EP3356318A1 - Procédé de production de résorcinol 2,4,6-tri-substituée - Google Patents

Procédé de production de résorcinol 2,4,6-tri-substituée

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Publication number
EP3356318A1
EP3356318A1 EP17786998.9A EP17786998A EP3356318A1 EP 3356318 A1 EP3356318 A1 EP 3356318A1 EP 17786998 A EP17786998 A EP 17786998A EP 3356318 A1 EP3356318 A1 EP 3356318A1
Authority
EP
European Patent Office
Prior art keywords
weight percent
resorcinol
catalyst
weight
reacting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17786998.9A
Other languages
German (de)
English (en)
Inventor
Kenchaiah LOHITH
Gurunath POZHAL VENGU
Ramesha GANGANAHALLI
Kiran Puthamane
Gaurav Mediratta
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP3356318A1 publication Critical patent/EP3356318A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom

Definitions

  • Ashtekar' s working examples used hydroquinone as the dihydroxy aromatic compound and methanol as the alkylating agent, and they produced primarily 2-methylhydroquinone, with 2,6-dimethylhydroquinone as a lesser product. No trimethylated product was reported.
  • One embodiment is a method of 2,4,6-trialkylresorcinol, the method comprising: reacting resorcinol and a Ci-12 alkanol in the presence of a catalyst comprising magnesium oxide to form 2,4, 6-tri(C 1-12 alkyl)resorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of Ci-12 alkanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the 2,4, 6-tri(C 1-12
  • Another embodiment is a method of producing 2,4,6-trimethylresorcinol, the method comprising: reacting resorcinol and methanol in the presence of a catalyst comprising magnesium oxide to form 2,4,6-trimethylresorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of methanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the
  • 2,4,6-trimethylresorcinol is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol.
  • Figure 1 is a gas chromatogram of unpurified reaction mixture after eluting from the reactor and passing through a condenser to form a mixture of liquid products and
  • DMR dimethylresorcinol (unspecified isomer(s));
  • TMR 2,4,6-trimethylresorcinol.
  • Figure 2 is a chromatogram from a gas chromatography - mass spectrometry (GC-MS) analysis of the product of the third purification method in Example 1, below.
  • GC-MS gas chromatography - mass spectrometry
  • Figure 3 is a mass chromatogram for the peak at 13.44 minutes in Figure 2.
  • the peak at 152.09 m/z is consistent with 2,4,6-trimethylresorcinol.
  • Figure 4 is a proton nuclear magnetic resonance ( l H NMR) spectrum of
  • the present inventors have determined that 2,4,6-trialkylresorcinol can be efficiently produced from resorcinol and a Ci-12 alkanol in a process that uses a robust catalyst and efficiently utilizes the Ci-12 alkanol.
  • the present inventors have determined that 2,4,6-trimethylresorcinol can be efficiently produced from resorcinol and methanol from the catalyst, and efficiently utilizes the methanol alkylating agent.
  • one embodiment is a method of producing 2,4,6-trialkylresorcinol, the method comprising reacting resorcinol and a Ci-12 alkanol in the presence of a catalyst comprising magnesium oxide to form 2,4,6-tri(Ci-i2 alkyl)resorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of Ci-12 alkanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the 2,4,6-tri(Ci- 12 alkyl)resorcinol is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol.
  • the Ci-12 alkanol can be, for example, methanol, ethanol, propanol, hexanol, 2- ethylhexanol, or a combination thereof.
  • the Ci-12 alkanol comprises methanol, ethanol, propanol, or a combination thereof. More preferably, the Ci-12 alkanol is methanol.
  • Another embodiment is a method of producing 2,4,6-trimethylresorcinol, the method comprising: reacting resorcinol and methanol in the presence of a catalyst comprising magnesium oxide to form 2,4,6-trimethylresorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of methanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the
  • 2,4,6-trimethylresorcinol is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol.
