EP1675815A1 - Method for producing polymerisable polyhydroxy compounds - Google Patents

Method for producing polymerisable polyhydroxy compounds

Info

Publication number
EP1675815A1
EP1675815A1 EP04741212A EP04741212A EP1675815A1 EP 1675815 A1 EP1675815 A1 EP 1675815A1 EP 04741212 A EP04741212 A EP 04741212A EP 04741212 A EP04741212 A EP 04741212A EP 1675815 A1 EP1675815 A1 EP 1675815A1
Authority
EP
European Patent Office
Prior art keywords
tocopherol
water
ppm
compounds
reaction
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Withdrawn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
EP04741212A
Other languages
German (de)
French (fr)
Inventor
Dirk BRÖLL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1675815A1 publication Critical patent/EP1675815A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • 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

Definitions

  • the invention relates to a process for the preparation of substituted esters of (meth) acrylic acid which have several hydroxyl groups in the ester group.
  • Beinert, Hild and Rempp (Die Makromolekulare Chemie, 175, 2069 - 2077 (1974)) describe the preparation of (2,2-dimethyl-1, 3-dioxolan-4-yl) methyl methacrylate by reacting a mixture of methacrylic acid and thionyl chloride contains in a solvent mixture of hexamethylene phosphoric acid triamide (HMPT) and diethyl ether with 2,3-0-isopropylidene glycerol.
  • HMPT hexamethylene phosphoric acid triamide
  • diethyl ether diethyl ether with 2,3-0-isopropylidene glycerol.
  • the methacrylate obtained is polymerized anionically.
  • the polymer is converted to poly (2,3-dihydroxypropyl methacrylate).
  • the monomer is produced at -5 ° C to 15 ° C in a toxicologically harmful solvent. This method cannot be used in industrial technology due to the toxicological problems.
  • WO 00/63149 (Hydron Ltd.) describes a method for producing a polymerizable diol by reacting a protected glycerol derivative of methacrylic acid with an immobilized acid in the form of an acidic ion exchanger. The resulting acetone is blown out of the reaction system with air. (2,2-Dimethyl-1, 3-dioxolan-4-yl) methyl methacrylate, deionized water and the washed cation exchanger are placed in the reaction vessel. An air stream is then passed through the mixture for 48 hours, which ensures that the reaction mixture is thoroughly mixed.
  • the ion exchanger is filtered off and excess water is discharged through a stream of dried air.
  • WO00 / 63150 also describes a process for the preparation of a polymerizable diol by the ion-exchange-catalyzed reaction of a protected glycerol derivative of methacrylic acid with the elimination of acetone.
  • the methacrylic acid which is inevitably formed as a by-product is captured in a second step using a basic ion exchanger.
  • This method also has the following disadvantages:
  • GMMA glycerol monomethacrylate
  • the increased thermal stress also creates crosslinking compounds in the monomer, which polymerize in the monomer and lead to an undesirable increase in viscosity that does not make the monomer salable.
  • crosslinkers in the monomer lead to changes in the properties of the polymer, which are also undesirable.
  • the increased thermal load during the manufacturing process must therefore be kept as low as possible.
  • A (CH 2 ), where m can have the values 0 or 1,
  • R 2 "6 may be the same or different and assume the meanings OH, H, aliphatic or aromatic hydrocarbon, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclohexyl , Isobornyl, heptyl, octyl, substituted hydrocarbon radicals, such as Hydroxyethyl, 2- (N, N-dimethylamino) ethyl, 2- (N, N-dimethylamino) propyl, 2-hydroxypropyl, 2-hydroxyethyl, 2-ethylhexyl, iso-octyl, n can have the values 0, 1 or 2 accept,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A, m and n have the meanings given above and R 7 and R 8 can be the same or different and can have the meanings methyl, ethyl or propyl , reacted with water in small amounts on an acidic ion exchanger in a fixed bed and the resulting compound III
  • a favorable ratio of compound II to water is between 1: 1 and 1: 3. Very good results are achieved with a ratio of 1: 1, 1 and 1: 2.5.
  • a special embodiment of the invention provides use at a ratio of 1: 1, 2 to 1: 2.
  • a ratio of 1: 1, 5 proves to be particularly useful.
  • the water content in the ion exchanger is included in all of the above.
  • a tocopherol compound is preferably used for the storage and color stabilization of ethylenically unsaturated monomers.
  • the tocopherol compounds which can be used in the context of the invention are chroman-6-oles (3,4-dihydro-2H-1-benzopyran-6-ole) substituted in the 2-position with a 4,8,12-trimethyltridecyl radical.
