专利摘要:
The present invention relates to methods for making an elastomeric-silica-carbon black composite with a destabilized dispersion that contains silica, as well as particle-reinforced elastomer composites made from these processes. The advantages obtained with the processes are further described.
公开号:FR3038901A1
申请号:FR1656795
申请日:2016-07-13
公开日:2017-01-20
发明作者:Jincheng Xiong；Green Martin C；Williams William R；Dimitry Fomitchev；Adler Gerald D；Mcdonald Duane G；Ron Grosz；Michael D Morris
申请人:Cabot Corp；
IPC主号:

专利说明:

*N-(1,3-diméthylbutyl)-N’-phényl-p-phénylènediamine (Fiexsys, St. Louis, MO) ""‘composant actif principal : S-(3-(triéthoxysilyl)propyl)octanéthioate (Momentive, Friendly, WV) *** DiphénylGuanidine (Akrochem, Akron, OH) ****N-tert-Butylbenzothiazole-2-sulphénamide (Emerald Performance Materials, Cuyahoga Faits, OH) NR = caoutchouc naturel S = comme indiqué
Tableau B
[0119] La vulcanisation a été effectuée dans une presse chauffée réglée à 150 °C pendant une durée déterminée par un rhéomètre à caoutchouc traditionnel (c'est-à-dire, T90 + 10 % de T90, où T90 est la durée pour obtenir 90 % de vulcanisation).
[0120] Propriétés des composés de caoutchouc/silice.
[0121] Les propriétés de traction des échantillons vulcanisés (T300 et T100, allongement de rupture, résistance à la traction) ont été mesurées selon la norme ASTM D-412. La tangente delta 60o a été déterminée en utilisant un balayage sous contrainte dynamique en torsion entre 0,01 % et 60 % à 10 Hz et 60 °C. La tangente Dmax a été prise comme valeur maximale de la tangente DDdans cette plage de contraintes.
[0122] Exemple 1.
[0123] Une bouillie de silice avec 27,8% en poids de silice Zeosil® 1165 a été préparée comme décrit ci-dessus pour la méthode de test du potentiel zêta de la bouillie. La bouillie a ensuite été diluée en utilisant soit de l'eau désionisée, soir un surnageant obtenu par l'ultracentrifugation des 27,8 % en poids de bouillie pour fabriquer une série de bouillies de silice à différentes concentrations de silice. Le potentiel zêta des différentes bouillies de silice a été mesuré pour montrer la relation entre la concentration de silice dans la bouillie et le potentiel zêta de la bouillie. Le potentiel zêta de la bouillie de silice, comme indiqué dans le tableau 1, semble dépendre de la concentration de silice lorsque la bouillie de silice est fabriquée en utilisant de l'eau désionisée. En revanche, comme indiqué dans le tableau 2, lorsque la bouillie a été diluée en utilisant le surnageant obtenu par l'ultracentrifugation des 27,8 % en poids de bouillie liquide, le potentiel zêta reste globalement le même aux différentes concentrations de silice.
Tableau 1
Potentiel zêta de la bouillie de silice fabriquée en utilisant de l'eau désionisée
Tableau 2
Potentiel zêta de la bouillie de silice obtenue par la dilution de 27,8 % en poids de bouillie de silice en utilisant le surnageant des 27,8 % en poids de bouillie de silice.
[0124] Ce résultat montre qu'une augmentation de l'amplitude du potentiel zêta lorsque de telles bouillies de silice sont diluées avec de l'eau désionisée est principalement due à la réduction de la force ionique de la bouillie. Les ions de la bouillie de silice sont supposés provenir des sels résiduels présents dans la silice issue du procédé de fabrication des particules de silice. L'amplitude élevée du potentiel zêta des bouillies de silice (toujours supérieur à 30 mV) indique que la silice a une stabilité électromagnétique élevée dans la bouillie.
[0125] Exemple 2.
[0126] L'effet de l'ajout de sel ou d'acide à différentes concentrations à des bouillies de silice sur le potentiel zêta de ces bouillies est décrit dans le tableau 3. Les bouillies ont été préparées dans de l'eau désionisée par la méthode de test Slurry Zêta Potential décrite ci-dessus. Les données résumées dans le tableau 3 décrivent la dépendance du potentiel zêta des bouillies liquides de silice et des bouillies liquides de silice déstabilisée sur la concentration de silice, la concentration de sel et la concentration d'acide. L'ajout de sel ou d'acide à la bouillie de silice réduit l'amplitude du potentiel zêta et ainsi la stabilité de la bouillie de silice. Comme indiqué dans le tableau 3, le potentiel zêta dépend principalement de la concentration de sel ou d'acide dans la bouillie ou la bouillie déstabilisée et non de la concentration de silice.
Tableau 3
Potentiel zêta de la bouillie déstabilisée de silice à différentes concentrations de bouillie, concentrations de
sel et concentrations d'acide.
ND = non déterminé.
[0127] Les résultats indiqués dans le tableau 3 décrivent la dépendance du potentiel zêta des bouillies de silice et des bouillies de silice déstabilisée sur la concentration d'acide acétique et la concentration de silice. Les données montrent que les valeurs du potentiel zêta dépendent plus de la concentration d'acide que de la concentration de silice. Une relation similaire entre le potentiel zêta et la concentration d'acide et la concentration de silice est observée avec l'acide formique. À une concentration donnée, l'acide formique réduit plus l'amplitude du potentiel zêta que l'acide acétique. Comme indiqué dans le tableau 3, une combinaison d'acide formique et de chlorure de calcium a été efficace pour réduire l'amplitude du potentiel zêta. Les résultats indiqués dans le tableau 3 montrent que la stabilité des particules de silice dans la bouillie peut être efficacement réduite par l'ajout d'agents de déstabilisation, comme un acide ou un sel ou une combinaison d'acide et de sel. Des résultats similaires ont été obtenus avec le nitrate de calcium et l'acétate de calcium.
[0128] Exemple 3.
[0129] Dans cet exemple, l'importance de la déstabilisation de la dispersion des particules de silice avant la mise en contact la dispersion de silice avec le latex d'élastomère a été établie. Plus précisément, quatre expériences ont été réalisées en utilisant l'appareil de mélange (c) de la figure 1 doté de trois entrées (3, 11, 14) pour introduire jusqu'à trois fluides dans une zone de réaction confinée (13), de sorte qu'un fluide percute les autres fluides selon un angle de 90 degrés par un jet à grande vitesse à une vitesse comprise entre 15 et 80 m/s (voir figure 1 (c)). Dans trois des quatre expériences, la silice a été concassée comme décrit ci-dessus dans le procédé B et de l'acide acétique a été éventuellement ajouté comme décrit dans les exemples 3-A à 3-D ci-dessous. La bouillie ou la bouillie déstabilisée a été ensuite mise sous pression entre 100 et 150 psig et introduite dans la zone de réaction confinée par l'entrée (3) à un débit volumétrique de 60 litres par heure (l/h) de manière à ce que la bouillie ou la bouillie déstabilisée soit introduite sous forme de jet à grande vitesse à 80 m/s dans la zone de réaction. Simultanément, un concentré de latex de caoutchouc naturel (latex 60CX12021, teneur en caoutchouc sec de 31 % en poids, de Chemionics Corporation, Tallmadge, Ohio, dilué dans de l'eau désionisée) a été introduit par la seconde entrée (11) par une pompe péristaltique à un débit volumétrique de 106 l/h et à une vitesse de 1,8 m/s. Ces débits ont été sélectionnés et les flux ont été ajustés pour obtenir un produit de composite d'élastomère comprenant 50 phr (parties par cent parties en poids de caoutchouc sec) de silice. La bouillie de silice ou la bouillie de silice déstabilisée et le latex ont été mélangés en combinant le flux de latex à vitesse réduite et le jet à grande vitesse de bouillie de silice ou de bouillie de silice déstabilisée entraînant le flux de latex dans le jet de bouillie ou de bouillie déstabilisée de silice au point d'impact. La cadence de production (sur une base de matière sèche) a été réglée à 50 kg/h. Les rapports spécifiques réels silice-caoutchouc dans les composites de caoutchouc obtenus avec le procédé sont répertoriés dans les exemples ci-dessous. L'analyse TGA a été effectuée après le séchage selon le procédé du procédé B.
[0130] Exemple 3-A : [0131] Premier fluide : Une dispersion aqueuse déstabilisée de 25 % en poids de silice avec 6,2% en poids (ou 1,18 M) d'acide acétique a été préparée comme décrit dans le procédé B ci-dessus. Le potentiel zêta de la bouillie déstabilisée était de -14 mV, ce qui indique que la bouillie était déstabilisée de façon significative par l'acide. La bouillie déstabilisée de silice a été pompée en continu sous pression dans la première entrée (3).
[0132] Deuxième fluide : Du latex d'élastomère a été introduit dans la zone de réaction par la seconde entrée (11).
[0133] Le premier fluide a percuté le deuxième fluide dans la zone de réaction.
[0134] Résultats : Une inversion de phase liquide-solide s'est produite dans la zone de réaction lorsque la bouillie déstabilisée de silice et le latex ont été intimement mélangés par l'entraînement du flux de latex à vitesse lente dans le jet à grande vitesse de bouillie déstabilisée de silice. Pendant le procédé d'entraînement, la silice a été intimement distribuée dans le latex et le mélange a coagulé en une phase solide qui contenait entre 70 % en poids et 85 % en poids d'eau. De ce fait, un flux d'une phase continue de caoutchouc solide contenant de la silice en forme de ver ou de corde a été obtenu à la sortie de la zone de réaction (15). Le composite était élastique et pouvait être étiré jusqu'à 130 % de la longueur initiale sans rompre. L'analyse TGA sur le produit séché a montré que le composite d'élastomère contenait 58 phr de silice.
[0135] Exemple 3-B : [0136] Premier fluide : Une dispersion aqueuse déstabilisée de 25 % en poids de silice avec 6,2 % en poids d'acide acétique a été préparée selon le procédé B décrit ci-dessus. Le potentiel zêta de la bouillie était de -14 mV, ce qui indique que la bouillie était déstabilisée de façon significative par l'acide. La bouillie déstabilisée de silice a été pompée en continu sous pression dans la première entrée (3).
[0137] Deuxième fluide : Du latex d'élastomère a été introduit dans la zone de réaction par la seconde entrée (11).
[0138] Troisième fluide : De l'eau désionisée a été également injectée dans la zone de réaction par la troisième entrée (14) à un débit volumétrique de 60 l/h et une vitesse de 1,0 m/s.
[0139] Les trois fluides sont entrés en contact et se sont percutés dans la zone de réaction.
[0140] Résultats : Une inversion de phase liquide-solide s'est produite dans la zone de réaction et une phase continue de caoutchouc solide ou semi-solide contenant de la silice en forme de corde ou de ver a été obtenue par la sortie de la zone de réaction. Une quantité significative de liquide trouble contenant de la silice et/ou du latex s'est écoulée par la sortie (7) avec la phase continue de caoutchouc solide ou semi-solide contenant de la silice. La phase continue de caoutchouc contenant de la silice contenait entre environ 70 % en poids et environ 75 % en poids d'eau sur la base du poids du composite. L'analyse TGA sur le produit séché a montré que le composite d'élastomère contenait 44 phr de silice. Ainsi, l'ajout d'eau par la troisième entrée a eu un impact négatif sur le procédé, donnant lieu à un produit ayant une teneur plus faible en silice (44 phr contre 58 phr dans l'exemple 3-A) et à des déchets importants.
[0141] Exemple 3-C : [0142] Premier fluide : Une solution aqueuse d'acide acétique à 10 % en poids sans silice a été préparée. Une alimentation continue de fluide acide a été pompée avec une pompe péristaltique à un débit volumétrique de 60 l/h par la troisième entrée (14) dans la zone de réaction à une vitesse de 1,0 m/s au moment de l'entrée dans la zone de réaction.
[0143] Deuxième fluide : Du latex d'élastomère a été introduit dans la zone de réaction par la deuxième entrée (11) avec une pompe péristaltique à une vitesse de 1,8 m/s et à un débit volumétrique de 106 l/h.
[0144] Les deux fluides sont entrés en contact et se sont percutés dans la zone de réaction.
[0145] Résultats : Une phase collante de caoutchouc solide en forme de ver a été formée. L'analyse TGA sur le produit séché a montré que la phase de caoutchouc solide ne contenait pas de silice.
[0146] Exemple 3-D : [0147] Premier fluide : Une dispersion aqueuse déstabilisée de 25 % en poids de silice sans acide acétique a été préparée selon le procédé B décrit ci-dessus. La bouillie de silice a été pompée sous pression continue et introduite par la première entrée (3) à un débit volumétrique de 60 l/h et à une vitesse de 80 m/s au point d'entrée dans la zone de réaction. Le potentiel zêta de la bouillie était de -32 mV, ce qui indique que la silice était dispersée de façon stable dans la bouillie. Ainsi, dans cet exemple 3-D, la bouillie de silice n'a pas été déstabilisée par l'ajout d'acide à la bouillie avant l'impact avec le fluide de latex.
[0148] Deuxième fluide : Du latex d'élastomère a été introduit dans la zone de réaction par la deuxième entrée (11) avec une pompe péristaltique à une vitesse de 1,8 m/s et à un débit volumétrique de 106 l/h.
[0149] Troisième fluide: Après une période initiale de flux continu des premier et second fluides, une solution aqueuse d'acide acétique à 10 % en poids a été injectée par la troisième entrée (14) dans la zone de réaction à un débit volumétrique passant de 0 à 60 l/h et à une vitesse passant de 0 à 1,0 m/s. Les trois fluides se sont percutés et mélangés dans la zone de réaction.
[0150] Résultats : Initialement, avant l'injection d'acide, aucune phase continue de caoutchouc contenant de la silice ne s'était formée et seul un liquide trouble était observé par la sortie (15) de la zone de réaction. Lors de l'injection d'acide dans la zone de réaction (13), une phase continue de caoutchouc semi-solide contenant de la silice a commencé à se former à mesure de l'augmentation du flux d'acide acétique par la troisième entrée de 0 à 60 l/h. Les matériaux s'écoulant par la sortie contenaient encore une quantité significative de liquide trouble, ce qui indique une quantité importante de déchet. L'analyse TGA du produit sec a montré que la phase continue de caoutchouc contenant de la silice formée dans ce cycle expérimental ne contenait que 25 phr de silice. Compte tenu des conditions de production sélectionnées et de la quantité de silice utilisée, si la silice avait été incorporée de façon importante dans la phase de caoutchouc contenant de la silice, comme dans l'exemple 3-A, la silice aurait donné lieu à une phase de caoutchouc contenant de la silice comprenant un excès de 50 phr de silice.
[0151] Ces expériences montrent que la bouillie de silice doit être déstabilisée avant l'impact initial avec le latex d'élastomère afin d'obtenir la phase continue de caoutchouc contenant de la silice souhaitée. L'exemple 3-A a permis d'obtenir ce que l'on peut considérer comme une capture efficace de la silice dans la phase continue de caoutchouc solide contenant de la silice, tandis que l'exemple 3-D illustre un procédé comparatif utilisant une bouillie de silice initialement stable et ayant une efficacité inférieure de moitié à l'efficacité de l'exemple 3-A utilisant une bouillie de silice initialement déstabilisée. L'observation d'un liquide trouble quittant le point de sortie de la zone de réaction indique un mélange insuffisant de la silice avec le latex et une proportion inférieure de silice capturée dans la phase continue de caoutchouc. En théorie, dans les procédés comparatifs 3B et 3D, la déstabilisation des fluides a été insuffisante pendant le mélange. Les résultats indiquent en outre que la capture insuffisante de la silice s'est produite lorsqu'un fluide supplémentaire a été ajouté alors que le premier fluide et le deuxième fluide étaient en train de se mélanger ; de telles conditions de procédé génèrent des quantités indésirables de déchet.
[0152] Exemple 4.
[0153] Procédé illustratif A-1. Aux endroits indiqués dans les exemples ci-dessous, un procédé a été effectué en utilisant le procédé illustratif A-1. Dans le procédé A-1, de la silice sèche précipitée et de l'eau (eau du robinet filtrée pour retirer la matière particulaire) ont été mesurées et combinées, puis concassées dans un broyeur à rotor-stator pour former de la bouillie de silice et la bouillie particulaire a été encore concassée dans un réservoir d'alimentation en utilisant un agitateur et un autre broyeur à rotor-stator. La bouillie de silice a ensuite été transférée dans un réservoir à cycle équipé de deux agitateurs. Le même procédé utilisé pour former la bouillie de silice a été utilisé pour préparer une bouillie de noir de carbone à partir de noir de carbone sec (noir de carbone grade N-134 fourni par Cabot Corporation). La bouillie de noir de carbone a été ajoutée au-dessus de la bouillie de silice dans le réservoir à cycle. La bouillie de silice-noir de carbone a été remise en circulation depuis le réservoir à cycle dans un homogénéisateur, puis remise dans le réservoir à cycle. Une solution d'acide (acide formique ou acide acétique, qualité industrielle, fourni par Kong Long Huât Chemicals, Malaisie) a ensuite été pompée dans le réservoir à cycle. La bouillie a été maintenue sous forme dispersée par agitation et, éventuellement, au moyen de la boucle de recirculation dans le réservoir à cycle. Après une période adaptée, la bouillie de silice-noir de carbone a été introduite dans une zone de réaction confinée (13), telle que celle illustrée sur la figure 1a, au moyen d'un homogénéisateur. La concentration de silice et de noir de carbone dans la bouillie et la concentration d'acide sont indiquées dans les exemples spécifiques ci-dessous.
[0154] Le latex a été pompé avec une pompe péristaltique (à moins d'environ 40 psig de pression) par la seconde entrée (11) dans la zone de réaction (13). Le débit de latex a été ajusté entre 300 et 1 600 kg de latex/h environ afin d'obtenir une cadence de production et des niveaux de charge en silice-noir de carbone souhaités dans le produit résultant. La bouillie homogénéisée contenant l'acide a été pompée sous pression depuis l'homogénéisateur vers une buse (diamètre interne (DI) compris entre 0,15 cm (0,060”) et 0,33 cm (0,130”) (3a), représentée par la première entrée (3) illustrée sur la figure 1 (a), de telle sorte que la bouillie est introduite en un jet à grande vitesse dans la zone de réaction. Au contact du latex dans la zone de réaction, le jet de bouillie de silice s'écoulant à une vitesse comprise entre 25 m/s et 120 m/s a entraîné le latex s'écoulant entre 1 ms et 11 m/s. Dans des exemples selon des modes de réalisation de la présente invention, l'impact de la bouillie de silice-noir de carbone sur le latex a provoqué un mélange intime des particules de silice-noir de carbone avec les particules de caoutchouc du latex, et le caoutchouc a coagulé, transformant la bouillie de silice-noir de carbone et le latex en un matériau comprenant une phase continue de caoutchouc solide ou semi-solide contenant de la silice et du noir de carbone contenant entre 40 et 95 % en poids d'eau, sur la base du poids total du matériau, piégée dans le matériau. Des ajustements ont été apportés au débit de la bouillie (500-1 800 kg/h) ou au débit de latex (300-1 800 kg/h), ou aux deux, pour modifier les rapports silice-caoutchouc (par ex., 15-180 phr de silice) dans le produit final et pour obtenir la cadence de production souhaitée. Les cadences de production (base de matière sèche) étaient comprises entre 200 et 800 kg/h. Des teneurs en silice spécifiques (par analyse TGA) dans le caoutchouc après assèchement et séchage du matériau sont répertoriées dans les exemples ci-dessous.
[0155] Procédé A-1 Assèchement. Le matériau a été déchargé de la zone de réaction à la pression atmosphérique à un débit compris entre 200 et 800 kg/h (poids sec) dans une extrudeuse d'assèchement (The French Oil Machinery Company, Piqua, OH). L'extrudeuse (D.l. de 21,59 cm (8,5 pouces)) était équipée d'une matrice ayant différentes configurations de boutons de perforation et actionnée à une vitesse de rotor typique comprise entre 90 et 123tr/min, une pression de matrice comprise entre 400 et 1 300 psig et une puissance comprise entre 80 et 125 kW. Dans l'extrudeuse, le caoutchouc contenant la silice et le noir de carbone a été comprimé et l'eau extraite du caoutchouc contenant de la silice a été éjectée par un fût à fentes de l'extrudeuse. Un produit asséché contenant typiquement entre 15 et 60 % en poids d'eau a été obtenu à la sortie de l'extrudeuse.
[0156] Procédé A-1 Séchage et refroidissement. Le produit asséché a été déposé dans un dispositif de mélangeage continu (mélangeur continu Farrel (FCM), Farrel Corporation, Ansonia, CT ; avec 7 et 15 rotors) où il a été séché, mastiqué et mélangé avec 1 à 2 phr d'antioxydant (par ex., 6PPD de Flexsys, St. Louis, MO) et éventuellement un agent de couplage silane (par ex., silane NXT, fourni par Momentive Performance Materials, Inc., Waterford, NY ; 8 % en poids de silane sur la base du poids de silice). La température de la chemise d'eau du FCM a été réglée à 100 °C et la température du FCM au niveau de l'orifice de sortie était comprise entre 140 et 180 °C. La teneur en humidité du composite d'élastomère mastiqué et asséché sortant du FCM était comprise entre 1 % en poids et 5 % en poids. Le produit a été encore mastiqué et refroidi dans un broyeur ouvert. Une feuille de caoutchouc du composite d'élastomère a été coupée directement depuis le broyeur ouvert, laminée et refroidie à l'air.
[0157] Préparation des composés de caoutchouc.
[0158] Le composite d'élastomère séché obtenu par le procédé A-1 a été soumis à un mélangeage selon la formulation du tableau C et la procédure décrite dans le tableau D. Pour les composites d'élastomère dans lesquels du silane ou un antioxydant a été ajouté pendant le séchage, la composition de composé finale est celle indiquée dans le tableau C. La quantité de l'agent de couplage silane et/ou de l'antioxydant pendant le mélangeage a été ajustée en conséquence.
Tableau C
*N-(1,3-diméthylbutyl)-N’-phényl-p-phénylènediamine (Flexsys, St. Louis, MO) ‘‘composant actif principal : S-(3-(triéthoxysilyl)propyl)octanéthioate (Momentive, Friendly, WV) *“ DiphénylGuanidine (Akrochem, Akron, OH) “**N-tert-Butylbenzothiazole-2-sulphénamide (Emerald Performance Materials, Cuyahoga Falls, OH) NR = caoutchouc naturel S = comme indiqué
Tableau D
[0159] La vulcanisation a été effectuée dans une presse chauffée réglée à 150DC pendant une durée déterminée par un rhéomètre à caoutchouc traditionnel (c'est-à-dire, T90 + 10 % de T90, où T90 est la durée pour obtenir 90 % de vulcanisation).
[0160] Propriétés des composés de caoutchouc/silice-noir de carbone.
