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WO2015191281A1 - Esters biphényliques, leur production et leur utilisation dans la fabrication de plastifiants - Google Patents

Esters biphényliques, leur production et leur utilisation dans la fabrication de plastifiants Download PDF

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Publication number
WO2015191281A1
WO2015191281A1 PCT/US2015/032596 US2015032596W WO2015191281A1 WO 2015191281 A1 WO2015191281 A1 WO 2015191281A1 US 2015032596 W US2015032596 W US 2015032596W WO 2015191281 A1 WO2015191281 A1 WO 2015191281A1
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Prior art keywords
biphenyl
group
formula
hydroalkylation
catalyst
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English (en)
Inventor
Jihad M. Dakka
Wei Tang
Stephen Zushma
Christine A. Costello
Diana Smirnova
Madhavi VADLAMUDI
Victor Deflorio
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/035—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with saturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

Definitions

  • the disclosure relates to biphenyl esters, their production and their use in the manufacture of plasticizers.
  • Plasticizers are incorporated into a resin (usually a plastic or elastomer) to increase the flexibility, workability, or distensibility of the resin.
  • the largest use of plasticizers is in the production of "plasticized” or flexible polyvinyl chloride (PVC) products.
  • Typical uses of plasticized PVC include films, sheets, tubing, coated fabrics, wire and cable insulation and jacketing, toys, flooring materials such as vinyl sheet flooring or vinyl floor tiles, adhesives, sealants, inks, and medical products such as blood bags and tubing, and the like.
  • plasticizers include polyvinyl butyral, acrylic polymers, nylon, polyolefins, polyurethanes, and certain fluoroplastics. Plasticizers can also be used with rubber (although often these materials fall under the definition of extenders for rubber rather than plasticizers).
  • Plasticizers A listing of the major plasticizers and their compatibilities with different polymer systems is provided in "Plasticizers," A. D. Godwin, in Applied Polymer Science 21st Century, edited by C. D. Craver and C. E. Carraher, Elsevier (2000); pp. 157-175.
  • Esters based on cyclohexanoic acid have also been proposed for use as plasticizers for PVC.
  • various compositions based on cyclohexanoate, cyclohexanedioates, and cyclohexanepolyoate esters were said to be useful for a range of goods from semi-rigid to highly flexible materials. See, for instance, WO 99/32427; WO 2004/046078; WO 2003/029339; US 2006-0247461 ; and US 7,297,738.
  • plasticizers include esters based on benzoic acid (see, for instance, US 6,740,254) and polyketones, such as described in US 6,777,514; and US 2008-0242895.
  • Epoxidized soybean oil which has much longer alkyl groups (Ci 6 to Cis)
  • Stabilizers are used in much lower concentrations than plasticizers.
  • US 2010-0159177 discloses triglycerides with a total carbon number of the triester groups between 20 and 25, produced by esterification of glycerol with a combination of acids derived from the hydroformylation and subsequent oxidation of C3 to C9 olefins. These are said to have excellent compatibility with a wide variety of resins.
  • dialkyl diphenates of Ci to Cs alcohols said to be useful as plasticizers for poly(vinyl chloride)
  • dialkyl diphenates of Ci to Cs alcohols can be formed by converting diphenic acid to diphenic anhydride and esterifying the diphenic anhydride.
  • these processes involve esterification of diphenic acid or anhydride, they necessarily result in 2,2 '-substituted diesters of diphenic acid.
  • diesters having substitution on the 2-carbons have proven to be too volatile for use as plasticizers.
  • novel biphenyl diesters having different ester groups on the phenyl rings can be produced by a process including the controlled oxidation of dimethylbiphenyl in the presence of acetic acid or benzoic acid as a solvent.
  • acetic acid solvent the oxidation not only produces diphenic acid but also produces significant quantities of a biphenyl compound having an acetate group on one phenyl ring and a carboxylic acid on the other phenyl ring.
  • the invention resides in a biphenyl diester having the formula (I):
  • R 1 is an alkyl group having 5 to 15 carbon atoms and R 2 is a methyl group or a phenyl group.
  • the invention resides in a process for producing a biphenyl diester of formula (I), the process comprising:
  • R 2 is a methyl group or a phenyl group
  • Figure 1 is the l H NMR spectrum of 3-bromo-benzoic acid, isononyl ester as produced in step (a) of the method of Example 1.
  • Figure 2 is the l H NMR spectrum of 4'-hydroxymethylbiphenyl-3-carboxylic acid, isononyl ester as produced in step (b) of the method of Example 1.
  • Figure 3 is the l H NMR spectrum of 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester as produced in step (c) of the method of Example 1.
  • Figure 4 is a bar graph comparing the TGA volatility of the 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester produced in Example 1 with that of other known plasticizers.
  • Figure 5 is a bar graph comparing the flex onset temperature of the 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester produced in Example 1 with that of other known plasticizers.
  • Figure 6 is a bar graph comparing the results of dynamic mechanical analysis (DMA) of the 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester produced in Example 1 with those of other known plasticizers.
  • DMA dynamic mechanical analysis
  • Figure 7 is a bar graph comparing the compatibility with PVC for the 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester produced in Example 1 with that of other known plasticizers.
  • a novel biphenyl ester useful as a plasticizer for PVC and other polymer resins is disclosed herein together with a method of producing the same.
  • the present biphenyl ester has the formula (I):
  • R 1 is an alkyl group having from 5 to 15 carbon atoms, such as from 7 to 14 carbon atoms, for example from 9 to 13 carbon atoms and R 2 is a methyl group or a phenyl group. In one preferred embodiment, R 2 is a methyl group. In an embodiment, R 1 has 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and/or 15 carbon atoms. [0020] In an embodiment described herein, R 1 may be one or more of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.
  • the biphenyl ester of formula (I) can exist as a number of isomeric forms depending on the locations of the ester groups on their respective phenyl rings.
