WO2011003669A2 - Procédé et installation de purification de mélanges réactionnels contenant des mono(méth)acrylates de polyalkylèneglycol - Google Patents

Procédé et installation de purification de mélanges réactionnels contenant des mono(méth)acrylates de polyalkylèneglycol Download PDF

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Publication number
WO2011003669A2
WO2011003669A2 PCT/EP2010/057101 EP2010057101W WO2011003669A2 WO 2011003669 A2 WO2011003669 A2 WO 2011003669A2 EP 2010057101 W EP2010057101 W EP 2010057101W WO 2011003669 A2 WO2011003669 A2 WO 2011003669A2
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WO
WIPO (PCT)
Prior art keywords
meth
reaction mixture
range
acrylate
glycol mono
Prior art date
Application number
PCT/EP2010/057101
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German (de)
English (en)
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WO2011003669A3 (fr
Inventor
Dirk BRÖLL
Joachim Knebel
Mario Gomez
Isabelle Klein
Thomas Ohl
Benedikt Laux
Christian Maul
Original Assignee
Evonik Röhm Gmbh
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Application filed by Evonik Röhm Gmbh filed Critical Evonik Röhm Gmbh
Publication of WO2011003669A2 publication Critical patent/WO2011003669A2/fr
Publication of WO2011003669A3 publication Critical patent/WO2011003669A3/fr

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Classifications

    • 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
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • 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