[0161] Les propriétés de traction des échantillons vulcanisés (T300 et T100, allongement de rupture, résistance à la traction) ont été mesurées selon la norme ASTM D-412. La tangente delta 60° a été déterminée en utilisant un balayage sous contrainte dynamique en torsion entre 0,01 % et 60 % à 10 Hz et 60 °C. La tangente Dmax a été prise comme valeur maximale de la tangente □ dans cette plage de contraintes.
[0162] Dans ces exemples, le procédé selon divers modes de réalisation de l'invention a été exécuté dans l'appareil illustré sur la figure 1 ((a) ou (b)) dans différentes conditions comme décrit dans le tableau 4, en utilisant le procédé A-1 décrit ci-dessus. Les conditions de fonctionnement ont été sélectionnées pour obtenir une phase continue de caoutchouc solide ou semi-solide contenant de la silice avec les rapports silice-noir de carbone-caoutchouc indiqués dans le tableau 4 (Plant.= de plantation).
Tableau 4
S/0 = sans objet, ND = non déterminé a. Tous les exemples ont utilisé de la silice précipitée ZEOSIL® Z1165 MP. Tous les exemples ont utilisé du noir de carbone N134 de Cabot Corporation. b. Les valeurs du potentiel zêta ont été estimées par interpolation des courbes déterminées expérimentalement de la dépendance du potentiel zêta.par rapport à la concentration du sel ou de l'acide des bouillies de la même qualité de silice.
Tableau 4 (suite)
c. La vitesse de la buse d'entrée correspond à la vitesse de la bouillie de silice-noir de carbone qui passe dans une buse (3a) au niveau de la première entrée (3) vers la zone de réaction (13) avant d'entrer en contact avec le latex. d. Les débits de la bouillie et du latex correspondent aux débits volumétriques en l/heure de la bouillie de silice-noir de carbone et du latex liquide, respectivement, lorsqu'ils sont introduits dans la zone de réaction.
[0163] Dans tous les exemples répertoriés ci-dessus dans le tableau 4, les conditions de fonctionnement sélectionnées ont permis d'obtenir une phase continue de caoutchouc solide contenant de la silice et du noir de carbone sous une forme cylindrique grossière. Le produit contenait une quantité importante d'eau, était élastique et compressible, et a expulsé l'eau et les solides retenus après compression manuelle. Le matériau solide pouvait être étiré, par exemple, le matériau pouvait être étiré ou allongé de 130 à 150 % de sa longueur, sans se rompre. Une partie des propriétés du caoutchouc des composites fabriqués est présentée dans le tableau 5 ci-dessous. On a observé que les particules de silice et de noir de carbone étaient uniformément distribuées dans une phase continue de caoutchouc et que ce produit était sensiblement dépourvu de particules de silice libres et de grains de silice plus gros sur les surfaces extérieure et intérieure. Pour la phase continue de caoutchouc contenant de la silice et du noir de carbone, non seulement la silice doit être déstabilisée (par ex., par un traitement préalable avec des acides et/ou des sels), mais les débits volumétriques de la bouillie de silice déstabilisée par rapport au latex ont dû être ajustés non seulement pour obtenir un rapport silice-caoutchouc (phr) souhaité dans le composite d'élastomère, mais également pour équilibrer le degré de déstabilisation de la bouillie avec la cadence de mélange de la bouillie et du latex et la vitesse de coagulation des particules de caoutchouc de latex. Grâce à ces ajustements, comme la bouillie de silice a entraîné le latex, distribuant intimement les particules de silice (et les particules de noir de carbone) dans le caoutchouc, le caoutchouc dans le latex est devenu une phase continue solide ou semi-solide en une fraction de seconde après combinaison des fluides dans le volume confiné de la zone de réaction. Ainsi, le procédé a formé des composites uniques élastomère-silice-noir de carbone au moyen d'une étape d'impact continu des fluides à une vitesse suffisante, des concentrations et des volumes liquides/solides sélectionnés et des débits de liquide ajustés pour distribuer uniformément et intimement la silice particulaire fine dans le latex et, parallèlement, pendant l'exécution d'une telle distribution, pour donner lieu à une inversion de phase liquide-solide du caoutchouc.
Tableau 5
[0164] Le composite d'élastomère formé à partir de ces exemples présente des propriétés de caoutchouc acceptables et en particulier des propriétés T300/T100 bénéfiques pour un composite ayant de la silice et du noir de carbone dispersés dans le composite. Comme le montrent ces exemples, un article de phase de caoutchouc solide contenant de la silice et du noir de carbone peut comprendre au moins 40 phr de silice dispersée dans du caoutchouc naturel et au moins 40 % en poids de fluide aqueux et avoir une dimension de longueur (L), dans lequel l'article de phase de caoutchouc solide contenant de la silice et du noir de carbone peut être étiré jusqu'à au moins 130 % à 150 % de (L) sans se rompre.
[0165] La présente invention comprend les aspects/modes de réalisation/attributs suivants dans tout ordre et/ou toute combinaison : 1. Procédé de fabrication d'un composite élastomère-silice comprenant : (a) la fourniture d'un flux continu sous pression d'au moins un premier fluide contenant des particules dispersées et comprenant une dispersion déstabilisée de silice et d'un flux continu d'au moins un second fluide comprenant du latex d'élastomère ; (b) la fourniture d'un débit volumétrique du premier fluide par rapport à celui du second fluide pour obtenir une teneur en silice allant d’environ 15phr à environ 180 phr dans le composite élastomère-silice ; (c) la combinaison du flux du premier fluide et du flux du second fluide avec un impact suffisamment énergique pour distribuer la silice dans le latex d'élastomère afin d'obtenir une phase continue de caoutchouc solide contenant de la silice ou une phase continue de caoutchouc semi-solide contenant de la silice. dans lequel ledit au moins un premier fluide est fourni sous forme de : i) deux flux comprenant une dispersion comprenant du noir de carbone et une dispersion déstabilisée comprenant de la silice ; ou ii) un seul flux comprenant une dispersion comprenant du noir de carbone et une dispersion déstabilisée comprenant de la silice ; ou iii) un seul flux de dispersion déstabilisée comprenant de la silice et du noir de carbone. 2. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents et suivants, dans lequel au moins un premier fluide est une dispersion déstabilisée comprenant de la silice et du noir de carbone, et ledit procédé comprend en outre une combinaison de noir de carbone sec, de silice sèche et d'un milieu aqueux pour former ladite dispersion déstabilisée comprenant au moins 45 % en poids de silice, sur une base particulaire totale, et de noir de carbone. 3. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre la soumission d'une ou plusieurs desdites dispersions à au moins une étape de traitement mécanique. 4. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite étape de traitement mécanique comprend le concassage, le broyage, la pulvérisation, la brisure ou le traitement à fort cisaillement ou des combinaisons de ceux-ci. 5. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite étape de traitement mécanique comprend le concassage desdites dispersions une ou plusieurs fois. 6. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite étape de traitement mécanique réduit l'agglomération des particules et/ou ajuste la distribution de la taille de particules. 7. Procédé de fabrication d'un composite élastomère-silice comprenant : (a) la fourniture d'un flux continu sous pression d'au moins un premier fluide comprenant une dispersion déstabilisée de silice et d'un flux continu d'au moins un second fluide comprenant du latex d'élastomère ; (b) la fourniture d'un débit volumétrique du premier fluide par rapport à celui du second fluide pour obtenir une teneur en silice allant d’environ 15 phr à environ 180 phr dans le composite élastomère-silice ; (c) la fourniture d'un flux continu de noir de carbone fluidifié sous forme sèche, (d) la combinaison du flux du premier fluide et du flux du second fluide et dudit noir de carbone avec un impact suffisamment énergique pour distribuer la silice et le noir de carbone dans le latex d'élastomère, pour obtenir un flux d'une phase continue de caoutchouc solide contenant de la silice et du noir de carbone ou d'une phase continue de caoutchouc semi-solide contenant de la silice et du noir de carbone. dans lequel ledit flux de noir de carbone est combiné audit premier fluide avant l'étape d, ou combiné audit second fluide avant l'étape d, ou ajouté à l'étape d. 8. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel du noir de carbone est présent dans ledit composite élastomère-silice dans une quantité comprise entre environ 10 % en poids et environ 50 % en poids sur la base de la matière particulaire totale présente dans ledit composite élastomère-silice. 9. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit flux de ladite phase continue de caoutchouc solide ou semi-solide contenant de la silice se forme en deux secondes ou moins après la combinaison dudit premier flux de fluide et dudit second flux de fluide. 10. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit flux de ladite phase continue de caoutchouc solide ou semi-solide contenant de la silice se forme en environ 50 millisecondes à environ 1 500 millisecondes après la combinaison dudit premier flux de fluide et dudit second flux de fluide. 11. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide à l'étape (a) comprend en outre au moins un sel. 12. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide à l'étape (a) comprend en outre au moins un acide. 13. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite phase continue de caoutchouc solide ou semi-solide contenant de la silice comprend entre de40 % en poids à environ 95 % en poids d'eau ou de fluide aqueux. 14. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite combinaison s'effectue dans une zone de réaction ayant un volume allant d’environ 10 cm3 à environ 500 cm3. 15. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les débits volumétriques relatifs se situent à un rapport de débit volumétrique du premier fluide par rapport au second fluide allant de 0,4:1 à 3,2:1. 16. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les débits volumétriques relatifs se situent à un rapport de débit volumétrique du premier fluide par rapport au second fluide allant de 0,2:1 à 2,8:1. 17. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les débits volumétriques relatifs se situent à un rapport de débit volumétrique du premier fluide par rapport au second fluide allant de 0,4:1 à 3,2:1, et ladite dispersion déstabilisée de la silice comprend au moins un sel. 18. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les débits volumétriques relatifs se situent à un rapport de débit volumétrique du premier fluide par rapport au second fluide allant de 0,2:1 à 2,8:1, et ladite dispersion déstabilisée de la silice comprend au moins un acide. 19. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit latex d'élastomère comprend une base, ladite dispersion déstabilisée de silice comprend au moins un acide et un rapport molaire d'ions hydrogène dans ledit acide dans ledit premier fluide par rapport à ladite base dans ledit second fluide est de 1 à 4,5. 20. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend au moins un acide et dans lequel ledit latex d'élastomère présent dans ledit second fluide a une concentration en ammoniac allant d’environ 0,3 % en poids à environ 0,7 % en poids sur la base du poids du latex d'élastomère, et un rapport molaire d'ions hydrogène dans ledit acide dans ledit premier fluide par rapport à l'ammoniac dans ledit second fluide est d'au moins 1:1. 21. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite teneur en silice dudit composite élastomère-silice est d’environ 26 phr à environ 80 phr. 22. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite teneur en silice dudit composite élastomère-silice est d’ environ 40 phr à environ 115 phr. 23. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend environ 6 % en poids à environ 35 % en poids de silice. 24. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend environ 10 % en poids à environ 28 % en poids de silice. 25. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre la récupération de ladite phase continue de caoutchouc solide ou semi-solide contenant de la silice à pression ambiante. 26. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide comprenant ladite dispersion déstabilisée de silice a une amplitude de potentiel zêta inférieure à 30 mV. 27. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend au moins un sel, dans lequel la concentration d'ions de sel dans ladite dispersion déstabilisée est d’environ 10 mM à environ 160 mM. 28. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend au moins un sel, dans lequel ledit sel est présent dans ladite dispersion déstabilisée dans une quantité allant d’environ 0,2 % en poids à environ 2 % en poids sur la base du poids de ladite dispersion déstabilisée. 29. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend au moins un acide, dans lequel ledit acide est présent dans ladite dispersion déstabilisée dans une quantité allant d’environ 0,8 % en poids à environ 7,5 % en poids sur la base du poids de ladite dispersion déstabilisée. 30. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion déstabilisée de silice comprend au moins un acide, dans lequel la concentration d'acide dans ladite dispersion déstabilisée est comprise d’environ 200 mM à environ 1 000 mM. 31. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel l'étape (c) est réalisée avec le flux continu du premier fluide à une vitesse A et le flux continu du second fluide à une vitesse B, et la vitesse A est au moins 2 fois plus rapide que la vitesse B. 32. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel l'étape (c) est réalisée dans une zone de réaction semi-confinée et le premier fluide a une vitesse suffisante pour induire une cavitation dans la zone de réaction lors de la combinaison avec le second fluide. 33. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel le second fluide a une vitesse suffisante pour créer un flux turbulent. 34. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite dispersion de silice comprend une silice modifiée en surface ayant des fragments de surface hydrophobes. 35. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide comprend un fluide aqueux. 36. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide comprend un fluide aqueux et environ 6 % en poids à environ 31 % en poids de silice et au moins 3 % en poids de noir de carbone. 37. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit premier fluide comprend un fluide aqueux, comprenant en outre au moins un sel et au moins un acide. 38. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, ledit procédé comprenant en outre la déstabilisation d'une dispersion de silice en abaissant un pH de la dispersion de silice de façon à former la dispersion déstabilisée de silice fournie à l'étape (a). 39. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, ledit procédé comprenant en outre la déstabilisation d'une dispersion de silice en abaissant un pH de la dispersion de silice jusqu'à un pH compris de 2 à 4 de façon à former la dispersion déstabilisée de silice fournie à l'étape (a). 40. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite silice a une surface hydrophile. 4L Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite silice est une silice hautement dispersible (HDS). 42. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit acide comprend l'acide acétique, l'acide formique, l'acide citrique, l'acide phosphorique ou l'acide sulfurique ou toute combinaison de ceux-ci. 43. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit acide a un poids moléculaire ou un poids moléculaire moyen inférieur à 200. 44. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit sel comprend au moins un sel métallique du groupe 1,2 ou 13. 45. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit sel comprend un sel de calcium, un sel de magnésium ou un sel d'aluminium ou une combinaison de ceux-ci. 46. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, ledit procédé comprenant en outre l’exposition de la silice à une étape mécanique pour réduire l'agglomération des particules et/ou ajuster la distribution de la taille de particules. 47. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel la silice est de la silice précipitée ou de la silice fumée ou de la silice colloïdale, ou des combinaisons de celles-ci. 48. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite silice a une zone de surface BET allant d’environ 20 m2/g àenviron 450 m2/g. 49. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit latex d'élastomère est du latex de caoutchouc naturel. 50. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit latex de caoutchouc naturel est sous la forme de latex de plantation, de concentré de latex, de latex décanté, de latex chimiquement modifié, de latex enzymatiquement modifié, ou toute combinaison de ceux-ci. 51. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit latex de caoutchouc naturel est sous la forme de latex de caoutchouc naturel époxydé. 52. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit latex de caoutchouc naturel est sous la forme de concentré de latex. 53. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre le mélange du composite élastomère-silice avec un élastomère supplémentaire pour former un mélange de composite élastomère. 54. Procédé pour fabriquer un composé de caoutchouc comprenant (a) l'exécution du procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, et (b) le mélange du composite élastomère-silice avec d'autres composants pour former le composé de caoutchouc, dans lequel lesdits autres composants comprennent au moins un antioxydant, du soufre, un polymère autre qu'un latex d'élastomère, un catalyseur, une huile de dilution, une résine, un agent de couplage, un ou plusieurs composites élastomère supplémentaires ou un agent de remplissage de renforcement, ou toute combinaison de ceux-ci. 55. Procédé pour fabriquer un article de caoutchouc sélectionné parmi les pneumatiques, les moulages, les fixations, les revêtements, les convoyeurs, les joints ou les chemises, comprenant (a) l'exécution du procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, et (b) le mélangeage du composite élastomère-silice avec d'autres composants pour former un composé, et (c) la vulcanisation du composé pour former ledit article de caoutchouc. 56. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre l'exécution d'une ou plusieurs étapes post-traitement supplémentaires après la récupération du composite élastomère-silice. 57. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les étapes de post-traitement comprennent au moins une étape parmi : a) l'assèchement du composite élastomère-silice pour obtenir un mélange asséché ; b) le mélange ou le mélangeage du mélange asséché pour obtenir un composite élastomère-silice composé ; c) le broyage du composite élastomère-silice composé pour obtenir un composite élastomère-silice broyé ; d) la granulation ou le mélange du composite élastomère-silice broyé ; e) le pressage du composite élastomère-silice après la granulation ou le mélange pour obtenir un composite élastomère-silice pressé ; f) l'extrusion du composite élastomère-silice ; g) le calandrage du composite élastomère-silice ; et/ou h) la décomposition facultative du composite élastomère-silice pressé et le mélange avec d'autres composants. 58. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les étapes de post-traitement comprennent au moins une étape de laminage du composite élastomère-silice. 59. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel les étapes de post-traitement comprennent la compression de la phase continue de caoutchouc solide ou semi-solide contenant de la silice pour éliminer environ 1 % en poids à environ 15 % en poids du fluide aqueux contenu dans celle-ci. 60. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel le latex d'élastomère est amené en contact avec au moins un agent de déstabilisation lorsque la dispersion déstabilisée de silice est combinée avec le latex d'élastomère. 61. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre la mise en contact du flux de phase continue de caoutchouc solide ou semi-solide contenant de la silice avec au moins un agent de déstabilisation. 62. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre l'étape d'exécution d'une ou plusieurs des étapes suivantes avec la phase continue de caoutchouc solide ou semi-solide contenant de la silice : a) le transfert de la phase continue de caoutchouc solide ou semi-solide contenant de la silice dans un réservoir ou un récipient de retenue ; b) le chauffage de la phase continue de caoutchouc solide ou semi-solide contenant de la silice pour réduire la teneur en eau ; c) l’exposition de la phase continue de caoutchouc solide ou semi-solide contenant de la silice à un bain d'acide ; d) le traitement mécanique de la phase continue de caoutchouc solide ou semi-solide contenant de la silice pour réduire la teneur en eau. 63. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit composite élastomère-silice est une phase continue de caoutchouc semi-solide contenant de la silice et ledit procédé comprenant en outre la conversion de ladite phase continue de caoutchouc semi-solide contenant de la silice en phase continue de caoutchouc solide contenant de la silice. 64. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite phase continue de caoutchouc semi-solide contenant de la silice est convertie en ladite phase continue de caoutchouc solide contenant de la silice par traitement avec un fluide aqueux comprenant au moins un acide ou au moins un sel ou une combinaison d'au moins un acide et d'au moins un sel. 65. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit second fluide comprend un mélange de deux ou plus latex d'élastomère différents. 66. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ledit procédé comprend en outre la fourniture d'un ou plusieurs fluides supplémentaires et la combinaison du ou des fluides supplémentaires avec lesdits premier et second flux de fluide, dans lequel ledit ou lesdits fluides supplémentaires comprennent un ou plusieurs fluides de latex d'élastomère et lesdits fluides supplémentaires sont identiques ou différents dudit latex d'élastomère présent dans ledit second flux de fluide. 67. Procédé selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, dans lequel ladite teneur en silice dudit composite élastomère-silice est comprise d’environ 26 phr à environ 180 phr. 68. Article de la phase continue de caoutchouc solide contenant de la silice et du noir de carbone comprenant au moins 25 parties par cent parties en poids de caoutchouc (phr) de silice dispersée dans du caoutchouc naturel et au moins 40 % en poids de fluide aqueux, et ayant une dimension en longueur (L), dans lequel l'article de la phase continue de caoutchouc solide contenant de la silice peut être étiré jusqu'à au moins 130 à 150 % de (L) sans se rompre. 69. Article de la phase continue de caoutchouc solide contenant de la silice et du noir de carbone selon l'un quelconque des modes de réalisation/attributs/aspects précédents ou suivants, comprenant en outre 10phr de noir de carbone dispersé dans ledit caoutchouc naturel.
[0166] La présente invention peut comprendre toute combinaison de ces différents attributs ou modes de réalisation ci-dessus selon la description figurant dans les phrases et/ou les paragraphes du présent document. Toute combinaison des attributs décrits dans le présent document est considérée comme une partie de la présente invention et aucune limitation n'est prévue par rapport aux attributs combinables.
[0167] Les demandeurs incorporent spécifiquement la totalité du contenu de toutes les références citées dans la présente invention. En outre, lorsqu'une quantité, une concentration ou une autre valeur ou paramètre est donnée sous forme de plage, de plage préférée ou de liste de valeurs préférables supérieures et de valeurs préférables inférieures, il faut les considérer comme.décrivant spécifiquement toutes les plages formées de toute paire de toute limite de plage supérieure ou de valeur préférée et de toute limite de plage inférieure ou de valeur préférée, que les plages soient ou non décrites séparément. Lorsqu'une plage de valeurs numériques est citée dans le présent document, sauf indication contraire, la plage est supposée inclure les extrémités de celle-ci, ainsi que tous les entiers et toutes les fractions à l'intérieur de la plage. Il n'est pas prévu que le champ d'application de l'invention soit limité aux valeurs spécifiques citées lors de la définition d'une plage.
[0168] D'autres modes de réalisation de la présente invention seront évidents aux hommes du métier en tenant compte des présentes spécifications et pratique de la présente invention décrites dans la présente description. Il est prévu que la présente spécification et les présents exemples soient considérés comme illustratifs uniquement, les véritables champs d'application et esprit de l'invention étant indiqués dans les revendications suivantes et équivalents de celles-ci.
The present invention relates to processes for manufacturing elastomer composites reinforced with particles. More specifically, the present invention relates to a particle-reinforced elastomer composite formed by a wet masterbatch process. [0002] Many commercial products are formed from elastomeric compositions in which a reinforcing material is dispersed in any of a variety of synthetic elastomers, natural rubber or elastomer blends. Carbon black and silica, for example, are widely used as reinforcing agents in natural rubber and other elastomers. It is common to manufacture a masterbatch, that is, a premix of reinforcing material, elastomer and various optional additives, such as the diluent oil. Many commercial products are formed of such elastomeric compositions. Such products are, for example, vehicle tires in which different elastomeric compositions can be used for the tread portion, the side walls, the metal siding and the carcass. Other products are, for example, motor support rings, conveyor belts, wipers, seals, liners, wheels, bumpers and the like.
The good dispersion of particulate reinforcing agents in rubber compounds has been recognized for some time as one of the main objectives for obtaining products of good quality and consistent performance and considerable efforts have been made. dedicated to the development of processes to improve the quality of dispersion. Masterbatch and other mixing operations have a direct impact on mixing efficiency and dispersion quality. In general, for example when carbon black is used to reinforce rubber, acceptable macrodispersions of carbon black can often be obtained in a dry blended masterbatch. On the other hand, the high quality and the uniform dispersion of the silica in dry blending processes are problematic and various solutions have been proposed by the industry to solve them, such as precipitated silica in the form of "highly dispersible silica" or "HDS" or granulated paste. More intensive mixing can improve the dispersion of the silica, but can also degrade the elastomer in which the filler is dispersed. This is a particularly important problem in the case of natural rubber which is very sensitive to mechanical / thermal degradation.
