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WO 2015/006423 Al 15 January 2015 (15.01.2015) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/006423 Al 15 January 2015 (15.01.2015) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07F 7/18 (2006.01) B01J 31/02 (2006.01) kind of national protection available): AE, AG, AL, AM, B01J 21/08 (2006.01) C07C 327/06 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (21) Number: International Application DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, PCT/US20 14/0459 15 HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (22) International Filing Date: KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, 9 July 2014 (09.07.2014) MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, (25) Filing Language: English SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, (26) Publication Language: English TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/844,558 10 July 2013 (10.07.2013) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: MOMENTIVE PERFORMANCE MATER¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, IALS INC. [US/US]; 260 Hudson River Road, Waterford, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, NY 12188 (US). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, (72) Inventors: SIMANDAN, Tiberiu, Ladislau; Via degli MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Eucalipti 40, 1-86039 Termoli (IT). TROTTO, Andrea; TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, Via delle Viole 62, 1-86039 Termoli (IT). VECCHI, Ii- KM, ML, MR, NE, SN, TD, TG). aria; Vico Π Villotta 29, 1-66021 Casalbordino (IT). URSITTI, Ottavio; Via Alessandro Manzoni 105, 1-86039 Published: Termoli (IT). — with international search report (Art. 21(3)) (74) Agents: DILWORTH, Peter, G. et al; Dilworth & Bar- rese, LLP, 1000 Woodbury Road, Suite 405, Woodbury, NY 11797 (US). (54) Title: CONTINUOUS PROCESS FOR THE PREPARATION OF THIOCARBOXYLATE SILANE octancthioic acid S-f3-(triethoxy- silanyl)-propyl] ester ©o Figure 1 (57) Abstract: The invention is directed to a process for the preparation of thiocarboxylate silane comprising reacting an aqueous o solution of a salt of a thiocarboxylic acid with a haloalkylalkoxysilane in the presence of a solid supported catalyst. The invention is also directed to a process for the preparation of an aqueous solution of a salt of a thiocarboxylic acid which comprises reacting an aqueous solution of a sulfide and/or hydrosulfide with a carboxylic acid halide and/or acid anhydride. CONTINUOUS PROCESS FOR THE PREPARATION OF T O A BOXYLATE SILANE This utility patent application claims priority to U.S. Provisional Patent Application No. 61/844,558, dated July 10, 2013, the entire contents of which are incorporated herein by reference in their entirety. FIELD OF THE INVENTION The present invention relates to a continuous process of making thiocarboxy!ate- functional silane. More specifically, the present invention relates to the use of a continuous stirred tank reactor and a continuous plug flow reactor and their use in continuously producing thiocarboxylate-functional siianes, such as octanethioic acid S-[3~(triethoxy-silanyl)-propyl] ester, in the presence of a solid-supported phase transfer catalyst. BACKGROUND OF THE INVENTION Thiocarboxylate-functional siianes are coupling agents which are used extensively in rubber applications such as tires and tire components. Several batch processes of making thiocarboxylate-functional silane are known. The batch processes include the reactions of alkali metal salts of mercapto-functional siianes with carbox ic acid chlorides or the reactions of alkali metal salts of alkyithioic acids with halo a ky -containing siianes. The later process, the reactions of alkali metal salts of alkyithioic acids with halo alkyl-containing siianes, are advantageously carried out in a two-phase batch process in which an aqueous phase of the alkali metal salts of alkyithioic acids is reacted with a non-aqueous phase of the halo alkyl-containing silane, often in the presence of phase transfer catalyst. The two-phase batch process eliminates the need to handle solid alkali halide salts, which are a byproduct of the reaction, because these salts are soluble in the aqueous phase. However, the two-phase batch process has the disadvantages of having to conduct washing of the non-aqueous phase, requiring long reaction times and forming meta-stable rag layers. The washing is needed to remove the phase transfer catalyst from the non-aqueous phase containing the reaction product. The phase transfer catalyst is an undesirable impurity in the product which may affect the curi n of the rubber compositions in which the thiocarboxylate- functional siianes are used. The long reaction times results from the diffusion control transport of the alkali metal salts into the non-aqueous phase, and the need to carry out the reaction to completion before the next batch can be started. The meia-stabie