EP3390338A1 - Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone - Google Patents

Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone

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Publication number
EP3390338A1
EP3390338A1 EP16809807.7A EP16809807A EP3390338A1 EP 3390338 A1 EP3390338 A1 EP 3390338A1 EP 16809807 A EP16809807 A EP 16809807A EP 3390338 A1 EP3390338 A1 EP 3390338A1
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EP
European Patent Office
Prior art keywords
hydroxybenzophenone
meth
acrylate
iii
polyglycol ether
Prior art date
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EP16809807.7A
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German (de)
English (en)
Inventor
Rupert Konradi
Eva-Maria REIS-WALTHER
Andrea Misske
Friederike Fleischhaker
Hermann Bergmann
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BASF SE
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BASF SE
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Publication of EP3390338A1 publication Critical patent/EP3390338A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic

Definitions

  • the invention relates to a process for the preparation of hydroxybenzophenone polyglycol ether (meth) acrylate.
  • Hydroxybenzophenone (meth) acrylate is used as UV crosslinker, for example in coating compositions. Hydroxybenzophenone (meth) acrylate can be prepared by (meth) acrylating hydroxybenzophenone.
  • WO 00/15629 discloses reacting hydroxybenzophenone with activated polyethylene glycol to give hydroxybenzophenone polyglycol ether.
  • the activated polyethylene glycol used is alkoxylated toluene sulfonic acid (polyethylene glycol monotosylate).
  • alkoxylated toluene sulfonic acid polyethylene glycol monotosylate
  • the object of the invention is to provide an easy to carry out process for preparing hydroxybenzophenone polyglycol ether (meth) acrylate, which leads to a product of high purity.
  • the object is achieved by a process for the preparation of Hydroxybenzophenonpolyglykolether- (meth) acrylate with the following steps:
  • Hydroxybenzophenone is generally 4-hydroxybenzophenone and 2-hydroxybenzophenone, preferably 4-hydroxybenzophenone.
  • hydroxybenzophenone is reacted with ethylene carbonate to give hydroxybenzophenone monoglycol ether.
  • the reaction is generally carried out in the presence of sodium iodide as catalyst, e.g. in WO201 1/089385.
  • the reaction can be carried out in the presence of a separate solvent, for example toluene.
  • the reaction can also be carried out without a separate solvent.
  • the reaction is carried out at a temperature in the range of 100 to 200 ° C, preferably 120 to 180 ° C. Ethylene carbonate is preferably used in slight stoichiometric excess.
  • the monoethoxylate formed is mixed with water and the hydroxybenzophenone monoglycol ether is extracted with an organic solvent, for example toluene.
  • hydroxybenzophenone monoglycol ether is ethoxylated with ethylene oxide to give hydroxybenzophenone polyglycol ether.
  • from 2 to 100, preferably from 2 to 50, particularly preferably from 4 to 50 mol of ethylene oxide are reacted per mole of hydroxybenzophenone monoglycol ether.
  • the ethoxylation can be carried out with gaseous ethylene oxide in the presence of basic catalysts at a pressure of generally 1 to 10 bar and temperatures of 80 to 200 ° C.
  • Suitable basic catalysts are, for example, NaOH, KOH, sodium or potassium methoxide or potassium tert-butoxide. Preference is given to potassium tert-butoxide.
  • hydroxybenzophenone polyglycol ether is transesterified with alkyl (meth) acrylate to give hydroxybenzophenone polyglycol ether (meth) acrylate.
  • the transesterification comprises steps (iii-a) to (iii-d):
  • step (iii-d) distilling off unreacted alkyl (meth) acrylate and entrainer from the product mixture.
  • step (iii-a) alkyl (meth) acrylate is allowed to react with hydroxybenzophenone polyglycol ether in the presence of a catalyst and a stabilizer and in the presence of an entrainer an azeotrope which forms an azeotrope with the alcohol bound in the alkyl (meth) acrylate
  • step (iii-b) the azeotrope of entrainer and alcohol is distilled off until hydroxybenzophenone polyglycol ether is substantially completely reacted.
  • the transesterification thus consists of the steps (iii-a) and (iii-b).
  • Suitable alkyl (meth) acrylates are the C 1 -C 4 -alkyl (meth) acrylates.
  • the methyl (meth) acrylate or ethyl (meth) acrylate is used, with methanol or ethanol being liberated as alcohols in the transesterification reaction.
  • alkyl (meth) acrylate with hydroxybenzophenone polyglycol ether is carried out in the presence of a homogeneous or heterogeneous catalyst.