In addition to dry mixing techniques, it is known to feed a stirred tank of elastomer latex or polymer solution and carbon black or silica slurry. Such "wet masterbatch" techniques can be used with natural rubber latex and emulsified synthetic elastomers, such as butadiene-styrene rubber (SBR). On the other hand, if this wet technique appeared promising when the filler is carbon black, this wet technique, when the filler is silica, is problematic in obtaining a composite of acceptable elastomer. Specific techniques for the production of a wet masterbatch, such as those described in US Patent No. 6,048,923, the contents of which have been incorporated by reference herein, have not been effective in producing elastomer composites using silica particles as the sole or major reinforcing agent.
[0005] Therefore, it is necessary to improve processes that incorporate silica and carbon black in elastomer composites in a wet masterbatch process, such as one that uses the combination of two fluids. in high continuous energy impact conditions, so as to obtain an acceptable elastomer composite comprising silica particles as sole or main reinforcing agent.
SUMMARY OF THIS INVENTION
According to one of its aspects, the present invention relates to processes for producing elastomer composites using a wet masterbatch process which makes it possible to use silica and carbon black, and thus obtaining elastomer composites reinforced with desired particles.
To achieve these and other advantages, and in accordance with the objectives of the present invention, set forth and widely described in the present description, the present invention relates to the controlled or selective placement or introduction of silica and silica. carbon black in a wet masterbatch process which forms a particle-reinforced elastomer composite.
The present invention further relates to a method of manufacturing an elastomer composite in a wet masterbatch process which includes, but is not limited to, the use of a fluid which comprises an elastomer latex. and the use of an additional fluid which comprises a destabilized dispersion of particulate silica and carbon black. The "additional fluid" is provided either as i) two streams comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or ii) a single stream comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or iii) a destabilized dispersion comprising silica and carbon black. Both fluids are combined under continuous flow conditions and at selected speeds. The combination is such that the silica and the carbon black are dispersed in the elastomer latex and, in parallel (or almost), the elastomer latex passes from a liquid elastomer composite to a solid elastomer composite or semi-solid, as in a continuous phase of solid or semi-solid rubber containing silica. This transformation can occur, for example, in about two seconds or less, as in a fraction of a second, because of the impact of the fluid on the other fluid with sufficient energy to cause a uniform and intimate distribution of the particles. silica and carbon black in the elastomer. The use of a destabilized silica dispersion in this masterbatch process allows the formation of an elastomer composite having desired properties.
The present invention further relates to elastomer composites formed from one or more methods of the present invention. The present invention also relates to articles which are made from the one or more elastomer composites according to the present invention or which comprise this or these.
It is understood that the preceding general description and the following detailed description are only illustrative and explanatory and are not intended to provide a further explanation of the present invention according to the claims.
The accompanying drawings, which are incorporated in and constitute a part of this invention, illustrate various aspects of the present invention and, together with the description, serve to explain the principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 (a), 1 (b) and 1 (c) are diagrams illustrating illustrative mixing apparatus which can be used in the present invention and which have been used in some of the examples.
[0013] FIG. 2 is a block diagram of various steps that may be performed during the formation of the elastomer composite according to embodiments of the present invention and in the manufacture of the rubber compounds with such elastomer composites.
FIGS. 3-7 are functional diagrams of the various steps that can be performed for the formation of the dispersion containing silica and carbon black for use in the mixing apparatuses that can be used in the present invention.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to the selective and strategic introduction of silica, as well as carbon black, into an elastomer latex during a continuous and rapid wet master batch process. This process can be carried out in a semi-confined reaction zone, such as a tubular mixing chamber or any other mixing chamber of an apparatus suitable for carrying out such a process under the control of volumetric flow rate and speed parameters. , giving rise to beneficial properties that would not be obtained except for this selective and strategic use of silica, in particular. As explained in more detail herein by "selective", the present invention utilizes a destabilized silica dispersion. And for the "strategic" introduction, the present invention utilizes at least two separate fluids, a fluid that comprises an elastomer latex and another fluid that comprises the destabilized dispersion of silica and carbon black. Both fluids can be pumped or transferred to a reaction zone, such as a semi-confined reaction zone. Both fluids can be combined under continuous flow conditions and under selected volumetric flow and velocity conditions. The pressurized combination with selected differential speed conditions is sufficiently energetic that the silica and the carbon black can be dispensed in two seconds or less, as in milliseconds, in the elastomer lastex, and the elastomer latex passes from a liquid phase to a solid phase, such as a particulate-reinforced elastomer composite in the form of a continuous phase of solid or semi-solid rubber containing silica and carbon black.
The present invention relates in part to a method for producing an elastomer-silica composite, consisting essentially of, or comprising: (a) providing a continuous stream under pressure of at least a first fluid comprising a destabilized dispersion of particles (eg, silica and carbon black) and providing a continuous stream of a second fluid comprising an elastomer latex; (b) adjusting the volumetric flow rates of the first fluid and the second fluid to obtain an elastomer composite having a silica content of from about 15 phr to about 180 phr; and (c) combining the flow of the first fluid and the flow of the second fluid (e.g. in a semi-confined reaction zone) with sufficient impact to dispense silica and carbon black into the elastomer latex, to to obtain a flow of a continuous phase of solid rubber containing silica and carbon black or a continuous phase of semi-solid rubber containing silica and carbon black. The process converts the elastomer latex of a liquid into a stream of a continuous phase of solid or semi-solid rubber containing silica and carbon black. The continuous phase of rubber containing silica and carbon black can be recovered as a substantially continuous stream of the solid or semi-solid rubber-containing continuous phase containing silica and carbon black. With respect to (a) the first fluid, the first fluid may be provided in either (i) two streams comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or in (ii) a single stream comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or iii) a destabilized dispersion comprising silica and carbon black. Other details and / or options for the methods of the present invention are described below. Other variants of i), ii) and iii) are also presented in detail below.
As used herein, the term "silica" refers to particulate silicone dioxide or a particle coated with silicone dioxide, and includes precipitated silica in any form, such as highly dispersible granules. (HDS), non-HDS granules, silica aggregates and silica particles; colloidal silica; fumed silica; and all combinations of these. This silicone dioxide or these silicone dioxide coated particles may have been chemically treated to include bonded (bonded (eg, chemically fixed) or adhered (eg, adsorbed) functional groups to the silica surface. silica "comprises any particle having a surface consisting essentially of silica or silica having functional groups bound to or attached thereto.
As used herein, the term "dispersion" refers to a stable suspension of solid particles in an aqueous fluid, wherein the charge on the surface of the particles prevents agglomeration of particles and the dispersion is characterized by an amplitude of zeta potential greater than or equal to 30 mV.
The zeta potential is used to measure the stability of charged particles, such as silica particles, dispersed in a fluid. The measurement of the zeta potential may have a variance of 1-2 mV, for example, and, used herein, the amplitude of the zeta potential refers to the absolute value of the number, e.g., a zeta potential value of minus 30 mV has an amplitude greater than the zeta potential value of minus 10 mV.
As used herein, the term "destabilized dispersion" refers to a suspension of solid particles in an aqueous fluid, wherein the charge on the surface of the particles has been reduced by the presence of an agent. or by the treatment of solid particles and is characterized by a zeta potential amplitude of less than 30 mV, or preferably a zeta potential of less than 28 mV or less than 25 mV. The aqueous fluid may be water, a water-miscible fluid (e.g., alcohol or ether), a fluid partially miscible with water, or a fluid mixture that contains at least one fluid miscible in water or partially miscible in water.
As used herein, the terms "silica slurry" and "dispersion" refer to a dispersion of silica (which may also include carbon black) in an aqueous fluid, wherein the the surface of the silica prevents agglomeration of particles and the dispersion is characterized by a zeta potential value of at least 30 mV amplitude. A slurry or a silica dispersion can be destabilized by treatment with one or more sufficient agents or by the treatment of the silica, to reduce the charge on the surface of the silica, and the resulting destabilized silica slurry (or dispersion of destabilized silica) is characterized by a zeta potential amplitude of less than 30 mV.
As used herein, the terms "uniform" and "uniformly" are meant to mean, traditionally for those skilled in the art, that the concentration of a component, for example a particulate filler, in any fraction or percentage (eg, 5%) of a volume, is the same (eg, within 2%) as the concentration of that component in the total volume of the material in question, eg a composite or an elastomer dispersion. Those skilled in the art will be able to verify the statistical uniformity of the material, if necessary, by measuring the concentration of the component using several samples taken at different locations (for example, near the surface or deeper into the mass). ).
As used herein, the term "elastomeric-silica composite" refers to a masterbatch (a premix of reinforcing material (which may include carbon black), elastomer, and various optional additives, such as coherent rubber diluent oil comprising an amount of reinforcement (e.g., from about 15 phr to about 180 phr) of dispersed silica. The elastomer-silica composite may optionally contain other components, such as an acid, a salt, an antioxidant, anti-degradants, coupling agents, minor amounts (e.g., 10% by weight or less of total mass of particles) of other particles, processing aids and / or dilution oil, or any combinations thereof.
As used herein, the term "continuous phase of solid rubber containing silica and carbon black" or "continuous phase of solid rubber containing particles" corresponds to a composite having a continuous phase of rubber and a uniformly dispersed phase of reinforcing particles (e.g., silica and carbon black) and, for example, up to 90%, by weight of aqueous fluid. The continuous phase of solid rubber containing silica and carbon black may be in the form of a rope or a continuous worm. When compressed, these items release water. The continuous phase of solid rubber containing silica and carbon black may optionally contain other optional components, such as an acid, a salt, an antioxidant, coupling agents, minor amounts of other particles (eg 10% by weight or less of total mass of particles) and / or dilution oil, or any combinations thereof.
As used herein, the term "continuous phase of semi-solid rubber containing silica and carbon black" refers to a composite having a paste consistency having a continuous rubber phase containing silica and carbon black. The semi-solid product has a continuous rubber phase, the trapped silica and carbon black being uniformly distributed in the rubber phase. The continuous phase of semi-solid rubber containing silica and carbon black remains coherent and expels the water, while retaining the solids content, during subsequent processing in one or more subsequent operations selected to evolve the material of the invention. paste or gel type in a continuous phase of solid rubber containing silica and carbon black.
As used herein, a "coherent" material is an existing material in a substantially unitary form that has been created by adhesion of many smaller particles, such as a solid elastic rubber mass created by the adhesion of many small particles. rubber to each other.
In this document, a "continuous flow" is a stable or constant flow of fluid without interruption from the power source (eg, a tank). But, it is understood that in case of temporary interruptions (eg, a second or a few minutes), the flow would nevertheless be considered as a continuous flow (eg, during a permutation of the feeding between different supply areas, such as tanks or the like, or flow interruption to accommodate downstream unit processes or maintenance of equipment).
FIGS. 3-7 show various process examples that can be used to prepare a destabilized dispersion that contains silica with carbon black. These exemplary methods do not exhaustively represent the various methods that can be carried out using the methods of the present invention. In FIG. 3, carbon black 300 (e.g., in the form of granules or particles) is combined with water or an aqueous fluid 302 to form a slurry of carbon black 306. The carbon black slurry can be then subjected to one or more shaking and / or grinding and / or crushing and / or other mechanical processing steps, to other non-mechanical processing steps, as described in Box 310. Designated Boxes dotted lines in the figures represent optional steps or methods that may be used. In general, with one or more of the treatment steps 310, a carbon black slurry 314 is obtained which is a uniformly dispersed carbon black slurry that is substantially free of larger agglomerated particles. In parallel with these steps, water or an aqueous fluid 302, from the same source or from a source different from that of the carbon black, is combined with the silica 304 to form a silica slurry 308. silica may be subjected to various processing steps, such as grinding and / or agitation and / or crushing and / or other mechanical and / or non-mechanical processing steps, as well as other steps described in the present document to obtain a destabilized dispersion which contains or comprises silica. As described herein, the additional step (s) 312 may comprise adding at least one acid and / or salt to form the destabilized slurry dispersion 316. Next, the carbon black slurry and the destabilized silica slurry may be considered the "first fluid" for purposes of the present invention, but as illustrated in FIG. 3, slurries are added as two separate streams in reaction zone 103; a stream containing the dispersion comprising the carbon black and the other stream containing the destabilized dispersion comprising the silica. The manner in which the two streams are introduced into the reaction zone 103 may use the same volumetric flow rates or different volumetric flow rates, and / or the same or different parameters and / or the same or different pressures. As illustrated in FIG. 3 and as described in the present invention, the second fluid which comprises the elastomer latex 105 is also introduced into the reaction zone 103.
[0029] Optionally, as illustrated in FIG. 4, a variant of the method of FIG. 3 can be used. For the purposes of the figures, the same reference numerals represent the same description as in FIG. 3, unless otherwise indicated. As illustrated in FIG. 4, carbon black 300 is combined with water or an aqueous fluid 302 to form a slurry of carbon black 306. In addition, water or an aqueous fluid 302, from the same source or from a different source, is combined with silica 304 to form a silica slurry 308. Further processing steps for the carbon black can be performed, as described in box 310, and further treatment of the silica slurry. to obtain a destabilized silica slurry can be performed as illustrated in box 312. Unlike FIG. 3, instead of using two separate streams to introduce the carbon black slurry and the silica slurry into the optional reaction zone 103, as illustrated in FIG. 4, the carbon black slurry and the destabilized dispersion comprising the silica are combined before the reaction zone 103, so as to form a single stream 318, which is identified as a mixed slurry (e.g., a destabilized particulate dispersion) , which is then introduced into the reaction zone 103.
In FIG. 5, an option is illustrated in which carbon black 300 and water or an aqueous fluid 302 are combined with silica 304 in a single tank 320 to form a slurry comprising carbon black and silica. The mixed slurry 320 may be optionally subjected to another treatment which may include milling, crushing, fluidizing, stirring and / or other processing steps to cause destabilization of the slurry with the silica present, such as the addition of at least one acid and / or a salt. It may be noted that since the mixed slurry comprises carbon black, the amount of destabilization may be less than that desired for a dispersion that contains an equivalent amount of carbon-free silica. Mixed slurry 324 (e.g., a destabilized particulate dispersion) can then be introduced into reaction zone 103.
In FIG. 6, carbon black 300 and silica 304 are combined to form a dry mixture of the two components 326, and then this dry mixture 326 is combined with water or aqueous fluid 350 to form a wet mix 328, which can then be subjected to further processing steps 330, which would be the same steps as those in FIG. For the treatment step 322. The well-mixed dispersed slurry 332 (eg, a destabilized particulate dispersion) then formed can then be introduced into the reaction zone 103.
In FIG. 7, silica 304 is combined with water or an aqueous fluid 302 to form a silica slurry 308 which can then be subjected to further processing steps 312, as shown in FIG. 3. This dispersion comprising silica 316 (eg, a destabilized silica dispersion) can then be introduced into the reaction zone 103. Then, dry carbon black in particulate form can be injected or otherwise introduced. either in the dispersion comprising the silica 316 before its introduction into the reaction zone 103 or can be introduced separately 338, for example, fluidized carbon black in a stream of air, in the reaction zone 103, while the destabilized dispersion comprising silica 316 is introduced into the reaction zone 103 or the carbon black can be introduced into the latex stream 340.
The ratio by weight (or on the basis of a total weight of filler) silica-carbon black for any of the processes according to the present invention may be between about 45:55 or 50: 50 (silica: carbon black) and less than 90:10 or 89.9: 10, or between 50:50 and 89:11 or between 60:40 and 85:15 or between 70:30 and 80:20.
The elastomer composite may be produced in a continuous flow process comprising a liquid mixture of elastomer latex and destabilized silica dispersion (which may comprise carbon black). Any device, apparatus or system may be used, so long as the device, apparatus or system can be operated such that a liquid mixture of elastomer latex and a destabilized dispersion of silica (which may contain carbon black) may be combined under continuous flow conditions and under controlled conditions of volumetric flow, pressure and velocity including, but not limited to, the apparatus shown in Figure 1 (a), (b) ) or (c), or any type of injection nozzle or ejector, or any other device designed to combine a continuous flow of two or more liquid streams under controlled conditions of volumetric flow, pressure and velocity and in a reaction zone. The apparatus disclosed in US20110021664, US6048923, WO2011034589, WO2011034587, US20140316058 and WO2014110499 (each fully incorporated for reference) may also be used or adapted for the methods herein. Similarly, ejectors and injection nozzles or siphons, such as water jet injection nozzles or water jet siphons, may be used (eg, those marketed by Schutte & Koerting, Trevose, PA).
The apparatus may comprise different feed tanks, pipes, valves, meters and pumps to control the volumetric flow, pressure and speed. Further, as indicated at the inlet (3) in Figs. 1 (a), (b) and (c), different types and sizes of nozzles or other orifice size control elements (3a) may be used to control the speed of the silica slurry. The volumetric dimension of the reaction zone (13) may be chosen to provide the desired volumetric flow rates of the fluids and the elastomer composite. The inlet (11) supplying the reaction zone with elastomer latex can be tapered to provide different volumetric flow rates and speeds. Devices may include an inlet (11) of uniform diameter without a cone at the orifice leading to the reaction zone.
In the process, a fluid which comprises an elastomer latex and an additional fluid which comprises a destabilized dispersion of silica and carbon black supplied in a stream or in separate streams, for example, in a jet under pressure, are combined in continuous flow conditions and at volumetric flow rates, pressure and speeds selected to rapidly and intimately mix the two fluids. The combination, for example in a semi-confined space under pressure, is such that the silica and the carbon black are distributed in the elastomer latex and, at the same time, the elastomer latex is transformed from a liquid phase to a solid or semi-solid phase, i.e. a liquid-solid inversion or coagulation, latex occurs, capturing the distributed silica and carbon black and the water in the rubber and forming a continuous phase of solid or semi-solid rubber containing silica and carbon black in a continuous or semi-continuous stream out of the reaction zone (eg, through the opening in the lower part (7) on Figures 1 (a) - (c)). At this point, the product can be considered as an elastomer composite of a continuous rubber phase containing silica particles, a coherent rubber containing silica or a particle-reinforced elastomer composite. It is believed that the silica and carbon black particles must first be distributed in the elastomer latex to obtain the desired product, the liquid-solid phase inversion occurring immediately after the distribution of the silica and carbon black. carbon. On the other hand, with the continuous and very fast speed of the combination of the fluids (that is to say less than 2 seconds, less than 1 second, less than 0.5 seconds, less than 0.25 seconds, less than 0.1 second or on the order of a few milliseconds), and the energetic and intimate mixing of relatively small volumes of fluids in the reaction zone (e.g., fluid volumes of the order of 10 to 500 cc) the parallel steps of distributing the silica and carbon black particles and the transition from the liquid phase to the solid phase of the elastomer latex can occur almost simultaneously. The "reaction zone" used in this document represents the area where intimate mixing occurs, as well as the coagulation of the mixture. The mixture moves in the reaction zone and to an outlet (7).
An illustrative method for preparing the elastomer composite comprises simultaneously feeding a first fluid comprising a destabilized dispersion of silica and carbon black (provided in one stream or in two separate streams) and a second one. fluid comprising an elastomer latex (eg, natural rubber latex) liquid to a reaction zone. The first fluid comprising the destabilized dispersion of silica and carbon black can be fed at a rate based on its volume and the second fluid comprising the elastomer latex can be fed at a rate based on its volume (i.e. ie, volumetric flow rates). The volumetric flow rates of the first fluid or the second fluid or the first and second fluids may be adjusted or provided to obtain an elastomer composite having a silica content of between 15 and 180 parts per hundred parts by weight of rubber (phr ) (eg between 35 and 180 phr, between 20 and 150 phr, between 25 and 125 phr, between 25 and 100 phr, between 35 and 115 phr or between 40 and 115 phr or between 40 and 90 phr and the like). The fluid that contains the destabilized dispersion of particles (eg, silica and carbon black) may be referred to as the first fluid in some embodiments of the present invention. This fluid is a fluid separated from the fluid containing the elastomer latex. Each fluid can be introduced through an inlet or an injection point or through several inputs or injection points.
The volumetric flow ratio between the first fluid (fluid which contains at least the destabilized dispersion of silica and carbon black) and the second fluid (liquid latex) can be adjusted to allow the desired elastomer composite to form. Examples of such volumetric flow ratios include, but are not limited to, a volumetric ratio of between 0.4: 1 (first fluid to second fluid) and 3.2: 1; between 0.2: 1 and 2: 1 and the like. The volumetric flow ratio between the first fluid and the second fluid can be adjusted by any means or technique. For example, the volumetric flow rate of the first or second fluid or both fluids can be adjusted by a) increasing the volumetric flow rate, b) reducing the volumetric flow rate, and / or c) adjusting the flow rates of the fluids. one compared to the other. The pressure created by physical stresses applied to the flow of the first fluid causes the formation of a high velocity jet which allows the combination of the destabilized silica dispersion with the elastomer latex to occur rapidly, ie say in a split second. As an example, the time during which two fluids are mixed and during which a liquid-solid phase inversion occurs can be of the order of a few milliseconds (e.g., between about 50 ms and about 1500 ms or about 100 msec. ms and about 1000 ms). For a given selection of fluids, if the speed of the first fluid is too slow for proper fluid mixing, or if the residence time is too short, a solid rubber phase and a solid product stream may not develop. . If the process time is too long, a return pressure may develop in the reaction zone and the continuous flow of materials will stop. Similarly, if the speed of the first fluid is too fast and the process time is too short, a solid rubber phase and a solid product stream may not develop.
As described above, the relative volumetric flow rates of the first fluid (slurry destabilized silica and carbon black in the form of a stream or two separate streams) and the second fluid (latex) can be adjusted and when the less a salt is used as a destabilizing agent, it is preferable to adjust the volumetric flow ratio of the destabilized particulate slurry with respect to the elastomer latex so that it is between 0.4: 1 and 3 , 2: 1. Other flow reports can be used.
When at least one acid is used as a destabilizing agent, it is preferable to adjust the volumetric flow ratio of the destabilized silica slurry (or destabilized particulate slurry) relative to the elastomer latex so that it is between 0.2: 1 and 2: 1. Other flow reports can be used.
The elastomer latex may contain at least one base (such as ammonia), and the destabilized silica dispersion (or the destabilized particulate dispersion) may be obtained by the addition of at least one acid, in wherein the molar ratio of the acid in the first fluid (silica) and the base (eg, ammonia) in the second fluid (latex) is at least 1.0 or at least 1.1 or minus 1.2, for example between 1 and 2 or between 1.5 and 4.5. The base may be present in different amounts in the elastomer latex, such as, but not limited to, 0.3% by weight to about 0.7% by weight (based on the total weight of the elastomer latex) or other quantities lower or higher than this range.