  • the above-described methods utilize a catalyst comprising magnesium oxide at 40 to 90 weight percent, or 50 to 90 weight percent, based on the weight of the catalyst.
  • the catalyst is the product of calcining a catalyst precursor
  • a binder comprising a hydrous magnesium aluminosilicate, 1 to 15 weight percent of a pore- former, 0.2 to 5 weight percent of a lubricant, and 0.2 to 15 weight percent water.
  • the magnesium oxide has a Brunauer-Emmett- Teller (BET) surface area of at least 70 meter 2 /gram. Within this limit, the magnesium oxide surface area can be 70 to 500 meter 2 /gram, or 100 to 500 meter 2 /gram, or 150 to 500 meter 2 /gram. BET surface areas were determined on a Micromeritics ASAP 2010 instrument. The samples were thoroughly degassed at 300 °C for 5 hours under vacuum to remove water and other physically adsorbed species. The measurements were made using nitrogen gas as the adsorbent at 77 K and a multipoint method of calculation was used for determining surface area of the catalyst.
  • BET Brunauer-Emmett- Teller
  • the magnesium oxide has an aspect ratio of less than or equal to 3: 1, or 1.1: 1 to 3: 1, or 1.2: 1 to 2.5: 1, or 1.3: 1 to 2: 1.
  • Aspect ratio is defined as the number average ratio of the largest particle dimension to the smallest orthogonal dimension of the same particle. Aspect ratio can be determined by laser diffraction.
  • the catalyst precursor comprises the magnesium oxide in an amount of 70 to 98 weight percent, based on the total weight of the catalyst precursor. Within this range, the magnesium oxide amount can be 75 to 95 weight percent, or 78 to 90 weight percent.
  • the catalyst precursor comprises copper oxide or a copper oxide precursor.
  • copper oxide refers to cupric oxide (CuO).
  • the copper oxide or a copper oxide precursor comprises cupric oxide, cupric nitrate, cuprous carbonate, a hydrate of one of the foregoing, or a combination thereof.
  • the catalyst precursor comprises the copper oxide or copper oxide precursor in an amount of 0.1 to 2 weight percent, based on the total weight of the catalyst precursor. Within this range, the copper oxide or copper oxide precursor amount can be 0.2 to 1 weight percent, or 0.3 to 0.8 weight percent.
  • the catalyst precursor further comprises a binder comprising a hydrous magnesium aluminosilicate.
  • Hydrous magnesium aluminosilicates are naturally occurring materials, and they are commercially available at various levels of purification. Examples of purified hydrous magnesium aluminosilicates include MIN-U-GELTM 200, MIN-U-GELTM 400, MIN-U-GELTM 500, MIN-U-GELTM PC, and MIN-U-GELTM FG, all available from ActiveMinerals International LLC.
  • An example of a highly purified hydrous magnesium aluminosilicate is ACTI-GELTM 208, available from ActiveMinerals International LLC.
  • the hydrous magnesium aluminosilicate comprises a hydrated or hydroxylated magnesium aluminosilicate.
  • the hydrous magnesium aluminosilicate can be used in an amount of 0.5 to 8 weight percent, based on the total weight of the catalyst precursor. Within this range, the hydrous magnesium aluminosilicate amount can be 1 to 6 weight percent, or 1.5 to 5.5 weight percent.
  • the catalyst precursor comprises a pore-former.
  • pore-former refers a substance capable of aiding the formation of pores in the calcined catalyst (i.e., the product of calcining the catalyst precursor).
  • Pore-formers include paraffin wax, polyethylene wax, microcrystalline wax, montan wax, cellulose, carboxymethyl cellulose, cellulose acetate, starch, walnut powder, citric acid, polyethylene glycol, oxalic acid, stearic acid, C10-C28 anionic surfactants (including those with neutralized carboxylic acid, phosphoric acid, and sulfonic acid groups), C10-C28 cationic surfactants (including those with ammonium and phosphonium groups), and combinations thereof.