  • a homogeneous or heterogeneous catalyst All suitable for transesterification are suitable suitable Lewis acids or bases, for example, tin, titanium or zirconium-containing catalysts and inorganic salts.
  • Suitable tin-containing catalysts are Sn (IV) -containing compounds, such as. Di-alkyltin dichloride, dialkyltin oxide, dialkyltin diacetate, bis (trialkyltin) oxide, bis (dibutylchlorotin) oxide, especially dibutyltin dichloride, dimethyltin dichloride and dibutyltin oxide.
  • the chloride-containing catalysts can be used together with alcoholates, for example with sodium methylate.
  • Suitable titanium (IV) or zirconium (IV) (here summarized as metal (IV)) containing catalysts are metal (IV) tetraalkoxylates of linear or branched C1-C6 alcohols, preferably metal (IV) tetraisopropylate, metal (IV) tetrabutylate and the metalate of the educt alcohol used or mixtures thereof. Also with different alcohols or acetylacetonate substituted metalates are possible.
  • the inorganic salt preferably has at least one anion selected from the group consisting of carbonate (C0 3 2 -), oxide (O 2 -), hydroxide (OH), bicarbonate (HCO 3 -) > phosphate (P0 4 3 - ) Hydrogen phosphate (HPO4 2 -), dihydrogen phosphate (H2PO4-), nitrate (NO3-), sulfate (S0 4 2 -), sulfite (SO3 2 -) and carboxylate (R 6 COO " ), wherein R 6 is Ci-C 4 alkyl or C 6 aryl. oxide, hydroxide and phosphate, or mixtures thereof are preferred, more preferably phosphate.
  • the inorganic salt preferably comprises at least one cation, on selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, iron , Manganese, chromium, molybdenum, cobalt, nickel or zinc, alkali metals and alkaline earth metals are preferred, and particularly preferred are lithium, sodium, potassium or calcium.
  • Particularly preferred inorganic salts including their hydrates are LiOH, L1NO3, L13PO4, Na3PÜ4, K3PO4, Na2CÜ3 , K 2 CO 3 and CaO, very particularly preferably K 3 PO 4.
  • heterogeneous catalysts or homogeneous catalysts which can be converted into heterogeneous residues, as used in the e.g. in DE 2 317 226 A1, DE 10 2004 036 930 A1 and WO2009 / 080380 can be used.
  • the catalysts or residues of the catalysts are usually separated by filtration, electrofiltration, absorption, centrifugation or decantation.
  • alkyl (meth) acrylate with Hydroxybenzophenonpolyglykolether continues to be in the presence of one or more stabilizers (polymerization inhibitors).
  • stabilizers polymerization inhibitors.
  • Particularly preferred is hydroquinone monomethyl ether (MeHQ).
  • oxygen can additionally be used as the polymerization inhibitor.
  • an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) may be present.
  • the transesterification reaction (steps (iii-a) and (iii-b)) is generally carried out at a temperature of 60 to 140 ° C, preferably 70 to 1 10 ° C. In this case, an azeotrope of entrainer and alcohol is distilled off continuously.
  • Suitable entrainers which form an azeotropically boiling mixture with methanol or ethanol are firstly methyl acrylate and methyl methacrylate and also ethyl acrylate and ethyl methacrylate itself.
  • Suitable separate entrainers include cyclohexane, methylcyclohexane, benzene, toluene, hexanes and heptanes and mixtures thereof. Preference is given to methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate and mixtures of these with n-heptene and cyclohexane.
  • the term entraining agent in this sense comprises the starting material itself and, if appropriate, an additionally used separate solvent.
  • no separate solvent is used as entraining agent.
  • the reactant alkyl (meth) acrylate itself acts as an entraining agent.
  • the entrainer can then be replenished in the reactor.
  • the azeotropic mixture of alcohol and entrainer is distilled off in a preferred embodiment via a suitable column, stirred in a mixing vessel with water and then transferred to a phase separator, wherein the alcohol, generally methanol or ethanol, dissolves in water and the organic phase separates as upper layer.
  • the organic phase is preferably fed back to the reaction mixture via the top of the column and thus recirculated to low losses.
  • alkyl (meth) acrylate is used in stoichiometric excess.
  • the excess of methyl (meth) acrylate per hydroxyl group to be esterified is 5 to 2500 mol%, particularly preferably 300 to 2000 mol%.
  • the catalyst is used in a concentration of 0.1 to 10 mol%, based on the amount of Hydroxybenzophenonpolyglykolether, preferably in a concentration of 0.1 to 5 mol%.
  • the reaction time is generally 1 to 24 hours, preferably 3 to 18 hours, more preferably 3 to 10 hours.