  • To the present invention is preferably usable tocopherols to alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, and eta tocopherol zeta2-tocopherol, all of the aforementioned compounds each belonging to the (2 R, 4 'R, 8' R) - Form, as well as alpha-tocopherol in the (aÜ-rac) form.
  • Alpha- tocopherol are preferred in the (2 R, 4 'R, 8'R) -form (common name: RRR-alpha-tocopherol) as well as the synthetic racemic alpha-tocopherol (all-rac-alpha-tocopherol). Of these, the latter is particularly interesting due to the relatively low price.
  • the amount of tocopherol compound which can be used for the storage and color stabilization of stabilized monomers can vary over a wide range depending on the monomer and the desired efficiency. For many areas of application, quantities of up to 1000 ppm, based on the monomer mass, are sufficient. Very small additions of 10 ppm are often sufficient to achieve a noticeable improvement in storage and color stabilization. If you use less than 10 ppm, however, a significant storage and color stabilization is generally not noticeable. A favorable range for the amount to be added is therefore between 10 and 1000 ppm of tocopherol compound based on the Monomer mass. Very good results are achieved in the range of 50 to 800 ppm. A particular embodiment of the invention provides for use in an amount of 100 to 600 ppm. About 500 ppm of tocopherol compound are very particularly advantageously used.
  • the notation (meth) acrylic includes methacrylic, acrylic and mixtures of both.
  • IPGMA isopropylidene glycerol methacrylate
  • GMMA glycerol monomethacrylate
  • the bottom (4) of a separation column (3) is filled with 500 g IPGMA, which is stabilized with hydroquinone monomethyl ether.
  • Basic stabilization is the stabilization of monomers or monomer mixtures with hydroquinones, such as, for example, hydroquinone monomethyl ether, 4-methyl-2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, which is generally customary in (meth) acrylate chemistry, Phenothiazine, N-nitrosophenylhydroxylamine, diethylhydroxylamine, 2,6-di-tert-butyl-alpha- (dimethylamino) -p-cresol or 4-hydroxy-2,2,6,6-tetramethylpiperidin-1 -oxyl (rad.) (eg TEMPOL®) or from mixtures of the aforementioned compounds.
  • hydroquinones such as, for example, hydroquinone monomethyl ether, 4-methyl-2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, which is generally customary in (meth) acrylate
  • the amount of stabilizer used is, for example, 35 ppm for each individual substance.
  • the basic stabilization is added before the reaction. In the event that the monomers are mixed with the basic stabilization described above, the amount of tocopherol added as a storage stabilizer after the reaction is 10-1000 ppm, based on the amount of monomer. Without basic stabilization of the monomers, the amount of tocopherol added as a storage stabilizer after the reaction is 100-600 ppm.
  • Preliminary reaction At the start of the experiment, the sump contents are placed under ambient pressure with the aid of a gear pump from above onto a tempered (40 ° C) water-moist ion exchanger fixed bed (e.g. from Dow Chemical, type: Dowex M-31) (1, 2) pumped. The water in the ion exchanger reacts with IPGMA to form GMMA and acetone. The reaction mixture then passes through a separation column - acetone is distilled out of the reaction mixture (6) - back into the sump, where it is pumped again to the fixed bed (recycle mode).
  • a gear pump from above onto a tempered (40 ° C) water-moist ion exchanger fixed bed (e.g. from Dow Chemical, type: Dowex M-31) (1, 2) pumped.
  • the water in the ion exchanger reacts with IPGMA to form GMMA and acetone.
  • the reaction mixture then passes through a separation column - acetone is distilled out of the reaction mixture (6)
  • Post-reaction The pressure is then gradually reduced to approx. 20 mbar in order to remove residual amounts of acetone and excess water. After a certain time interval (approx. 2 h), the plant is shut down and the finished reaction product from the sump and the fixed bed is discharged.
  • the table shows the results of the turbidity measurement.
  • the measuring device corresponds to the standard EN 270 27 (ISO 7027).
  • the Formazin Standard is defined in the 13th edition (1971) Standard Methods of the Examination of Water and Wastewater, published by AWWA (American Waterworks Association).
  • the sample to be measured is filled into the measuring cell. This is then rubbed off with a lint-free cloth and a thin film of silicone oil is applied on the outside. After inserting the filter module into the measuring device, the cuvette is inserted and the turbidity value is determined.
  • HQME hydroquinone monomethyl ether