  • Polyalkylene glycol mono (meth) acrylates include The present invention relates to a process for
  • Polyalkylene glycol mono (meth) acrylates Polyalkylene glycol mono (meth) acrylates.
  • the present invention describes a process for the preparation of polyalkylene glycol mono (meth) acrylates.
  • Polyalkylene glycol mono (meth) acrylates are known monomers which are used for the modification of many polymers.
  • Polyalkylene glycol mono (meth) acrylates are set forth, for example, in WO 2005/000929. According to this document, the monomers mentioned by reaction of
  • Hydroxyalkyl (meth) acrylates are obtained with alkylene oxides in the presence of catalysts. To separate off the catalyst, the reaction mixture can be mixed with aqueous Na 2 CO 3 solution. The thus obtained
  • Reaction mixture includes quite large amounts of water, which can not be readily separated completely.
  • Reaction mixture includes quite large amounts of water, which can not be readily separated completely.
  • the present invention accordingly provides a process for the purification of reaction mixtures which comprise BF 3 and / or at least one BF 3 complex and at least one polyalkylene glycol mono (meth) acrylate, which is characterized in that, for the separation of the BF 3 from the reaction mixture Na2CO 3
  • reaction mixtures comprising BF 3 and / or at least one BF 3 complex and at least one polyalkylene glycol mono (meth) acrylate
  • Product quality which is characterized in particular by a low water and acid content, can be achieved.
  • the product can be obtained in high yields and, overall, with low energy consumption.
  • the reaction mixture of the present invention comprises at least one polyalkylene glycol mono (meth) acrylate.
  • polyalkylene glycol mono (meth) acrylate is used in the context of the present invention in particular
  • (meth) acrylic acid derived from an ether, especially a polyether.
  • (meth) acrylic acid includes methacrylic acid
  • Acrylic acid and mixtures thereof.
  • (Meth) acrylic ester is derived, include in particular poly-C 2 -C 4 -alkylene glycol compounds, the various also known as poly-C2-C4-alkylene oxides or poly (oxy-C2-C4 - alkylene) compounds are referred to.
  • These ethers usually have at least 2, often at least 4 and especially at least 5 and usually not more than 500, often not more than 400, z. B. 2 to 100 and in particular 3 to 50 repeating units derived from C 2 -C 4 - alkylene glycols.
  • These compounds can be linear or branched.
  • Preferred polyalkylene glycol mono (meth) acrylates can be described by the general formula (I)
  • R is hydrogen or a methyl group
  • n indicates the number of repeating units and usually for a number in the range of 2 to 100, in particular in the range of 3 to 50, particularly preferably in the range of 4 to 15 and very particularly preferably in the range of 5 to 10
  • A is C 2 -C 4 -alkylene, such as 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,2-butanediyl or 1, 4-butanediyl and R 1 is hydrogen.
  • Polyalkylene glycol mono (meth) acrylates which preferably have a number average molecular weight in the range of 200 to 2000 g / mol, more preferably in the range of 300 to 1000 g / mol, determined by their hydroxyl number.
  • the reaction mixture preferably comprises Polyethylene mono (meth) acrylate, which comprises on average about 3 to 10, particularly preferably about 4 to 6 units derived from ethylene oxide.
  • the radical R 1 in these compounds particularly preferably represents hydrogen, A
  • n is an integer in the
  • Invention preferably comprises the reaction mixture
  • Polypropylene glycol mono (meth) acrylate which comprises on average about 3 to 10, particularly preferably about 4 to 6 units derived from propylene oxide.
  • the radical R 1 in these compounds is particularly preferably, the radical R 1 in these compounds
  • Hydrogen is exclusively 1, 2-propanediyl and n is an integer in the range of 3 to 10, particularly preferably 4 to 6 represents.
  • Polyalkylene glycol mono (meth) acrylates can be obtained in particular by the reaction of hydroxyalkyl (meth) acrylates with at least one alkylene oxide.
  • hydroxyalkyl (meth) acrylates includes
  • Hydroxyalkyl (meth) acrylates are well-known in the art esters of (meth) acrylic acid whose alcohol radical has at least one hydroxyl group.
  • the preferred hydroxyalkyl (meth) acrylates include, for example, 2-hydroxyethyl methacrylate,
  • Hydroxypropyl methacrylate and / or hydroxypropyl acrylate, in particular 2-hydroxypropyl acrylate and
  • Hydroxypropyl acrylate The previously stated Hydroxyalkyl (meth) acrylates can be used individually or as a mixture.
  • the preferred alkylene oxides include in particular
  • Ethylene oxide, propylene oxide and / or butylene oxide, these compounds can be used individually or in the form of mixtures.
  • the weight ratio of hydroxyalkyl (meth) acrylate to alkylene oxide may preferably be in the range from 1: 1 to 1:10, more preferably in the range from 1: 2 to 1: 3.
  • Alkylene oxide preferably in the range of 1: 1 to 1: 100, more preferably in the range of 1: 2 to 1:50 and most preferably from 1: 4 to 1:15.
  • Hydroxyalkyl (meth) acrylate with at least one alkylene oxide can be in a wide range. According to one
  • the reaction is preferably carried out at a temperature in the range from 30 ° C. to 90 ° C., especially
  • the reaction can be carried out at overpressure or underpressure.
  • Present invention can be the implementation of
  • BF 3 or at least one BF 3 complex is used. These compounds can be used singly or as a mixture.
  • BF 3 Boron trifluoride
  • BF 3 complexes can continue, even BF 3 - adducts referred to are used as the catalyst such as BF 3 - methanol, BF 3 -phenol, BF3 dibutyl ether, BF3 -diethylether, BF3 dimethyl ether, BF 3 - THF (tetrahydrofuran), BF 3 acetic acid, BF 3 acetonitrile, BF 3 dihydrate and / or BF 3 phosphoric acid.
  • the BF 3 complexes can be used individually or as a mixture.
  • the amount of catalyst (BF 3 and / or BF 3 complex) may preferably be in the range of 0.1% to 1%, more preferably in the range of 0.5% to 0.7%, based on the weight of the reaction mixture ,
  • the reaction mixture may comprise 1000 to 5000 ppm, more preferably about 2000 to 4000 ppm BF 3 .
  • reaction of the hydroxyalkyl (meth) acrylate with at least one alkylene oxide can be carried out batchwise or continuously, and so-called semibatch processes can also be used.
  • the process according to the invention can be carried out in bulk, i. without the use of another
  • Solvent be carried out.
