical pressure or the critical temperature are 73 bar and 31 ° C. In addition, the compressed carbon dioxide used as compressed gas may have a bacteriostatic effect.
Compressed gases can be defined according to E.Stahl, KWQuirin, D.Gerard, "Compressed Gases for Extraction and Refining", Springer-Verlag, page 12-13. Compressed gases can be supercritical gases, critical gases or gases in the liquefied state.
The compressed gas is extremely advantageous for this particular application. Due to the high solubility and diffusivity, the low viscosity and the ability specifically silanes or silane oligomers to allow high rates of diffusion in the compressed gas, so that a substance can be deposited in the interstices of the microporous substrate, they are excellent for impregnating microporous solids with monomeric or oligomeric substances. The silanes can be transported into the pores and channels of the porous fillers by the compressed gas after the application. On the other hand, compressed gases, since they are gaseous under normal conditions, can easily be separated from it after the treatment of the filler and, especially in the case of carbon dioxide, have hardly any potential for the environment because they can be absorbed in the natural carbon cycle or can easily be recycled.
The compressed gas may be pressurized in an airtight space or container containing the material to be treated. During this process, the pressure, generally from atmospheric pressure, to the working pressure of the process according to the invention can be increased.
First, one can bring the biopolymer, bio-oligomeric, oxidic or siliceous filler in contact with a liquid which consists of the pure solvent, more specifically the gas potentially transformed into the compressed state, or of an already prepared solution of the silane in the aforementioned gas, the subsequently brought into the compressed state. This contact can be made, for example, in a container or in a hermetically sealed room into which the unmodified filler and the silane-containing gas matrix are introduced. By "contacting" it can be understood that said material is immersed in and wetted and covered by the impregnating liquid, preferably that the biopolymer, bio-oligomeric, oxidic or siliceous filler is fully immersed or that all outer and inner surfaces of the biopolymers, biooligomers, oxidic or siliceous filler with the silane-containing impregnating liquid in contact.
In the method according to the invention, the pressure, which is also called working pressure, generally between 1 and 500 bar, preferably between 1 and 400 bar, more preferably between 1 and 300 bar, be.
The temperature (working temperature) at which the process can be carried out is between 0 and 300 ° C, preferably between 0 and 200 ° C, more preferably between 10 and 120 ° C.
The solubility of the silane in the compressed gas may be dependent on the nature thereof, the pressure and the temperature; it can also be modulated and optimized by, above all, modifying the last two parameters to adjust the physical properties of the silane-containing impregnating mixture. In some cases, the concentration of silane in the solution used as the reaction medium can affect the efficacy of the treatment.
The reaction can be carried out in a typical reaction vessel for high temperature / high pressure reactions or high pressure extraction.
The pressure may be maintained constant during the modification at different pressure levels for periods of 5-720 minutes, preferably 5-240 minutes, more preferably 5-30 minutes, and the filler may be submerged, infiltrated, or flowed through the compressed gas during this time to be stirred in this.
The biopolymer, bio-oligomeric, oxidic or siliceous filler and silane can be continuously circulated with a suitable agitator. In this case, the stirring speed of the prevailing temperature and the prevailing pressure can be adjusted.
Stirrers, blade stirrers, bar stirrers, perforated bar stirrers, crossbar stirrers, anchor stirrers, lattice stirrers, blade rollers, propeller stirrers, screw stirrers, turbine stirrers, disk stirrers, planetary stirrers, centrifugal mixers or impeller stirrers can be used as stirrer.
The agitator can operate with 1-200 revolutions, strokes or revolutions per minute.
The silanes used may be undissolved, partially or completely dissolved in the compressed gas.
The biopolymer, bio-oligomeric, oxide or siliceous filler and silane may first be mixed or contacted and then mixed with the compressed gas.
The biopolymer, bio-oligomeric, oxidic or siliceous filler can only be mixed with the gas present in the compressed state, or brought into contact and only then mixed with the silane.
The silane can first be mixed or brought into contact with the gas present in the compressed state and only then mixed with the corresponding biopolymer, bio-oligomeric, oxidic or siliceous filler.
Subsequent to surface modification, the silane-modified biopolymer, bio-oligomeric, oxide or siliceous filler may comprise an evacuation or relaxation step with separation of the compressed gas from the final product.
The evacuation or relaxation step can be done in less than 10 minutes.
The evacuation or relaxation stage can be carried out in a time between 10 minutes and 180 minutes, preferably between 10 minutes and 120 minutes, more preferably between 10 minutes and 60 minutes.
The evacuation or relaxation step can be carried out at temperatures between 1 and 300 ° C, preferably between 1 and 100 ° C, more preferably between 50 and 100 ° C, and most preferably at temperatures between 70-100 ° C.