The destabilized particulate dispersion in the form of a stream or two separate streams may be fed into the reaction zone preferably in the form of a continuous jet at high speed of injected fluid, for example, between about 6 m / s and about 250 m / s, or between about 30 m / s and about 200 m / s, or between about 10 m / s and about 150 m / s, or between about 6 m / s and about 200 m / s, and the fluid containing the elastomer latex can be fed at a relatively slower rate, e.g., between about 0.4 m / s and about 11 m / s, or between about 0.4 m / s and about 5 m or s, or between about 1.9 m / s and about 11 m / s, or between about 1 m / s and about 10 m / s or between about 1 m / s and about 5 m / s. The fluid velocities are chosen to optimize the mixing between the fluids and the rapid coagulation of the elastomer latex. The velocity of the elastomer latex introduced into the reaction zone should preferably be high enough to generate a turbulent flow to optimize mixing with the destabilized particulate slurry. Nevertheless, the velocity of the elastomer latex should be kept low enough so that the latex does not coagulate by shearing before it is well mixed with the destabilized particulate slurry. In addition, the speed of the elastomer latex should be kept low enough before it enters the reaction zone to prevent clogging of latex feed lines due to coagulation of the latex due to high shear. Likewise, there is also an optimized range of the speed of the destabilized particulate dispersion. In theory, if the velocity of the destabilized particulate slurry is too high, shear rate-induced particle agglomeration may be too high to allow adequate uniform mixing between the silica (and carbon black) particles and the particles. elastomer latex particles.
If in the present invention, silica and carbon black are mixed with the latex, the silica is generally the particle which requires destabilization in this process in order to obtain a continuous phase of solid rubber or semi-solid desirable. Thus, part of the discussion in this discussion concerns silica and its stabilization, knowing that it also applies to particulate dispersions that include not only silica, but also carbon black.
The shear thickening resulting from the agglomeration and the formation of a network of silica particles could also reduce the turbulence of the destabilized silica slurry and adversely affect the mixture between the silica and the latex. On the other hand, if the velocity of the destabilized silica slurry is too low, mixing between the silica particles and the elastomer latex particles may not be sufficient. Preferably, at least one of the fluids entering the reaction zone has a turbulent flow. In general, because of the much higher viscosity of a typical destabilized silica dispersion over a typical elastomer latex, a much higher velocity of the destabilized silica dispersion is required to generate good fluid dynamics with the latex. of elastomer and rapid coagulation of the latex. Such a high velocity flow of the destabilized silica dispersion can induce cavitation in the reaction zone to improve rapid fluid mixing and distribution of silica particles in the elastomer latex. The speed of the destabilized silica dispersion can be varied using different volumetric flow rates, or different nozzle or nozzle (having a wider or narrower diameter) at the inlet (3a) which introduces the first fluid comprising a destabilized silica dispersion. By using a nozzle to increase the speed of the destabilized silica dispersion, the latter can be supplied at a pressure of between about 30 psi and about 3000 psi, or about 30 psi to about 200 psi, or about 200 psi to about 3000 psi, or between about 500 psi and about 2000 psi or a relative pressure at least 2 times higher than the pressure applied to the fluid containing the elastomer latex or between 2 and 100 times greater. The second elastomeric latex fluid may be provided, for example, at a pressure of from about 20 psi to about 30 psi. The pressure in the first fluid supply system can be up to about 500 psi.
On the basis of the production variables described in the present invention, such as the velocity of the destabilized particulate slurry fluid, the velocity of the latex fluid, the relative flow rates of destabilized particulate slurry fluids and latex, the concentration of the destabilizing agent, such as a salt and / or an acid, the concentration of silica in the destabilized slurry, the percentage of rubber weight in the latex, the concentration of ammonia in the latex and / or the acid / ammonia ratio (If present), it is possible to control, obtain and / or predict the formation of a continuous phase of solid or semi-solid rubber containing silica over a desired silica content range. Thus, the method can be performed over an optimized range of variables. Thus, a) the velocity of one or both fluids, b) the volumetric flow ratio between the fluids, c) the destabilized nature of the silica, d) the particulate silica concentration, e.g., between 6 and 35 % by weight, of the destabilized silica dispersion, and e) the dry rubber content, e.g., between 10 and 70% by weight of the latex, can allow mixing under high impact conditions so as to cause an inversion liquid-solid elastomer latex and uniformly disperse the silica in the latex at a selected silica-rubber ratio, and thereby form a stream of a continuous phase of solid or semi-solid rubber containing silica. The recovery of the continuous phase flow of solid or semi-solid rubber containing silica can be obtained by any conventional technique for recovering a solid or semi-solid flow of material. The recovery may allow the solid or semi-solid stream to enter a container or reservoir or other restraining device. Such a container or holding tank may contain a solution of salt or acid or both to further coagulate the product in a more elastic state. For example, the recovery may be the transport or pumping of the solid stream to other areas or treatment devices some of whose options are described in this document. Recovery can be continuous, semi-continuous or discontinuous. The end of the flow leaving the reaction zone is preferably semi-confined and open to the atmosphere and the flow of solid or semi-solid elastomer composite is preferably recovered at ambient pressure to allow the continuous operation of the process. .
The flow of a continuous phase of solid rubber containing silica and carbon black may be in the form of one or more "worms" of rope type or more or less elastic globules. The continuous phase of solid rubber containing silica and carbon black may be capable of being stretched between 130 and 150% of its original length without breaking. In other cases, a continuous phase of semi-solid rubber containing silica and carbon black may be in the form of non-elastic viscous paste or gel material which can develop elastic properties. In each case, the outlet is a coherent solid flowing, whose consistency can be very elastic or slightly elastic and viscous. The output of the reaction zone may be a substantially constant flow concurrent with the current feed of elastomer latex fluids and destabilized silica dispersion into the reaction zone. Process steps, such as fluid preparation, can be performed in continuous, semi-continuous, or batch operations. The continuous phase of solid or semi-solid rubber containing silica and resulting carbon black may be subjected to subsequent additional processing steps, including continuous, semicontinuous or discontinuous operations.
The continuous phase of solid or semi-solid rubber containing silica and carbon black created in the process contains water, or other aqueous fluid, and solutes from the original fluids, and, for example, may contain from about 40% by weight to about 95% by weight of water or from about 40% by weight to about 90% by weight of water, or from about 45% by weight to about 90% by weight of water, or between about 50% by weight and about 85% by weight of water content, or between about 60 and about 80% by weight of water, based on the total weight of the flow of the reinforced elastomer composite in particles. Optionally, after formation of the continuous phase of solid or semi-solid rubber containing silica and carbon black comprising such a water content, this product may be subjected to suitable dewatering and chewing steps and mixing steps to develop the desired rubber properties and manufacture rubber compounds. Further details of the process and other post-processing steps are described below and may be used in any embodiment of the present invention.
A continuous phase of semi-solid rubber containing silica and carbon black can be converted into a continuous phase of solid rubber containing silica and carbon black. This can be done by subjecting the continuous phase of semisolid rubber containing silica and carbon black to mechanical steps which remove the water from the composite and / or allowing the semisolid material to stand for a certain time ( eg, after recovery in the reaction zone at an off-line site) for example, between 10 minutes and 24 hours or more; and / or by heating the continuous phase of semisolid rubber containing silica and carbon black to remove the water content (e.g., at a temperature of from about 50 ° C to about 200 ° C); and / or subjecting the semi-solid material to an additional acid or acid such as an acid bath, or to an additional salt or salt, or to a salt bath, or to a combination of acid and salt, and the like. One or more or all of these steps may be used. In fact, one or more or all of these steps may be used for one or more additional processing steps, even when a continuous phase of solid rubber containing silica and carbon black is initially or subsequently recovered.
The degree of destabilization of the silica slurry determines, at least in part, the amount of silica that may be present in the elastomer-silica composite (e.g., captured and evenly distributed in the composite) for a concentration of silica given in the silica slurry and a given dry rubber content of the latex. At selected lower silica-rubber target ratios (e.g., between 15 phr and 45 phr), the concentration of destabilizing agent may not be sufficiently high in the silica slurry and ultimately the silica / latex mixture may be at risk. rapidly coagulate and form a continuous phase of solid or semi-solid rubber containing silica. In addition, the selection of appropriate concentrations of silica and rubber and appropriate relative fluid flow rates, as described herein, are aspects to be considered in forming the solid or semi-solid product. For example, at relatively low volumetric flow ratios between the destabilized slurry and the latex, the amount of destabilizing agent in the destabilized silica slurry may not be sufficient to allow rapid coagulation of the elastomeric latex in the zone. of reaction. In general, for a given elastomer latex, lower silica fillers can be obtained by increasing the destabilization of the silica slurry and / or reducing the weight percent of the silica in the destabilized slurry.
When a silica dispersion is destabilized, the silica particles tend to flocculate. When a silica dispersion is too strongly destabilized, the silica may "fall" from the solution and become unsuitable for use in the preferred embodiments.
When destabilization occurs, the surface charges on the silica are generally not completely eliminated. On the other hand, sometimes, when the silica particle, or the silica dispersion, is treated to be destabilized, the isoelectric point (IEP) may change from a negative zeta potential to a positive zeta potential value. In general, for silica, the net charge on the surface of the silica particles is reduced and the amplitude of the zeta potential is reduced during destabilization.
For higher silica-rubber ratios in the elastomer and silica composite, higher silica concentrations can be selected in the destabilized slurry and / or volumetric flow ratio between the silica fluid and the fluid. higher latex. Once the silica slurry is destabilized and initially combined with the latex fluid, if the mixture does not coagulate, the volumetric flow ratio between the first fluid and the second fluid can be adjusted, for example by decreasing the volumetric flow rate of latex, which effectively achieves a higher silica-to-rubber ratio in the elastomer composite. At this step of adjusting the amount of latex present, the amount of latex is, or becomes, an amount which does not cause excessive dilution of the destabilizing agent concentration in the overall mixture so that the desired product can be formed in the residence time in the reaction zone. To obtain a desired silica-rubber ratio in the elastomer composition, various options are available. Optionally, the destabilization level of the silica slurry can be increased, for example by reducing the amplitude of the zeta potential of the destabilized silica slurry (e.g., by adding more salt and / or acid). Or, optionally, the concentration of silica in the destabilized silica slurry can be adjusted, for example, by reducing or increasing the concentration of silica in the destabilized silica slurry. Or, optionally, a latex having a higher rubber content may be used or a latex may be diluted to a lower rubber content, or the relative flow rate of the latex may be increased. Or, optionally, the flow rate and orifice size (where each can control or change the speed of the fluid or fluids), or the relative orientation of the two fluid streams can be modified to shorten or lengthen the residence time fluids combined in the reaction zone and / or modify the amount and type of turbulence at the point of impact of the first fluid on the second fluid. One, two or more of these options may be used to adjust the process parameters and achieve a target or desired silica-rubber ratio in the elastomer composite.
The amount or level of destabilization of the silica slurry is a major factor in the determination of the silica-rubber ratio obtainable in the elastomer-silica composite. A destabilizing agent used to destabilize the silica in the slurry may play a role in accelerating the coagulation of the elastomeric latex particles as the destabilized silica slurry is mixed with the elastomeric latex in the reaction zone. In theory, the coagulation rate of the latex in the reaction zone may depend on the concentration of the destabilizing agent in the combined fluids. It has been observed that by executing the process to produce an elastomer-silica composite under different conditions, a threshold concentration of a destabilizing agent present in the combined mixture of fluids at the time of mixing which is effective to produce can be determined. a continuous phase of solid or semi-solid rubber containing silica. An example of selection and adjustment of the process conditions to obtain the threshold concentration for obtaining a continuous phase of solid or semi-solid rubber containing silica is described in the examples below. If the threshold concentration for a given selection and composition of fluids, volumetric flows and velocities is not reached or exceeded, a continuous phase of solid or semi-solid rubber containing solid silica is generally not produced. .
The minimum amount of destabilization of the silica slurry (or destabilization of the particulate slurry) is indicated by an amplitude of the zeta potential of less than 30 mV (e.g., with zeta potentials in the range of -29.9 mV and about 29.9 mV, from about -28 mV to about 20 mV, from about -27 mV to about 10 mV, from about -27 mV to about 0 mV, from about -25 mV to about 0 mV, from about 20 mV and about 0 mV, between about -15 mV and about 0 mV, about -10 mV to about 0 mV and the like). If the particulate slurry has been destabilized to this zeta potential range, the silica in the destabilized slurry can be incorporated into a continuous phase of solid or semi-solid rubber containing silica when combined with the latex. elastomer.
If it may be desirable to destabilize the latex before combining it with the silica-containing slurry, under shear conditions such as those present during continuous pumping of the latex into the reaction zone, it is difficult to destabilizing the latex fluid beforehand without causing premature coagulation of the latex. In contrast, the destabilizing agent used in the destabilized silica slurry may be present in a higher amount to enhance destabilization of the latex and / or mitigate the dilution of the agent once the silica slurry has been destabilized and the latex combined. In another option, at particularly high silica concentrations (e.g.,> 25 wt% silica in the silica slurry), some destabilizing agent may be added separately to the destabilized silica slurry mixture. and elastomer latex in the reaction zone to enhance coagulation of the latex.
Without wishing to rally to any theory, the process for producing an elastomer-silica composite would form coherent networks interpenetrated rubber particles and silica aggregates in about two seconds or less, as in a fraction of second, when the two fluids combine and the phase inversion takes place, which produces a solid or semi-solid material comprising these networks with encapsulated water. Such rapid network formation allows the continuous production of a continuous phase of solid or semi-solid rubber containing silica. In theory, the shear-induced agglomeration of silica particles during the passage of the destabilized silica slurry through the inlet nozzle to be combined with the elastomer latex could be useful for creating a single particle arrangement and uniform in rubber masterbatches and capture silica particles in the rubber by hetero-coagulation between the silica and rubber particles. According to another theory, in the absence of an interpenetrating network, there could be no composite of a continuous phase of solid or semi-solid rubber containing dispersed silica particles, in the form of a worm, or solid pieces, for example, which encapsulates between 40 and 95% by weight of water and retains all or most of the silica in subsequent dewatering processes, including pressing and high-energy mechanical work. .
In theory, the formation of a silica network is due, at least in part, to the agglomeration of silica particles induced by shearing when the destabilized silica slurry passes through a nozzle under pressure (3a) to high speed through the first inlet (3) in the reaction zone (13), as illustrated in FIG. 1. This process is facilitated by reducing the stability of the silica in the destabilized slurry when the silica slurry has been destabilized (eg, treating the silica slurry with salt or acid or both).
In theory, the liquid-solid phase inversion of the latex may result from various factors, in particular shear-induced coagulation from the mixture with the high-speed jet of destabilized silica slurry, the interaction of the silica surface with the latex components, ionic or chemical coagulation due to contact with the silica slurry containing the destabilizing agent and the combination of these factors. In order to form a composite material comprising the interpenetrating silica network and the rubber network, the formation rates of each network, as well as the mixing speed, must be balanced. For example, for highly destabilized silica slurries having a high salt concentration in the slurry, agglomeration and formation of the silica particle network occurs rapidly under shear conditions. In this case, volumetric flow rates and velocities are adjusted so that the latex has a rapid coagulation rate for interpenetrating silica / rubber network formation. The formation velocities are slower with silica slurries slightly destabilized.
An exemplary method for producing a particulate-reinforced elastomer composite comprises a continuous flow of a fluid which contains at least one elastomer latex (sometimes called the second fluid) through the inlet 11. (Figure 1 (a), (b) and / or (c)), in a reaction zone 13 at a volumetric flow rate of between about 20 l / h and about 1900 l / h. The method further comprises introducing a continuous flow of another fluid containing a particulate dispersion destabilized by the inlet 3 (sometimes called the first fluid) under pressure which can be obtained by means of nozzle tips (on Figure 1 in 3a) at a volumetric flow rate of between 30 l / h and 1700 l / h. The destabilized state of the particle dispersion and the impact of the two fluid streams (introduced by the inputs 3 and 11) under high energy conditions created by the introduction of the first fluid in the form of a high-speed jet ( e.g., between about 6 m / s and about 250 m / s) that collides with the slower velocity latex stream (e.g., between 0.4 and 11 m / s) entering the reaction zone at a lower velocity. angle approximately perpendicular to the high velocity jet of the first fluid are effective for intimately mixing the particles (eg, silica and carbon black) with the latex flow, which promotes uniform particle distribution in the phase flow continuous solid rubber containing silica and carbon black from the exit of the reaction zone.
As an option, the elastomer latex introduced, for example, through the inlet 11 may be a mixture of two or more synthetic latexes, such as a blend of two or more synthetic latexes. Optionally, the devices of Figures 1 (a), (b) and / or (c) can be modified to have one or more additional inputs to introduce other components into the reaction zone, such as one or more additional latexes. . For example, in Fig. 1 (c), input 14 may be used to introduce another latex in addition to use of input 11. The additional input (s) may be sequential to each other, or adjacent to each other or defined in any orientation as long as the material (eg, latex) being introduced through the entry (s) has sufficient time to disperse or be incorporated into the resulting stream. In WO 2011/034587, incorporated in its entirety for reference in the present description, FIGS. 1, 2A and 2B provide examples of additional inputs and their orientations which may be adopted for use in embodiments of the present invention. the present invention. In one particular example, an inlet can introduce a stream that comprises natural rubber latex and an additional inlet can introduce a synthetic elastomer latex and these latex streams are combined with the flow of the destabilized silica dispersion to create the flow. of a continuous solid or semi-solid continuous rubber phase containing silica. When several inputs are used for the introduction of the elastomer latex, the flow rates may be identical or different from each other.
FIG. 2 depicts an example, using a functional diagram of different steps that can occur for the formation of the elastomer composite. As illustrated in FIG. 2, the destabilized dispersion of particles that comprises silica (first fluid) 100 is introduced into the reaction zone 103 and the fluid containing the elastomer latex (second fluid) 105 is also introduced into the reaction zone. 103. Optionally, a continuous phase stream of solid or semi-solid rubber containing silica and carbon black leaves the reaction zone 103 and may optionally enter a holding zone 116 (e.g., a reservoir). with or without the addition of a solution of salt or acid to further enhance the coagulation of rubber and the formation of networks of silica / rubber); and can optionally enter, directly or after diversion to a holding zone 116, in a dewatering zone 105; may possibly enter a mixer / continuous mixing device 107; may possibly enter a mill (eg, an open mill, also called a roll mill) 109; can be subjected to an additional grinding 111 (identical or different conditions of the grinder 109) (as an identical or different energy input); may be subjected to optional mixing by a mixer 115 and / or may be granulated using a granulator 117 and may then be optionally pressed, using a press 119 and may optionally be decomposed using an additional mixer 121.
As regards silica, one or more types of silica, or any combination of silicas, may be used in any embodiment of the present invention. Silica suitable for reinforcing elastomer composites may be characterized by a surface area (BET) of between about 20 m 2 / g and about 450 m 2 / g; between about 30 m 2 / g and about 450 m 2 / g; between about 30 m 2 / g and about 400 m 2 / g; or between about 60 m2 / g and about 250 m2 / g; and for heavy truck tire treads, a BET surface area of between about 60 m2 / g and about 250 m2 / g or for example between about 80 m2 / g and about 200 m2 / g. Highly dispersible precipitated silica may be used as a filler in the present processes. The term "highly dispersible silica" (HDS) is any silica having a significant ability to disagglomerate and disperse in an elastomeric matrix. Such determinations can be observed in a known manner by electron or optical microscopy on thin sections of elastomer composite. Examples of commercial grade HDS include: WR Grace's Perkasil® GT 3000GRAN Thanksgiving & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165 MP silica and 1115 MP Solvay SA, Hi-Sil® EZ 160G silica from PPG Industries, Inc. and Zeopol® 8741 or 8745 silica from JM Huber Corporation. Conventional non-HDS precipitated silica may also be used. Examples of commercial grade conventional precipitated silica include: Perkasil® KS 408 silica from WR Grace & Co, Zeosil® 175GR silica from Solvay SA, Ultrasil® VN3 silica from Evonik Industries, Hi-Sil® 243 silica from PPG Industries, Inc. and Hubersil® 161 silica from JM Huber Corporation. Hydrophobic precipitated silica with silane coupling agents attached to the surface can also be used. Examples of commercial grade hydrophobic precipitated silica include: Agilon® 400, 454 or 458 silica from PPG Industries, Inc. and Coupsil silicas from Evonik Industries, eg Coupsil 6109 silica.
In general, the silica (eg, silica particles) has a silica content of at least 20% by weight, at least 25% by weight, of at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight % by weight, at least 90% by weight or at least 100% by weight or 100% by weight or between about 20% by weight and about 100% by weight based on the total weight of the particle. Any of these silicas may be chemically functionalized to have attached or adsorbed chemical groups, such as attached or adsorbed organic groups. Any combination of silica (s) can be used. The silica that forms the silica slurry and / or the destabilized silica slurry may be partly or wholly silica having a hydrophobic surface, which may be a silica that is hydrophobic or a silica that becomes hydrophobic by rendering the surface of the silica hydrophobic by treatment (eg, chemical treatment). The hydrophobic surface can be obtained by chemical modification of the silica particle with hydrophobicizing silanes without ionic groups, eg, bis-triethoxysilylpropyltetrasulfide. Such a surface reaction on the silica may be carried out in a separate process step prior to dispersion or carried out in situ in a silica dispersion. The surface reaction reduces the silanol density on the surface of the silica, thereby reducing the ionic charge density of the silica particle in the slurry. Silica particles having a hydrophobic surface treatment that can be used in dispersions can be obtained from commercial sources, such as Agilon® 454 silica and Agilon® 400 silica from PPG Industries. Silica dispersions and destabilized silica dispersions can be made using silica particles having low surface silanol density. Such silica can be obtained by dehydroxylation at temperatures above 150 ° C through, for example, a calcination process.
Any quality of reinforcing or non-reinforcing carbon black may be selected to achieve the desired property in the final rubber composition. Examples of reinforcing grades are N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358 and N375. Examples of semi-reinforcing grades are N539, N550, N650, N660, N683, N762, N765, N774, N787 and / or N990.
The carbon black may have any STSA, for example between 10 m2 / g and 250 m2 / g, between 11 m2 / g and 250 m2 / g, between 20 m2 / g and 250 m2 / g or more, for example at least 70 m2 / g, for example from 70 m2 / g to 250 m2 / g, or from 80 m2 / g to 200 m2 / g or from 90 m2 / g to 200 m2 / g, or from 100 m2 / g g to 180 m2 / g, from 110 m2 / g to 150 m2 / g, or from 120 m2 / g to 150 m2 / g and the like. Optionally, the carbon black may have an iodine number (No. 12) of from about 5 to about 35 mg 12 / g of carbon black (according to ASTM D1510). The carbon black may be furnace black or a carbon product containing silicon-containing species and / or metal-containing species and the like. The carbon black may be, for the purpose of the present invention, a multi-phase aggregate comprising at least one carbon phase and at least one species phase containing metal or a species phase containing silicon (also called black silicon-treated carbon, such as ECOBLACK ™ materials from Cabot Corporation). As indicated, the carbon black may be a rubber black and in particular a carbon black reinforcement grade or a carbon black semi-reinforcing grade. The iodine number (# 12) is determined by the ASTM D1510 test procedure. The statistical thickness surface area (STSA) is determined by the ASTM D-5816 test procedure (measured by nitrogen adsorption). OAN is determined by ASTM procedure D1765-10. Carbon blacks marketed under the trade names Regai®, Black Pearls®, Spheron®,
Sterling®, Emperor®, Monarch®, Shoblack ™ and Vulcan® marketed by Cabot Corporation under the trademarks Raven®, Statex®, Furnex® and Neotex® and the CD and HV ranges of Columbian Chemicals and under the brand names Corax®, Durax®, Ecorax® and Purex® and the CK range from Evonik (Degussa) Industries, and other fillers suitable for rubber or tire applications, can also be used in various embodiments. Suitable chemically functionalized carbon blacks include those described in WO 96/18688 and US2013 / 0165560, the disclosures of which have been incorporated by reference in this specification. Any mixture of these carbon blacks can be used.