  • an inert solvent can also be used. These include, but are not limited to, gasoline, benzene, toluene, n-hexane, cyclohexane and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK).
  • MIBK methyl isobutyl ketone
  • MEK methyl ethyl ketone
  • Alkylene oxide more preferably at least 95% by weight
  • inventive method only small amounts, more preferably no solvents used.
  • reaction according to the invention are all components, such as the hydroxyalkyl (meth) acrylate, the
  • Alkylene oxide and the catalyst after which this reaction mixture is heated to at least 40 0 C, preferably about 50 to 60 ° C.
  • This reaction can be carried out in the presence of atmospheric oxygen, but preference is given to processes which are carried out under an oxygen-reduced atmosphere, for example a nitrogen atmosphere.
  • reaction times are among other things of the selected parameters, such as pressure and temperature,
  • the residence times are generally in the range of 2 to 24 hours, preferably 3 to 20 hours and most preferably 4 to 8 hours. In continuous processes, the residence times are generally in the
  • Range from 5 minutes to 14 hours, preferably from 10 minutes to 8 hours and most preferably 15
  • the reaction of the hydroxyalkyl (meth) acrylates with at least one alkylene oxide is preferably carried out in the presence of a polymerization inhibitor.
  • hydroquinones for example, hydroquinones, hydroquinone ethers, such as
  • Hydroquinone monomethyl ether or di-tert-butyl catechol Phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, methylene blue or sterically hindered phenols, for example 2,4-dimethyl-6-tert-butylphenol, are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially. For further details, reference is made to the usual technical literature, in particular to the Rompp-Lexikon Chemie; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); keyword
  • phenols are preferred as
  • the proportion of inhibitors individually or as a mixture can generally be 0.01-0.5% (wt / wt). These polymerization inhibitors may be added to the reaction mixture before or at the beginning of the reaction.
  • Polymerization inhibitors are added during the reaction.
  • the reaction can take place with stirring, wherein the stirring speed is particularly preferably in Range from 50 to 2000 rpm, most preferably in the range of 100 to 500 rpm.
  • the pH can be in a wide range.
  • the reaction may be carried out at a pH in the range of 0 to 8, preferably 2 to 7, this value being measured from a sample of the reaction mixture mixed with a 10-fold excess of water.
  • a suitable plant for carrying out the present reaction may comprise, for example, a stirred tank reactor with stirrer and steam heating.
  • stirrer and steam heating are known per se and, for example, in Ullmann's Encyclopedia of Industrial Chemistry (6th edition), published by Wiley-VCH
  • Polyalkylene glycol mono (meth) acrylate dependent the present method can be carried out both on a laboratory scale and on an industrial scale.
  • the stirred tank reactor the stirred tank reactor
  • a boiler volume in the range of Im 3 to 30 m 3 , preferably 3 m 3 to 20 m 3 have.
  • the agitator of the reactor vessel may in particular in the form of a
  • Anchor stirrer, impeller, blade or Inter-MIG stirrer be configured.
  • the crystal water-containing Na 2 CO 3 may contain additives containing a Blocking (aggregation, lumping) of added
  • These additives include in particular sodium phosphates and / or silicates,
  • aerosils which preferably have a particle size in the range from 20 ⁇ m to 1000 ⁇ m and particularly preferably from 30 ⁇ m to 200 ⁇ m.
  • the amount of water containing Na2CO3 to be added depends, among other things, on the amount and type of
  • the total water content of the reaction mixture when separating the catalyst in the range of 0.1 to 5%, preferably 0.2 to 2%, particularly preferably in the range of 0.9% to 1.5%, based on the total weight of
  • the resulting composition can be mixed for a time to achieve a neutralization of the catalyst, in particular a formation of sodium borates or fluoroboraten ⁇ .
  • the reaction mixture can be filtered to give the
  • Precoat filtration can be used.
  • the reaction time which can be provided between the addition of crystal water-containing Na 2 CO 3 and the filtration, is preferably in the range of 60 to 360 minutes, more preferably in the range of 120 to 300 minutes.
  • the reaction time is preferably in the range of 60 to 360 minutes, more preferably in the range of 120 to 300 minutes.
  • Temperature preferably in the range of 50 to 100 0 C, more preferably in the range of 60 to 90 0 C and most preferably in the range of 70 to 80 0 C.
  • Neutralization may preferably be carried out in the presence of
  • Oxygen, especially atmospheric oxygen can be effected.
  • low boiling components of the reaction mixture can be mixed with a
  • Evaporator can be removed.
  • evaporator in the context of the present invention denotes a
  • Components is suitable in the gas phase. These include in particular thin film evaporators, such as falling film evaporator and evaporator with a rotating wiper system, as well as circulation evaporator. Also, thin film evaporators, such as falling film evaporator and evaporator with a rotating wiper system, as well as circulation evaporator. Also, thin film evaporators, such as falling film evaporator and evaporator with a rotating wiper system, as well as circulation evaporator. Also
  • Short path evaporators can be used. Such
  • Ingredients generally have a boiling point of at most 120 0 C, more preferably at most 100 0 C, measured at atmospheric pressure (1013 mbar).
  • the low-boiling constituents which can be converted into the gas phase include, in particular, water and the alkylene oxide used as starting material.
  • Evaporator is preferably in the range of 100 to 150 0 C, more preferably in the range of 110 to 140 0 C.
  • the pressure in the evaporator can correspondingly preferably be in the range from 0.5 to 100 mbar, particularly preferably in the range from 1 to 25 mbar and very particularly preferably in the range from 2 to 4 mbar.
  • the proportion of water in the purified reaction mixture at most 0.3%, more preferably at most 0.2% and most preferably at most 0.1%, based on the weight of
  • purified reaction mixture has an acid number of
  • Thin film evaporator (DS 125 from. Normschliff GmbH, Wertheim), which was equipped with a column (30 cm long, diameter 2.5 cm, filled with 6x6 mm 2 glass snap rings).
  • Thin-film evaporator (DS 125 from. Normschliff GmbH, Wertheim), which is equipped with a column (30 cm long, diameter 2.5 cm, filled with 6x6 mm 2 -Glasraschigringen).