Another object of the invention are rubber mixtures, which are characterized in that they contain rubber, the inventive silane-modified biopolymer, bio-oligomeric, oxidic or siliceous filler, optionally precipitated silica and / or carbon black and / or other rubber auxiliaries.
For the production of rubber mixtures according to the invention, natural rubber or synthetic rubbers can be used. Preferred synthetic rubbers are, for example, W. Hofmann, rubber technology, Genter Verlag, Stuttgart 1980, described. They include, inter alia, polybutadiene (BR), polyisoprene (IR), styrene / butadiene copolymers having styrene contents of 1 to 60, preferably 5 to 50 wt .-% (E or S-SBR), isobutylene / isoprene copolymers (IIR ), Butadiene / acrylonitrile copolymers having acrylonitrile contents of 5 to 60, preferably 10 to 50 wt. % (NBR), ethylene / propylene / diene copolymers (EPDM), as well as mixtures of these rubbers.
The rubber mixtures according to the invention may contain other rubber auxiliary products, such as reaction accelerators, retardants, aging inhibitors, stabilizers, processing aids, plasticizers, waxes, metal oxides and activators, such as triethanolamine, polyethylene glycol or hexanetriol, and other rubber auxiliary products known to the rubber industry.
The rubber auxiliaries can be used in customary amounts, which depend inter alia on the intended use. Typical amounts are, for example, amounts of from 0.1 to 50% by weight, based on rubber.
Crosslinkers which can be used are sulfur, organic sulfur donors or free-radical formers. The rubber mixtures according to the invention may additionally contain vulcanization accelerators.
Examples of suitable vulcanization accelerators are mercaptobenzothiazoles, sulfenamides, guanidines, thiurams, dithiocarbamates, thioureas and thiocarbonates.
The vulcanization accelerators and crosslinkers can be used in amounts of 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on rubber.
The blending of the rubbers with the filler according to the invention, if appropriate with precipitated silica and / or carbon black and / or further rubber auxiliaries, can be carried out in customary mixing units, such as rollers, internal mixers and mixing extruders. Customarily, such rubber mixtures can be prepared in internal mixers, the rubbers, the filler according to the invention, optionally the precipitated silica and / or carbon black and / or further rubber auxiliaries being mixed in at 100 to 170 ° C. first in one or more successive thermomechanical mixing stages. The order of addition and the time of addition of the individual components can have a decisive effect on the mixture properties obtained. The rubber mixture thus obtained can then be mixed in known manner in an internal mixer or on a roller at 40-110 ° C with the crosslinking chemicals and processed to form the so-called raw mixture for the subsequent process steps, such as molding and vulcanization.
The vulcanization of the rubber mixtures according to the invention can be carried out at temperatures of 80 to 200 ° C, preferably 130 to 180 ° C, optionally under pressure of 10 to 200 bar.
The rubber mixtures according to the invention are suitable for the production of moldings from rubber, for example, for the production of pneumatic tires for passenger cars and trucks, Tire treads for passenger cars and trucks, Tire components for passenger cars and trucks, like sidewall, Inner liner and undertread, Cable sheathing, hoses, Drive belts, conveyor belts, Roll coverings, Bicycle and motorcycle tires and their parts, Shoe soles, Sealing rings, Profiles and damping elements.
The silane-modified biopolymer, bio-oligomeric, oxidic or siliceous fillers according to the invention have the advantage of a high level of compatibility with purely physical mixtures, for example of bis (3-triethoxysilylpropyl) tetrasulfane with silicic acid, as are known, for example, from US Pat. No. 4,076,550 Storage stability and thus performance stability.
Compared with the in situ process used in the rubber industry for years and the necessary untreated filler, the inventive silane-modified biopolymers, bio-oligomers, oxidic or siliceous fillers have the advantages of a low water content of the treated filler, a lower moisture absorption, and a higher ramming weight and a higher bulk density over the untreated filler. Compared with known silane-modified fillers, they are distinguished by better storage stability, better dispersion in the rubber and, moreover, by a better processing behavior for the user in the rubber processing industry (homogeneous mixture production, saving of mixing stages and mixing times).
While the in-situ mixing process requires a chemical reaction that requires optimal process control, and the silanization reaction liberates significant amounts of alcohol that escape from the mixture, causing problems in the exhaust air, it does so avoided when using the fillers of the invention.
Examples:
Examples of the preparation of a filler according to the invention:
Inventive Filler Example A:
1500 g Ultrasil VN3 are filled in a drum mixer (4 installations with a height of 7 cm). The drum is rotated on a roll stand at an angle of 18 ° with 20 rpm. Within 55 minutes, 120 g of Si 69 (8 phf) are sprayed through a 6 cm hole in the drum lid by means of a commercially available manual spray pump. Subsequently, a follow-up time of the drum of 5 min is maintained.