The carbon black may be an oxidized carbon black, for example pre-oxidized using an oxidizing agent. Oxidizing agents include, but are not limited to, air, oxygen, ozone, NO 2 (including mixtures of NO 2 and air), peroxides such as hydrogen peroxide, persulfates, including sodium, potassium or ammonium persulfate, hypohalites such as sodium hydrochloride, halites, halides or perhalates (such as sodium chlorite, sodium chlorate or sodium perchlorate), oxidants such as nitric acid, and transition metal-containing oxidants, such as permanganate salts, osmium tetroxide, chromium oxides, or sodium and ammonium nitrate. Mixtures of oxidants may be used, particularly mixtures of gaseous oxidants, such as oxygen and ozone. In addition, carbon blacks prepared using other surface modification methods for introducing ionic or ionizable groups onto a pigment surface, such as chlorination and sulfonation, can also be used. Methods that can be used to generate pre-oxidized carbon blacks are known in the art and several types of oxidized carbon black are commercially available.
In addition, the silica slurry and / or the destabilized silica slurry may contain, optionally, a minor amount (10% by weight or less, based on a total weight of the particulate material) of any particle which is neither silica nor carbon black, such as zinc oxide or calcium carbonate, or other particulate materials useful in rubber compositions.
The silica may be dispersed in an aqueous fluid according to any technique known to those skilled in the art. A particulate silica dispersion may be mechanically treated, for example, to reduce particle size. This operation may be carried out before or during or after the destabilization of the dispersion and may contribute in a minor or major way to the destabilization of the dispersion. The mechanical treatment may include or include crushing, grinding, spraying, breaking or high shear treatment or any combinations thereof.
For example, a silica slurry can be made by dispersing silica in a fluid by means of a crushing process. Such a crushing process reduces the size of most silica agglomerates (e.g., more than 80% by volume) in the fluid to less than 10 microns, and preferably less than 1 micron, the size range. typical of colloidal particles. The fluid may be water, an aqueous fluid or a non-aqueous polar fluid. The slurry, for example, may comprise from about 6% to about 35% by weight of silica-containing particles, based on the weight of the slurry. The size of the silica particles can be determined using a light scattering technique. Such a slurry, when made in water using silica particles having a low residual salt content at pH between 6 and 8, generally has a zeta potential amplitude greater than or equal to 30 mV and exhibits good stability against aggregation, gelation and sedimentation in a storage tank with low agitation (eg, agitation speed below 60 rpm). Since well-crushed silica particles are generally stable in water at a pH of about 7 because of the high negative charges on the silica, very high shear is generally required to overcome the repulsive energy barrier between particles to induce the agglomeration of particles.
In an illustrative process using silica, such as H DS granules, the silica may be combined with water and the resulting mixture passed through a colloid mill, a pipe crusher or the like to form a dispersion fluid. . This fluid then passes into a homogenizer which more finely disperses the filler in the carrier liquid to form the slurry. Examples of homogenizers include, but are not limited to, the Microfluidizer® system marketed by Microfluidics International Corporation (Newton, Mass., USA). Homogenizers such as models MS18, MS45 and MC120, and serial homogenizers marketed by APV Homogenizer Division APV Gaulin, Inc. (Wilmington, Mass., USA) are also suitable. Other suitable homogenizers are commercially available and will be recognized by those skilled in the art based on the advantages of the present invention. The optimum operating pressure in a homogenizer depends on the device itself, the type of silica and / or the silica content. For example, a homogenizer may be used at a pressure of from about 10 psi to about 5,000 psi or more, for example, from about 10 psi to about 1000 psi, from about 1,000 psi to about 1,700 psi, from about 1,700 psi and about 2,200 psi, between about 2,200 psi and about 2,700 psi, between about 2,700 psi and about 3,300 psi, between about 3,300 psi and about 3,800 psi, between about 3,800 psi and about 4,000 psi. 300 psi, or between about 4300 psi and about 5000 psi. As indicated above, the dispersion of particulate silica is destabilized before the masterbatch process is carried out and the dispersion can be destabilized by one of the techniques mentioned in the present invention, before, during or after any crushing process or similar mechanics.
According to the wet masterbatch method used, a high concentration of silica in the slurry can be used to reduce the task of removing excess water or other carrier. For the destabilized dispersion of the silica particles, the liquid used may be water or an aqueous fluid or other fluid. For the destabilized dispersion, between about 6% by weight and about 35% by weight of filler may be used, for example, between about 6% by weight and 9% by weight, between about 9% by weight and about 12% by weight. % by weight, from about 12% by weight to about 16% by weight, from about 10% by weight to about 28% by weight, from about 16% by weight to about 20% by weight, from about 20% by weight, and about 24% by weight, about 24% by weight to about 28% by weight, or about 28% by weight to about 30% by weight based on the weight of the destabilized dispersion. For the destabilized dispersion, a higher silica concentration may have advantages. For example, a concentration of silica in the destabilized slurry can be at least 10% by weight or at least 15% by weight based on the weight of the slurry (e.g., between about 12% by weight and about 35% by weight or between about 15.1% by weight and about 35% by weight or between about 20% by weight and about 35% by weight), which may have advantages such that, not exclusively, the reduction of wastewater, increasing production rates and / or reducing the size of the equipment required for the process. Those skilled in the art will recognize, based on the advantages of the present invention, that the silica concentration (percent by weight) of the silica slurry (and the destabilized silica slurry) should be coordinated with other variables. process during the wet process to obtain a desired silica-to-rubber ratio (in phr) in the final product.
The details of a dispersion which comprises silica are described below. In general, a dispersion may be a material comprising a plurality of phases in which at least one of the phases contains or comprises or consists of finely divided phase domains, optionally in the colloidal size range, dispersed in a continuous phase. A dispersion or slurry that comprises silica or a silica dispersion can be prepared as a stable suspension of silica particles in an aqueous fluid, wherein the charge on the surface of the particles prevents agglomeration of particles and dispersion. is characterized by an amplitude of zeta potential greater than or equal to 30 mV. In such dispersions, the silica particles remain in a dispersion and / or suspension stable with respect to aggregation and coalescence, for example, for at least 8 hours. A stable dispersion can be a dispersion in which the constant size of the particles is preserved, and in which the particles do not settle or gell or take a long time to deposit significantly in the presence of slow or periodic agitation, for example, do not settle significantly after 8 hours, or 12 hours or 24 hours or 48 hours. For example, for colloidal silica particles well dispersed in an aqueous fluid, the stability can generally be observed at a pH of between 8 and 10. In addition, with slow stirring of the dispersion, the silica particles remain suspended in the water. fluid by means of particle surface charge, particle surface polarity, pH, selected particle concentration, particle surface treatment and combinations thereof. The fluid may be or include water, an aqueous mixture, or a miscible or partially water-miscible fluid, such as various alcohols, ethers, and other miscible water-soluble solvents of low molecular weight, preferably having organic groups. C1-C5 (e.g., ethanol, methanol, propanol, ethyl ether, acetone and the like). As indicated above, the dispersion, for example, may comprise from about 6% by weight to about 35% by weight, from about 10% by weight to about 28% by weight, from about 12% by weight to about 25% by weight, or between about 15% by weight and about 30% by weight of silica-containing particles, based on the weight of the dispersion.
A stable dispersion may be a colloidal dispersion. In general, a colloidal dispersion or a colloid may be a substance in which dispersed particles are suspended in another substance. The dispersed phase particles have a diameter of from about 1 nanometer to about 1000 nanometers and generally from about 100 nanometers to about 500 nanometers. In a stable colloidal dispersion, particle size, density, and concentration are such that gravity easily does not sediment particles out of the dispersion. Colloids with a zeta potential amplitude of 30 mV or greater are generally considered stable colloidal systems. The reduction of particle stability (eg, silica) in a colloid or dispersion due to charge stabilization can be measured by reducing the zeta potential amplitude. The particle size can be measured by a light scattering method.
A destabilized silica dispersion or a destabilized particulate dispersion can be understood as a dispersion of silica in a fluid in which weakened repulsive forces between particles allow the particles to be grouped together and the formation of a network between silica particles or dusts. a gel once the destabilized dispersion is subjected to an effective amount of shear. In some cases, mechanical shear can cause destabilization of silica dispersions and consolidation of silica particles. The greater the degree of destabilization of the silica slurry, the lower the shear required for particle aggregation and the higher the rate of aggregation of the particles. For destabilized dispersion, the dispersion may comprise from about 6% by weight to about 35% by weight of particulate silica (based on the weight of the dispersion), e.g. between about 8 wt.% and about 35 wt.%, about 10 wt.% to about 28 wt.%, about 12 wt.% to about 25 wt.%, about 15 wt.% to about 30 wt. weight. The aqueous fluid in the destabilized dispersion of silica particles may be or include water, an aqueous mixture or a miscible or partially water-miscible fluid, such as various alcohols, ethers and other miscible solvents in low water. molecular weight, preferably having C1-C5 organic groups (e.g., ethanol, methanol, propanol, ethyl ether, acetone and the like). To form elastomer-silica composites, the stability of the silica particles in a slurry or dispersion is reduced (i.e., destabilized) by lowering the electrostatic energy barrier between particles using an effective amount of a destabilizing agent, such as an acid or a salt or both, before the slurry is mixed with the latex. A destabilizing agent may be selected for its ability to reduce the interaction of repulsive charges among particle surfaces that prevent agglomeration of particles in the fluid.
A destabilized dispersion of silica or which comprises silica can be obtained by lowering the pH of the silica dispersion in order to close the isoelectric point of the silica (around pH 2 for typical hydrophilic silicas). For example, destabilized silica may be obtained by adding acid to lower a pH of the particulate silica dispersion to between 2 and 4, thereby reducing the zeta potential amplitude of the dispersion to less than 30 mV, such as about less than 28 mV (e.g., zeta potentials of about 18 mV to about 6 mV for formic acid as a destabilizing agent). The addition of acid and / or salt to the silica slurry can effectively reduce the stability of the silica particles dispersed in the water. The molar concentration of acid or salt is generally the dominant factor that determines the zeta potential of the destabilized silica slurry. In general, a sufficient amount of acid or salt or both can be used to reduce the zeta potential amplitude of the silica slurry to less than 30 mV, such as 28 mV or less, preferably 25 mV or less. least, to produce a continuous phase of semi-solid or solid rubber containing silica.
The amount of acid used to destabilize the silica dispersion may be an amount to obtain a zeta potential amplitude in the destabilized dispersion of less than 30 mV, for example 28 mV or less, or 25 mV or less. The acid may be at least one organic or inorganic acid. The acid may be or include acetic acid, formic acid, citric acid, phosphoric acid or sulfuric acid or any combinations thereof. The acid may be or include a C1 to C4 alkyl-containing acid. The acid may be or include an acid having a molecular weight or a weight average molecular weight of less than 200, for example less than 100 MV, or less than 75 MW or between about 25 MW and about 100 MW. The amount of acid may vary and depend on the silica dispersion to be destabilized. The amount of acid may be, for example, from about 0.8% by weight to about 7.5% by weight, for example from about 1.5% by weight to about 7.5% by weight or more ( based on the total weight of the fluid comprising the silica dispersion). If an acid is the sole destabilizing agent used, the amount of acid may be an amount that lowers the pH of the silica dispersion by at least 2 pH units or at least a pH of 5 or less, or the range of pKa of the acid or acids used, so as to reduce charge interactions among the particles.
[0077] A destabilized dispersion can be obtained by treating a dispersion which comprises silica with a destabilizing agent comprising one or more salts to modify the zeta potential of the slurry to the range described above. The salt may be or include at least one metal salt (e.g., Group 1, 2 or 13 metals). The salt may be or include a calcium salt, a magnesium salt or an aluminum salt. Illustrative counterions include nitrate, acetate, sulfate, halogen ions, such as chloride, bromide, iodine and the like. The amount of salt may be, for example, from about 0.2% by weight to about 2% by weight or more, for example from about 0.5 or 1% by weight to about 1.6% by weight (based on the weight basis of the fluid comprising the destabilized silica dispersion).
A combination of at least one salt and / or at least one acid may be used to destabilize the dispersion which comprises silica.
When the destabilized dispersion which comprises silica is obtained with the addition of at least one salt, the concentration of salt in the destabilized dispersion may be between approximately 10 mM and approximately 160 mM, or other quantities. above or below this range.
When the destabilized dispersion which comprises silica is obtained with the addition of at least one acid, the concentration of acid in the destabilized dispersion can be between about 200 mM and about 1000 mM, for example, from about 340 mM to about 1000 mM, or other amounts greater or less than this range.
A destabilized dispersion can be obtained by using treated silica particles to comprise an appropriate amount of surface functional groups bearing positive charges so that the net charges on the silica surface are sufficiently reduced to decrease the amplitude of the zeta potential of the dispersion at a level below 30 mV. The net charge on the surface of the silica may be positive, instead of being negative, because of such a surface treatment. The positively charged functional group can be introduced to the surface of the silica by chemical fixation or physical adsorption. For example, the silica surface may be treated with N-trimethoxylsilylpropyl-Ν, Ν, Ν-trimethylammonium chloride either before or after preparation of the silica dispersion. It is also possible to adsorb cationic coating agents, such as amine-containing molecules and basic amino acids on the surface of the silica. In theory, a net positive charge on the surface of the silica particles can enhance the coagulation of the latex, which comprises negatively charged rubber particles, by means of hetero-coagulation.
As regards the "second fluid", which contains at least one elastomer latex, this fluid may contain one or more elastomer latexes. An elastomer latex can be considered a stable colloidal rubber dispersion and can contain, for example, from about 10% by weight to about 70% by weight of rubber based on the total weight of latex. The rubber may be dispersed in a fluid, such as water or other aqueous fluid, for example. The aqueous content of this fluid (or the water content) may be 40% by weight or more, for example 50% by weight or more, or 60% by weight or more or 70% by weight or more, for example between about 40% by weight and about 90% by weight based on the weight of the fluid comprising the at least one elastomer latex. Suitable elastomer latexes are natural and synthetic elastomer latexes and latex blends. For example, the elastomer latex may be made synthetically by polymerizing a monomer such as styrene which has been emulsified with surfactants. The latex must be suitable for the selected wet masterbatch process and the intended purpose or application of the final rubber product. It is within the ability of those skilled in the art to select a suitable elastomer latex or elastomer latex blend suitable for use in the methods and apparatus described herein, based on the advantages of the present invention.
The elastomer latex may be or include natural rubber, such as a natural rubber emulsion. Illustrative natural elastomer latices include, but are not limited to, planting latex, latex concentrate (produced, for example, by evaporation, centrifugation or skimming), skim latex (e.g., the supernatant remaining after the production of latex concentrate by centrifugation) and mixtures of any two or more thereof in any proportion. The natural rubber latex is generally treated with ammonia to preserve it and the pH of the treated latex is generally between 9 and 11. The ammonia content of the natural rubber latex can be adjusted and can be reduced, for example by bubbling with nitrogen in or through the latex. In general, latex suppliers decant the latex by adding diammonium phosphate. They can also stabilize the latex by adding ammonium laurate. The natural rubber latex can be diluted to the desired dry rubber content (DRC). Thus, the latex that can be used herein can be a decanted latex. A secondary preservative, a mixture of tetramethylthiuram disulfide and zinc oxide (TZ solution) may also be included. The latex must be suitable for the selected wet masterbatch process and the intended purpose or application of the final rubber product. The latex is generally provided in an aqueous carrier liquid (e.g., water). The amount of aqueous carrier liquid may vary, for example, may be from about 30% by weight to about 90% by weight based on the weight of the fluid. In other words, such natural rubber latices may contain, or may be adjusted to contain, eg, from about 10% by weight to about 70% by weight of rubber. Selection of a suitable latex or latex blend is within the skill of those skilled in the art based on the advantages of the present invention and knowledge of selection criteria generally well recognized in the industry.
The natural rubber latex may also be chemically modified in any manner. For example, it can be processed to chemically or enzymatically modify or reduce different non-rubbery components or the rubber molecules themselves can be modified with different monomers or other chemical groups such as chlorine. The epoxidized natural rubber latex may be particularly beneficial because the epoxidized rubber is expected to interact with the silica surface (Martin, et al., Rubber Chemistry and Technology, May 2015, 10.5254 / rct15.85940). Illustrative methods of chemical modification of natural latex are described in European Patent Nos. 1489102, 1816144 and 1834980, Japanese Patent Nos. 2006152211, 2006152212, 2006169483, 2006183036, 2006213878, 2006213879, 2007154089 and 2007154095 and British Pat. GB2113692, U.S. Patent Nos. 6,841,606 and 7,312,271, and U.S. Patent No. 2005-0148723. Other methods known to those skilled in the art can also be used.
[0085] Other illustrative elastomers include, but are not limited to, rubbers, polymers (eg, homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3 -dialkyl-1,3-butadiene, wherein the alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene and the like. The elastomer may have a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of from about -120 ° C to about 0 ° C. Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber, and its derivatives, such as chlorinated rubber, polybutadiene, polyisoprene, poly (styrene-co-butadiene), and extended derivatives thereof. oil from one of these. Mixtures of any of the foregoing may also be used. The latex may be in an aqueous carrier liquid. Particularly suitable synthetic rubbers include: copolymers of styrene and butadiene comprising from about 10% by weight to about 70% by weight of styrene and from about 90% to about 30% by weight of butadiene, such as a 19 part copolymer of styrene and 81 parts of butadiene, a copolymer of 30 parts of styrene and 70 parts of butadiene, a copolymer of 43 parts of styrene and 57 parts of butadiene and a copolymer of 50 parts of styrene and 50 parts of butadiene ; polymers and copolymers of conjugated dienes, such as polybutadiene, polyisoprene, polychloroprene and the like, and copolymers of such dienes conjugated with a monomer containing an ethylenic group copolymerizable therewith, such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, substituted allyl acrylates, ketone vinylic acid, methylisopropenyl ketone, methyl vinyl ether, alpha-methylenic carboxylic acids and esters and amides thereof, such as acrylic acid and dialkylacrylic acid amide. Also useful in the present invention are copolymers of ethylene and other high molecular weight alpha olefins, such as propylene, 1-butene and 1-pentene. Mixtures of two or more types of elastomer latex, including mixtures of synthetic and natural rubber latex or with two or more types of synthetic or natural rubber, may also be used.
The rubber compositions may contain, in addition to the elastomer, the filler and the coupling agent, various processing aids, such as dilution oils, anti-degradants, antioxidants and / or other additives.
The amount of silica (in parts per hundred parts by weight of rubber or phr) present in the elastomer composite may range from about 15 phr to about 180 phr, from about 20 phr to about 150 phr, from about 25 phr and about 80 phr, between about 35 phr and about 115 phr, between about 35 phr and about 100 phr, between about 40 phr and about 100 phr, between about 40 phr and about 90 phr, between about 40 phr and about 80 phr. phr, between about 29 phr and about 175 phr, between about 40 phr and about 110 phr, between about 50 phr and about 175 phr, between about 60 phr and about 175 phr, and the like.
The elastomer composite may optionally include a quantity of carbon black for the stability of the color, conductivity and / or UV and / or other purposes.
As indicated, the carbon black contained in the elastomer composite (reinforcing grades and non-reinforcing grades) may range from greater than 10% by weight to about 55% by weight or more than 10% by weight. by weight and about 50% by weight or between more than 15 and about 40% by weight, based on the weight of the total particles present in the elastomer composite. Any grade or type of carbon black may be used, such as air-strengthened or semi-reinforcing carbon blacks of pneumatic quality and the like.
In any process for producing an elastomer composite, the process may further comprise one or more of the following steps, after the formation of the continuous phase of solid or semi-solid rubber containing silica and black. carbon: one or more holding steps or other steps of solidification or coagulation to enhance the development of elasticity; one or more dewatering steps may be used to dewater the composite and obtain a dried composite; one or more extrusion steps; one or more calendering steps; one or more grinding steps to obtain a crushed composite; one or more granulation steps; one or more pressing steps to obtain a product or a pressed mixture; the mixture or the pressed product can be decomposed to form a granulated mixture; one or more mixing or mixing steps to obtain a mixed composite.
By way of further example, the following sequence of steps can be performed and each step can be repeated any number of times (with identical or different settings) after the formation of the solid or semi-solid rubber phase. -Solid containing silica and carbon black. one or more holding steps or other coagulation steps to enhance the development of elasticity; dewatering the composite (eg, the elastomer composite exiting the reaction zone) to obtain a dried composite; mixing or mixing the dried composite to obtain a mixture of compounds; grinding the mixture of compounds to obtain a ground mixture (eg, rolling); granulation or mixing of the ground mixture; optional pressing of the mixture after granulation or mixing to obtain a pressed mixture; optional decomposition of the pressed mixture and mixing.
According to one embodiment, a coupling agent may be introduced in any one of the steps (or in several steps or locations) insofar as the coupling agent has the possibility of dispersing in the composite of elastomer.
As an example, the continuous phase of solid or semi-solid rubber containing silica and carbon black leaving the reaction zone can be transferred to a suitable apparatus (eg a conveyor belt or a conveyor belt). ) to a dewatering extruder. Suitable dewatering extruders are well known and marketed, for example, by the French Oil Mill Machinery Co. (Piqua, Ohio, USA). Alternatively or in addition, the continuous phase of solid or semi-solid rubber containing silica and carbon black may be compressed, for example, between metal plates, to expel at least a portion of the aqueous fluid phase, by for example, to expel the aqueous fluid until the water content of such material is less than 40% by weight.
