WO2015112252A1 - Production et utilisation d'isomères 3,4'-diméthylbiphényle et 4,4'-diméthylbiphényle - Google Patents

Production et utilisation d'isomères 3,4'-diméthylbiphényle et 4,4'-diméthylbiphényle Download PDF

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WO2015112252A1
WO2015112252A1 PCT/US2014/066857 US2014066857W WO2015112252A1 WO 2015112252 A1 WO2015112252 A1 WO 2015112252A1 US 2014066857 W US2014066857 W US 2014066857W WO 2015112252 A1 WO2015112252 A1 WO 2015112252A1
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stream
mixture
dimethylbiphenyl
hydroalkylation
isomers
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PCT/US2014/066857
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English (en)
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Jihad M. Dakka
Lorenzo C. Decaul
Keith H. Kuechler
Gary D. Mohr
Neeraj Sangar
Michael Salciccioli
Alan A. Galuska
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US14/164,889 external-priority patent/US9085669B2/en
Priority claimed from US14/480,363 external-priority patent/US9464166B2/en
Priority claimed from US14/480,379 external-priority patent/US20150080546A1/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2015112252A1 publication Critical patent/WO2015112252A1/fr

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    • C07C63/33—Polycyclic acids
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    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C07C2523/44—Palladium
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    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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Definitions

  • This disclosure relates to the production of 3, 4' and 4,4'-dimethylbiphenyl isomer mixtures and their use in the production of plasticizers and polyesters.
  • DMBP Dimethylbiphenyl
  • polyesters and plasticizers for PVC and other polymer compositions include polyesters and plasticizers for PVC and other polymer compositions.
  • DMBP can readily be converted to an ester plasticizer by a process comprising oxidation of the DMBP to produce the corresponding mono- or dicarboxylic acid followed by esterification with a long chain alcohol.
  • ester plasticizer For certain uses, it is important to maximize the level of the 3,4'-isomer and particularly the 4,4'-isomer in the product.
  • 4,4'-diphenyl-dicarboxylic acid is a potential precursor, either alone or as a modifier for polyethylene terephthalate (PET), in the production of polyester fibers, engineering plastics, liquid crystal polymers for electronic and mechanical devices, and films with high heat resistance and strength.
  • PET polyethylene terephthalate
  • Copolyesters of 4,4'-biphenyl dicarboxylic acid and terephthalic acid, and certain aliphatic diols are disclosed in the literature, for example, in the Journal of Polymer Science, Polym. Letters, 20, 109 (1982) by Krigbaum et al.
  • U.S. Patent No. 5,138,022 disclosed copolyester of 3,4' biphenyl dicarboxylic acid and optionally 4,4' -biphenyl dicarboxylic acid, and certain aliphatic diols like ethylene glycol, 1 ,4-butanediol, and 1 ,4-cyclohexanedimethanol.
  • dimethyl biphenyl may be produced by hydroalkylation of toluene followed by dehydrogenation of the resulting (methylcyclohexyl)toluene (MCHT).
  • the invention resides a process for producing 3,4' and/or 4,4' dimethyl-substituted biphenyl compounds, the process comprising:
  • (cl) separating the dehydrogenation reaction product into at least a first stream containing at least 50% of 3,4' and 4,4' dimethylbiphenyl isomers by weight of the first stream and at least one second stream comprising one or more 2,X' (where X' is 2', 3', or 4') and 3,3' dimethylbiphenyl isomers.
  • the invention resides a process for producing 3,4' and/or 4,4' dimethyl-substituted biphenyl compounds, the process comprising:
  • (d2) separating the methylation reaction product into at least a first stream containing at least 50% of 3,4' and 4,4' dimethylbiphenyl isomers by weight of the first stream and at least one second stream comprising one or more 2,X' (where X' is 2', 3', or 4') and 3,3' dimethylbiphenyl isomers.
  • the invention resides a process for producing 3,4' and/or 4,4' dimethyl-substituted biphenyl compounds, the process comprising:
  • (c3) separating the methylation reaction product into at least a first stream comprising at least 50% of 3,4' and 4,4' dimethylbiphenyl isomers by weight of the first stream and at least one second stream comprising one or more 2,X' (where X' is 2', 3', or 4') and 3,3' dimethylbiphenyl isomers.
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound of the formula:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound of the formula:
  • each R is, independently, a C 1 to C 16 hydrocarbyl.
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of one or more compounds having the formulas:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of one or more compounds having the formulas:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the invention resides in a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the invention resides in polyesters produced from the diacids and/or the dialcohols described herein. BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 is a flow diagram of a process of producing 4,4'-dimethylbiphenyl from toluene according to one embodiment of the invention.
  • Figure 2 is a bar graph comparing the amount of di(methylcyclohexyl)toluenes produced in the hydroalkylation of toluene over the catalysts of Examples 1 to 4.
  • Figure 3 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-MCM-49 catalyst of Example 1.
  • Figure 4 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-beta catalyst of Example 2.
  • Figure 5 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-Y catalyst of Example 3.
  • Figure 6 is a graph of toluene conversion against time on stream (TOS) in the hydroalkylation of toluene over the Pd-W0 3 /Zr0 2 catalyst of Example 4.
  • Figure 7 is the GC spectrum of the product of hydroalkylation testing of the catalyst of Example 1 according to the process of Example 5.
  • Figure 8 is the GC spectrum of the product of hydroalkylation testing of the catalyst of Example 2 according to the process of Example 5.
  • Figure 9 is a bar graph comparing the reaction effluents produced by the nonselective dehydrogenation of the hydroalkylation products of Examples 1 and 2.
  • Figure 10 is a bar graph comparing the product compositions obtained with the different dehydrogenation catalysts in the process of Example 10.
  • Figure 11 is a graph plotting oxygen in the reaction effluent against time on stream for the oxidation reactions of Examples 11 and 12.
  • Figure 12 is a graph plotting 4,4'-DMBP conversion against selectivity to the corresponding aldehyde, monoacid and diacid for the process of Example 14.