  • the Transesterification (steps (iii-a) and (iii-b)) can be carried out continuously, for example in a stirred tank cascade, or discontinuously.
  • the reaction can be carried out in all reactors suitable for such a reaction. Such reactors are known to the person skilled in the art.
  • the reaction preferably takes place in a stirred tank reactor.
  • any devices may be used, such as e.g. Stirrers.
  • the mixing can also be effected by feeding in a gas, preferably an oxygen-containing gas.
  • the removal of the alcohol formed is carried out continuously or stepwise in a manner known per se by azeotropic distillation in the presence of an entraining agent.
  • methanol can also be removed by stripping with a gas.
  • the alcohol is separated off from the azeotrope and alcohol azeotrope distilled off in step (iii-b) by washing with water, and the entraining agent is returned to the reaction vessel.
  • Steps (iii-a) and (iii-b) are carried out until the hydroxybenzophenone polyglycol ether used is essentially completely reacted. This is the case when hydroxybenzophenone polyglycol ether is reacted to 95%, preferably 97%, particularly preferably 98%.
  • the degree of conversion can be most easily analyzed by determining the OH number. This indicates the content of OH groups as sum parameter in the unit mg KOH / g substance and can be converted assuming a certain molar mass of the alcohol in percent by weight.
  • step (iii-c) the catalyst is separated from the hydroxybenzophenone polyglycol ether (meth) acrylate-containing product mixture, e.g. by filtration or centrifugation.
  • the filtration can be carried out for example with a pressure suction filter.
  • a pressure suction filter In terms of process technology, all known filtration processes and apparatuses can be used for filtration in the process according to the invention, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, 2013 Electronic Release, Chapter: Filtration, 1. Fundamentals and filtration 2. Equipment, are described.
  • these may be candle filters, filter presses, plate pressure filters, bag filters or drum filters.
  • candle filters or plate pressure filters are used.
  • the filtration can be carried out with or without filter aid. Suitable filter aids are filter aids based on kieselguhr, perlite and cellulose. Suitable centrifuges and separators are known to the expert.
  • centrifuging in the process according to the invention can be carried out using all known centrifuging methods and apparatuses, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, 2013 Electronic Release, Chapter: Centrifuges, Filtering and Centrifuges, Sedimenting are.
  • the separation of the catalyst can also be carried out as an aqueous extraction by adding water.
  • the product mixture containing unreacted alkyl (meth) acrylate and optionally separate entraining agent and the stabilizer and the catalyst brought into contact with water. It is also possible to carry out several washing steps, for example 3 washing steps.
  • the amount of wash water per wash is generally 0.1 to 2 times, preferably 0.2 to 0.5 times, the product mixture.
  • the laundry may be placed in a stirred tank or other conventional apparatus, e.g. be carried out in a column or mixer-settler apparatus.
  • the washed reaction mixture is optionally mixed with a storage stabilizer so that the desired concentration of stabilizer is achieved in the target product, for example 100 ppm.
  • This concentration which can be set as desired with this method, depends on the particular specification of the end product and is e.g. for commercial alkyl (meth) acrylates in the range of 15 to 200 ppm.
  • a stabilizer usually serve stabilizers selected from the group of phenols such. For example, 2,6-di-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, hydroquinone and hydroquinone monomethyl ether, preferred is hydroquinone monomethyl ether.
  • a distillation step (iii-d).
  • This distillation is generally carried out at a temperature of 40 to 100 ° C, preferably 60 to 80 ° C and a variable pressure of 2 to 700 mbar.
  • these components can also be removed by stripping with a gas, preferably an oxygen-containing gas.
  • the distillative separation is carried out, for example, in a stirred tank with double wall heating and / or internal heating coils under reduced pressure. Of course, the distillation can also take place in a falling film or thin film evaporator.
  • the reaction mixture preferably several times in the circulation, under reduced pressure, for example at 20 to 700 mbar, preferably 30 to 500, more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C passed through the apparatus.