In general, the post-treatment steps may comprise compressing the elastomer composite to remove between about 1% by weight and about 15% by weight, or more, of an aqueous liquid phase, based on the weight total elastomer composite. The dewatering extruder can bring the elastomer composite between eg about 40% and about 95% water content and between about 5% and about 60% water content (for example, between about 5% and about 10% water content, between about 10% and about 20% water content, between about 15% and about 30% water content or between about 30% and about 50% water content), all the percentages by weight being based on the total weight of the composite. The dewatering extruder can be used to reduce the water content of the elastomer composite to about 35% by weight or other amounts. The optimum water content may vary depending on the elastomer used, the amount and / or type of filler and devices used for chewing the dried product. The elastomer composite can be dried to a desired water content, after which the resulting dried product can be further chewed while being dried to a desired moisture level (e.g. and about 10%, for example, from about 0.5% to about 1%, from about 1% to about 3%, from about 3% to about 5%, or from about 5% to about 10%, preferably from less than 1% by weight based on the total weight of the product). The mechanical energy imparted to the material can improve the properties of the rubber. For example, the dried product can be mechanically worked with one or more continuous mixers, an internal mixer, a twin screw extruder, a single screw extruder or a roller mill. This optional mixing step may have the ability to chew the mixture and / or generate a surface or expose a surface that may allow the removal of water (at least a portion thereof) possibly present in the mixture. Suitable chewing devices are well known and commercially available, including, for example, a Unimix continuous mixer and an MVX machine (mixing, degassing, extruding) from Farrel Corporation of Ansonia, CT, USA, a continuous long mixer from Pomini, Inc. a Pomini continuous mixer, two-rotor co-rotating cross-fed extruders, two-rotor counter-rotating non-intercrossed extruders, Banbury mixers, Brabender mixers, intercross-type internal mixers, kneading-type internal mixers, continuous mixing extruders, biaxial milling extruder produced by Kobe Steel, Ltd. and a Kobe continuous mixer. An alternative chewing apparatus will be familiar to those skilled in the art and may be used.
As the dried product is processed in a desired apparatus, the apparatus imparts energy to the material. Without being bound to a particular theory, it is believed that the friction generated during mechanical chewing heat the dried product. Some of this heat is dissipated by heating and vaporizing the moisture in the dried product. Some of the water can also be removed by pressing the material parallel to the heating. The temperature must be high enough to rapidly vaporize the water with vapor that is released into the atmosphere and / or is removed from the apparatus, but not too high so as not to burn the rubber. The dried product can reach a temperature of from about 130 ° C to about 180 ° C, for example, from about 140 ° C to about 160 ° C, particularly when the coupling agent is added before or during mastication. The coupling agent may comprise a small amount of sulfur and the temperature must be kept low enough to prevent the rubber from curing during chewing.
Optionally, additives may be combined with the dried product in a mechanical mixer. Specifically, additives such as a filler (which may be the same or different from the filler used in the blender; illustrative fillers include silica, carbon black and / or zinc oxide) , other elastomers, another masterbatch or an additional masterbatch (i.e., one or more identical or different elastomer composites, including silica and / or carbon black), antioxidants, coupling agents, plasticizers, processing aids (eg, stearic acid which may also be used as a hardener, liquid polymers, oils, waxes and the like), resins, flame retardants , dilution oils and / or lubricants and a mixture of any of these may be added in a mechanical mixer. Additional elastomers can be combined with the dried product to produce elastomer blends. Suitable elastomers include any of the elastomers used in latex form in the mixing process described above and elastomers, such as EPDM, which are not available in latex form and may be the same or different from the elastomer in the elastomer composite containing silica. Illustrative elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1, 3-butadiene, wherein the alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene and the like. Methods of producing masterbatches are described in US Patent Co-Ownership Nos. 7,105,595, 6,365,663 and 6,075,084 and PCT Publication WO2014 / 189826. The antioxidant (an example of a degradation inhibitor) may be an amine antioxidant, a phenol antioxidant, an imidazole antioxidant, a carbamate metal salt, one or more para-phenylene diamines and / or dihydrotrimethylquinolines, a polymerized quinine antioxidant and / or wax and / or other antioxidants used in elastomeric formulations. Specific examples include, but are not limited to, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6-PPD, e.g., ANTIGEN 6C, available from Sumitomo Chemical Co., Ltd. and NOCLAC. 6C, sold by Ouchi Shinko Chemical Industrial Co., Ltd.), "Ozonon" 6C from Seiko Chemical Co., Ltd., polymerized 1,2-dihydro-2,2,4-trimethyl quinoline (TMQ, e.g. Agerite Resin D, commercially available from RT Vanderbilt), 2,6-di-t-butyl-4-methylphenol (available under the trademark Vanox PC from Vanderbilt Chemicals LLC), butylated hydroxytoluene (BHT) and the like. Other representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those described in The Vanderbilt Rubber Handbook (1978), pages 344-346.
The coupling agent may be or include one or more silane coupling agents, one or more zirconate coupling agents, one or more titanate coupling agents, one or more nitrogen coupling agents, or any combination thereof. this. The coupling agent can be or include bis (3-triethoxysilylpropyl) tetrasulfane (eg, Si 69 from Evonik Industries, Struktol SCA98 from Struktol Company), bis (3-triethoxysilylpropyl) disulfane (e.g., Si 75 and If 266 from Evonik Industries, Struktol SCA985 from Struktol Company), 3-thiocyanatopropyl-triethoxy silane (e.g., Si 264 from Evonik Industries), gamma-mercaptopropyl-trimethoxy silane (e.g., VP Si 163 from Evonik Industries Struktol SCA989 from Struktol Company), gamma-mercaptopropyl-triethoxy silane (eg, VP Si 263 from Evonik Industries), zirconium dineoalkanolatodi (3-mercapto) propionato-O, N, N'-bis (2- methyl-2-nitropropyl) -1,6-diaminohexane, S- (3- (triethoxysilyl) propyl) octanethioate (e.g., Momentive NXT coupling agent, Friendly, WV) and / or coupling agents which are chemically similar or have one or more identical chemical groups. Additional specific examples of coupling agents, by their brand names, include, but are not limited to, VP Si 363 from Evonik Industries. It is recognized that any combination of elastomers, additives and additional masterbatches may be added to the dried product, for example in a mixing device.
As an option, the dried product may be chewed using an internal mixer, such as a Banbury or Brabender mixer. The dried product may first be brought to a moisture content of from about 3% by weight to about 40% by weight, for example from about 5% by weight to about 20% by weight, or about 20% by weight. and about 30% by weight. Moisture content can be achieved by drying to the desired level or by drying the dried product crumbs to an intermediate moisture content in the first step and then further reducing the moisture content by heating the resulting dried product. or allowing the water to evaporate from the dried product at room temperature or by other methods familiar to those skilled in the art. The dried product can then be dried in an internal mixer to a desired moisture level or a mechanical energy input is obtained. The dried product may be chewed until it reaches a predetermined temperature, allowed to cool, and then returned to the internal mixer one or more times to impart additional energy to the material. Examples of temperatures include from about 140 ° C to about 180 ° C, for example from about 145 ° C to about 160 ° C or from about 150 ° C to about 155 ° C. The dried product can be pulled into sheets in a roller mill after each chewing in the internal mixer. Alternatively or in addition, the dried product which has been masticated in a Banbury or Brabender mixer may be further masticated in an open mill.
As an option, the masticated product can be further processed in an open mill. The chewed product can be discharged from the continuous mixing device as an extrudate length and can be cut into shorter lengths before being introduced into the open mill. The chewed product may optionally be introduced into the open mill via a conveyor. The conveyor may be a conveyor belt, a pipe, a pipe or any other suitable means for transporting the masticated product, from a continuous mixing device to an open mill. The open mill may comprise a pair of rolls which may optionally be heated or cooled to improve the operation of the open mill. Other functional parameters of the open mill may include the spacing distance between the rolls, the bench height, i.e., the material reservoir in the space between the rolls and above them , and the speed of each roll. The speed of each roll and the temperature of the fluid used to cool each roll can be independently controlled for each roll. The spacing distance may be from about 3 mm to about 10 mm or from about 6 mm to about 8 mm. The speed of the roll can be from about 15 rpm to about 70 rpm and the rollers can roll toward each other from the input side of the mill. The friction ratio, the ratio of the speed of the pickup roller, e.g., the roll on which the masticated product is collected, and that of the return roll, may be from about 0.9 to about 1.1. The fluid used to cool the rolls may be at a temperature of from about 35 ° C to about 90 ° C, for example from about 45 ° C to about 60 ° C, from about 55 ° C to about 75 ° C or from about 70 ° C and about 80 ° C. In addition to controlling the operation of the open mill to provide a desired level of chewing and desiccation to the chewed product, it is also desirable that the output of the open mill collect on the pickup roll as a smooth sheet. Without being bound by any particular theory, it is believed that cooler roll temperatures facilitate this purpose. The open mill can reduce the temperature of the masticated product to an approximate temperature of 110 ° C to 140 ° C. The residence time of the masticated product in the mill may be determined in part by the speed of the roll, the spacing distance and the desired amount of mastication and drying and may be from about 10 to 20 minutes for a material which has already masticated, for example, in a continuous mixer with two rotors.
Those skilled in the art will consider that different combinations of devices can be used to provide mastication and desiccation to a continuous phase of solid rubber containing silica and carbon black produced according to the different embodiments. Depending on the devices used, it may be desirable to use them in conditions different from those described above to provide varying amounts of work and desiccation to the material. In addition, it may be desirable to use more than one particular type of device, e.g., an open mill or an internal mixer, in series or to pass the masticated product in a given device more than once. For example, the masticated product may be passed through an open mill two or three times or more or passed through two or more open mills in series. In the latter case, it may be desirable to operate each open mill under different operating conditions, eg, speed, temperature, different energy input (eg, higher), etc. The chewed product can be passed into one, two or three open mills after being chewed in an internal mill.
The elastomer composite can be used to produce an elastomer or rubber-containing product. Optionally, the elastomer composite can be used in different parts of a tire or produced for use in these different parts, for example, tires, treads, sidewalls, metal tire siding and a tire. contact rubber for escaped tires. Alternatively or additionally, the elastomer composite can be used for caterpillars, crawler equipment pads, bulldozers, etc., engine mounts, earthquake stabilizers, mine equipment such as sieves, mining equipment coatings, conveyor belts, chute coatings, slurry coatings, slurry pump components, such as turbines, valve seats, valve bodies, hubs piston, piston rods, plungers, turbines for various applications, such as mixing mixers and pump turbines, mill mill coatings, cyclones and hydrocyclones, expansion joints , marine equipment, such as pump coatings (eg, dredge pumps or outboard motor pumps), hoses (eg, dredging hoses and outboard motor hoses) and other marine equipment, shaft seals for marine, petroleum, aerospace and other applications, propeller shafts, pipeline liners for transportation, eg, oil sands, and and / or tar sands, and other applications in which abrasion resistance is desired. The vulcanized elastomer composite can be used in rollers, cams, shafts, pipes, tread rings for vehicles, or other applications in which abrasion resistance is desired.
Conventional formulation techniques can be used to combine vulcanizing agents and other additives known in the art, including additives presented above in connection with the dried product, with the dried elastomer composite, according to the desired use.
The present invention further relates to an elastomer composite formed by one or more of the methods described in the present disclosure of the present invention. With the present invention, a solid rubber continuous article containing silica and carbon black may be produced and comprise at least 25 phr of silica (e.g., at least 29 phr, at least 35 phr, at least 40 phr of silica) dispersed in rubber (such as natural rubber) and at least 40% by weight of aqueous fluid and having a length dimension (L), wherein the solid rubber continuous phase article containing silica and carbon black can be stretched to at least 130% to 150% (L) without breaking. The solid rubber continuous article containing silica and carbon black may have at least 10 phr of carbon black dispersed in the rubber (eg, natural rubber), such as at least 10 phr of carbon black. carbon, at least 15 phr of carbon black or at least 20 phr of carbon black.
[0104] Unless otherwise indicated, all the percentages of material indicated in percentage in the present description are in percentage by weight.
The present invention will be further clarified by the following examples which are given for illustrative purposes only.
EXAMPLES
In these examples, the "plantation latex" was planting latex (Muhibbah Lateks Sdn Bhd, Malaysia) having a dry rubber content of about 30% by weight. The "concentrated latex" was a concentrated latex (high ammonia content of Muhibbah Lateks Sdn Bhd, Malaysia or Chemionics Corporation, Tallmadge, Ohio) diluted, unless indicated otherwise, to about 50% for a dry rubber content of about 30%. by weight using either pure water or water containing between 0.6% by weight and 0.7% by weight of ammonia. Unless otherwise indicated, "silica" was ZEOSIL® Z1165 MP precipitated silica from Solvay USA Inc., Cranbury, NJ (formerly Rhodia).
[0107] Thermogravimetric analysis. The actual silica loading levels were determined by thermogravimetric analysis (TGA) according to the ISO 6231 method.
Moisture content of the product. The test material was cut into lumps and loaded into a moisture balance (eg Model MB35 and Model MB45, Ohaus Corporation, Parsippany NJ) for measurement. The water content was measured at 130 ° C for a period of between 20 and 30 minutes until the tested sample reached a uniform weight.
Zeta potential of the slurry. In these examples, the zeta potential of the particulate slurries was measured using a ZetaProbe Analyzer ™ from Colloidal Dynamics, LLC, Ponte Vedra Beach, Florida USA. With a multifrequency electro-acoustic technology, ZetaProbe measures the zeta potential directly at particle concentrations of up to 60% by volume. The instrument was first calibrated using KSiW calibration fluid supplied by Colloidal Dynamics (2.5 mS / cm). A 40 g sample was then placed in a 30 ml Teflon cup (reference A80031) with a stirrer, and the cup was placed on a stirring base (reference A80051) at a stirring speed. 250tr / min. The measurement was made using an immersion probe 173 in a single point mode with a 5-point cycle at room temperature (about 25 ° C). The data was analyzed using ZP version 2.14c Polar ™ software provided by Colloidal Dynamics. The values of the zeta potential can be negative or positive depending on the charge polarity of the particles. The magnitude of the zeta potential is the absolute value (eg, a zeta potential value of -35 mV has an amplitude greater than a zeta potential value of -20 mV). The magnitude of the zeta potential reflects the degree of electrostatic repulsion between similarly charged particles in the dispersion. The higher the amplitude of the zeta potential, the more stable the particles in the dispersion. Zeta potential measurements were taken on particulate silica slurries prepared as described below.
Dry silica was weighed and combined with deionized water using a 5 gallon bucket and a high shear vertical laboratory mixer with a wrapped agitator (Silverson Model AX3, Silverson Machines, Inc., East Longmeadow, MA, operating between 5,200 and 5,400 rpm for 30 to 45 minutes). Once the silica was roughly dispersed in water and pumpable, the silica slurry was transferred by a peristaltic pump (Masterflex 7592-20 system - drive and controller, 77601-10 pumphead using tubing 1 / P 73, Cole-Palmer, Vernon Hills, IL) in a mixing loop with a high-shear rotor-stator line mixer (Silverson Model 150LB located after the peristaltic pump, operating at 60 Hz) in a cycle tank (tank with a 30 gallon convex lower orifice) and was crushed to further decompose the silica agglomerates and any remaining silica granules. The slurry in the cycle tank was then circulated at a rate of 2 l / min using the same peristaltic pump in the mixing loop for a time sufficient for rotation of at least 5 to 7 times the total volume. slurry (> 45 minutes) to ensure that all silica agglomerates were properly crushed and dispensed. A vertical mixer (Ika Eurostar power control visc-P7, IKA-Works, Inc., Wilmington, NC) with a low shear anchor blade rotating at about 60 rpm was used in the cycle tank to prevent gelation or sedimentation of the silica particles. An acid (formic acid or acetic acid, Sigma Aldrich reagent grade, St. Louis, MO) or a salt (calcium nitrate, calcium chloride, calcium acetate or aluminum sulfate, reagent grade from Sigma Aldrich, St. Louis, MO) was added to the slurry in the cycle tank after crushing. The amount of silica in the slurry and the type and concentration of acid or salt are indicated in the specific examples below.
[0111] Illustrative method B. When indicated in the examples below, an illustrative method was carried out using the illustrative method B. In method B, dry silica was weighed and combined with water deionized using a 19-liter (5-gallon) tub and a high shear vertical laboratory mixer with a wrapped stirrer (Silverson Model AX3, Silverson Machines, Inc., East Longmeadow, MA) operating between 5,200 and 5,400 rpm min for 30 to 45 minutes). Once the silica was roughly dispersed in water and pumpable, the silica slurry was transferred via a peristaltic pump (Masterflex 7592-20 system - drive and controller, 77601-10 pumphead using tubing Cole-Palmer, Vernon Hills, IL) in a mixing loop with a high shear rotor-stator in-line mixer (Silverson Model 150LB located after the peristaltic pump, operating at 60 Hz) in a cycle reservoir ( 30 gallon convex bottom port vessel) and was crushed to further decompose the silica agglomerates and any remaining granules. The slurry in the cycle tank was then circulated at a rate of 2 l / min in the mixing loop for a time sufficient for a rotation of at least 5 to 7 times the total slurry volume (> 45 minutes ) to ensure that all silica agglomerates have been properly crushed and distributed. A vertical mixer (Ika Eurostar power control visc-P7; KA-Works, Inc., Wilmington, NC) with a low shear anchor blade rotating at about 60 rpm was used in the cycle tank to prevent gelation or sedimentation of silica particles. An acid (formic acid or acetic acid, reagent grade from Sigma Aldrich, St. Louis, MO) or a salt (calcium nitrate, calcium chloride, calcium acetate or aluminum sulfate salt, reagent grade from Sigma Aldrich, St. Louis, MO) was added to the slurry in the cycle tank after crushing.
The latex was pumped using a peristaltic pump (Masterflex 7592-20 system - drive and controller, 77601-10 pumphead using L / P 73 tubing, Cole-Palmer, Vernon Hills, IL) by a second. inlet (11) and in the reaction zone (13) configured similarly to that illustrated in Fig. 1 (b). The latex flow rate was adjusted from about 25 kg / hr to about 250 kg / hr to modify the silica-rubber ratios of the elastomer composites.
Once the silica was well dispersed in water, the slurry was pumped from the cycle tank into a diaphragm metering pump (LEWA-Nikkiso America, Inc., Holliston, MA) by a pulsation damper (for reduce the pressure swing due to the action of the diaphragm) in the reaction zone or the cycle tank via a T-recirculation connector. The direction of the slurry was controlled by pneumatic ball valves, one directing the slurry to the reaction zone and the other directing it to the cycle tank. Once the silica slurry is ready to be mixed with the latex, the line feeding the first inlet (3) to the reaction zone has been pressurized to between 100 and 150 psig by closing the two valves. The ball valve directing the slurry to the reaction zone was then opened and the pressurized slurry was fed to a nozzle (ID between 0.05 cm (0.020 ') and 0.17 cm (0.070 ")) illustrated. in Fig. 1 (b) at an initial pressure of 100 psig to 150 psig, such that the slurry was jet fed at high speed into the reaction zone. In contact with the latex in the reaction zone, the stream of silica slurry flowing at a rate between 15 and 80 m / sec resulted in the latex flowing between 0.4 ms and 5 m / s. In examples according to embodiments of the present invention, the impact of the silica slurry on the latex caused an intimate mixing of the silica particles with the rubber particles of the latex, and the rubber coagulated, transforming the slurry of silica and the latex of an elastomer composite comprising silica particles and between 40 and 95% by weight of water entrapped in a continuous phase of solid or semi-solid rubber containing silica. Adjustments were made to the silica slurry flow rate (40 to 80 kg / h) or latex flow rate (25 to 300 kg latex / h), or both, to modify the silica-rubber ratios (by eg, between 15 and 180 phr of silica) in the final product and to obtain the desired production rates (between 30 kg / h and 200 kg / h on the dry matter basis). The specific contents of the silica-rubber (phr) ratio after drying and drying are listed in the examples below.
[0114] Process B Dewatering.
The material discharged from the reaction zone was covered and interposed between two aluminum plates inside a tray. The "sandwich" was then inserted between two plates of a hydraulic press. With 2,500 psig pressure exerted on the aluminum plates, water trapped inside the rubber product was removed. If necessary, the pressed material was folded into a smaller piece and the pressing process was repeated using the hydraulic press until the water content of the rubber product was less than 40% by weight.
[0116] Method B Drying and cooling. The dried product was placed in a Brabender mixer (300 cc) for drying and chewing to form a dried and masticated elastomer composite. Sufficient dried material was loaded into the mixer to cover the rotors. The initial temperature of the mixer was set at 100 ° C and the rotor speed was generally 60 rpm. The water remaining in the dried product was converted to steam and evaporated out of the mixer during the mixing process. As the material in the mixer expanded due to evaporation, the overflow of material was removed as needed. A silane coupling agent (NXT silane supplied by Momentive Performance Materials, Inc., Waterford, NY, 8 wt% silane based on silica weight) and / or an antioxidant (6-PPD, N- (1, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, Flexsys, St. Louis, MO) was optionally added to the mixer at a temperature above 140 ° C. When the mixer temperature reached 160 ° C, the material inside the mixer was maintained at a temperature between 160 ° C and 170 ° C by varying the rotor speed for 2 minutes before discharging the material. The masticated and dried elastomer composite was then processed in an open mill. The moisture content of the material removed from the mill was generally less than 2% by weight.
[0117] Preparation of rubber compounds
The dried elastomer composite obtained by Method B was subjected to mixing according to the formulation of Table A and the procedure described in Table B. For elastomer-silica composites in which silane or antioxidant was added during drying, the final compound composition is as shown in Table A. The amount of silane coupling agent and / or antioxidant during mixing was adjusted accordingly.
Table A
N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Fiexsys, St. Louis, MO) "" Main active ingredient: S- (3- (triethoxysilyl) propyl) octanethioate (Momentive, Friendly , WV) *** DiphenylGuanidine (Akrochem, Akron, OH) **** N-tert-Butylbenzothiazole-2-sulphenamide (Emerald Performance Materials, Cuyahoga Facts, OH) NR = natural rubber S = as indicated
Table B
The vulcanization was carried out in a heated press set at 150 ° C for a time determined by a traditional rubber rheometer (ie, T90 + 10% T90, where T90 is the time to obtain 90% vulcanization).
Properties of the rubber / silica compounds.
The tensile properties of the vulcanized samples (T300 and T100, elongation of rupture, tensile strength) were measured according to the ASTM D-412 standard. Delta tangent 60o was determined using a dynamic torsional strain sweep of between 0.01% and 60% at 10 Hz and 60 ° C. The tangent Dmax has been taken as the maximum value of the tangent DD in this constraint range.
Example 1
A silica slurry with 27.8 wt% Zeosil® 1165 silica was prepared as described above for the zeta potential test method of the slurry. The slurry was then diluted using either deionized water, followed by a supernatant obtained by ultracentrifugation of the 27.8% by weight slurry to make a series of silica slurries at different concentrations of silica. The zeta potential of the various silica slurries was measured to show the relationship between the silica concentration in the slurry and the zeta potential of the slurry. The zeta potential of the silica slurry, as shown in Table 1, appears to depend on the concentration of silica when the silica slurry is made using deionized water. On the other hand, as shown in Table 2, when the slurry was diluted using the supernatant obtained by ultracentrifugation of the 27.8% by weight liquid slurry, the zeta potential remains broadly the same at the different silica concentrations.