130 The silicic acid pre-loaded with Si 69 is then filled into the 600 ml feed tank of a high pressure extraction autoclave preheated to 70 ° C. The pressure is released by pumping CO<sub>2</sub> slowly increased to 150 bar. After standing for 15 minutes, the temperature is raised to 100 ° C. by the jacket heating of the autoclave. At 100 ° C and 200 bar, the system is kept constant for one hour. Then the pressure is slowly lowered to 80 bar. At 80 bar and 100 ° C for 25 min with 1.2 kg of CO<sub>2</sub> extracted. Finally, at 300 bar and 80 ° C with 0.5 kg of CO<sub>2</sub> extracted for 30 min.
Subsequently, the system is relaxed and removed the finished filler.
Inventive filler Example B:
2000 g Ultrasil VN3 are dried in a convection oven at 105 ° C for 2 h. 1500 g of the dried Ultrasil VN3 are poured into a drum mixer (4 installations with a height of 7 cm). The drum is rotated on a roll stand at an angle of 18 ° with 20 rpm. Within 55 minutes, 120 g of Si 69 (8 phf) are sprayed through a 6 cm hole in the drum lid by means of a commercially available manual spray pump. Subsequently, a follow-up time of the drum of 5 min is maintained.
130 The silicic acid pre-loaded with Si 69 is then filled into the 600 ml feed tank of a high pressure extraction autoclave preheated to 70 ° C. The pressure is released by pumping CO<sub>2</sub> slowly increased to 150 bar. After standing for 15 minutes, the temperature is raised to 100 ° C. by the jacket heating of the autoclave. At 100 ° C and 200 bar, the system is kept constant for one hour. Then the pressure is slowly lowered to 80 bar. At 80 bar and 100 ° C for 25 min with 1.2 kg of CO<sub>2</sub> extracted. Finally, at 300 bar and 80 ° C with 0.5 kg of CO<sub>2</sub> extracted for 30 min. Subsequently, the system is relaxed and removed the finished filler.
Inventive filler Example C:
Into a 15 l steel autoclave with magnetically coupled stirrer, 1650 g of the powder of a precipitated silica Ultrasil VN3 and 132 g (8 phf) of Si69 are added. Subsequently, with CO<sub>2</sub> and a jacket heating an autoclave pressure of 155 bar at a temperature of 90 ° C set. The mixture is left for 1 hour at 90 ° C and 155 bar. The sample is then decompressed to atmospheric pressure while cooling. There is obtained a finely powdered, colorless filler which can be used without special workup.
Based on the in rubber, rubber, plastics 51, (1998) 525 by Hunsche et al. described in the operating procedure, the residual alcohol (ethanol) present on the filler is determined as follows:<ul id="ul0009" list-style="none" compact="compact"><li>In a glass ampoule, which is provided after filling with a tight-fitting cap, 1 g of the filler according to the invention with 10 ml of diethylene glycol monobutyl ether (DEGMBE) and 0.3 ml of 0.5 mol H<sub>2</sub>SO<sub>4</sub> added. The mixture is mixed for 20 min at 60 ° C in a water bath in the glass ampoule. Subsequently, 10 ml of decane are added to the rapidly heated to 25 ° C mixture. From the organic phase are then corresponding amounts for HPLC analysis (HPLC device with Jasco Autosampler 851-AS, pump Jasco PU 980, RI detector 7515A, TiO<sub>2</sub>Column, 250x4.5 mm, 5 μm, YMC; mobile phase: DEGMBE with cyclohexane; Temperature 25 ° C) was removed on ethanol.</li></ul>
For example, it can be shown that from originally 6 equivalents of ethanol per molecule Si69 ([(C<sub>2</sub>H<sub>5</sub>)O]<sub>3</sub>Yourself<sub>2</sub>)<sub>3</sub>]<sub>2</sub>S<sub>4</sub>) in the inventive filler Example C only 0.71 equivalents of ethanol are present. The silane has attached to the silica surface, releasing 5.29 equivalents of ethanol and forming Si-O-Si bonds to the silica surface. The analytical values of the fillers according to the invention are shown in Table 1.
The tamped density is determined according to DIN EN 787-11.
The samples are dried for 15-20 h at 105 ° C and the BET surface area determined according to DIN 66131 (volumetric method).
The samples are dried for 15-20 h at 105 ° C and the Mesoporenverteilung determined by the BJH method based on DIN 66134.
The macro pore volume (pores with widths> 30 or > 50 nm) with a mercury porosimeter Autopore II 9220 (Fa. Micromeritics) determined in accordance with the generally known rules and operating instructions in the range up to 400 microns. The samples are previously dried for 15-20 h at 105 ° C. The method is used to determine the pore volume and the pore distribution of porous solids by measuring the volume of mercury injected under increasing pressure according to the method of Ritter and Drake according to DIN 66133.