  • an inert gas preferably an oxygen-containing gas, more preferably air or a mixture of air and nitrogen (lean air) can be introduced into the distillation apparatus, for example 0.1 to 1, preferably 0.2 to 0.8 and particularly preferably 0, 3 to 0.7 m 3 / m 3 h, based on the volume of the reaction mixture.
  • a product After carrying out steps (iii-c) and (iii-d), a product remains as a bottom product which has a high purity. This is generally at least 95 wt .-%, preferably at least 98 wt .-%.
  • the invention also Hydroxybenzophenonpolyglykolether- (meth) acrylates having 5 to 100 ethylene oxide units and their use as UV crosslinkers in radiation-curable coating compositions.
  • Example 1 Synthesis of hydroxyethoxybenzophenone (HEBP) 94.2 g (1.70 mol) of ethylene carbonate, 206 g (1.02 mol) of 4-hydroxybenzophenone (HBP), 4.5 g (0.030 mol) of sodium iodide and 8.0 g of toluene are charged and slowly heated to 165 ° C with stirring. From 135 ° C, gas evolution begins. It is stirred for 1 h at 165 ° C. After cooling to room temperature, water and toluene are added, the phases are separated and the organic phase is washed with water, dried and concentrated. The solid is taken up in cold toluene and filtered with suction. This gives 194 g (0.802 mol, 79% of theory) of a pale beige solid.
  • HBP 4-hydroxybenzophenone
  • Example 2 Synthesis of HEBP + 4 EO 242 g (1.00 mol) of HEBP are initially charged with 834 mg (7.43 mmol) of KOtBu at 80 ° C. in an autoclave. At 120 ° C., 176 g (4.00 mol) of ethylene oxide are metered in and stirred at this temperature for 10 h. After cooling to room temperature, the mixture is freed from volatiles on a rotary evaporator. 415 g of a brown liquid are obtained.
  • the OH number differs by 4% from theory.
  • the OH number differs by 2% from theory.
  • the transesterification takes place with introduction of air in a 750 mL jacketed reactor equipped with an anchor stirrer, an air inlet, a separation column and a liquid divider.
  • 347 g of HBP * 5EO, 0.1 g of methylhydroquinone (MEHQ) and 600 g of methyl methacrylate (MMA, stabilized with 15 ppm MEHQ) are initially charged at room temperature.
  • 9.1 g potassium phosphate are added and the reaction mixture is heated at a bath temperature of 100 ° C.
  • the return ratio is variable 2: 1 to 10: 1 (return: drain).
  • the product is filtered through a paper filter and the reaction mixture concentrated in vacuo.
  • the conversion is determined to> 99% via TAI NMR.
  • the OH number is ⁇ 2.
  • the stabilizer content is 170 ppm MEHQ (determined by HPLC).
  • Example 6 163 g benzophenone * 10EO, 0.06 g methylhydroquinone (MEHQ) and 400 g of methyl methacrylate (MMA, stabilized with 15 ppm MEHQ) are charged at room temperature. 2.9 g of potassium phosphate are added and the reaction mixture is heated at a bath temperature of 100 ° C. It is set to a pressure of 300 mbar (abs.) And continuously distilled off an azeotrope of methanol and MMA, with a bottom temperature of 66 ° C sets. The reflux ratio is variable 2: 1 to 25: 1 (return: Procedure). After completion of the reaction, the product is filtered through a paper filter and the reaction mixture concentrated in vacuo. The conversion is> 99%, determined by TAI NMR. The OH number is ⁇ 2. The stabilizer content is 260 ppm MEHQ (determined by HPLC).
  • Example 7 Synthesis of HBP * 20 EO methacrylate
  • Example 6 In the apparatus of Example 6, 300 g of benzophenone * 20EO, 0.08 g of methylhydroquinone (MEHQ) and 600 g of methyl methacrylate (MMA, stabilized with 15 ppm MEHQ) are charged at room temperature. 4.8 g of potassium phosphate are added and the reaction mixture is heated at a bath temperature of 100 ° C. It is set to a pressure of 300 mbar (abs.) And continuously distilled off an azeotrope of methanol and MMA, with a bottom temperature of 66 ° C sets. The return ratio is variable 5: 1 to 10: 1 (return: drain). After completion of the reaction, the product is filtered through a paper filter and the reaction mixture concentrated in vacuo. The conversion is> 99%, determined by TAI NMR.
  • MEHQ methylhydroquinone
  • MMA methyl methacrylate
  • the OH number differs by 21% from theory.
  • the substance was examined by LC-MS coupling.
  • the mixture contains in addition to the desired product polyethylene glycol, polyethylene glycol bisbenzophenone and trimers and higher homologues of hydroxybenzophenone.
  • the substance was examined by LC-MS coupling.
  • the mixture contains in addition to the desired product polyethylene glycol, polyethylene glycol bisbenzophenone and trimers and higher homologues of hydroxybenzophenone.