  • Described herein are (a) processes of producing 3,4' and/or 4,4' dimethyl- substituted biphenyl compounds from low cost feeds, particularly toluene and/or benzene, (b) novel isomer mixtures produced by these processes, and (c) use of the resultant isomer mixtures in producing biphenyl dicarboxylic acids and derivatives thereof useful in the manufacture of plasticizers and polyesters.
  • the feed employed in the present process comprises toluene, which is initially converted to (methylcyclohexyl)toluenes by reaction with hydrogen over a hydroalkylation catalyst according to the following reaction:
  • the catalyst employed in the hydroalkylation reaction is a bifunctional catalyst comprising a hydrogenation component and a solid acid alkylation component, typically a molecular sieve.
  • the catalyst may also include a binder such as clay, alumina, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica- magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.
  • any known hydrogenation metal or compound thereof can be employed as the hydrogenation component of the catalyst, although suitable metals include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous.
  • the amount of hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt%, such as between about 0.1 and about 5 wt%, of the catalyst.
  • the solid acid alkylation component comprises a large pore molecular sieve having a Constraint Index (as defined in U.S. Patent No. 4,016,218) less than 2.
  • Suitable large pore molecular sieves include zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-18, and ZSM-20.
  • Zeolite ZSM- 4 is described in U.S. Patent No. 4,021,447.
  • Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983.
  • Zeolite Beta is described in U.S. Patent Nos. 3,308,069, and Re. No.
  • Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293,192 and 3,449,070.
  • Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Patent No. 3,442,795.
  • Zeolite UHP-Y is described in U.S. Patent No. 4,401,556.
  • Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetic mordenite prepared from a reaction mixture comprising a tetraethylammonium directing agent).
  • TEA-mordenite is disclosed in U.S. Patent Nos. 3,766,093 and 3,894,104.
  • the solid acid alkylation component comprises a molecular sieve of the MCM-22 family.
  • MCM-22 family material includes one or more of:
  • molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
  • molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
  • the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof;
  • molecular sieves made by any regular or random 2-dimensional or 3 -dimensional combination of unit cells having the MWW framework topology.
  • Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstrom.
  • the X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • Molecular sieves of MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U.S. Patent No.
  • ERB-1 (described in European Patent No. 0293032)
  • ITQ-1 (described in U.S. Patent No 6,077,498)
  • ITQ-2 (described in International Patent Publication No. WO97/17290)
  • MCM-36 (described in U.S. Patent No. 5,250,277)
  • MCM-49 (described in U.S. Patent No. 5,236,575)
  • MCM-56 (described in U.S. Patent No. 5,362,697) and mixtures thereof.
  • the feed to the hydroalkylation reaction may include benzene and/or xylene which can undergo hydroalkylation to produce various methylated cyclohexylbenzene molecules of C 12 to C1 ⁇ 2 carbon number.
  • a diluent which is substantially inert under hydroalkylation conditions, may also be included in the hydroalkylation feed.
  • the diluent is a hydrocarbon, in which the desired cycloalkylaromatic product is soluble, such as a straight chain paraffinic hydrocarbon, a branched chain paraffinic hydrocarbon, and/or a cyclic paraffinic hydrocarbon.
  • Suitable diluents are decane and cyclohexane.
  • the amount of diluent is not narrowly defined, desirably the diluent is added in an amount such that the weight ratio of the diluent to the aromatic compound is at least 1 : 100; for example, at least 1 : 10, but no more than 10: 1, desirably no more than 4: 1.
  • the hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers.
  • the hydroalkylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages.
  • Suitable reaction temperatures are between about 100°C and about 400°C, such as between about 125°C and about 250°C, while suitable reaction pressures are between about 100 and about 7,000 kPa, such as between about 500 and about 5,000 kPa.
  • the molar ratio of hydrogen to aromatic feed is typically from about 0.15: 1 to about 15: 1.
  • MCM-22 family molecular sieves are particularly active and stable catalysts for the hydroalkylation of toluene or xylene.
  • catalysts containing MCM-22 family molecular sieves exhibit improved selectivity to the 3,3 '-dimethyl, the 3,4'-dimethyl, the 4,3'-dimethyl and the 4,4'-dimethyl isomers in the hydroalkylation product, while at the same time reducing the formation of fully saturated and heavy by-products.
  • the hydroalkylation reaction product may comprise:
  • the hydroalkylation reaction product may also contain significant amounts of residual toluene, for example up to 50 wt%, such as up to 90 wt%, typically from 60 to 80 wt% of residual toluene based on the total weight of the hydroalkylation reaction product.
  • the residual toluene can readily be removed from the reaction effluent by, for example, distillation.
  • the residual toluene can then be recycled to the hydroalkylation reactor, together with some or all of any unreacted hydrogen.
  • the remainder of the hydroalkylation reaction effluent composed mainly of (methylcyclohexyl)toluenes, is then dehydrogenated to convert the (methylcyclohexyl)toluenes to the corresponding methyl-substituted biphenyl compounds.
  • the dehydrogenation is conveniently conducted at a temperature from about 200°C to about 600°C and a pressure from about 100 kPa to about 3550 kPa (atmospheric to about 500 psig) in the presence of dehydrogenation catalyst.
  • a suitable dehydrogenation catalyst comprises one or more elements or compounds thereof selected from Group 10 of the Periodic Table of Elements, for example platinum, on a support, such as silica, alumina or carbon nanotubes.
  • the Group 10 element is present in an amount from 0.1 to 5 wt% of the catalyst.
  • the dehydrogenation catalyst may also include tin or a tin compound to improve the selectivity to the desired methyl-substituted biphenyl product.
  • the tin is present in an amount from 0.05 to 2.5 wt% of the catalyst.
  • the product of the dehydrogenation step comprises dimethylbiphenyl compounds in which the concentration of the 3,3'-, 3,4'-, and 4,4' isomers is at least 50 wt%, such as at least 60 wt%, for example at least 70 wt% based on the total weight of dimethylbiphenyl compounds.