  • the pore-former comprises a polyethylene glycol.
  • the pore-former can be used in an amount of 1 to 15 weight percent, based on the total weight of the catalyst precursor. Within this range, the pore-former amount can be 2 to 10 weight percent.
  • the catalyst precursor comprises a lubricant.
  • Suitable lubricants include graphite, C8-C24 carboxylic acids (including octanoic acid (caprylic acid), decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), and tetracosanoic acid), magnesium salts of C8-C24 carboxylic acids, talcs, silicas, waxes, glycerol, starches, and combinations thereof.
  • C8-C24 carboxylic acids including octanoic acid (caprylic acid), decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexade
  • the lubricant comprises magnesium stearate.
  • the lubricant can be used in an amount of 0.2 to 5 weight percent, based on the total weight of the catalyst precursor. Within this range, the lubricant amount can be 0.4 to 3.5 weight percent, or 0.6 to 2.5 weight percent.
  • the catalyst precursor comprises water.
  • the water is deionized.
  • the water can be used in an amount of 0.2 to 15 weight percent, based on the total weight of the catalyst precursor. Within this range, the water amount can be 0.6 to 12 weight percent.
  • the catalyst precursor has a density of 1.2 to 2 grams per milliliter, or 1.3 to 1.8 grams per milliliter, at 23 °C.
  • density refers to the unpacked density of catalyst precursor pellets, determined as described in the working examples.
  • the catalyst precursor comprises 75 to 95 weight percent of the magnesium oxide; 0.2 to 1 weight percent of the copper oxide or copper oxide precursor; 1 to 6 weight percent of the binder comprising a hydrous magnesium
  • aluminosilicate 2 to 10 weight percent of the pore-former; 0.4 to 3.5 weight percent of the lubricant; and 0.6 to 12 weight percent of the water.
  • the catalyst can be prepared from the catalyst precursor by a method comprising: exposing the catalyst precursor in any of its above-described variations to a nitrogen gas flow having a weight hourly space velocity of 0.05 to 0.8 hour "1 , or 0.1 to 0.4 hour "1 , wherein the nitrogen gas flow has a temperature of 350 to 550 °C, or 400 to 500 °C, and is conducted for a time of 5 to 30 hours, or 8 to 24 hours, and wherein the temperature of the nitrogen gas flow is increased to the temperature of 350 to 550 °C at a rate of 0.5 to 5 °C/minute, or 1 to 4 °C/minute.
  • This method of forming a resorcinol alkylation catalyst can also be called a method of calcining the catalyst precursor.
  • the freshly calcined resorcinol alkylation catalyst exhibits a crush strength of 1 to 20 Newtons/millimeter, or 5 to 20 Newtons/millimeter, determined according to ASTM D4179-11, "Standard Test Method for Single Pellet Crush Strength of Formed Catalysts and Catalyst Carriers".
  • the reaction of resorcinol and the Ci-12 alkanol is conducted at a temperature of 300 to 500 °C. Within this range, the temperature can be 330 to 480 °C, or 350 to 450 °C.
  • the reaction of resorcinol and the Ci-12 alkanol is conducted at a pressure (absolute) of 100 to 1000 kilopascals. Within this range, the pressure can be 150 to 500 kilopascals.
  • the reaction of resorcinol and the Ci-12 alkanol is conducted at a molar ratio of the Ci-12 alkanol to resorcinol of 5: 1 to 20: 1. Within this range, the molar ratio can be 6: 1 to 15: 1.
  • the reaction of resorcinol and methanol is conducted at a molar ratio of methanol to resorcinol of 5: 1 to 20: 1. Within this range, the molar ratio can be 6: 1 to 15: 1.
  • the reaction is conducted at a weight hourly space velocity of 0.1 to 2 hour "1 .
  • the weight hourly space velocity is the combined hourly mass flow of the Ci-12 alkanol (e.g., methanol) and resorcinol divided by the catalyst mass.