  • the mixture comprises less than 10 wt% of the 2,X' isomers, where X' is 2', 3 ' or 4'.
  • the mixture comprises at least 50 wt% of the 3,3', 3,4', and 4,4' isomers.
  • One suitable process for producing the biphenyl diester of formula (I) comprises reacting a dimethyl biphenyl compound having the formula (II):
  • R 2 is a methyl group or a phenyl group.
  • the oxidation reaction may be conducted at a temperature from 50 to 200°C, such as from 90 to 170°C, in the presence of a catalyst comprising cobalt and/or manganese and/or one or more compounds thereof.
  • a catalyst comprising cobalt and/or manganese and/or one or more compounds thereof.
  • Relatively high concentration of high catalyst oxidation state e.g., Co (III) and low oxygen pressure favor the formation of the monoester of formula (III).
  • the resultant biphenyl monoester can then be esterified with an alcohol having 5 to 15 carbon atoms (such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and/or 15 carbon atoms) to produce the desired biphenyl diester, with or without separating the monoester from the acid medium used for the oxidation process.
  • Suitable conditions for the esterification reaction include a temperature from 20 to 300°C, such as from 150 to 250°C, optionally in the presence of a presence of a catalyst, such as a Lewis acid catalyst, e.g., a titanium alkoxide.
  • dimethyl biphenyl compound having the formula (II) used as a precursor in the above process can be produced by hydroalkylation of toluene to produce (methylcyclohexyl)toluene (MCHT) followed by dehydrogenation of the MCHT.
  • MCHT methylcyclohexyltoluene
  • Hydroalkylation of toluene to MCHT involves reacting toluene with hydrogen in the presence of the catalyst in accordance with the following equation:
  • 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, 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.
  • 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 US 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 US 4,021,447.
  • Zeolite ZSM-20 is described in US 3,972,983.
  • Zeolite Beta is described in US 3,308,069, and Re. 28,341.
  • Low sodium Ultrastable Y molecular sieve US 3,293, 192 and 3,449,070.
  • Dealuminized Y zeolite (Deal Y) may be prepared by the method found in US 3,442,795.
  • Zeolite UHP-Y is described in US 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 US 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 the 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.
  • MCM-22 (described in US 4,954,325), PSH-3 (described in US 4,439,409), SSZ-25 (described in US 4,826,667), ERB-1 (described in EP 0293032), ITQ-1 (described in US 6,077,498), ITQ-2 (described in WO 97/17290), MCM-36 (described in US 5,250,277), MCM-49 (described in US 5,236,575), MCM-56 (described in US 5,362,697) and mixtures thereof.
  • a diluent which is substantially inert under hydroalkylation conditions, may be included in the feed to the hydroalkylation reaction.
  • 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. Examples of 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 typically 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: • at least 60 wt%, such as at least 70 wt%, for example at least 80 wt% of the 3,3', 3,4', 4,3' and 4,4'-isomers of (methylcyclohexyl)toluene based on the total weight of all the (methylcyclohexyl)toluene isomers;
  • the hydroalkylation reaction product may also contain significant amounts of residual toluene, for example up to 90 wt%, such as up to 80 wt%, typically from 60 to 80 wt% of residual toluene based on the total weight of the hydroalkylation reaction product.
  • the major components of the hydroalkylation reaction effluent are (methylcyclohexyl)toluenes, residual toluene and fully saturated single ring by-product (methylcyclohexane).
  • the residual toluene and light by-products can readily be removed from the reaction effluent by, for example, distillation.
  • the residual toluene can then be recycled to the hydroalkylation reactor, while the saturated by-products can be dehydrogenated to produce additional recyclable feed.
  • 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 of 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 of 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 40 wt%, such as less than 30 wt%, for example from 0 to 20 wt% based on the total weight of dimethylbiphenyl compounds.
  • This invention further relates to:
  • R 1 is an alkyl group having 5 to 15 carbon atoms and R 2 is a methyl group or a phenyl group.
  • R 2 is a methyl group or a phenyl group
  • hydroalkylation catalyst comprises an acidic component and a hydrogenation component.
  • the acidic component of the hydroalkylation catalyst comprises a molecular sieve.
  • the molecular sieve is selected from the group consisting of BEA, FAU and MTW structure type molecular sieves, molecular sieves of the MCM-22 family and mixtures thereof.
  • Example 1 The 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester of Example 1 was blended with PVC and subjected to TGA volatility testing using a TA Instruments TGA5000 instrument calibrated to vendor specifications. Sample sizes of 10 ⁇ 1 mg were used. Samples were heated at 10°C/min to 300°C in nitrogen (25 cc 2/min flow through furnace and 10 cc 2/min flow through balance) and weight loss at 220°C was used as the volatility metric.
  • Example 1 The 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester of Example 1 was blended with PVC and was subjected to low temperature flexibility testing using a TA Instruments Q800 Dynamic Mechanical Analyzer (DMA) with a three-point bending clamp. Samples were cooled at 3°C/min and data was collected upon heating at 3°C/min using a frequency of 1 Hz, amplitude of 20 ⁇ , 0.01 N preload force, and 120% force track. From the DMA measurements, flex onset was determined from the onset of the tan ⁇ peak.
  • DMA Dynamic Mechanical Analyzer
  • Example 2 The 4'-acetoxymethylbiphenyl-3-carboxylic acid, isononyl ester of Example 1 was subjected to dynamic mechanical analysis (DMA) testing as described in Example 3.
  • Compatible systems are expected to exhibit a symmetric tan ⁇ peak and yield lower DMA compatibility values.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un diester de biphényle utile en tant que plastifiant représenté par la formule (I) : C02R1 (I) CH2-0-CR2 O dans laquelle R1 est un groupe alkyle ayant 5 à 15 atomes de carbone et R2 est un groupe méthyle ou un groupe phényle.
PCT/US2015/032596 2014-06-13 2015-05-27 Esters biphényliques, leur production et leur utilisation dans la fabrication de plastifiants Ceased WO2015191281A1 (fr)