  • the concentration of the 2,X'- dimethylbiphenyl isomers in the dehydrogenation product is less than 50 wt%, such as less than 30 wt%, for example, from 5 to 25 wt% based on the total weight of dimethylbiphenyl compounds.
  • the present process for producing dimethyl-substituted biphenyl compounds employs benzene as the feed and comprises initially converting the benzene to biphenyl.
  • benzene can be converted directly to biphenyl by reaction with oxygen over an oxidative coupling catalyst as follows:
  • benzene can be converted to biphenyl by hydroalkylation to cyclohexylbenzene according to the reaction:
  • the benzene hydroalkylation can be conducted in the same manner as described above for the hydroalkylation of toluene, while the dehydrogenation of the cyclohexylbenzene can be conducted in the same manner as described above for the dehydrogenation of (methylcyclohexyl)toluene.
  • the biphenyl product of the oxidative coupling step or the hydroalkylation/dehydrogenation sequence is then methylated, for example with methanol, to produce dimethylbiphenyl.
  • Any known alkylation catalyst can be used for the methylation reaction, such as an intermediate pore molecular sieve having a Constraint Index (as defined in U.S. Patent No. 4,016,218) of 3 to 12, for example ZSM-5.
  • the composition of the methylated product will depend on the catalyst and conditions employed in the methylation reaction, but inevitably will comprise a mixture of the different isomers of dimethylbiphenyl.
  • the methylated product will contain from 50 to 100 wt% of 3,3'-, 3,4'-, and 4,4' dimethylbiphenyl isomers and from 0 to 50 wt% of 2, ⁇ ' (where X' is 2', 3' or 4') -dimethylbiphenyl isomers based on the total weight of dimethylbiphenyl compounds in the methylation product.
  • the raw dimethylbiphenyl product from the production sequences described will contain unreacted components and by-products in addition to a mixture of dimethylbiphenyl isomers.
  • the initial feed comprises toluene and the production sequence involves hydroalkylation to MCHT and dehydrogenation of the MCHT
  • the raw dimethylbiphenyl product will tend to contain residual toluene and MCHT and by-products including hydrogen, methylcyclohexane dimethylcyclohexylbenzene, and C 15 + heavy hydrocarbons in addition to the target dimethylbiphenyl isomers.
  • the raw product of the MCHT dehydrogenation is subjected to a rough cut separation to remove at least part of the residues and by-products with significantly different boiling points from the dimethylbiphenyl isomers.
  • the hydrogen byproduct can be removed and recycled to the hydroalkylation and/or MCHT dehydrogenation steps, while residual toluene and methylcyclohexane by-product can be removed and recycled to the hydroalkylation step.
  • part of the heavy (C 15 +) components can be removed in the rough cut separation and can be recovered for use as a fuel or can be reacted with toluene over a trans alky lation catalyst to convert some of the dialkylate to additional MCHT.
  • a suitable rough cut separation can be achieved by distillation.
  • the H 2 and C 7 components can be stripped from the C12+ components without reflux.
  • the remaining dimethylbiphenyl product is subjected to a first DMBP separation step, in which the product is separated into at least a first stream rich in 3,4' and 4,4' dimethylbiphenyl and at least one second stream comprising one or more 2,x' (where x' is 2', 3', or 4') and 3,3' dimethylbiphenyl isomers.
  • the second stream will also typically contain most of the unreacted MCHT and most of the dimethylcyclohexylbenzene by-product in the raw dimethylbiphenyl product.
  • the first stream contains at least 50%, such as at least 60%, for example at least 70%, such as at least 80%, for example at least 90%, of 3,4' and 4,4' dimethylbiphenyl isomers by weight of the first stream.
  • the first stream may contain from 50 to 95%, such as from 70 to 95%, for example from 80 to 95%, of 3,4' and 4,4' dimethylbiphenyl by weight of the first stream.
  • the first stream may contain at least 50 wt%, preferably at least 90 wt%, preferably from 90 to 100 wt%, of a compound of the formula:
  • the first stream may also contain up to 40%, such as from 0 to 40%, for example from 1 to 10%, of 3,3' dimethylbiphenyl by weight of the first stream.
  • the second stream contains at least 30%, such as from 30 to 50%, of the 2,X' dimethylbiphenyl isomers and at least 30%, such as from 30 to 50%, 3,3' dimethylbiphenyl, with all percentages being by weight based on the total weight of the second stream.
  • the DMBP synthesis route includes toluene hydroalkylation followed by dehydrogenation of MCHT
  • the second stream will also typically contain most of the unreacted MCHT and most of the dimethylcyclohexylbenzene by-product in the raw dimethylbiphenyl product.
  • Part or all of the 2,X' dimethylbiphenyl isomers in the second stream may be converted, as described below, to 3,Y' (where Y' is 3' or 4') and 4,4' dimethylbiphenyl isomers.
  • the converted stream can then be recycled back to the rough cut separation or to the first DMBP separation step to recover the additional 3,Y' and 4,4' isomers.
  • a light overhead stream may also be removed in the initial separation step to recover any residual toluene remaining from the rough cut separation. This light overhead stream may be recycled to the hydroalkylation step.
  • the initial separation may also be used to remove additional heavy components remaining in the raw dimethylbiphenyl product after the rough cut separation. These heavy components may be directed to fuel use.
  • part or all of the first stream can be recovered and, optionally after further purification, can be forwarded for certain end-use applications, such as the production of plasticizers.
  • the first stream can be subjected to oxidation to convert one or both the methyl groups to carboxylic acid group(s) and then the or each acid group can be esterified with a long chain alcohol, such as an OXO-alcohol.
  • part or all of the first stream is subjected to a second DMBP separation step to separate the first stream into a third stream rich in 4,4' dimethylbiphenyl and a fourth stream comprising 3,4' dimethylbiphenyl.
  • the second DMBP separation is conveniently effected by fractional crystallization.
