WO2018060811A1 - Procédé de production de résorcinol 2,4,6-tri-substituée - Google Patents

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

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Publication number
WO2018060811A1
WO2018060811A1 PCT/IB2017/055672 IB2017055672W WO2018060811A1 WO 2018060811 A1 WO2018060811 A1 WO 2018060811A1 IB 2017055672 W IB2017055672 W IB 2017055672W WO 2018060811 A1 WO2018060811 A1 WO 2018060811A1
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Prior art keywords
weight percent
resorcinol
catalyst
weight
reacting
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PCT/IB2017/055672
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English (en)
Inventor
Kenchaiah LOHITH
Gurunath POZHAL VENGU
Ramesha GANGANAHALLI
Kiran Puthamane
Gaurav Mediratta
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Sabic Global Technologies B.V.
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Priority to EP17786998.9A priority Critical patent/EP3356318A1/fr
Publication of WO2018060811A1 publication Critical patent/WO2018060811A1/fr

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    • 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
  • DMR dimethylresorcinol (unspecified isomer(s));
  • TMR 2,4,6-trimethylresorcinol.
  • 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.
  • 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 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 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 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.
  • 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 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 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 .
  • 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.
  • 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 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%.

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

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.
PCT/IB2017/055672 2016-09-28 2017-09-19 Procédé de production de résorcinol 2,4,6-tri-substituée WO2018060811A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US11007508B2 (en) * 2016-07-29 2021-05-18 Shpp Global Technologies B.V. Phenol alkylation catalyst precursor and catalyst, method of forming catalyst, method of regenerating catalyst, and method of alkylating phenol
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
US11078329B2 (en) 2018-05-07 2021-08-03 Shpp Global Technologies B.V. Functional phenylene ether oligomer, curable and thermoset compositions prepared therefrom

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11007508B2 (en) * 2016-07-29 2021-05-18 Shpp Global Technologies B.V. Phenol alkylation catalyst precursor and catalyst, method of forming catalyst, method of regenerating catalyst, and method of alkylating phenol
US11078329B2 (en) 2018-05-07 2021-08-03 Shpp Global Technologies B.V. Functional phenylene ether oligomer, curable and thermoset compositions prepared therefrom
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
WO2021134013A1 (fr) * 2019-12-24 2021-07-01 Shpp Global Technologies B.V. Précurseur et catalyseur de catalyseur d'alkylation de phénol, et procédé d'alkylation de phénol
CN114514069A (zh) * 2019-12-24 2022-05-17 高新特殊工程塑料全球技术有限公司 苯酚烷基化催化剂前体和催化剂及苯酚烷基化方法

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