The pore maxima for meso and macropores can be read directly from the corresponding diagrams (cumulative intrusion volume (ml / g) or log differential pore volume dV / dlog D) for the pore volume distribution (ml / g) as a function of pore diameter (μm).<tables id="tabl0001" num="0001"><img file="EP1256604A2_D0007.tif" /></tables>
The coupling reagent Si 69 is a bis (triethoxysilylpropyl) tetrasulfane from Degussa AG. Ultrasil VN3 is a precipitated silica from Degussa AG with a BET surface area of 170 m<sup>2</sup>/G. The presilanized silica VP Coupsil 8108 is available from Degussa AG as a trial product. This is a silica comparable to Ultrasil 7000 GR with a BET surface area of 175 m<sup>2</sup>/ g, which is presilanized with 8% Si 69.
rubber compounds
The recipe used for the rubber compounds is given in Table 2 below. The unit phr means parts by weight, based on 100 parts of the raw rubber used. The general process for preparing rubber blends and their vulcanizates is described in the following book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994.<tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" rowsep="0" align="left">substance</entry><entry namest="col2" nameend="col2" align="center">Mixture A / C</entry><entry namest="col3" nameend="col3" rowsep="0" align="center">Mixture B</entry><entry namest="col4" nameend="col4" align="center">Mixture D</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" rowsep="0" /><entry namest="col2" nameend="col2" align="center">In-situ</entry><entry namest="col3" nameend="col3" rowsep="0" /><entry namest="col4" nameend="col4" rowsep="0" align="center">reference</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" rowsep="0" /><entry namest="col2" nameend="col2" align="center">reference</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">[Phr]</entry><entry namest="col3" nameend="col3" align="center">[Phr]</entry><entry namest="col4" nameend="col4" align="center">[Phr]</entry></row><row rowsep="1"><entry namest="col1" nameend="col4" align="left"><b>1. step</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Buna VSL 5025-1</entry><entry namest="col2" nameend="col2" align="center">96</entry><entry namest="col3" nameend="col3" align="center">96</entry><entry namest="col4" nameend="col4" align="center">96</entry></row><row><entry namest="col1" nameend="col1" align="left">Buna CB 24</entry><entry namest="col2" nameend="col2" align="center">30</entry><entry namest="col3" nameend="col3" align="center">30</entry><entry namest="col4" nameend="col4" align="center">30</entry></row><row><entry namest="col1" nameend="col1" align="left">Ultrasil 7000 GR</entry><entry namest="col2" nameend="col2" align="center">80</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Inventive vorsilanii</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Silica Example C</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">83</entry><entry namest="col4" nameend="col4" align="center">-</entry></row><row><entry namest="col1" nameend="col1" align="left">VP Coupsil 8108</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="center">83</entry></row><row><entry namest="col1" nameend="col1" align="left">ZnO</entry><entry namest="col2" nameend="col2" align="center">3</entry><entry namest="col3" nameend="col3" align="center">3</entry><entry namest="col4" nameend="col4" align="center">3</entry></row><row><entry namest="col1" nameend="col1" align="left">stearic acid</entry><entry namest="col2" nameend="col2" align="center">2</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">2</entry></row><row><entry namest="col1" nameend="col1" align="left">Naftolen ZD</entry><entry namest="col2" nameend="col2" align="center">10</entry><entry namest="col3" nameend="col3" align="center">10</entry><entry namest="col4" nameend="col4" align="center">10</entry></row><row><entry namest="col1" nameend="col1" align="left">Vulcanox 4020</entry><entry namest="col2" nameend="col2" align="center">1.5</entry><entry namest="col3" nameend="col3" align="center">1.5</entry><entry namest="col4" nameend="col4" align="center">1.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Protector G35P</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="center">1</entry><entry namest="col4" nameend="col4" align="center">1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Si 69</entry><entry namest="col2" nameend="col2" align="center">6.4</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="center">-</entry></row></tbody></tgroup><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="left"><b>Second step</b></entry></row></thead><tbody valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="left">Batch level 1</entry></row></tbody></tgroup><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="left"><b>Third step</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Batch level 2</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Vulkacit D</entry><entry namest="col2" nameend="col2" align="center">2</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">2</entry></row><row><entry namest="col1" nameend="col1" align="left">Vulkacit CZ</entry><entry namest="col2" nameend="col2" align="center">1.5</entry><entry namest="col3" nameend="col3" align="center">1.5</entry><entry namest="col4" nameend="col4" align="center">1.5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">sulfur</entry><entry namest="col2" nameend="col2" align="center">1.5</entry><entry namest="col3" nameend="col3" align="center">1.5</entry><entry namest="col4" nameend="col4" align="center">1.5</entry></row></tbody></tgroup></table></tables>
The polymer VSL 5025-1 is a polymerized in solution SBR copolymer of Bayer AG with a styrene content of 25 wt .-% and a butadiene content of 75 wt .-%. Of the butadiene, 73% are 1,2, 10% cis 1,4 and 17% trans 1,4 linked. The copolymer contains 37.5 phr of 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 97%, a trans 1,4 content of 2%, a 1,2- Content of 1% and a Mooney viscosity of 44 ± 5.