  • the fractional crystallization is assisted by the addition of a solvent, preferably a C 3 to C 12 aliphatic hydrocarbon, more preferably pentane and/or hexane, to the first stream. Suitable amounts for the solvent addition comprise as from 10 to 75%, for example from 25 to 50% solvent by weight of the first stream.
  • the 4,4' DMBP-rich third stream contains at least 70%, such as at least 80%, for example at least 90%, even up to 100%, of 4,4' dimethylbiphenyl by weight of the third stream.
  • the third stream may contain from 70 to 100%, such as from 80 to 100%, for example from 95 to 100%, of 4,4' dimethylbiphenyl by weight of the first stream.
  • the third stream will normally contain at least 1% and up to 30%, such as up to 20%, for example up to 10%, by weight of 3,4' dimethylbiphenyl by weight of the third stream.
  • the third stream contains less than 5%, such as less than 1%, by weight, even no measurable amount of, 3,3' dimethylbiphenyl.
  • the fourth stream contains at least 70%, such as at least 80%, for example at least 90%, even up to 100%, of 3,4' dimethylbiphenyl by weight of the third stream.
  • the fourth stream may contain from 70 to 100%, such as from 80 to 100%, for example from 90 to 100%, of 3,4' dimethylbiphenyl by weight of the fourth stream.
  • the fourth stream may contain up to 30%, such as up to 20%, for example up to 10%, by weight of 3,3' dimethylbiphenyl by weight of the fourth stream.
  • the fourth stream contains less than 10%, such as less than 5%, by weight, even no measurable amount of, 4,4' dimethylbiphenyl.
  • part or all of the third stream can be recovered and, optionally after further purification, can be forwarded for certain end-use applications, such as the production of polyesters.
  • the third stream can also be used in the production of plasticizers in the same way as the first stream but, in general, this is not the highest value use of the third stream.
  • part or all of the fourth stream can be recovered and, optionally after further purification, can be forwarded for certain end-use applications, such as the production of plasticizers or, more preferably, polyesters.
  • the fourth stream is subjected to a third DMBP separation step to separate the fourth stream into a fifth stream rich in 3,4' dimethylbiphenyl and a sixth stream containing 3,3' dimethylbiphenyl.
  • the third DMBP separation can be effected by distillation or fractional crystallization.
  • the fractional crystallization may be assisted by the addition of a solvent, preferably a C 3 to C 12 aliphatic hydrocarbon, more preferably pentane and/or hexane, to the fourth stream.
  • a solvent preferably a C 3 to C 12 aliphatic hydrocarbon, more preferably pentane and/or hexane.
  • Suitable amounts for the solvent addition comprise as from 10 to 75%, for example from 25 to 50% solvent by weight of the fourth stream.
  • the 3,4' DMBP-rich fifth stream contains at least 80%, for example at least 90%, even up to 100%, of 3,4' dimethylbiphenyl by weight of the fifth stream.
  • the fifth stream contains less than 20%, such as less than 10%, by weight, even no measurable amount of, 3,3' dimethylbiphenyl.
  • the fifth stream may be recovered and, optionally after further purification, can be forwarded for certain end-use applications, such as the production of polyesters, either alone or in combination with 4,4' DMBP-rich third stream or a product thereof. Conversion of 2,X'-Dimethylbiphenyl Isomers
  • part or all of the 2,X'-dimethylbiphenyl (DMBP) isomers in the second stream described above, either alone or together with part or all 3,3' dimethylbiphenyl present in the second stream, can be processed to increase the concentration of 3,4' and 4,4' dimethylbiphenyl (DMBP) in the second stream.
  • One suitable process comprises a combination of hydrogenation of the DMBP back to MCHT, followed by transalkylation of the MCHT with toluene and then dehydrogenation of the transalkylation product back to DMBP. Such a process is described in our co-pending U.S.
  • Patent Application Serial Number 62/012,024, both filed June 13, 2014 (Attorney Docket No. 2014EM136), the entire contents of which are incorporated by reference herein.
  • this process of increasing 3,4' and 4,4' DMBP concentration can be achieved by recycling the second stream to the hydroalkylation/dehydrogenation sequence.
  • Any of the dimethylbiphenyl isomer-containing streams described above can be oxidized to produce the corresponding biphenyldicarboxylic acid or (methyl-phenyl)benzoic acid.
  • the oxidation can be performed by any process known in the art, such as by reacting the methyl-substituted biphenyl compounds with an oxidant, such as oxygen, ozone or air, or any other oxygen source, such as hydrogen peroxide, in the presence of a catalyst and with or without a promoter such as Br at temperatures from 30°C to 300°C, such as from 60°C to 200°C.
  • Suitable catalysts comprise Co or Mn or a combination of both metals.
  • oxidation of part or all of the 3,4'-DMBP and 4,4'-DMBP rich first stream can produce a mixture of biphenyldicarboxylic acid isomers comprising at least 50 wt%, preferably at least 80 wt%, preferably from 90 to 99 wt%, of a compound of the formula:
  • oxidation of part or all of the 4,4' DMBP-rich third stream can produce a mixture of biphenyldicarboxylic acid isomers comprising at least 70 wt%, preferably at least 80 wt%, preferably from 90 to 99 wt%, of a compound of the formula:
  • the oxidation can be conducted in the presence of p-xylene so that the oxidation product comprises terephthalic acid in addition to the mixtures of biphenyldicarboxylic acid isomers described above.
  • Any of the biphenyldicarboxylic acid and/or (methylphenyl)benzoic acid mixtures produced by the oxidation process described above, or their methyl esters, can be hydrogenated by methods known in the art to saturate one or both benzene rings and/or to convert one or both of the acid groups to an alcohol.
  • Suitable hydrogenation conditions include, but are not limited to temperatures of 0-300°C, pressures of 1-500 atmospheres, and the presence of homogeneous or heterogeneous hydrogenation catalysts such as, but not limited to, platinum, palladium, ruthenium, nickel, zinc, tin, cobalt, copper, chromium, iron, or a combination of these metals, with palladium being particularly advantageous.