  • the desired 2,4,6-trialkylresorcinol (e.g., 2,4,6-trimethylresorcinol) is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol. Within this limit, the selectivity can be 30 to 80 mole percent, or 50 to 70 mole percent.
  • the reactor feed can comprise water.
  • the reaction is conducted in the presence of 5 to 25 weight percent water, or 10 to 25 weight percent water, based on the total weight of Ci-12 alkanol, resorcinol, and water.
  • reacting the Ci-12 alkanol and resorcinol comprises converting at least 50 percent of the resorcinol.
  • the resorcinol conversion can be 50 to 100 percent, or 60 to 100 percent.
  • a conversion of greater than 99 percent is demonstrated.
  • reacting resorcinol and methanol is conducted at a temperature of 330 to 480 °C, a pressure of 150 to 500 kilopascals, and a molar ratio of methanol to resorcinol of 6: 1 to 15: 1;
  • the catalyst is the product of calcining a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide, 0.1 to 2 weight percent copper oxide or a copper oxide precursor, 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate, 1 to 15 weight percent of a pore-former, 0.2 to 5 weight percent of a lubricant, and 0.2 to 15 weight percent water;
  • reacting is conducted in the presence of 5 to 25 weight percent water, based on the total weight of methanol, resorcinol, and water; and reacting comprises converting at least 50 percent of the resorcinol.
  • the invention includes at least the following embodiments.
  • Embodiment 1 A method of producing 2,4,6-trialkylresorcinol, the method comprising: reacting resorcinol and a Ci-12 alkanol in the presence of a catalyst comprising magnesium oxide to form 2,4, 6-tri(C 1-12 alkyl)resorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of Ci-12 alkanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the 2,4,6-tri(Ci-i2 alkyl)resorcinol is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol.
  • Embodiment 2 The method of embodiment 1, wherein the Ci-12 alkanol comprises methanol, ethanol, propanol, hexanol, 2-ethylhexanol, or a combination thereof.
  • Embodiment 3 The method of embodiments 1 or 2, wherein the catalyst is the product of calcining a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide; 0.1 to 2 weight percent copper oxide or a copper oxide precursor; 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate; 1 to 15 weight percent of a pore-former; 0.2 to 5 weight percent of a lubricant; and 0.2 to 15 weight percent water.
  • a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide; 0.1 to 2 weight percent copper oxide or a copper oxide precursor; 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate; 1 to 15 weight percent of a pore-former; 0.2 to 5 weight percent of a lubricant; and 0.2 to 15 weight percent water.
  • Embodiment 4 The method of any one of embodiments 1 to 3, wherein said reacting is conducted in the presence of 5 to 25 weight percent water, based on the total weight of Ci-12 alkanol, resorcinol, and water.
  • Embodiment 5 The method of any one of embodiments 1 to 4, wherein said reacting comprises converting at least 50 percent of the resorcinol.
  • Embodiment 6 The method of any one of embodiments 1 to 5, wherein the catalyst has a surface area of 50 to 200 meter 2 /gram.
  • Embodiment 7 The method of any one of embodiments 1 to 6, wherein said reacting is conducted at a weight hourly space velocity of 0.1 to 2 hour "1 .
  • Embodiment 8 A method of producing 2,4,6-trimethylresorcinol, the method comprising: reacting resorcinol and methanol in the presence of a catalyst comprising magnesium oxide to form 2,4,6-trimethylresorcinol; wherein said reacting is conducted at a temperature of 300 to 500 °C, a pressure of 100 to 1000 kilopascals, and a molar ratio of methanol to resorcinol of 5: 1 to 20: 1; wherein the catalyst comprises 40 to 90 weight percent of the magnesium oxide based on the weight of the catalyst; and wherein the 2,4,6- trimethylresorcinol is formed with a selectivity of at least 30 mole percent, based on converted moles of resorcinol.