The aromatic oil used is Naftolen ZD Chemetall. Vulkanox 4020 is 6PPD from Bayer AG and protector G35P is an ozone protection wax from HB-Fuller GmbH. Vulkacit D (DPG) and Vulkacit CZ (CBS) are commercial products of Bayer AG.
Ultrasil 7000 GR is an easily dispersible precipitated silica from Degussa AG with a BET surface area of 175 m<sup>2</sup>/G.
The rubber mixtures are prepared in an internal mixer according to the mixing instructions in Table 3.<tables id="tabl0003" num="0003"><img file="EP1256604A2_D0008.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP1256604A2_D0009.tif" /></tables>
Table 4 summarizes the methods for rubber testing. <tables id="tabl0005" num="0005"><table frame="all"><title>Table 4</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Physical testing</entry><entry namest="col2" nameend="col2" align="left">Standard / conditions</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">ML 1 + 4, 100 ° C, 3rd stage</entry><entry namest="col2" nameend="col2" align="left">DIN 53523/3, ISO 667</entry></row><row><entry namest="col1" nameend="col1" align="left">Vulcameter test, 165 ° C</entry><entry namest="col2" nameend="col2" align="left">DIN 53529/3, ISO 6502</entry></row><row><entry namest="col1" nameend="col1" align="left"> Dmax - Dmin [dNm]</entry><entry namest="col2" nameend="col2" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left"> t10% and t90% [min]</entry><entry namest="col2" nameend="col2" /></row><row><entry namest="col1" nameend="col1" align="left">Tensile test on the ring, 23 ° C</entry><entry namest="col2" nameend="col2" align="left">DIN 53504, ISO 37</entry></row><row><entry namest="col1" nameend="col1" align="left"> Tensile strength [MPa]</entry><entry namest="col2" nameend="col2" /></row><row><entry namest="col1" nameend="col1" align="left"> Voltage values [MPa]</entry><entry namest="col2" nameend="col2" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left"> Elongation at break [%]</entry><entry namest="col2" nameend="col2" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Shore A hardness, 23 ° C [SH]</entry><entry namest="col2" nameend="col2" align="left">DIN 53 505</entry></row><row><entry namest="col1" nameend="col1" align="left">Viscoelastic properties,</entry><entry namest="col2" nameend="col2" align="left">DIN 53 513, ISO 2856</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">0 and 60 ° C, 16 Hz, 50 N pre-load and 25 N amplitude force Dynamic module E * [MPa] Loss factor tan δ []</entry><entry namest="col2" nameend="col2" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Ball Rebound, 23 ° C, 60 ° C [%]</entry><entry namest="col2" nameend="col2" align="left">ASTM D 5308</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">DIN abrasion, 10 N force [mm<sup>3</sup>]</entry><entry namest="col2" nameend="col2" align="left">DIN 53 516</entry></row></tbody></tgroup></table></tables>
example 1
In Example 1, the in situ mixed reference mixture (A) is compared with 6.4 phr of the coupling reagent Si 69 against the mixture (B) with the silane-modified silica according to the invention. The formulations used for blends (A) and (B) are listed in Table 2 and the blending recipe used is shown in Table 3. The results of the rubber technical examination are summarized in Table 5.<tables id="tabl0006" num="0006"><table frame="all"><title>Table 5:</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col4" align="center">Results Example 1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>mixture</b></entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="left"><b>(A)</b></entry><entry namest="col4" nameend="col4" align="left"><b>(B)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">ML (1 + 4)</entry><entry namest="col2" nameend="col2" align="left">[ME]</entry><entry namest="col3" nameend="col3" align="left">63</entry><entry namest="col4" nameend="col4" align="left">67</entry></row><row><entry namest="col1" nameend="col1" align="left">Dmax Dmin</entry><entry namest="col2" nameend="col2" align="left">[DNm]</entry><entry namest="col3" nameend="col3" align="left">16.6</entry><entry namest="col4" nameend="col4" align="left">18.4</entry></row><row><entry namest="col1" nameend="col1" align="left">t10%</entry><entry namest="col2" nameend="col2" align="left">[Min]</entry><entry namest="col3" nameend="col3" align="left">1.8</entry><entry namest="col4" nameend="col4" align="left">1.3</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">t90%</entry><entry namest="col2" nameend="col2" align="left">[Min]</entry><entry namest="col3" nameend="col3" align="left">28.2</entry><entry namest="col4" nameend="col4" align="left">31.7</entry></row><row><entry