  • such hydrogenation produces a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of one or more compounds having the formulas:
  • such hydrogenation can produce a mixture of dicyclohexyldicarboxylic acids comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the hydrogenation produces a mixture comprising at least 50 wt%, preferably from 90 to 99 wt%, of one or more compounds having the formulas:
  • such hydrogenation can produce a mixture of biphenyldialcohols comprising at least 50 wt%, preferably from 90 to 99 wt%, of a compound having the formula:
  • the hydrogenation can produce a mixture dicyclohexyldialcohols comprising at least 50 wt%, preferably from 90 to 99 wt%, of compounds having the formula:
  • biphenyldicarboxylic acid, phenylcyclohexyldicarboxylic acid and/or dicyclohexyldicarboxylic acid isomers and/or mixtures described above can be reacted with one or more diols and optionally with co-produced, or separately added, terephthalic acid to produce polyesters by any known method.
  • suitable biphenyldicarboxylic acid compositions include:
  • Suitable diols for reaction with the above-mentioned diacid compositions include alkanediols having 2 to 12 carbon atoms, such as monoethylene glycol, diethylene glycol, 1,3 -propanediol, or 1,4-butane diol, 1,6-hexanediol, and 1 ,4-cyclohexanedimethanol.
  • any of the biphenyldicarboxylic acid, phenylcyclohexyldicarboxylic acid and/or dicyclohexyldicarboxylic acid isomers and/or mixtures described above can be reacted with one or more of the mixtures of biphenyldialcohols, phenylcyclohexyldialcohols and/or dicyclohexyldialcohols described above to produce polyesters.
  • the polyesters may be prepared by conventional direct esterification or transesterification methods.
  • Suitable catalysts include but not limited to titanium alkoxides such as titanium tetraisopropoxide, dialkyl tin oxides, antimony trioxide, manganese (II) acetate and Lewis acids.
  • Suitable conditions include a temperature 170 to 350°C for a time from 0.5 hours to 10 hours. Generally, the reaction is conducted in the molten state and so the temperature is selected to be above the melting point of the monomer mixture but below the decomposition temperature of the polymer. A higher reaction temperature is therefore needed for higher percentages of biphenyl dicarboxlic acid in the monomer mixture.
  • the polyester may be first prepared in the molten state followed by a solid state polymerization to increase its molecular weight or intrinsic viscosity for applications like bottles.
  • the biphenyl dicarboxylic acids may be substituted by the corresponding biphenyl dicarboxylates (esters of corresponding biphenyl dicarboxylic acids), resulting in a transesterification reaction instead of direct esterification reaction.
  • Any of the biphenyldicarboxylic acid, phenylcyclohexyldicarboxylic acid and/or dicyclohexyldicarboxylic acid isomers and/or mixtures described above can also be reacted with one of more Ci to Ci 6 alcohols to produce an esterification product.
  • Suitable esterification conditions are well-known in the art and include, but are not limited to, temperatures of 0-300°C and the presence or absence of homogeneous or heterogeneous esterification catalysts, such as Lewis or Bronsted acid catalysts.
  • Suitable alcohols are "oxo- alcohols", by which is meant an organic alcohol, or mixture of organic alcohols, which is prepared by hydroformylating an olefin, followed by hydrogenation to form the alcohols.
  • the olefin is formed by light olefin oligomerization over heterogeneous acid catalysts, which olefins are readily available from refinery processing operations. The reaction results in mixtures of longer-chain, branched olefins, which subsequently form longer chain, branched alcohols, as described in U.S. Patent No. 6,274,756, incorporated herein by reference in its entirety.
  • Another source of olefins used in the OXO process are through the oligomerization of ethylene, producing mixtures of predominately straight chain alcohols with lesser amounts of lightly branched alcohols.
  • FIG. 1 One embodiment of a process of producing 4,4'-dimethylbiphenyl from a toluene- containing feed is illustrated in Figure 1, in which toluene and hydrogen are fed by a single line 11 or, if preferred by separate lines (not shown), to a hydroalkylation unit 12.
  • the hydroalkylation unit 12 contains a bed of a bifunctional catalyst which comprises a hydrogenation component and a solid acid alkylation component and which converts at least part of the toluene to (methylcyclohexyl)toluene (MCHT).
  • MCHT methylcyclohexyl)toluene
  • the effluent from the hydroalkylation unit 12, comprising MCHT and unreacted toluene together with a small amount of di(methylcyclohexyl)toluene, is initially fed to a first distillation unit 13, where the di(methylcyclohexyl)toluene is removed as a heavy steam 14.
  • the remainder of the hydroalkylation unit effluent is then fed to a dehydrogenation unit 15 where the MCHT is dehydrogenated to produce dimethylbiphenyl (DMBP) and hydrogen.
  • DMBP dimethylbiphenyl
  • the dehydrogenation effluent also contains unreacted toluene.
  • the effluent from the dehydrogenation unit 15 is then supplied to a rough-cut separation unit 16, such as a second distillation unit, where hydrogen is removed via line 17 and at least some of the toluene is removed via line 18.
  • the hydrogen in line 17 is then recycled to the hydroalkylation unit 12 via line 19 and/or to the dehydrogenation unit 15 via line 21, while the toluene in line 18 is recycled to the hydroalkylation unit 12.
  • the raw DMBP-containing product leaving the separation unit 16 is then fed via line 23 to a third distillation unit 24 where further toluene impurity is removed via overhead line 25 to be merged with the impurity stream in line 18 and C 5+ heavies are removed as bottoms stream 26.
  • the third distillation unit 24 separates the raw DMBP product into a first stream containing at least 50 wt% of 3,4' and 4,4' DMBP and at least one second stream comprising one or more 2,x' (where x' is 2', 3', or 4') and 3,3' DMBP isomers.
  • the 3,4' and 4,4' DMBP-containing first stream exits the third distillation unit 24 as a first side stream and is fed via line 27 to a 4,4'-DMBP separation unit 28, where a third stream rich in 4,4 '-DMBP is crystallized out of the first stream and recovered in line 29.
  • the remaining 4,4'-DMBP depleted fourth stream is collected by line 31 for recovery and/or further treatment.