  • Embodiment 9 The method of embodiment 8, wherein the catalyst is the product of calcining a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide, 0.1 to 2 weight percent copper oxide or a copper oxide precursor, 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate, 1 to 15 weight percent of a pore-former, 0.2 to 5 weight percent of a lubricant, and 0.2 to 15 weight percent water.
  • a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide, 0.1 to 2 weight percent copper oxide or a copper oxide precursor, 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate, 1 to 15 weight percent of a pore-former, 0.2 to 5 weight percent of a lubricant, and 0.2 to 15 weight percent water.
  • Embodiment 10 The method of embodiment 8 or 9, wherein said reacting is conducted in the presence of 5 to 25 weight percent water, based on the total weight of methanol, resorcinol, and water.
  • Embodiment 11 The method of any one of embodiments 8-10, wherein said reacting comprises converting at least 50 percent of the resorcinol.
  • Embodiment 12 The method of any one of embodiments 8-11, wherein the catalyst has a surface area of 50 to 200 meter 2 /gram.
  • Embodiment 13 The method of any one of embodiments 8-12, wherein said reacting is conducted at a weight hourly space velocity of 0.1 to 2 hour "1 .
  • Embodiment 14 The method of embodiment 8, wherein said reacting is conducted at a temperature of 330 to 480 °C, a pressure of 150 to 500 kilopascals, and a molar ratio of methanol to resorcinol of 6: 1 to 15: 1;
  • the catalyst is the product of calcining a catalyst precursor comprising, based on the weight of the catalyst precursor, 70 to 98 weight percent magnesium oxide, 0.1 to 2 weight percent copper oxide or a copper oxide precursor, 0.5 to 8 weight percent of a binder comprising a hydrous magnesium aluminosilicate, 1 to 15 weight percent of a pore-former, 0.2 to 5 weight percent of a lubricant, and 0.2 to 15 weight percent water;
  • said reacting is conducted in the presence of 5 to 25 weight percent water, based on the total weight of methanol, resorcinol, and water; and said reacting comprises converting at least 50 percent of the resorcinol.
  • a catalyst precursor was prepared using the formulation summarized in Table 2, where component amounts are expressed in parts by weight. To 85.5 grams of magnesium oxide, 4.3 grams of PEG, 4.3 grams of HPMAS, 0.9 grams of Cu(N0 3 ) 2 .3H 2 0 and 0.9 gram of graphite were added and thoroughly mixed. To the resulting powder mix, 4.3 grams of water was added dropwise and dispersed by mixing. The powder mixture was pressed into 4.76 millimeters (3/16 inch) diameter pellets using a die press. The pellets were used as the catalyst precursor.
  • the vapor phase methylation reaction between resorcinol and methanol was conducted in a continuous packed bed reactor.
  • the reactor is a stainless steel tube having a 12.7 millimeter (0.5 inch) inner diameter.
  • the reactor is heated using an electric furnace.
  • the feed to the reactor was a homogenous solution of resorcinol and methanol (1:8 molar ratio) and water (20% of total weight).
  • the liquid feed was pumped into the reactor using a high performance liquid chromatography (HPLC) pump at a flow rate of 0.2 millimeters/minute.
  • HPLC high performance liquid chromatography
  • the reactor temperature was very high (350-450°C)
  • the liquid feed that enters into the reactor vaporizes before it encounters the catalyst.
  • the alkylation reactions occurred in the catalyst bed, and all the gaseous material exiting the reactor passed through a condenser to form a mixture of liquid products and non-condensable gases.
  • Figure 1 is a gas chromatogram of the unpurified reaction mixture.
  • DMR dimethylresorcinol (unspecified isomer(s)); and “TMR” is 2,4,6-trimethylresorcinol.
  • TMR 2,4,6-trimethylresorcinol
  • the oven temperature was initially at 60 °C (hold for 0 mins), ramped to 130 °C (ramp rate of 10 °C/minute, hold for 3 minutes) and ramped to 300 °C (ramp rate of 10 °C/minute, hold for 1 minute).