Table 1
Zeta potential of silica slurry made using deionized water
Table 2
Zeta potential of the silica slurry obtained by the dilution of 27.8% by weight of silica slurry using the supernatant of 27.8% by weight of silica slurry.
This result shows that an increase in the amplitude of the zeta potential when such silica slurries are diluted with deionized water is mainly due to the reduction of the ionic strength of the slurry. The ions of the silica slurry are supposed to come from the residual salts present in the silica resulting from the manufacturing process of the silica particles. The high zeta potential of the silica slurries (always greater than 30 mV) indicates that the silica has high electromagnetic stability in the slurry.
Example 2
The effect of the addition of salt or acid at different concentrations to silica slurries on the zeta potential of these slurries is described in Table 3. The slurries were prepared in deionized water by the Slurry Zeta Potential test method described above. The data summarized in Table 3 describe the zeta potential dependence of liquid silica slurries and destabilized liquid silica slurries on silica concentration, salt concentration and acid concentration. Adding salt or acid to the silica slurry reduces the magnitude of the zeta potential and thus the stability of the silica slurry. As shown in Table 3, the zeta potential depends primarily on the concentration of salt or acid in the destabilized slurry or slurry and not on the silica concentration.
Table 3
Zeta potential of the destabilized silica slurry at different slurry concentrations,
salt and acid concentrations.
ND = not determined.
The results indicated in Table 3 describe the dependence of the zeta potential of silica slurries and destabilized silica slurries on the acetic acid concentration and the silica concentration. The data show that zeta potential values are more dependent on acid concentration than silica concentration. A similar relationship between zeta potential and acid concentration and silica concentration is observed with formic acid. At a given concentration, formic acid reduces the magnitude of the zeta potential more than acetic acid. As shown in Table 3, a combination of formic acid and calcium chloride was effective in reducing the amplitude of the zeta potential. The results shown in Table 3 show that the stability of the silica particles in the slurry can be effectively reduced by the addition of destabilizing agents, such as an acid or a salt or a combination of acid and salt. Similar results were obtained with calcium nitrate and calcium acetate.
Example 3
In this example, the importance of the destabilization of the dispersion of the silica particles before contacting the silica dispersion with the elastomer latex has been established. Specifically, four experiments were performed using the mixing apparatus (c) of Figure 1 with three inlets (3, 11, 14) for introducing up to three fluids into a confined reaction zone (13), so that a fluid hits the other fluids at a 90 degree angle by a high speed jet at a speed between 15 and 80 m / s (see Figure 1 (c)). In three of the four experiments, the silica was crushed as described above in Method B and acetic acid was optionally added as described in Examples 3-A to 3-D below. The destabilized slurry or slurry was then pressurized to between 100 and 150 psig and introduced into the reaction zone confined by the inlet (3) at a volumetric flow rate of 60 liters per hour (l / h) so that that the destabilized slurry or slurry is introduced as a high speed jet at 80 m / s into the reaction zone. Simultaneously, a concentrate of natural rubber latex (60CX12021 latex, dry rubber content 31% by weight, from Chemionics Corporation, Tallmadge, Ohio, diluted in deionized water) was introduced through the second inlet (11) by a peristaltic pump with a volumetric flow rate of 106 l / h and a speed of 1.8 m / s. These flow rates were selected and the fluxes were adjusted to obtain an elastomer composite product comprising 50 phr (parts per hundred parts by weight of dry rubber) of silica. The silica slurry or destabilized silica slurry and the latex were mixed by combining the low velocity latex flow and the high velocity jet of silica slurry or destabilized silica slurry resulting in the flow of latex into the slurry jet. boiled or destabilized silica slurry at the point of impact. The production rate (on a dry matter basis) was set at 50 kg / h. The specific silica-rubber specific ratios in the rubber composites obtained with the process are listed in the examples below. TGA analysis was carried out after drying according to the process of Method B.
Example 3-A: [0131] First fluid: A destabilized aqueous dispersion of 25% by weight of silica with 6.2% by weight (or 1.18 M) of acetic acid was prepared as described in US Pat. method B above. The zeta potential of the destabilized slurry was -14 mV, indicating that the slurry was significantly destabilized by the acid. The destabilized silica slurry was pumped continuously under pressure into the first inlet (3).
Second fluid: Elastomer latex was introduced into the reaction zone by the second inlet (11).
The first fluid has struck the second fluid in the reaction zone.
Results: A liquid-solid phase inversion occurred in the reaction zone when the destabilized silica slurry and the latex were intimately mixed by the entrainment of the slow-speed latex flow in the large jet. slurry velocity destabilized silica. During the training process, the silica was intimately distributed in the latex and the mixture coagulated into a solid phase which contained between 70% by weight and 85% by weight of water. As a result, a flow of a continuous solid rubber phase containing worm or rope-shaped silica was obtained at the exit of the reaction zone (15). The composite was elastic and could be stretched up to 130% of the initial length without breaking. TGA analysis on the dried product showed that the elastomer composite contained 58 phr of silica.
Example 3-B: First fluid: A destabilized aqueous dispersion of 25% by weight of silica with 6.2% by weight of acetic acid was prepared according to method B described above. The zeta potential of the slurry was -14 mV, indicating that the slurry was significantly destabilized by the acid. The destabilized silica slurry was pumped continuously under pressure into the first inlet (3).
Second fluid: Elastomer latex was introduced into the reaction zone by the second inlet (11).
Third fluid: Deionized water was also injected into the reaction zone by the third inlet (14) at a volumetric flow rate of 60 l / h and a speed of 1.0 m / s.
The three fluids came into contact and collided in the reaction zone.
Results: A liquid-solid phase inversion occurred in the reaction zone and a continuous phase of solid or semi-solid rubber containing rope or worm-shaped silica was obtained by the exit of the reaction zone. A significant amount of turbid liquid containing silica and / or latex has flowed through the outlet (7) with the continuous phase of solid or semi-solid rubber containing silica. The continuous phase of silica-containing rubber contained between about 70% by weight and about 75% by weight of water based on the weight of the composite. TGA analysis on the dried product showed that the elastomer composite contained 44 phr of silica. Thus, the addition of water through the third inlet had a negative impact on the process, giving rise to a product having a lower silica content (44 phr vs. 58 phr in Example 3-A) and significant waste.
Example 3-C: [0142] First Fluid: A 10% by weight aqueous solution of acetic acid without silica was prepared. A continuous feed of acidic fluid was pumped with a peristaltic pump at a volumetric flow rate of 60 l / h through the third inlet (14) into the reaction zone at a speed of 1.0 m / s at the time of entry in the reaction zone.
Second fluid: Elastomer latex was introduced into the reaction zone by the second inlet (11) with a peristaltic pump at a speed of 1.8 m / s and a volumetric flow rate of 106 l / h .
The two fluids came into contact and collided in the reaction zone.
Results: A sticky phase of worm-shaped solid rubber was formed. TGA analysis on the dried product showed that the solid rubber phase did not contain silica.
Example 3-D: [0147] First fluid: A destabilized aqueous dispersion of 25% by weight of silica without acetic acid was prepared according to method B described above. The silica slurry was pumped under continuous pressure and introduced through the first inlet (3) at a volumetric flow rate of 60 l / h and at a rate of 80 m / s at the point of entry into the reaction zone. The zeta potential of the slurry was -32 mV, indicating that the silica was stably dispersed in the slurry. Thus, in this 3-D example, the silica slurry was not destabilized by the addition of acid to the slurry prior to impact with the latex fluid.
Second fluid: Elastomer latex was introduced into the reaction zone by the second inlet (11) with a peristaltic pump at a speed of 1.8 m / s and a volumetric flow rate of 106 l / h .
Third fluid: After an initial period of continuous flow of the first and second fluids, an aqueous solution of acetic acid at 10% by weight was injected by the third inlet (14) into the reaction zone at a volumetric flow rate. from 0 to 60 l / h and at a speed from 0 to 1.0 m / s. The three fluids collided and were mixed in the reaction zone.
Results: Initially, before the acid injection, no continuous phase of silica-containing rubber had formed and only a cloudy liquid was observed by the outlet (15) of the reaction zone. Upon injection of acid into the reaction zone (13), a continuous phase of silica-containing semi-solid rubber began to form as the acetic acid flux increased through the third inlet. from 0 to 60 l / h. Materials flowing through the outlet still contained a significant amount of cloudy liquid, indicating a significant amount of waste. TGA analysis of the dry product showed that the continuous phase of silica-containing rubber formed in this experimental cycle contained only 25 phr of silica. Given the selected production conditions and the amount of silica used, if the silica had been substantially incorporated into the silica-containing rubber phase, as in Example 3-A, the silica would have given rise to silica-containing rubber phase comprising an excess of 50 phr of silica.
These experiments show that the silica slurry must be destabilized before the initial impact with the elastomer latex in order to obtain the continuous phase of rubber containing the desired silica. Example 3-A made it possible to obtain what can be considered as an effective capture of the silica in the continuous phase of solid rubber containing silica, while the example 3-D illustrates a comparative method using a silica slurry initially stable and having an efficiency less than half the efficiency of Example 3-A using an initially destabilized silica slurry. Observation of a turbid liquid leaving the exit point of the reaction zone indicates insufficient mixing of the silica with the latex and a lower proportion of silica captured in the continuous rubber phase. In theory, in Comparative Methods 3B and 3D, destabilization of fluids was insufficient during mixing. The results further indicate that insufficient silica uptake occurred when an additional fluid was added while the first fluid and the second fluid were in the process of mixing; such process conditions generate undesirable amounts of waste.
Example 4
[0153] Illustrative method A-1. In the places indicated in the examples below, a method was carried out using the illustrative method A-1. In Method A-1, precipitated dry silica and water (tap water filtered to remove particulate matter) were measured and combined, and then crushed in a rotor-stator mill to form silica slurry. and the particulate slurry was further crushed in a feed tank using a stirrer and another rotor-stator mill. The silica slurry was then transferred to a cycle tank equipped with two agitators. The same method used to form the silica slurry was used to prepare a slurry of carbon black from dry carbon black (N-134 grade carbon black supplied by Cabot Corporation). The carbon black slurry was added over the silica slurry in the cycle tank. The silica-carbon black slurry was recirculated from the cycle tank into a homogenizer and returned to the cycle tank. An acid solution (formic acid or acetic acid, industrial grade, supplied by Kong Long Huat Chemicals, Malaysia) was then pumped into the cycle tank. The slurry was maintained in dispersed form by stirring and, optionally, by means of the recirculation loop in the cycle tank. After a suitable period, the silica-carbon black slurry was introduced into a confined reaction zone (13), such as that illustrated in Figure 1a, by means of a homogenizer. The concentration of silica and carbon black in the slurry and the acid concentration are indicated in the specific examples below.
The latex was pumped with a peristaltic pump (at less than about 40 psig pressure) through the second inlet (11) into the reaction zone (13). The latex flow rate was adjusted to between 300 and 1600 kg of latex / hr in order to achieve a desired rate of production and desired silica-carbon black filler levels in the resulting product. The homogenized slurry containing the acid was pumped under pressure from the homogenizer to a nozzle (inner diameter (ID) of between 0.15 cm (0.060 ") and 0.33 cm (0.130") (3a), represented by the first inlet (3) illustrated in Fig. 1 (a), so that the slurry is introduced in a jet at high speed into the reaction zone.In contact with the latex in the reaction zone, the jet of silica flowing at a rate of between 25 m / s and 120 m / sec entrained the latex flowing between 1 ms and 11 m / s. In examples according to embodiments of the present invention, the impact of the silica-black carbon slurry on the latex caused an intimate mixture of the silica-black carbon particles with the rubber particles of the latex, and the rubber coagulated, transforming the silica-black carbon slurry and the latex in a material comprising a continuous phase of solid or semi-solid rubber c containing silica and carbon black containing between 40 and 95% by weight of water, based on the total weight of the material trapped in the material. Adjustments were made to the slurry flow rate (500-1,800 kg / h) or latex flow rate (300-1,800 kg / h), or both, to modify the silica-rubber ratios (e.g. 15-180 phr of silica) in the final product and to obtain the desired production rate. The production rates (dry matter basis) were between 200 and 800 kg / h. Specific silica contents (by TGA analysis) in the rubber after dewatering and drying of the material are listed in the examples below.
[0155] Method A-1 Dewatering. The material was discharged from the reaction zone at atmospheric pressure at a rate between 200 and 800 kg / h (dry weight) in a dewatering extruder (The French Oil Machinery Company, Piqua, OH). The 21.59 cm (8.5 inch) extruder (Dl) was equipped with a die having different punch button configurations and operated at a typical rotor speed of between 90 and 123 rpm, die pressure between 400 and 1300 psig and a power between 80 and 125 kW. In the extruder, the rubber containing silica and carbon black was compressed and the water extracted from the silica-containing rubber was ejected through a slotted drum of the extruder. A dried product typically containing between 15 and 60% by weight of water was obtained at the exit of the extruder.
[0156] Method A-1 Drying and Cooling. The dried product was deposited in a continuous mixing device (Farrel Continuous Mixer (FCM), Farrel Corporation, Ansonia, CT, with 7 and 15 rotors) where it was dried, chewed and mixed with 1 to 2 phr of antioxidant (eg, Flexasys 6PPD, St. Louis, MO) and optionally a silane coupling agent (eg, NXT silane, supplied by Momentive Performance Materials, Inc., Waterford, NY, 8% by weight of silane on the basis of the weight of silica). The temperature of the FCM water jacket was set at 100 ° C and the temperature of the FCM at the outlet was 140-180 ° C. The moisture content of the chewed and dried elastomer composite exiting the FCM was between 1% by weight and 5% by weight. The product was further chewed and cooled in an open mill. A rubber sheet of the elastomer composite was cut directly from the open mill, rolled and cooled in air.
[0157] Preparation of rubber compounds
The dried elastomer composite obtained by process A-1 was subjected to mixing according to the formulation of Table C and the procedure described in Table D. For elastomer composites in which silane or antioxidant was added during drying, the final compound composition is as shown in Table C. The amount of the silane coupling agent and / or antioxidant during mixing was adjusted accordingly.
Table C
N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Flexsys, St. Louis, MO) main active ingredient: S- (3- (triethoxysilyl) propyl) octanethioate (Momentive, Friendly, WV) * "DiphenylGuanidine (Akrochem, Akron, OH)" ** N-tert-Butylbenzothiazole-2-sulphenamide (Emerald Performance Materials, Cuyahoga Falls, OH) NR = natural rubber S = as indicated
Table D
The vulcanization was carried out in a heated press set at 150DC for a time determined by a traditional rubber rheometer (ie, T90 + 10% T90, where T90 is the time to obtain 90% vulcanization).
Properties of the rubber / silica-carbon black compounds.
The tensile properties of the vulcanized samples (T300 and T100, elongation of rupture, tensile strength) were measured according to the ASTM D-412 standard. Delta tangent 60 ° was determined using dynamic torsional strain sweeping between 0.01% and 60% at 10 Hz and 60 ° C. The tangent Dmax has been taken as the maximum value of the tangent □ in this constraint range.
In these examples, the method according to various embodiments of the invention has been executed in the apparatus illustrated in FIG. 1 ((a) or (b)) under different conditions as described in Table 4, in using method A-1 described above. The operating conditions were selected to obtain a continuous phase of solid or semi-solid rubber containing silica with the silica-black carbon-rubber ratios shown in Table 4 (Planting = planting).
Table 4
S / 0 = not applicable, ND = not determined a. All of the examples used ZEOSIL® Z1165 MP precipitated silica. All of the examples used Cabot Corporation N134 carbon black. b. Zeta potential values were estimated by interpolation of the experimentally determined zeta potential dependence curves on salt or acid concentration of slurries of the same silica grade.
Table 4 (continued)
c. The speed of the inlet nozzle corresponds to the speed of the silica-carbon black slurry which passes into a nozzle (3a) at the first inlet (3) to the reaction zone (13) before entering in contact with the latex. d. The flow rates of the slurry and the latex correspond to the volumetric flow rates in l / hour of the silica-black carbon slurry and the liquid latex, respectively, when they are introduced into the reaction zone.
In all the examples listed above in Table 4, the selected operating conditions made it possible to obtain a solid rubber continuous phase containing silica and carbon black in a coarse cylindrical form. The product contained a significant amount of water, was elastic and compressible, and expelled water and retained solids after manual compression. The solid material could be stretched, for example, the material could be stretched or lengthened from 130 to 150% of its length, without breaking. Some of the rubber properties of the composites produced are shown in Table 5 below. It was observed that the silica and carbon black particles were uniformly distributed in a continuous rubber phase and that this product was substantially free of free silica particles and larger silica grains on the outer and inner surfaces. For the continuous phase of rubber containing silica and carbon black, not only must the silica be destabilized (eg by prior treatment with acids and / or salts), but the volumetric flow rates of the slurry of The destabilized silica with respect to the latex had to be adjusted not only to obtain a desired silica-rubber (phr) ratio in the elastomer composite, but also to balance the degree of destabilization of the slurry with the mixing rate of the slurry and latex and the coagulation rate of latex rubber particles. With these adjustments, as the silica slurry has resulted in the latex, intimately distributing the silica particles (and the carbon black particles) in the rubber, the rubber in the latex has become a solid or semi-solid continuous phase in the rubber. a fraction of a second after combining the fluids in the confined volume of the reaction zone. Thus, the process has formed unique elastomer-silica-carbon black composites by a step of continuously impacting the fluids at a sufficient rate, selected concentrations and liquid / solids volumes, and liquid flow rates adjusted to dispense uniformly and intimately the fine particulate silica in the latex and, in parallel, during the execution of such a distribution, to give rise to a liquid-solid phase inversion of the rubber.
Table 5
The elastomer composite formed from these examples exhibits acceptable rubber properties and particularly beneficial T300 / T100 properties for a composite having silica and carbon black dispersed in the composite. As shown in these examples, a solid rubber phase article containing silica and carbon black may comprise at least 40 phr of silica dispersed in natural rubber and at least 40% by weight of aqueous fluid and have a length (L), wherein the solid rubber phase article containing silica and carbon black can be stretched to at least 130% to 150% (L) without breaking.