  • the 2,x' and 3,3' DMBP-containing second stream exits the third distillation unit 24 as a second side stream and is recycled via line 34 to the hydroalkylation unit 12.
  • MCM-49 zeolite crystals 80 parts are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the MCM-49 and pseudoboehmite alumina dry powder are placed in a muller and mixed for about 10 to 30 minutes.
  • Sufficient water and 0.05% polyvinyl alcohol is added to the MCM-49 and alumina during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch (0.13 cm) quadrulobe extrudate using an extruder and the resulting extrudate is dried at a temperature ranging from 250°F to 325°F (120°C to 163°C). After drying, the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen. The extrudate is then cooled to ambient temperature and humidified with saturated air or steam.
  • the extrudate is ion exchanged with 0.5 to 1 N ammonium nitrate solution.
  • the ammonium nitrate solution ion exchange is repeated.
  • the ammonium nitrate exchanged extrudate is then washed with deionized water to remove residual nitrate prior to calcination in air. After washing the wet extrudate, it is dried.
  • the exchanged and dried extrudate is then calcined in a nitrogen/air mixture to a temperature 1000°F (538°C). Afterwards, the calcined extrudate is cooled to room temperature.
  • the 80% MCM-49, 20% AI2O 3 extrudate is incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121°C.
  • the dried catalyst is calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538°C at l°C/min and hold for 3 hours.
  • beta zeolite crystals 80 parts beta zeolite crystals are combined with 20 parts pseudoboehmite alumina, on a calcined dry weight basis.
  • the beta and pseudoboehmite are mixed in a muller for about 15 to 60 minutes.
  • Sufficient water and 1.0% nitric acid is added during the mixing process to produce an extrudable paste.
  • the extrudable paste is formed into a 1/20 inch quadrulobe extrudate using an extruder. After extrusion, the l/20th inch quadrulobe extrudate is dried at a temperature ranging from 250°F to 325°F (120°C to 163°C).
  • the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen and then calcined in air at a temperature of 1000°F (538°C). Afterwards, the calcined extrudate is cooled to room temperature.
  • the 80% Beta, 20% AI2O 3 extrudate is incipient wetness impregnated with a tetraammine palladium (II) nitrate solution (target: 0.30% Pd) and then dried overnight at 121°C.
  • the dried catalyst is calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538°C at l°C/min and hold for 3 hours.
  • Example 3 Synthesis of 0.3%Pd/USY Catalyst
  • the dried extrudate is heated to 1000°F (538°C) under flowing nitrogen and then calcined in air at a temperature of 1000°F (538°C).
  • the 80% CBV-720 USY, 20% A1 2 0 3 extrudate is incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121°C.
  • the dried catalyst is calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538°C at l 0 C/min and hold for 3 hours.
  • a W0 3 /Zr0 2 extrudate (11.5% W, balance Zr) 1/16" cylinder is obtained from Magnesium Elektron in the form of a 1/16 inch (0.16 cm) diameter extrudate.
  • the WC ZrC ⁇ extrudate is calcined in air for 3 hours at 538°C. On cooling, the calcined extrudate is incipient wetness impregnated with a palladium (II) chloride solution (target: 0.30% Pd) and then dried overnight at 121°C.
  • the dried catalyst is calcined in air at the following conditions: 5 volumes air per volume catalyst per minute, ramp from ambient to 538°C at l°C/min and hold for 3 hours.
  • the reactor comprised a stainless steel tube having an outside diameter of 3/8 inch (0.95 cm), a length of 20.5 inch (52 cm) and a wall thickness of 0.35 inch (0.9 cm).
  • a piece of stainless steel tubing having a length of 83 ⁇ 4 inch (22 cm) and an outside diameter of 3/8 inch (0.95 cm) and a similar length of 1 ⁇ 4 inch (0.6 cm) were used in the bottom of the reactor (one inside of the other) as a spacer to position and support the catalyst in the isothermal zone of the furnace.
  • a 1/4 inch (0.6 cm) plug of glass wool was placed on top of the spacer to keep the catalyst in place.
  • a 1/8 inch (0.3 cm) stainless steel thermo-well was placed in the catalyst bed to monitor temperature throughout the catalyst bed using a movable thermocouple.
  • the catalyst was sized to 20/40 sieve mesh or cut to 1 : 1 length to diameter ratio, dispersed with quartz chips (20/40 mesh) then loaded into the reactor from the top to a volume of 5.5 cc.
  • the catalyst bed typically was 15 cm. in length.
  • the remaining void space at the top of the reactor was filled with quartz chips, with a 1 ⁇ 4 plug of glass wool placed on top of the catalyst bed being used to separate quartz chips from the catalyst.
  • the reactor was installed in a furnace with the catalyst bed in the middle of the furnace at a pre-marked isothermal zone. The reactor was then pressure and leak tested typically at 300 psig (2170 kPa).
  • the catalyst was pre-conditioned in situ by heating to 25°C to 240°C with H2 flow at 100 cc/min and holding for 12 hours.
  • a 500 cc ISCO syringe pump was used to introduce a chemical grade toluene feed to the reactor.
  • the feed was pumped through a vaporizer before flowing through heated lines to the reactor.
  • a Brooks mass flow controller was used to set the hydrogen flow rate.
  • a Grove "Mity Mite" back pressure controller was used to control the reactor pressure typically at 150 psig (1135 kPa). GC analyses were taken to verify feed composition.
  • the feed was then pumped through the catalyst bed held at the reaction temperature of 120°C to 180°C at a WHSV of 2 and a pressure of 15-200 psig (204- 1480 kPa).
  • the liquid products exiting the reactor flowed through heated lines routed to two collection pots in series, the first pot being heated to 60°C and the second pot cooled with chilled coolant to about 10°C. Material balances were taken at 12 to 24 hrs intervals. Samples were taken and diluted with 50% ethanol for analysis. An Agilent 7890 gas chromatograph with FID detector was used for the analysis. The non-condensable gas products were routed to an on line HP 5890 GC.