  • Samples were further analyzed by gas chromatography-mass spectrometry. A Thermo Scientific Trace GC Ultra with quadrupole detector was used for peak identification. Fifty (50) microliters of sample were diluted with 950 microliters of acetonitrile for analysis. The GC inlet temperature was maintained at 280 °C with a split ratio of 9 and a flow rate of 1.1 milliliter s/minute.
  • the GC was equipped with an HP-5 column of dimensions 30 meters (length) by 0.320 millimeters (inner diameter) by 0.25 micrometer (film thickness).
  • the MS ion source temperature was maintained at 200 °C with solvent cut-off time of 4 minutes.
  • the oven temperature was initially at 60 °C (hold for 2 minutes), and ramped to 300 °C (ramp rate of 10 °C/minute, hold for 10 minutes).
  • the auxiliary temperature was maintained at 280 °C.
  • the resorcinol alkylation conditions were the same as those in Example 1, except that the weight hourly space velocity (WHSV) was 1 hour "1 rather than 0.11 hour "1 in Example 1.
  • WHSV weight hourly space velocity
  • the reaction achieved >99% resorcinol conversion and a TMR selectivity of 61%.

Abstract

La présente invention concerne un composé 2,4,6-trialkylrésorcinol produit par la réaction de résorcinol et d'un alcanol C 1-12 . La réaction est mise en œuvre en présence d'un catalyseur à base d'oxyde de magnésium. La réaction est mise en œuvre à une température de 300 à 500 °C, une pression de 100 à 1000 kilopascals, et un rapport molaire d'un alcanol C 1-12 au résorcinol de 5 : 1 à 20 : 1. La réaction permet une conversion élevée de résorcinol et une sélectivité pour 2,4,6-trialkylrésorcinol.
EP17786998.9A 2016-09-28 2017-09-19 Procédé de production de résorcinol 2,4,6-tri-substituée Withdrawn EP3356318A1 (fr)

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JP2019523131A (ja) * 2016-07-29 2019-08-22 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ フェノールアルキル化触媒前駆体および触媒、触媒の形成方法、触媒の再生方法、並びにフェノールのアルキル化方法
EP3567068A1 (fr) 2018-05-07 2019-11-13 SABIC Global Technologies B.V. Oligomère d'éther de phénylène fonctionnel et durcissable et compositions thermodurcies préparées à partir de celui-ci
EP3842138A1 (fr) * 2019-12-24 2021-06-30 SHPP Global Technologies B.V. Précurseur de catalyseur et catalyseur d'alkylation de phénol et procédé d'alkylation de phénol

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US3446856A (en) 1964-05-29 1969-05-27 Gen Electric Methylation of phenols
US4108909A (en) * 1976-01-19 1978-08-22 Continental Oil Company N-alkylated cresylic acids via direct alkylation in a liquid phase
US4060561A (en) * 1976-09-20 1977-11-29 Continental Oil Company Method for the preparation of trimethylhydroquinone
JPS5872530A (ja) 1981-10-28 1983-04-30 Mitsui Petrochem Ind Ltd アルキル基置換二価フエノ−ル類の製造方法
US4954475A (en) 1984-08-13 1990-09-04 General Electric Company Zinc-containing ortho-alkylation catalyst precursor and catalyst, and process of use in alkylation of phenols
US6303801B1 (en) * 1999-03-09 2001-10-16 Sumitomo Chemical Company, Limited Process for producing alkyl-substituted hydroquinones
JP4294209B2 (ja) 2000-09-18 2009-07-08 旭化成ケミカルズ株式会社 オルト位アルキル化ヒドロキシ芳香族化合物の製造方法
US7081432B2 (en) 2003-07-10 2006-07-25 General Electric Company Alkylation catalyst and method for making alkylated phenols
US7087705B2 (en) 2004-03-31 2006-08-08 General Electric Company Process for the monoalkylation of dihydroxy aromatic compounds

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