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(2006.0 1) (21) International Application Number: PCT/EP20 18/083 934 (22) International Filing Date: 07 December 2018 (07

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(2006.0 1) (21) International Application Number: PCT/EP20 18/083 934 (22) International Filing Date: 07 December 2018 (07 ( (51) International Patent Classification: C07F 5/00 (2006.0 1) C07F 5/06 (2006.0 1) (21) International Application Number: PCT/EP20 18/083 934 (22) International Filing Date: 07 December 2018 (07. 12.2018) (25) Filing Language: English (26) Publication Language: English (30) Priority Data: 17207086.4 13 December 2017 (13. 12.2017) EP (71) Applicant: AKZO NOBEL CHEMICALS INTER¬ NATIONAL B.V. [NL/NL]; Velperweg 76, 6824 BM Arn¬ hem (NL). (72) Inventors: TE NIJENHUIS, Marcellinus Antonius Maria; Het Boschloo 12, 7232 GK Warnsveld (NL). WOUDENBERG, Richard Herman; Stijne van Sallandt- straat 58, 743 1 GS Diepenveen (NL). (74) Agent: AKZO NOBEL CHEMICALS IP GROUP; Velperweg 76, 6824 BM Arnhem (NL). (81) Designated States (unless otherwise indicated, for every kind of national protection available) : AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, 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, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (84) Designated States (unless otherwise indicated, for every kind of regional protection available) : ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, 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, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, Cl, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). Published: — with international search report (Art. 21(3)) (54) Title: PROCESS FOR PURIFICATION OF DIMETHYL ALUMINIUM CHLORIDE (57) Abstract: Process for the removal of gallium compounds from dimethyl aluminium chloride (DMAC)-containing compositions, comprising the steps of: (i) adding methyl aluminium sesquichloride (MASC) to said DMAC-containing composition, thereby forming dimethyl aluminium chloride (DMAC) and methyl gallium chloride (MexGaCI(3_x , wherein x= 1or 2), (ii) reducing said methyl gallium chloride with metallic aluminium to form methyl aluminium dichloride (MADC) and metallic gallium, and (iii) removing metallic gallium from the DMAC-containing composition. PROCESS FOR PURIFICATION OF DIMETHYL ALUMINIUM CHLORIDE The present invention relates to a process for the removal of gallium compounds from dimethyl aluminium chloride-containing compositions, a process for producing trimethyl gallium and purified dimethyl aluminium chloride, and a process for the production of trimethyl aluminium using said purified dimethyl aluminium chloride. With the advancement of mobile phones and optical communication technologies, demand is rapidly growing for compound semiconductors for use in high speed electronic devices such as high electron mobility transistors (HEMTs), heterojunction bipolar transistors (HBTs), semiconductor lasers, optical devices such as white and blue super high-intensity LEDs, and other applications. In general, alkyl derivatives of group 12 and group 13 metals, and in particular the methyl or ethyl derivatives, are often used as metalorganic precursors for compound semiconductors. A great demand exists for, in particular, trimethyl gallium for the production of compound semiconductors by MOCVD with group 15 elements, such as nitrogen, arsenic, and the like. Trimethyl gallium (TMG) is conventionally prepared by reacting gallium trichloride with trimethyl aluminium (TMAL). According to this reaction, the production of one mole of TMG requires the use of 3 moles of TMAL: → GaC + 3 AI(CH 3)S Ga(CH 3)3 + 3 AI(CH 3)2C I The resulting TMG is isolated by distillation. Documents disclosing TMG production are WO 2012/083450, WO 2013/083449, US 2006/0471 32, and JP-A 2006-3421 0 1. TMAL is considerably more expensive than other alkyl aluminum compounds, such as triethyl aluminium and dimethyl aluminium chloride. With three moles of TMAL being required for the production of only one mole of TMG, it will be clear that the TMG production costs are heavily determined by the TMAL price. A by-product of this TMG production process is dimethyl aluminium chloride (DMAC). DMAC can be used to make TMAL, according to the following reaction: → 3 (CH 3)2AICI + 3 Na 2 (CH3)3A I + 3 NaCI + Al Using the by-product DMAC for the production of TMAL would reduce the TMAL price, and, hence the TMG production costs. Unfortunately, however, DMAC ends up in the distillation residue, which also contains residual TMG, while for its use in the production of TMAL, DMAC should be free (which means: containing less than 5 ppm) of gallium compounds. Otherwise, the resulting TMAL becomes polluted with gallium compounds. However, removal of gallium to such an extent is not possible with distillation or other known purification methods. An object of the present invention is, therefore, the provision of a process for obtaining Ga-free DMAC from the TMG distillation