namest="col1" nameend="col1" align="left">Shore A hardness</entry><entry namest="col2" nameend="col2" align="left">[SH]</entry><entry namest="col3" nameend="col3" align="left">63</entry><entry namest="col4" nameend="col4" align="left">61</entry></row><row><entry namest="col1" nameend="col1" align="left">tensile strenght</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">15.5</entry><entry namest="col4" nameend="col4" align="left">15.9</entry></row><row><entry namest="col1" nameend="col1" align="left">Voltage value 100%</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">1.6</entry><entry namest="col4" nameend="col4" align="left">1.7</entry></row><row><entry namest="col1" nameend="col1" align="left">Voltage value 300%</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">7.8</entry><entry namest="col4" nameend="col4" align="left">8.4</entry></row><row><entry namest="col1" nameend="col1" align="left">RF 300% / 100%</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">4.9</entry><entry namest="col4" nameend="col4" align="left">4.9</entry></row><row><entry namest="col1" nameend="col1" align="left">elongation at break</entry><entry namest="col2" nameend="col2" align="left">[%]</entry><entry namest="col3" nameend="col3" align="left">450</entry><entry namest="col4" nameend="col4" align="left">440</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">DIN abrasion</entry><entry namest="col2" nameend="col2" align="left">[mm<sup>3</sup>]</entry><entry namest="col3" nameend="col3" align="left">77</entry><entry namest="col4" nameend="col4" align="left">82</entry></row><row><entry namest="col1" nameend="col1" align="left">Ball rebound, 60 ° C</entry><entry namest="col2" nameend="col2" align="left">[%]</entry><entry namest="col3" nameend="col3" align="left">59</entry><entry namest="col4" nameend="col4" align="left">62</entry></row><row><entry namest="col1" nameend="col1" align="left">E * (0 ° C)</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">14.3</entry><entry namest="col4" nameend="col4" align="left">14.1</entry></row><row><entry namest="col1" nameend="col1" align="left">tan δ (0 ° C)</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">0,483</entry><entry namest="col4" nameend="col4" align="left">0.461</entry></row><row><entry namest="col1" nameend="col1" align="left">E * (60 ° C)</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">6.4</entry><entry namest="col4" nameend="col4" align="left">6.4</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">tan δ (60 ° C)</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">0.146</entry><entry namest="col4" nameend="col4" align="left">0.144</entry></row></tbody></tgroup></table></tables>
As can be seen from the data in Table 5, the viscosities ML (1 + 4) of the blends (A) and (B) are at a comparable level and also the vulcanization characteristics are similar. The static and dynamic rubber data are also comparable within the usual variations in rubber testing. The value for the amplification factor RF 300% / 100% which is identical for mixtures (A) and (B) shows the same high silicic acid-silane binding. This clearly shows that the use of the silica according to the invention leads to a rubber value image that is comparable to that of the in-situ reference.
Example 2
Example 2 shows that, compared with the in-situ reference mixture (C), the rubber-technical property pattern drops when using the commercially available silicic acid VP Coupsil 8108 (D). The mixtures (C) and (D) are based on the recipes shown in Table 2. As a modification to the mixing instructions used in Example 1 and given in Table 2, the first mixing stage with a speed of 70 min<sup>-1</sup> at a flow temperature of 70 ° C and the 2nd mixing stage with an initial speed of 80 min<sup>-1</sup> mixed at a flow temperature of 80 ° C. The results are summarized in Table 6.<tables id="tabl0007" num="0007"><table frame="all"><title>Table 6: Results Example 2</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>mixture</b></entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="left"><b>(C)</b></entry><entry namest="col4" nameend="col4" align="left"><b>(D)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">ML (1 + 4)</entry><entry namest="col2" nameend="col2" align="left">[ME]</entry><entry namest="col3" nameend="col3" align="left">60</entry><entry namest="col4" nameend="col4" align="left">82</entry></row><row><entry namest="col1" nameend="col1" align="left">Dmax Dmin</entry><entry namest="col2" nameend="col2" align="left">[DNm]</entry><entry namest="col3" nameend="col3" align="left">18.9</entry><entry namest="col4" nameend="col4" align="left">22.1</entry></row><row><entry namest="col1" nameend="col1" align="left">t10%</entry><entry namest="col2" nameend="col2" align="left">[Min]</entry><entry namest="col3" nameend="col3" align="left">1.6</entry><entry namest="col4" nameend="col4" align="left">1.