  • the Pd/MCM-49 catalyst is less active than the Pd/Y catalyst, it has much lower selectivity towards the production of the fully saturated by-products, methylcyclohexane and dimethylbi(cyclohexane) than either Pd/Y or Pd/beta.
  • the data shown in Figure 2 clearly demonstrate that Pd/MCM-49 provides the lowest yield loss, less than 1 wt% of total converted feed, to dialkylate products.
  • the data shown in Figures 3 to 6 demonstrate that Pd/MCM-49 has improved stability and catalyst life as compared with the other catalysts tested. It is believed that the stability is related to the formation of heavies which remain on the surface of the catalyst and react further to create coke which prevents the access to the acid and hydrogenation sites.
  • a 1%Pt/0.15%Sn/SiO2 catalyst was prepared by incipient wetness impregnation, in which a 1/20" (1.2 mm) quadrulobe silica extrudate was initially impregnated with an aqueous solution of tin chloride and then dried in air at 121°C. The resultant tin-containing extrudates were then impregnated with an aqueous solution of tetraammine Pt nitrate and again dried in air at 121°C. The resultant product was calcined in air at 350°C for 3 hours before being used in subsequent catalyst testing.
  • ⁇ - ⁇ 2 ⁇ 3 2.5 mm trilobe extrudates were used as support for Pt deposition.
  • the extrudates had a surface area of 126 m 2 /g, pore volume of 0.58 cmVg, and pore size of 143 A, as measured by BET N2 adsorption.
  • Pt was added to ⁇ - ⁇ 2 ⁇ 3 support by impregnating with aqueous solution of (NH 3 ) 4 Pt(NO 3 )2.
  • the Pt metal loading on the supports is adjusted at lwt%. After impregnating, the sample was placed in the glass dish at room temperature for 60 minutes to reach equilibrium. Then it was dried in air at 250°F (120°C) for 4 hrs.
  • the calcination was carried out in a box furnace at 680°F (360°C) in air for 3 hrs. The furnace was ramped at 3°F/minute. The air follow rate for the calcination was adjusted at 5 volume/volume catalyst/minute.
  • Example 8 Preparation of l%Pt + 0.3%Sn/ ⁇ -Al 2 O 3
  • the sample was prepared by sequential impregnations.
  • SnCl 2 was added to ⁇ - AI2O3 support by impregnation of aqueous solutions of tin chloride.
  • the Sn metal oxide loading on the ⁇ - ⁇ 2 ⁇ 3 support as Sn is 0.3wt%.
  • Pt was added to AI2O 3 support containing Sn by impregnating with aqueous solutions of (NH 3 ) 4 Pt(NO 3 )2.
  • the Pt metal loading on the supports is lwt%.
  • the sample was dried in air at 120°C for 4 hrs, and then calcined at 360°C in air for 3 hrs.
  • ⁇ - ⁇ 1 2 O 3 extrudates were also used to support Pt and Sn, which have surface area of 306 m 2 /g, pore volume of 0.85 cm 3 /g, and pore size of 73 A.
  • A1 2 O 3 extrudates are 0.3%Pt/y-Al 2 O 3 , and 0.3%Pt + 0.15%Sn/y-Al 2 O 3 .
  • the catalysts of Examples 6-8 were used to perform dehydrogenation testing on part of the effluent of the hydroalkylation reaction of Example 5.
  • the same reactor and testing protocol as described in Example 5 were used to perform dehydrogenation tests, except the dehydrogenation catalyst was pre-conditioned in situ by heating to 375°C to 460°C with 3 ⁇ 4 flow at 100 cc/min and holding for 2 hours.
  • the catalyst bed was held at the reaction temperature of 375°C to 460°C at a WHSV of 2 and a pressure of 100 psig (790 kPa).
  • the analysis is done on an Agilent 7890 GC with 150 vial sample tray.
  • Oxidation was done batchwise.
  • a 300 ml Parr reactor was charged with 50 grams of 4,4'dimethylbiphenyl, 150 gms acetic acid, 1500 ppm cobalt acetate, and 1000 ppm NaBr.
  • the reactor was sealed and pressurized to 500 psig with nitrogen.
  • the reactor was heated to 150°C with a stir rate of 1200 rpm under 1500cc/min N 2 . When the temperature reached 150°C, 2 was switched to air at the same flow rate.
  • oxygen concentration in the gas effluent was monitored and, as shown in Figure 11, dropped to less than 2% after about 30 minutes on stream before returning to its initial value after about 250 minutes.
  • Oxidation was again done batchwise.
  • a 300ml Parr reactor was charged with 50 grams of 4,4'dimethylbiphenyl, 150 gms acetic acid, 1500 ppm Co acetate, and 500 ppm NaBr.
  • the reactor was sealed and pressurized to 500 psig with nitrogen.
  • the reactor was heated to 150°C with a stir rate of 1200 rpm under 1500cc/min N 2 . When the temperature reached 150°C, 2 was switched to air at the same flow rate.
  • oxygen concentration dropped to less than 2% in the gas effluent (see Figure 11).
  • the air flow was switched to N 2 , and the reactor was cooled to room temperature; then depressurized.
  • the reactor was disassembled and the contents removed and analyzed by GC. The conversion is 100% and the selectivity to diacid > 95%, less than 0.5% aldehyde acid and the rest is mono acid.
  • the reactor was disassembled and the contents removed and analyzed by GC.
  • P-xylene and dimethylbiphenyl conversion is 100%.
  • the selectivity to terephthalic acid is 99%, less than 0.1% aldehyde acid and the rest is mono acid.
  • the selectivity to biphenyl diacid is > 98%, less than 0.2% aldehyde acid and the rest is mono acid.
  • This example illustrates the preparation of a melt polyester by reaction of mono ethylene glycol with a mixture of 20% 4,4' biphenyl dicarboxylate and 80% dimethyl terephthalate.