residue. A further object is the provision of TMAL using said Ga-free DMAC. An additional object the provision of a process for the production of TMG and Ga- free DMAC. In a first embodiment, the present invention relates to a process for the removal of gallium compounds from dimethyl aluminium chloride (DMAC)-containing compositions, comprising the steps of: adding methyl aluminium sesquichloride (MASC) to said DMAC-containing composition, thereby forming dimethyl aluminium chloride (DMAC) and is in methyl gallium chloride (MexGaCI(3-X) , wherein x an average value the range 1-2), reducing said methyl gallium chloride with metallic aluminium to form methyl aluminium dichloride (MADC) and metallic gallium, and - removing said metallic gallium from the DMAC-containing composition. The first step of this process involves the addition of methyl aluminium sesquichloride (MASC) - (C A Cl - to the DMAC-containing composition. A preferred DMAC-containing composition is the distillation residue (bottoms) of a trimethyl gallium (TMG) production process. MASC reacts with the TMG to form DMAC and methyl gallium chloride: → -x x (CH3)3A I2Cl3 + (CH 3)3Ga 2x (CH3)2AICI + (CH3)(3 )GaCl x wherein x is an average value in the range 1 to 2 . If the DMAC-containing composition also contains trimethyl aluminium (TMAL), as in the distillation residue (bottoms) of a trimethyl gallium (TMG) production process, MASC also reacts with TMAL to produce even more DMAC: → (CH3)3A I2C I3 + (CH 3)3A I 3 (CH3) AICI The first step of the process of the first embodiment is preferably conducted under inert (e.g. nitrogen) atmosphere and at a temperature in the range -20 to 200°C, more preferably 0-100°C, even more preferably 20-70°C, and most preferably 20- 50°C. MASC is preferably added to the DMAC-containing composition in an amount ranging from equimolar up to a 20-fold molar excess, more preferably up to a 10- fold molar excess, even more preferably up to a 7-fold molar excess, and most preferably up to a 4-fold molar excess, based on the total molar amount of gallium compounds (calculated as Ga) and TMAL in the DMAC-containing composition. The amount of Ga compound (calculated as Ga) can be determined with ICP and the level of TMAL can be determined by 1H-NMR. MASC can be added in pure form or dissolved in a solvent. Examples are suitable solvents are saturated aliphatic hydrocarbons like pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane; saturated alicyclic hydrocarbons like cyclohexane and cycloheptane; and aromatic hydrocarbons like toluene, xylene, trimethylbenzene, ethylbenzene, ethyltoluene, and indene. The second step of the process of the first embodiment involves the reduction of the formed methyl gallium chloride with metallic aluminium to form dimethyl aluminium chloride (DMAC) and/or methyl aluminium dichloride (MADC) and metallic gallium: → (CH3)GaCI2 + Al (CH3)AICI2 + Ga → (CH3)2GaCI + Al (CH3)2AICI + Ga The metallic aluminium required for this step is preferably added to the DMAC- containing composition in powder form, either before addition of the MASC, after addition of the MASC, or at the same time (e.g. in admixture with MASC). The metallic aluminium can be added in stoichiometric amounts relative to Ga. It is, however, preferred to add the aluminium in excess, preferably up to a 100-fold excess, preferably up to a 20-fold excess, more preferably up to a 10-fold excess, and most preferably up to a 5-fold excess, relative to Ga. This second step is preferably conducted under inert (e.g. nitrogen) atmosphere and at a temperature in the range -20 to 200°C, more preferably 0-100°C, even more preferably 20-70°C, and most preferably 20-50°C. Preferably, the process is conducted as a one pot process, wherein the first and the second step occur simultaneously in the same reactor. The formed metallic gallium separates from the reaction mixture and forms an alloy with excess metallic aluminium. The metallic gallium can be removed from the reaction mixture by conventional separation methods, such as distillation, filtration, or decantation. The resulting reaction mixture is free, i.e. contains less than 5 ppm, of dissolved gallium compounds. In a second embodiment, the present invention relates to a process for the preparation trimethyl gallium (TMG) and dimethyl aluminium chloride (DMAC) comprising the steps of: reacting trimethyl aluminium (TMAL) with GaCI3 to form trimethyl gallium (TMG) and dimethyl aluminium chloride (DMAC), isolating trimethyl gallium (TMG) from the reaction mixture by distillation, - adding methyl aluminium sesquichloride (MASC) to the residue of said distillation, thereby forming dimethyl aluminium chloride (DMAC) and methyl is an in gallium chloride (MexGaCI(3-X) , wherein x average value the range 1- 2), reducing said methyl gallium chloride with metallic aluminium to form methyl aluminium dichloride (MADC) and metallic gallium, and removing said metallic gallium from the DMAC-containing composition.
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