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">t90%</entry><entry namest="col2" nameend="col2" align="left">[Min]</entry><entry namest="col3" nameend="col3" align="left">23.2</entry><entry namest="col4" nameend="col4" align="left">36.0</entry></row><row><entry namest="col1" nameend="col1" align="left">Shore A hardness</entry><entry namest="col2" nameend="col2" align="left">[SH]</entry><entry namest="col3" nameend="col3" align="left">62</entry><entry namest="col4" nameend="col4" align="left">69</entry></row><row><entry namest="col1" nameend="col1" align="left">tensile strenght</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">13.0</entry><entry namest="col4" nameend="col4" align="left">13.0</entry></row><row><entry namest="col1" nameend="col1" align="left">Voltage value 100%</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">1.9</entry><entry namest="col4" nameend="col4" align="left">2.3</entry></row><row><entry namest="col1" nameend="col1" align="left">Voltage value 300%</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">8.9</entry><entry namest="col4" nameend="col4" align="left">9.1</entry></row><row><entry namest="col1" nameend="col1" align="left">RF 300% / 100%</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">4.7</entry><entry namest="col4" nameend="col4" align="left">4.0</entry></row><row><entry namest="col1" nameend="col1" align="left">elongation at break</entry><entry namest="col2" nameend="col2" align="left">[%]</entry><entry namest="col3" nameend="col3" align="left">380</entry><entry namest="col4" nameend="col4" align="left">380</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">DIN abrasion</entry><entry namest="col2" nameend="col2" align="left">[mm<sup>3</sup>]</entry><entry namest="col3" nameend="col3" align="left">91</entry><entry namest="col4" nameend="col4" align="left">88</entry></row><row><entry namest="col1" nameend="col1" align="left">Ball rebound, 23 ° C</entry><entry namest="col2" nameend="col2" align="left">[%]</entry><entry namest="col3" nameend="col3" align="left">32</entry><entry namest="col4" nameend="col4" align="left">33</entry></row><row><entry namest="col1" nameend="col1" align="left">E * (0 ° C)</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">15.4</entry><entry namest="col4" nameend="col4" align="left">20.5</entry></row><row><entry namest="col1" nameend="col1" align="left">tan δ (0 ° C)</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">0.486</entry><entry namest="col4" nameend="col4" align="left">0.502</entry></row><row><entry namest="col1" nameend="col1" align="left">E * (60 ° C)</entry><entry namest="col2" nameend="col2" align="left">[MPa]</entry><entry namest="col3" nameend="col3" align="left">6.5</entry><entry namest="col4" nameend="col4" align="left">7.7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">tan δ (60 ° C)</entry><entry namest="col2" nameend="col2" align="left">[]</entry><entry namest="col3" nameend="col3" align="left">0.138</entry><entry namest="col4" nameend="col4" align="left">0.144</entry></row></tbody></tgroup></table></tables>
The values in Table 6 show that the use of the known, silicified VP Coupsil 8108 silica does not achieve the high level of in situ reference mixture. Both the higher Mooney viscosity, the higher Shore A hardness, and the higher dynamic moduli E * indicate insufficiently homogeneous silanization resulting in a higher filler network of Blend (D). In addition, the amplification factor RF 300% / 100% of the mixture (D) compared to the reference (C) drops significantly.
The advantage of using the silicas of the invention is that, contrary to the known in-situ silanization of the prior art with liquid silanes, such as Si 69, during the mixing process, no chemical reaction must be performed, in which an optimal process control required is. In addition, in the known in-situ silanization disadvantageously significant amounts of alcohol are released, which escape from the mixture and thus lead to problems in the exhaust air.
The examples clearly show that the use of the silicas of the invention in the rubber achieves a property profile which is comparable to the prior art without causing the abovementioned disadvantages, as occur in the known in-situ silanization. By contrast, the use of commercial silicates such as VP Coupsil 8108, while avoiding the problem of ethanol evolution during mixing, does not achieve the high rubber-technical level of the in-situ reference.