  • reaction temperature between 200 and 350°C, for example 200°C, first for 10 minutes to 3 hours, for example 2 hours, and then heated to 220°C for 10 minutes to 3 hours, for example 2 hours, and then heated to 275-300°C, for example, 280°C for 10 to 30 minutes, for example, 15 minutes, in the presence of 0.01 weight% of titanium butoxide.
  • a vacuum of 0.1-1 mm Hg, for example 0.1 mm Hg is then introduced and maintained between 10 minutes and 1 hour, for example 1 hour, while continuously stirring polymer, in order to remove glycol vapor and drive polycondensation equilibrium.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Dans un procédé selon l'invention pour produire des composés de biphényle substitué par diméthyle en position 3,4' et/ou 4,4', une charge comprenant du toluène est mise en contact avec de l'hydrogène en présence d'un catalyseur d'hydroalkylation dans des conditions efficaces pour produire un produit de réaction d'hydroalkylation comprenant des (méthylcyclohexyl)toluènes. Au moins une partie du produit de la réaction d'hydroalkylation est déshydrogénée en présence d'un catalyseur de déshydrogénation dans des conditions efficaces pour produire un produit de réaction de déshydrogénation comprenant un mélange d'isomères de biphényle substitué par diméthyle. Le produit de la réaction de déshydrogénation est ensuite séparé en au moins un premier flux contenant au moins 50 % en poids du premier flux d'isomères 3,4'-diméthylbiphényle et 4,4'-diméthylbiphényle et en au moins un deuxième flux comprenant un ou plusieurs isomères 2,x'-diméthylbiphényle (x' représentant 2', 3' ou 4') et 3,3'-diméthylbiphényle.
PCT/US2014/066857 2014-01-27 2014-11-21 Production et utilisation d'isomères 3,4'-diméthylbiphényle et 4,4'-diméthylbiphényle WO2015112252A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US14/164,889 US9085669B2 (en) 2013-01-28 2014-01-27 Alkyl aromatic hydroalkylation for the production of plasticizers
US14/164,889 2014-01-27
US201462026889P 2014-07-21 2014-07-21
US62/026,889 2014-07-21
US14/480,363 2014-09-08
US14/480,363 US9464166B2 (en) 2013-01-28 2014-09-08 Production and use of 3,4' and 4,4'-dimethylbiphenyl isomers
US14/480,379 US20150080546A1 (en) 2013-01-28 2014-09-08 Production and Use of 3,4' and 4,4'-Dimethylbiphenyl Isomers
US14/480,379 2014-09-08

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US10767005B2 (en) 2015-12-22 2020-09-08 Exxonmobil Chemical Patents Inc. Bibenzoate copolyesters and methods to produce them
WO2017112031A1 (fr) 2015-12-22 2017-06-29 Exxonmobil Chemical Patents Inc. Polyesters de téréphtalate-co-bibenzoate
EP3440038A4 (fr) * 2016-04-08 2019-03-27 ExxonMobil Chemical Patents Inc. Oxydation de composés biphényle substitués par méthyle
WO2017176391A2 (fr) 2016-04-08 2017-10-12 Exxonmobile Chemical Patents Inc. Oxydation de composés biphényle substitués par méthyle
WO2017176391A3 (fr) * 2016-04-08 2018-07-26 Exxonmobil Chemical Patents Inc. Oxydation de composés biphényle substitués par méthyle
US10287402B2 (en) 2016-04-29 2019-05-14 Exxonmobil Chemical Patents Inc. Polycarbonate-polyolefin block copolymers and methods of making them
WO2018097909A1 (fr) 2016-11-23 2018-05-31 Exxonmobil Chemical Patents Inc. Copolyesters de bibenzoate
WO2018097908A1 (fr) 2016-11-23 2018-05-31 Exxonmobil Chemical Patents Inc. Copolyesters modifiés par un diacide
US10287230B2 (en) 2016-12-22 2019-05-14 Exxonmobil Research And Engineering Company Selective aerobic oxidation of dimethylbiphenyls
US10322991B2 (en) 2016-12-22 2019-06-18 Exxonmobil Research And Engineering Company Selective aerobic oxidation of dimethylbiphenyls
US10138176B2 (en) 2017-02-01 2018-11-27 Exxonmobil Research And Engineering Company Production and separation of 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers
US10550050B2 (en) 2017-02-01 2020-02-04 Exxonmobil Research And Engineering Company Processes for separating dimethyl biphenyl isomers using zeolite adsorbents
US11091419B2 (en) 2017-11-22 2021-08-17 Exxonmobil Chemical Patents Inc. Preparation and purification of biphenyldicarboxylic acids
WO2019143495A1 (fr) 2018-01-22 2019-07-25 Exxonmobil Chemical Patents Inc. Production et utilisation d'isomères de 3,4'-diméthylbiphényle et de 4,4'-diméthylbiphényle
US11236028B2 (en) 2018-01-22 2022-02-01 Exxonmobil Chemical Patents Inc. Production and use of 3,4′ and 4,4′-dimethylbiphenyl isomers
US10093597B1 (en) 2018-02-01 2018-10-09 Exxonmobil Research And Engineering Company Processes for separating dimethyl biphenyl isomers using zeolite adsorbents
WO2019182693A1 (fr) 2018-03-21 2019-09-26 Exxonmobil Chemical Patents Inc. Bifuranne fonctionnalisé et synthèse de ce dernier
US11926605B2 (en) 2018-03-21 2024-03-12 Exxonmobil Chemical Patents Inc. Functionalized bifuran and synthesis thereof
US10676413B2 (en) 2018-03-30 2020-06-09 Exxonmobil Research & Engineering Company Production and separation of dimethyl biphenyl isomers
US10676412B2 (en) 2018-03-30 2020-06-09 Exxonmobil Research & Engineering Company Production and separation of dimethyl biphenyl isomers
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WO2020018253A1 (fr) * 2018-07-17 2020-01-23 Exxonmobil Chemical Patents Inc. Préparation et purification de composés de diméthylbiphényle

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TWI546277B (zh) 2016-08-21
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TW201630858A (zh) 2016-09-01

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