The present invention comprises the following aspects / embodiments / attributes in any order and / or combination: 1. A method of manufacturing an elastomer-silica composite comprising: (a) providing a continuous flow under pressure of at least a first fluid containing dispersed particles and comprising a destabilized silica dispersion and a continuous stream of at least a second fluid comprising elastomeric latex; (b) providing a volumetric flow rate of the first fluid relative to that of the second fluid to obtain a silica content ranging from about 15phr to about 180 phr in the elastomer-silica composite; (c) combining the flow of the first fluid and the flow of the second fluid with an impact strong enough to dispense the silica into the elastomer latex to obtain a continuous phase of solid rubber containing silica or a continuous phase of semi-solid rubber containing silica. wherein said at least one first fluid is provided as: i) two streams comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or ii) a single stream comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or iii) a single destabilized dispersion stream comprising silica and carbon black. A method according to any one of the preceding and following embodiments / attributes / aspects, wherein at least one first fluid is a destabilized dispersion comprising silica and carbon black, and said method further comprises a combination of dry carbon black, dry silica and an aqueous medium to form said destabilized dispersion comprising at least 45% by weight silica, on a total particulate basis, and carbon black. A method according to any one of the preceding or following embodiments / attributes / aspects, further comprising subjecting one or more of said dispersions to at least one mechanical processing step. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said mechanical treatment step comprises crushing, grinding, spraying, breaking or high shear treatment or combinations thereof. -this. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said mechanical processing step comprises crushing said dispersions one or more times. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said mechanical processing step reduces agglomeration of the particles and / or adjusts the particle size distribution. A method of manufacturing an elastomer-silica composite comprising: (a) providing a continuous stream under pressure of at least a first fluid comprising a destabilized silica dispersion and a continuous stream of at least one second fluid comprising elastomer latex; (b) providing a volumetric flow rate of the first fluid relative to that of the second fluid to obtain a silica content ranging from about 15 phr to about 180 phr in the elastomer-silica composite; (c) providing a continuous stream of dry-flow carbon black, (d) combining the flow of the first fluid and the flow of the second fluid and said carbon black with an impact strong enough to dispense the silica and the carbon black in the elastomer latex, to obtain a flow of a continuous phase of solid rubber containing silica and carbon black or a continuous phase of semi-solid rubber containing silica and black of carbon. wherein said carbon black stream is combined with said first fluid prior to step d, or combined with said second fluid prior to step d, or added in step d. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein carbon black is present in said elastomer-silica composite in an amount of from about 10% by weight to about 50% by weight based on the total particulate matter present in said elastomeric-silica composite. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, wherein said flow of said solid or semi-solid rubber-containing continuous phase is formed in two seconds or less after combining said first fluid stream and said second fluid stream. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, wherein said flow of said continuous silica-solid or semi-solid rubber phase is formed in about 50 milliseconds to about 1500 milliseconds. after combining said first fluid stream and said second fluid stream. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid in step (a) further comprises at least one salt. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid in step (a) further comprises at least one acid. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said continuous phase of solid or semi-solid rubber containing silica comprises from 40 wt% to about 95 wt% of water or aqueous fluid. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, wherein said combining occurs in a reaction zone having a volume ranging from about 10 cm3 to about 500 cm3. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.4: 1 to 3.2: 1. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the relative volumetric flow rates are at a volumetric flow rate ratio of the first fluid to the second fluid ranging from 0.2: 1 to 2.8: 1. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.4: 1 to 3.2: 1, and said destabilized dispersion of the silica comprises at least one salt. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the relative volumetric flow rates are at a volumetric flow rate ratio of the first fluid to the second fluid ranging from 0.2: 1 to 2.8: 1, and said destabilized dispersion of the silica comprises at least one acid. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said elastomer latex comprises a base, said destabilized silica dispersion comprises at least one acid and a molar ratio of hydrogen ions in said acid in said first fluid with respect to said base in said second fluid is from 1 to 4.5. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises at least one acid and wherein said elastomer latex present in said second fluid has an ammonia concentration. ranging from about 0.3% by weight to about 0.7% by weight based on the weight of the elastomer latex, and a molar ratio of hydrogen ions in said acid in said first fluid to ammonia in said second fluid is at least 1: 1. 21. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica content of said elastomeric-silica composite is from about 26 phr to about 80 phr. 22. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica content of said elastomeric-silica composite is from about 40 phr to about 115 phr. 23. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises about 6 wt% to about 35 wt% silica. 24. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises about 10% by weight to about 28% by weight silica. 25. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, further comprising recovering said continuous phase of solid or semi-solid rubber containing silica at ambient pressure. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid comprising said destabilized silica dispersion has a zeta potential amplitude of less than 30 mV. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises at least one salt, wherein the concentration of salt ions in said destabilized dispersion is about 10 mM to about 160 mM. A process according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises at least one salt, wherein said salt is present in said destabilized dispersion in an amount of from 0.2% by weight to about 2% by weight based on the weight of said destabilized dispersion. A process according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises at least one acid, wherein said acid is present in said destabilized dispersion in an amount of from 0.8% by weight to about 7.5% by weight based on the weight of said destabilized dispersion. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said destabilized silica dispersion comprises at least one acid, wherein the acid concentration in said destabilized dispersion is about 200. mM at about 1000 mM. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein step (c) is performed with the continuous flow of the first fluid at a speed A and the continuous flow of the second fluid at a rate of speed B, and the speed A is at least 2 times faster than the speed B. 32. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the step (c) is performed in a semi-confined reaction zone and the first fluid has a velocity sufficient to induce cavitation in the reaction zone when combined with the second fluid. 33. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the second fluid has a velocity sufficient to create a turbulent flow. 34. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica dispersion comprises a surface-modified silica having hydrophobic surface fragments. 35. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid comprises an aqueous fluid. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid comprises an aqueous fluid and about 6% by weight to about 31% by weight of silica and at least 3% by weight of carbon black. 37. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said first fluid comprises an aqueous fluid, further comprising at least one salt and at least one acid. 38. A method according to any one of the preceding or following embodiments / attributes / aspects, said method further comprising destabilizing a silica dispersion by lowering a pH of the silica dispersion to form the destabilized dispersion of silica provided in step (a). 39. A method according to any one of the preceding or following embodiments / attributes / aspects, said method further comprising destabilizing a silica dispersion by lowering a pH of the silica dispersion to a pH of 2 to 4 to form the destabilized silica dispersion provided in step (a). 40. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica has a hydrophilic surface. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica is a highly dispersible silica (HDS). 42. A process according to any one of the preceding or following embodiments / attributes / aspects, wherein said acid comprises acetic acid, formic acid, citric acid, phosphoric acid or sulfuric acid or any combination of these. 43. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said acid has a molecular weight or an average molecular weight of less than 200. 44. A method according to any one of the embodiments preceding or following attributes / aspects, wherein said salt comprises at least one metal salt of group 1, 2 or 13. 45. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said salt comprises a calcium salt, a magnesium salt or an aluminum salt or a combination thereof. A method according to any of the preceding or following embodiments / attributes / aspects, said method further comprising exposing the silica to a mechanical step to reduce agglomeration of the particles and / or adjust the distribution of the particle size. 47. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the silica is precipitated silica or fumed silica or colloidal silica, or combinations thereof. 48. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica has a BET surface area ranging from about 20 m 2 / g to about 450 m 2 / g. 49. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said elastomer latex is natural rubber latex. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said natural rubber latex is in the form of planting latex, latex concentrate, decanted latex, chemically modified latex, enzymatically modified latex, or any combination thereof. 51. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said natural rubber latex is in the form of epoxidized natural rubber latex. 52. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said natural rubber latex is in the form of latex concentrate. 53. A method according to any of the preceding or succeeding embodiments / attributes / aspects, further comprising mixing the elastomeric-silica composite with an additional elastomer to form an elastomeric composite blend. A process for making a rubber compound comprising (a) carrying out the method according to any one of the preceding or following embodiments / attributes / aspects, and (b) mixing the elastomeric-silica composite with other components for forming the rubber compound, wherein said other components comprise at least one antioxidant, sulfur, a polymer other than an elastomer latex, a catalyst, a diluent oil, a resin, a coupling agent, a or a plurality of additional elastomeric composites or a reinforcing filler, or any combination thereof. A process for manufacturing a rubber article selected from tires, moldings, fasteners, coatings, conveyors, seals or liners comprising (a) performing the method according to any one of the embodiments previous / next attributes / aspects, and (b) mixing the elastomer-silica composite with other components to form a compound, and (c) vulcanizing the compound to form said rubber article. A method according to any of the preceding or succeeding embodiments / attributes / aspects, further comprising performing one or more additional post-processing steps after recovering the elastomeric-silica composite. 57. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the post-processing steps comprise at least one of: a) drying the elastomer-silica composite to obtain a dry blend ; b) mixing or mixing the dried mixture to obtain a composite elastomer-silica composite; c) milling the composite elastomer-silica composite to obtain a crushed elastomer-silica composite; d) granulating or mixing the elastomer-milled silica composite; e) pressing the elastomer-silica composite after granulation or mixing to obtain a pressed elastomer-silica composite; f) extruding the elastomer-silica composite; g) the calendering of the elastomer-silica composite; and / or h) optionally decomposing the pressed elastomer-silica composite and mixing with other components. 58. A method according to any of the preceding or following embodiments / attributes / aspects, wherein the post-processing steps comprise at least one step of rolling the elastomer-silica composite. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the post-processing steps comprise compressing the continuous phase of solid or semi-solid rubber containing silica to remove about 1 % by weight to about 15% by weight of the aqueous fluid contained therein. 60. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein the elastomer latex is brought into contact with at least one destabilizing agent when the destabilized silica dispersion is combined with the latex. elastomer. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, further comprising contacting the continuous phase stream of solid or semi-solid rubber containing silica with at least one destabilizing agent. . A method according to any one of the preceding or succeeding embodiments / attributes / aspects, further comprising the step of performing one or more of the following steps with the continuous phase of solid or semi-solid rubber containing silica: a) the transfer of the continuous phase of solid or semi-solid rubber containing silica into a reservoir or a holding vessel; b) heating the continuous phase of solid or semi-solid rubber containing silica to reduce the water content; c) exposing the continuous phase of solid or semi-solid rubber containing silica to an acid bath; d) the mechanical treatment of the continuous phase of solid or semi-solid rubber containing silica to reduce the water content. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said elastomer-silica composite is a continuous phase of silica-containing semi-solid rubber and said method further comprises converting said continuous phase of semi-solid rubber containing silica in continuous phase of solid rubber containing silica. A method according to any one of the preceding or succeeding embodiments / attributes / aspects, wherein said silica-containing semi-solid rubber continuous phase is converted to said solid silica-containing solid rubber phase by treatment with an aqueous fluid comprising at least one acid or at least one salt or a combination of at least one acid and at least one salt. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said second fluid comprises a blend of two or more different elastomer latexes. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said method further comprises providing one or more additional fluids and combining the one or more fluids with said first and second streams. fluid, wherein said additional fluid (s) comprises one or more elastomer latex fluids and said additional fluids are the same or different from said elastomer latex present in said second fluid stream. 67. A method according to any one of the preceding or following embodiments / attributes / aspects, wherein said silica content of said elastomeric-silica composite is from about 26 phr to about 180 phr. 68. Article of the continuous phase of solid rubber containing silica and carbon black comprising at least 25 parts per hundred parts by weight of rubber (phr) of silica dispersed in natural rubber and at least 40% by weight of fluid Aqueous, and having a length dimension (L), wherein the article of the silica solid solid rubber continuous phase can be stretched to at least 130-150% (L) without breaking. 69. An article of the continuous phase of solid rubber containing silica and carbon black according to any of the foregoing or following embodiments / attributes / aspects, further comprising 10 phr of carbon black dispersed in said natural rubber.
The present invention may include any combination of these different attributes or embodiments above as described in the sentences and / or paragraphs of this document. Any combination of the attributes described herein is considered a part of the present invention and no limitation is provided with respect to the combinable attributes.
The applicants specifically incorporate the entire contents of all references cited in the present invention. In addition, when a quantity, concentration or other value or parameter is given as a range, preferred range or list of preferable higher values and lower preferable values, these should be considered as specifically describing all ranges. formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, whether or not the ranges are described separately. When a range of numerical values is cited in this document, unless otherwise indicated, the range is assumed to include the ends thereof, as well as all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values mentioned when defining a range.
Other embodiments of the present invention will be apparent to those skilled in the art in view of the present specifications and practice of the present invention described herein. It is intended that this specification and the present examples be considered illustrative only, the true fields of application and spirit of the invention being indicated in the following and equivalent claims thereof.

权利要求:
Claims (70)
[1" id="c-fr-0001]
CLAIMS:
[2" id="c-fr-0002]
A method of manufacturing an elastomeric-silica composite comprising: (a) providing a continuous stream under pressure of at least a first fluid containing dispersed particles and comprising a destabilized dispersion of silica and a continuous flow at least one second fluid comprising elastomer latex; (b) providing a volumetric flow rate of the first fluid relative to that of the second fluid to obtain a silica content ranging from about 15phr to about 180 phr in the elastomer-silica composite; (c) combining the flow of the first fluid and the flow of the second fluid with an impact strong enough to dispense the silica into the elastomer latex to obtain a continuous phase of solid rubber containing silica or a continuous phase of semi-solid rubber containing silica. wherein said at least one first fluid is provided as: iv) two streams comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or v) a single stream comprising a dispersion comprising carbon black and a destabilized dispersion comprising silica; or vi) a single destabilized dispersion stream comprising silica and carbon black.
[3" id="c-fr-0003]
The method of claim 1, wherein at least one first fluid is a destabilized dispersion comprising silica and carbon black, and said method further comprises the combination of dry carbon black, dry silica and a aqueous medium for forming said destabilized dispersion comprising at least 45% by weight silica, on a total particulate basis, and carbon black.
[4" id="c-fr-0004]
The method of claim 1, further comprising exposing one or more of said dispersions to at least one mechanical treatment step.
[5" id="c-fr-0005]
The method of claim 3, wherein said mechanical treatment step comprises crushing, grinding, spraying, breaking or high shear treatment or combinations thereof.
[6" id="c-fr-0006]
The method of claim 4, wherein said mechanical treatment step comprises crushing said dispersions one or more times.
[7" id="c-fr-0007]
The method of claim 3, wherein said mechanical treatment step reduces agglomeration of the particles and / or adjusts the particle size distribution.
[8" id="c-fr-0008]
A method of manufacturing an elastomer-silica composite comprising: (a) providing a continuous stream under pressure of at least a first fluid comprising a destabilized silica dispersion and a continuous stream of at least one second fluid comprising elastomer latex; (b) providing a volumetric flow rate of the first fluid relative to that of the second fluid to obtain a silica content ranging from about 15 phr to about 180 phr in the elastomer-silica composite; (c) providing a continuous flow of fluidized carbon black in dry form, (d) combining the flow of the first fluid and the flow of the second fluid and said carbon black with sufficient impact to dispense the silica and the carbon black in the elastomer latex, to obtain a flow of a continuous phase of solid rubber containing silica and carbon black or a continuous phase of semi-solid rubber containing silica and carbon black; carbon. wherein said carbon black stream is combined with said first fluid prior to step d, or combined with said second fluid prior to step d, or added in step d.
[9" id="c-fr-0009]
The method of claim 1, wherein carbon black is present in said elastomeric-silica composite in an amount of from about 10 wt% to about 50 wt% based on total particulate matter present in said elastomer-silica composite.
[10" id="c-fr-0010]
The method of claim 1, wherein said flow of said solid or semi-solid silica-containing continuous phase is formed in two seconds or less after combining said first fluid stream and said second fluid stream.
[11" id="c-fr-0011]
The method of claim 1, wherein said flow of said solid or semi-solid silica-containing continuous phase is formed from about 50 milliseconds to about 1500 milliseconds after combining said first fluid stream and said second stream of silica. fluid.
[12" id="c-fr-0012]
The method of claim 1, wherein said first fluid in step (a) further comprises at least one salt.
[13" id="c-fr-0013]
The method of claim 1, wherein said first fluid in step (a) further comprises at least one acid.
[14" id="c-fr-0014]
The method of claim 1, wherein said continuous phase of solid or semi-solid rubber containing silica comprises from about 40% by weight to about 95% by weight of water or aqueous fluid.
[15" id="c-fr-0015]
The process of claim 1, wherein said combining occurs in a reaction zone having a volume ranging from about 10 cm3 to about 500 cm3.
[16" id="c-fr-0016]
The method of claim 1, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.4: 1 to 3.2: 1.
[17" id="c-fr-0017]
The method of claim 1, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.2: 1 to 2.8: 1.
[18" id="c-fr-0018]
The method of claim 1, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.4: 1 to 3.2: 1, and said destabilized dispersion of the silica comprises at least one salt.
[19" id="c-fr-0019]
The method of claim 1, wherein the relative volumetric flow rates are at a volumetric flow ratio of the first fluid to the second fluid ranging from 0.2: 1 to 2.8: 1, and said destabilized silica dispersion. comprises at least one acid.
[20" id="c-fr-0020]
The method of claim 1, wherein said elastomer latex comprises a base, said destabilized silica dispersion comprises at least one acid and a molar ratio of hydrogen ions in said acid in said first fluid with respect to said base in the second fluid is from 1 to 4.5.
[21" id="c-fr-0021]
The process according to claim 1, wherein said destabilized silica dispersion comprises at least one acid and wherein said elastomer latex present in said second fluid has an ammonia concentration of from about 0.3% by weight to about 0.7% by weight based on the weight of the elastomer latex, and a molar ratio of hydrogen ions in said acid in said first fluid to ammonia in said second fluid is at least 1: 1 .
[22" id="c-fr-0022]
The method of claim 1, wherein said silica content of said elastomeric silica composite is from about 26 phr to about 80 phr.
[23" id="c-fr-0023]
The method of claim 1, wherein said silica content of said elastomeric-silica composite is from about 40 phr to about 115 phr.
[24" id="c-fr-0024]
The process of claim 1, wherein said destabilized silica dispersion comprises from about 6 wt% to about 35 wt% silica.
[25" id="c-fr-0025]
25. The process of claim 1, wherein said destabilized silica dispersion comprises from about 10 wt% to about 28 wt% silica.
[26" id="c-fr-0026]
The method of claim 1 further comprising recovering said continuous phase of solid or semi-solid rubber containing silica at ambient pressure.
[27" id="c-fr-0027]
The method of claim 1, wherein said first fluid comprising said destabilized silica dispersion has a zeta potential amplitude of less than 30 mV.
[28" id="c-fr-0028]
The method of claim 1, wherein said destabilized silica dispersion comprises at least one salt, wherein the concentration of salt ions in said destabilized dispersion is from about 10 mM to about 160 mM.
[29" id="c-fr-0029]
The process of claim 1, wherein said destabilized silica dispersion comprises at least one salt, wherein said salt is present in said destabilized dispersion in an amount of from about 0.2 wt% to about 2 wt% based on the weight of said destabilized dispersion.
[30" id="c-fr-0030]
The process of claim 1, wherein said destabilized silica dispersion comprises at least one acid, wherein said acid is present in said destabilized dispersion in an amount of from about 0.8 wt% to about 7.5 wt. by weight based on the weight of said destabilized dispersion.
[31" id="c-fr-0031]
The process of claim 1, wherein said destabilized silica dispersion comprises at least one acid, wherein the concentration of acid in said destabilized dispersion is from about 200 mM to about 1000 mM.
[32" id="c-fr-0032]
32. The method of claim 1, wherein step (c) is performed with the continuous flow of the first fluid at a speed A and the continuous flow of the second fluid at a speed B, and the speed A is at least 2 times. faster than speed B.
[33" id="c-fr-0033]
33. The method of claim 1 wherein step (c) is performed in a semi-confined reaction zone and the first fluid has a velocity sufficient to induce cavitation in the reaction zone when combined with the second fluid. .
[34" id="c-fr-0034]
The method of claim 32, wherein the second fluid has a velocity sufficient to create a turbulent flow.
[35" id="c-fr-0035]
The method of claim 1, wherein said silica dispersion comprises a surface-modified silica having hydrophobic surface moieties.
[36" id="c-fr-0036]
The method of claim 1, wherein said first fluid is an aqueous fluid.
[37" id="c-fr-0037]
37. The process of claim 1, wherein said first fluid comprises an aqueous fluid and about 6% by weight to about 31% by weight of silica and at least 3% by weight of carbon black.
[38" id="c-fr-0038]
38. The method of claim 1, wherein said first fluid is an aqueous fluid, further comprising at least one salt and at least one acid.
[39" id="c-fr-0039]
The method of claim 1, said method further comprising destabilizing a silica dispersion by lowering a pH of the silica dispersion to form the destabilized silica dispersion provided in step (a).
[40" id="c-fr-0040]
The method of claim 1, said method further comprising destabilizing a silica dispersion by lowering a pH of the silica dispersion to a pH of from 2 to 4 to form the destabilized silica dispersion provided. in step (a).
[41" id="c-fr-0041]
41. The process of claim 1, wherein said silica has a hydrophilic surface.
[42" id="c-fr-0042]
42. The process of claim 1, wherein said silica is a highly dispersible silica (HDS).
[43" id="c-fr-0043]
43. The process according to claim 12, wherein said acid comprises acetic acid, formic acid, citric acid, phosphoric acid or sulfuric acid or any combination thereof.
[44" id="c-fr-0044]
44. The process of claim 12, wherein said acid has a molecular weight or an average molecular weight of less than 200.
[45" id="c-fr-0045]
45. The method of claim 11, wherein said salt comprises at least one metal salt of group 1,2 or 13.
[46" id="c-fr-0046]
46. The method of claim 11, wherein said salt comprises a calcium salt, a magnesium salt or an aluminum salt or a combination thereof.
[47" id="c-fr-0047]
The method of claim 1, said method comprising exposing the silica to a mechanical step to reduce agglomeration of the particles and / or adjust the particle size distribution.
[48" id="c-fr-0048]
48. The process of claim 1, wherein the silica is precipitated silica or fumed silica or colloidal silica, or combinations thereof.
[49" id="c-fr-0049]
49. The process of claim 1 wherein said silica has a BET surface area of from about 20 m 2 / g to about 450 m 2 / g.
[50" id="c-fr-0050]
The method of claim 1, wherein said elastomer latex is natural rubber latex.
[51" id="c-fr-0051]
The method of claim 49, wherein said natural rubber latex is in the form of planting latex, latex concentrate, decanted latex, chemically modified latex, enzymatically modified latex, or any combination thereof. .
[52" id="c-fr-0052]
52. The method of claim 49, wherein said natural rubber latex is in the form of epoxidized natural rubber latex.
[53" id="c-fr-0053]
The method of claim 49, wherein said natural rubber latex is in the form of latex concentrate.
[54" id="c-fr-0054]
The method of claim 1, further comprising mixing the elastomeric-silica composite with an additional elastomer to form an elastomeric composite blend.
[55" id="c-fr-0055]
A method of making a rubber compound comprising (a) carrying out the method of claim 1 and (b) mixing the elastomeric-silica composite with other components to form the rubber compound, wherein said other components comprise at least one antioxidant, sulfur, a polymer other than an elastomer latex, a catalyst, a diluent oil, a resin, a coupling agent, one or more additional elastomeric composites or a reinforcing filler, or any combination of these.
[56" id="c-fr-0056]
A process for manufacturing a rubber article selected from tires, moldings, fasteners, coatings, conveyors, seals or liners comprising (a) performing the method of claim 1 and (b) mixing elastomer-silica composite with other components to form a compound, and (c) vulcanizing the compound to form said rubber article.
[57" id="c-fr-0057]
The method of claim 1, further comprising performing one or more additional post-processing steps after recovering the elastomeric-silica composite.
[58" id="c-fr-0058]
The method of claim 56, wherein the post-treatment steps comprise at least one of: a) drying the elastomeric-silica composite to obtain a dry mixture; b) mixing or mixing the dried mixture to obtain a composite elastomer-silica composite; c) milling the composite elastomer-silica composite to obtain a crushed elastomer-silica composite; d) granulating or mixing the elastomer-milled silica composite; e) pressing the elastomer-silica composite after granulation or mixing to obtain a pressed elastomer-silica composite; f) extruding the elastomer-silica composite; g) the calendering of the elastomer-silica composite; and / or h) optionally decomposing the pressed elastomer-silica composite and mixing with other components.
[59" id="c-fr-0059]
The method of claim 56, wherein the post-processing steps comprise at least rolling of the elastomeric-silica composite.
[60" id="c-fr-0060]
The method of claim 56, wherein the post-treatment steps comprise compressing the continuous phase of solid or semi-solid rubber containing silica to remove about 1 wt.% To about 15 wt.% Of aqueous fluid. contained in it.
[61" id="c-fr-0061]
61. The process according to claim 1, wherein the elastomer latex is brought into contact with at least one destabilizing agent when the destabilized silica dispersion is combined with the elastomer latex.
[62" id="c-fr-0062]
62. The method of claim 1, further comprising contacting the stream of elastomer-solid silica or semisolid composite with at least one destabilizing agent.
[63" id="c-fr-0063]
The method of claim 1, further comprising the step of performing one or more of the following steps with the continuous phase of solid or semi-solid rubber containing silica: a) transfer of the continuous phase of solid or semi-solid rubber containing silica in a holding tank or container; b) heating the continuous phase of solid or semi-solid rubber containing silica to reduce the water content; c) exposing the continuous phase of solid or semi-solid rubber containing silica to an acid bath; d) the mechanical treatment of the continuous phase of solid or semi-solid rubber containing silica to reduce the water content.
[64" id="c-fr-0064]
The method of claim 1, wherein said elastomeric-silica composite is a continuous phase of silica-containing semi-solid rubber and said method further comprising converting said continuous phase of silica-containing semi-solid rubber to continuous phase of solid rubber containing silica.
[65" id="c-fr-0065]
The method of claim 63, wherein said continuous phase of silica-containing semi-solid rubber is converted to said solid silica-containing solid rubber phase by treatment with an aqueous fluid comprising at least one acid or at least one salt or a combination of at least one acid and at least one salt.
[66" id="c-fr-0066]
The method of claim 1, wherein said second fluid comprises a blend of two or more different elastomeric latexes.
[67" id="c-fr-0067]
The method of claim 1, wherein said method further comprises providing one or more additional fluids and combining the one or more additional fluids with said first and second fluid streams, wherein said one or more additional fluids comprise a or a plurality of elastomeric latex fluids and said additional fluids are the same or different from said elastomer latex present in said second fluid stream.
[68" id="c-fr-0068]
The method of claim 1, wherein said silica content of said elastomeric-silica composite is from about 26 phr to about 180 phr.
[69" id="c-fr-0069]
69. Article of the continuous phase of solid rubber containing silica and carbon black comprising at least 25 parts per hundred parts by weight of rubber (phr) of silica dispersed in natural rubber and at least 40% by weight of fluid Aqueous, and having a length dimension (L), wherein the article of the silica solid solid rubber continuous phase can be stretched to at least 130-150% (L) without breaking.
[70" id="c-fr-0070]
An article of the solid rubber-containing solid phase of carbon black according to claim 68, further comprising 10 phr of carbon black dispersed in said natural rubber.

类似技术:

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法律状态:
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2021-06-25| PLFP| Fee payment|Year of fee payment: 6 |

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2021-10-01| PLSC| Publication of the preliminary search report|Effective date: 20211001 |

优先权:

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申请号 | 申请日 | 专利标题

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US201562192891P| true| 2015-07-15|2015-07-15|

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US201662294599P| true| 2016-02-12|2016-02-12|

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