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

Abstract

La présente invention concerne un procédé de purification de mélanges réactionnels contenant BF3 et/ou au moins un complexe de BF3 et au moins un mono(méth)acrylate de polyalkylèneglycol, du Na2CO3 contenant de l'eau de cristallisation étant ajouté pour permettre de séparer le BF3 et/ou le complexe de BF3 contenu dans le mélange réactionnel. L'invention porte également sur un procédé de production de mono(méth)acrylates de polyalkylèneglycol, selon lequel le mélange réactionnel obtenu après la réaction est purifié selon un procédé de l'invention. Les procédés de l'invention permettent d'obtenir des compositions de mono(méth)acrylates de polyalkylèneglycol particulièrement pauvres en eau.
PCT/EP2010/057101 2009-07-09 2010-05-25 Procédé et installation de purification de mélanges réactionnels contenant des mono(méth)acrylates de polyalkylèneglycol WO2011003669A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009027579.7 2009-07-09
DE102009027579A DE102009027579A1 (de) 2009-07-09 2009-07-09 Verfahren und Anlage zur Aufreinigung von Reaktionsmischungen, die Polyalkylenglykolmono(meth)acrylate umfassen

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WO2011003669A2 true WO2011003669A2 (fr) 2011-01-13
WO2011003669A3 WO2011003669A3 (fr) 2011-03-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9162998B2 (en) 2011-12-13 2015-10-20 Basf Se Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005000929A2 (fr) * 2003-06-17 2005-01-06 Rhodia Inc. Monomer polyether

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB796556A (en) * 1955-03-01 1958-06-11 Celanese Corp Process for the production of polyethers
DE4101431A1 (de) * 1991-01-18 1992-07-23 Henkel Kgaa Verfahren zum entfernen von fettsaeuren aus rohen fettsaeureestern

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005000929A2 (fr) * 2003-06-17 2005-01-06 Rhodia Inc. Monomer polyether

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9162998B2 (en) 2011-12-13 2015-10-20 Basf Se Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short)

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WO2011003669A3 (fr) 2011-03-24
TW201113251A (en) 2011-04-16
DE102009027579A1 (de) 2011-01-13

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