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US201462012037P 2014-06-13 2014-06-13
US62/012,037 2014-06-13
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EP14177012.3 2014-07-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287230B2 (en) 2016-12-22 2019-05-14 Exxonmobil Research And Engineering Company Selective aerobic oxidation of dimethylbiphenyls

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4695651A (en) * 1984-09-10 1987-09-22 Ajinomoto Co., Inc. Biphenyl-based diester compounds and liquid crystal compositions containing same
US5380460A (en) * 1991-09-20 1995-01-10 Displaytech, Inc. Ferroelectric liquid crystal compounds containing chiral haloalkoxy tail units and compositions containing them
US20110184105A1 (en) * 2009-09-29 2011-07-28 Exxonmobil Research And Engineering Company Phenylene Oxo-Diester Plasticizers and Methods of Making

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4695651A (en) * 1984-09-10 1987-09-22 Ajinomoto Co., Inc. Biphenyl-based diester compounds and liquid crystal compositions containing same
US5380460A (en) * 1991-09-20 1995-01-10 Displaytech, Inc. Ferroelectric liquid crystal compounds containing chiral haloalkoxy tail units and compositions containing them
US20110184105A1 (en) * 2009-09-29 2011-07-28 Exxonmobil Research And Engineering Company Phenylene Oxo-Diester Plasticizers and Methods of Making

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KYOU SUGA ET AL.: "Selective Oxygenation of 4,4' -Dimethylbiphenyl with Molecular Oxygen, Catalyzed by 9-Phenyl-10-methylacridinium Ion via Photoinduced Electron Transfer", J. PHYS. CHEM. A, vol. 109, no. 44, 2005, pages 10168 - 10175, XP055243422, ISSN: 1089-5639 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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