rag layer, which is an emulsified mixture of water, the reaction products and the phase transfer catalyst, make the separation of the two-phases difficult, often resulting in loss of reaction product. The use of the two-phase batch process results in the process having the problems of being expensive, long and of limited capacity. Thus, there still exists a need for a process of making thiocarboxylate-functional silane that provides for efficient reaction of a two-phase reaction mixture, reduction of rag layers and very ow amounts and advantageously, absence of phase transfer catalysts in the final product. SUMMARY OF THE INVENTION The invention is directed to the continuous production of a thiocarboxylate-functional silane coupling agent by utilizing a process that involves two liquid phases and employs a solid- supported catalyst, a continuous stirred tank reactor and a continuous plug flow reactor. The inventive process provides for a continuous production of thiocarboxylate-functional siianes such as octanethioic acid S-{3-(triethoxy~silanyI)~propyl] ester in satisfactory amounts an purity without the limitations of batch processes. In one embodiment herein there is provided a process for the continuous preparation of thiocarboxylate silane comprising continuously reacting in a continuous plug flow reactor an aqueous phase solution of a salt of a thiocarboxylic acid with a non-aqueous phase haloalkylalkoxysilane in the presence of a solid phase supported catalyst comprising a salt of a positively charged nitrogen-containing functional group. The continuous process for the preparation of a thiocarboxylate silane comprises: (i) continuously feeding into a plug flow reactor containing a solid phase supported catalyst comprising a salt of a positively charged nitrogen-containing functional group, (a) an aqueous liquid phase solution of an ammonium or alkali metal salt of thiocarboxylate acid, and (b) a non-aqueous liquid phase haloalkylaikoxysilane; (ii) continuously contacting the aqueous liquid phase solution of the ammonium or alkali metal salt of thiocarboxylate acid (a) with the non-aqueous liquid phase haloalkylaikoxysilane (b); (iii) continuously reacting the ammonium or alkali metal salt of thiocarboxylate acid with the haloalkylaikoxysilane to form a non-aqueous liquid phase thiocarboxylate silane and an aqueous liquid phase solution of the ammonium or alkali metal salt of the halide; (iv) continuously removing fro the plug flow reactor the non-aqueous liquid phase thiocarboxylate silane and aqueous liquid phase solution of the ammonium alkali metal sa t of the halide formed in step (iii); and (v) separating the non-aqueous liquid phase thiocarboxylate siiane from the aqueous liquid phase solution of the ammoni or alkali metal salt of the halide formed in step (iv). In one other embodiment there is provided a process for the continuous preparation of an aqueous solution of a ammonium or alkali metal salt of a thiocarboxylic acid. The process for the continuous preparation of an aqueous liquid phase solution of an ammonium or alkali metal salt of a thiocarboxylic acid comprises: (i) continuously feeding into a continuously stirred tank reactor an aqueous liquid phase solution of an ammonium or alkali metal salt of a sulfide and/or hydrosulfide; (ii) continuously feeding into a stirred tank reactor a non-aqueous liquid phase carboxvlic acid halide or carboxy!ic acid anhydride; (iii) continuously reacting the ammonium or alkali metal salt of a sulfide and/or hydrosulfide of step (i) with the non-aqueous liquid phase carboxvlic acid halide or carboxvlic acid anhydride of step (ii), optionally in the presence of a catalyst; and (iv) continuously removing the aqueous liquid phase solution of an ammonium or alkali metal salt of a thiocarboxylic acid from the continuously stirred tank reactor. In yet one other embodiment there is provided a process for the continuous preparation of thiocarboxylate silane comprising: (i) continuously reacting in a continuous stirred tank reactor a aqueous liquid phase solution of an ammonium or alkali metal salt of a sulfide and/or hydrosuiilde with a carboxyiic acid halide and/or carboxylic acid anhydride, optionally in the presence of at least one of a catalyst, to provide a continuous stream of aqueous solution of a salt of a thiocarboxylic acid; and (ii) continuously sending the continuous stream of aqueous iiquid phase soiution of a ammonium or alkali metal salt of a thiocarboxylic acid to a continuous p ug flow reactor containing a solid phase supported catalyst comprising a salt of a positively charged nitrogen-containing functional group, wherein the continuous stream of aqueous liquid phase soiution of an ammonium or alkali metal salt of a thiocarboxylic acid is continuously reacted with a non-aqueous liquid phase haloalkylaikoxysiiane to provide a continuous stream of thiocarboxylate silane reaction product.
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