15 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US7705076B2 | Cited by | United States of America | Applicant |
| EP1609516A1 | Cited by | European Patent Office (EPO) | Search report |
| DE102015221449A1 | Cited by | Germany | Applicant |
| WO2007141109A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US7518009B2 | Cited by | United States of America | Applicant |
| WO2019105613A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US7777063B2 | Cited by | United States of America | Applicant |
| US7799938B2 | Cited by | United States of America | Applicant |
| US7462221B2 | Cited by | United States of America | Applicant |
| EP1043357A1 | Cites | European Patent Office (EPO) | Search report |
| DE19541404A1 | Cites | Germany | Applicant |
| DE19734295C1 | Cites | Germany | Applicant |
| FR2094859A5 | Cites | France | Applicant |
| DE2141159A1 | Cites | Germany | Applicant |
| DE2212239A1 | Cites | Germany | Applicant |
| DE2405758A1 | Cites | Germany | Applicant |
| DE2542534A1 | Cites | Germany | Applicant |
| US3227675A | Cites | United States of America | Applicant |
| DE3314742A1 | Cites | Germany | Applicant |
| US3978103A | Cites | United States of America | Applicant |
| US3997356A | Cites | United States of America | Applicant |
| US3997356A | Cites | United States of America | Search report |
| US4099981A | Cites | United States of America | Search report |
| US4151154A | Cites | United States of America | Applicant |
24 members in 13 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 10122269 | Germany | A | |
| 10122269 | Germany | A | |
| 10122269 | Germany | – | |
| 10122269 | – | – | – |
| DE2001122269 | – | – | – |
Members24
| Document | Office | Kind | |
|---|---|---|---|
| EP1256604A2This record | European Patent Office (EPO) | A2 | |
| KR20020085837A | Republic of Korea | A | |
| PL353728A1 | Poland | A1 | |
| MXPA02004560A | Mexico | A | |
| DE10122269A1 | Germany | A1 | |
| CN1384136A | China | A | |
| JP2003064221A | Japan | A | |
| BR0201625A | Brazil | A | |
| US2003083516A1 | United States of America | A1 | |
| EP1256604A3 | European Patent Office (EPO) | A3 | |
| US6893495B2 | United States of America | B2 | |
| EP1256604B1 | European Patent Office (EPO) | B1 | |
| AT303420T | Austria | T | |
| ATE303420T1 | Austria | T1 | |
| DE50204057D1 | Germany | D1 | |
| US2005223946A1 | United States of America | A1 | |
| ES2244695T3 | Spain | T3 | |
| CN1261494C | China | C | |
| US7208038B2 | United States of America | B2 | |
| UA82043C2 | Ukraine | C2 | |
| KR100859104B1 | Republic of Korea | B1 | |
| TWI302554B | Taiwan Province of China | B | |
| BR0201625B1 | Brazil | B1 | |
| JP5044080B2 | Japan | B2 |
67 legal events, as 7 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Notification of lapseLapsedST | ST | FR | |
| Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal feeWithdrawnR119 | R119 | DE | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Announcement of lapse in spainLapsedFD2A | FD2A | ES | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Be: lapsedLapsedBERE | BERE | EP | |
| Transfer of patentPC2A | PC2A | ES | |
| Change of addressCA | CA | FR | |
| Change of name or company nameCD | CD | FR | |
| Change in legal formCJ | CJ | FR | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Nl: lapsed or anulled due to non-payment of the annual feeLapsedNLV4 | NLV4 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Fr: translation filedET | ET | EP | |
| Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]GBV | GBV | EP | |
| European patents designating ireland treated as always having been voidFD4D | FD4D | IE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Definitive protectionFG2A | FG2A | ES | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Corresponds to:REF | REF | EP | |
| European patents granted designating irelandGrantedLANGUAGE OF EP DOCUMENT: GERMANFG4D | FG4D | IE | |
| Designated contracting statesAK | AK | EP | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| European patent grantedGrantedNOT ENGLISHFG4D | FG4D | GB | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Designation fees paidAKX | AKX | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAX | AX | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAL;LT;LV;MK;RO;SIAX | AX | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 1256604
- Publication, DOCDB
- 1256604
- Publication, EPODOC
- EP1256604
- Application
- 2009844
- Application, DOCDB
- 02009844
- Application, EPODOC
- EP20020009844
Titles3
- German
- Silanmodifizierter biopolymerer, biooligomerer, oxidischer oder silikatischer Füllstoff, Verfahren zu seiner Herstellung und seine Verwendung
- English
- Biopolymers, biooligomers, oxidic or silicate Filler modified by silanes, method for its production and use
- French
- Matériau de remplissage à base de biopolymères, biooligomères ou silice modifiés avec des silanes, méthode de préparation et utilisation
Classification
- CPC, 8
- C09C3/12
- C08K9/06
- C01P2006/10
- C01P2006/12
- C01P2006/14
- C01P2006/16
- C09C1/3081
- C09C1/42
- IPC, 9
- C08J5 00
- C01B33 18
- C08K3 04
- C08K3 34
- C08K9 06
- C08L21 00
- C09C1 30
- C09C1 42
- C09C3 12
Designated states26
- Contracting states, 20
- Austria
- Belgium
- Switzerland
- Cyprus
- Germany
- Denmark
- Spain
- Finland
- France
- United Kingdom
- Greece
- Ireland
- Italy
- Liechtenstein
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Portugal
- Sweden
- Türkiye
- Extension states, 6
- Albania
- Lithuania
- Latvia
- North Macedonia
- Romania
- Slovenia