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

Abstract

Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone comprenant les étapes suivantes : (i) mise en réaction de l'hydroxybenzophénone avec le carbonate d'éthylène pour former le monoglycol éther d'hydroxybenzophénone, (ii) éthoxylation du monoglycol éther d'hydroxybenzophénone avec l'oxyde d'éthylène pour former le polyglycol éther d'hydroxybenzophénone, transestérification du polyglycol éther d'hydroxybenzophénone avec le (méth)acrylate d'alkyle pour former le (méth)acrylate de polyglycol éther d'hydroxybenzophénone.
EP16809807.7A 2015-12-15 2016-12-13 Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone Withdrawn EP3390338A1 (fr)

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US201562267301P 2015-12-15 2015-12-15
DE102015225264 2015-12-15
PCT/EP2016/080714 WO2017102675A1 (fr) 2015-12-15 2016-12-13 Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone

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US11028040B2 (en) 2017-01-27 2021-06-08 Basf Se Methods for producing (meth)acrylic acid norbornyl esters
CN108558657A (zh) * 2018-06-05 2018-09-21 李守莉 一种甲基丙烯酸特种酯的制备方法
BR112021009343A2 (pt) * 2018-12-17 2021-08-10 Dow Global Technologies Llc método
CN115776992B (zh) 2020-08-21 2024-10-22 富士胶片株式会社 聚合性组合物、聚合物、紫外线遮蔽材料、层叠体、化合物、紫外线吸收剂及化合物的制造方法
WO2022236524A1 (fr) * 2021-05-10 2022-11-17 怀化金鑫新材料有限公司 Photo-initiateur et son procédé de préparation

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2317226C3 (de) 1973-04-06 1980-10-30 Deutsche Texaco Ag, 2000 Hamburg Verfahren zur Herstellung von höhermolekularen Alkylacrylaten bzw. -methacrylaten
US4737559A (en) * 1986-05-19 1988-04-12 Minnesota Mining And Manufacturing Co. Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers
EP1112263B1 (fr) 1998-09-11 2005-06-08 Transitions Optical, Inc. Naphthopyranes polyalcoxyles polymerisables
DE102004036930A1 (de) 2004-07-29 2006-03-23 Basf Ag Katalysiertes Verfahren zur Herstellung von(Meth)acrylaten von N-hydroxyalkylierten Amiden
JP4868915B2 (ja) * 2006-04-04 2012-02-01 日東電工株式会社 粘着剤層付光学部材の製造方法、粘着剤層付光学部材及び画像表示装置
JP2011506517A (ja) 2007-12-19 2011-03-03 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング （メタ）アクリレートの製造方法
WO2011089385A1 (fr) 2010-01-19 2011-07-28 Cambrex Karlskoga Ab Nouveaux procédés de production de dérivés de benzophénone
CN104788300B (zh) * 2014-01-22 2017-01-11 南京华威医药科技开发有限公司 欧司哌米芬多晶型

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CN108368020A (zh) 2018-08-03
WO2017102675A1 (fr) 2017-06-22

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