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for producing glycerol monomethacrylate (GMMA).

Description

Verfahren zur Herstellung von polymerisierbaren PolyhydroxyverbindungenProcess for the preparation of polymerizable polyhydroxy compounds
Die Erfindung betrifft ein Verfahren zur Herstellung von substituierten Estern der (Meth)acrylsäure, die mehrere Hydroxylgruppen in der Estergruppe aufweisen.The invention relates to a process for the preparation of substituted esters of (meth) acrylic acid which have several hydroxyl groups in the ester group.
Stand der TechnikState of the art
Beinert, Hild und Rempp (Die Makromolekulare Chemie, 175, 2069 - 2077 (1974)) beschreiben die Herstellung von (2,2-Dimethyl-1 ,3-dioxolan-4-yl) methylmethacrylat durch Umsetzung eines Gemisches, das Methacrylsäure und Thionylchlorid enthält in einem Lösungsmittelgemisch aus Hexamethylenphosphorsäuretriamid (HMPT) und Diethylether mit 2,3-0- isopropylidenglycerin. Das erhaltene Methacrylat wird anionisch polymerisiert. In einer polymeranalogen Reaktion wird das Polymer zum Poly(2,3- dihydroxypropylmethacrylat) umgesetzt.Beinert, Hild and Rempp (Die Makromolekulare Chemie, 175, 2069 - 2077 (1974)) describe the preparation of (2,2-dimethyl-1, 3-dioxolan-4-yl) methyl methacrylate by reacting a mixture of methacrylic acid and thionyl chloride contains in a solvent mixture of hexamethylene phosphoric acid triamide (HMPT) and diethyl ether with 2,3-0-isopropylidene glycerol. The methacrylate obtained is polymerized anionically. In a polymer-analogous reaction, the polymer is converted to poly (2,3-dihydroxypropyl methacrylate).
Die Herstellung des Monomers erfolgt bei - 5 °C bis 15 °C in einem toxikologisch bedenklichen Lösungsmittel. Dieses Verfahren kann in der industriellen Technik aufgrund der toxikologischen Probleme nicht angewandt werden.The monomer is produced at -5 ° C to 15 ° C in a toxicologically harmful solvent. This method cannot be used in industrial technology due to the toxicological problems.
WO 00/63149 (Hydron Ltd.) beschreibt ein Verfahren zur Herstellung eines polymerisierbaren Diols durch Umsetzung eines geschützten Glycerin-Derivats der Methacrylsäure mit einer immobilisierten Säure in Form eines sauren Ionenaustauschers. Das entstehende Aceton wird mit Luft aus dem Reaktionssystem ausgeblasen. Im Reaktionsgefäß werden (2,2-Dimethyl-1 ,3-dioxolan-4-yl)methylmethacrylat, entionisiertes Wasser und der gewaschene Kationenaustauscher vorgelegt. Anschließend wird durch die Mischung 48 h ein Luftstrom geleitet, der für die Durchmischung des Reaktionsansatzes sorgt.WO 00/63149 (Hydron Ltd.) describes a method for producing a polymerizable diol by reacting a protected glycerol derivative of methacrylic acid with an immobilized acid in the form of an acidic ion exchanger. The resulting acetone is blown out of the reaction system with air. (2,2-Dimethyl-1, 3-dioxolan-4-yl) methyl methacrylate, deionized water and the washed cation exchanger are placed in the reaction vessel. An air stream is then passed through the mixture for 48 hours, which ensures that the reaction mixture is thoroughly mixed.
Nach Ende der Reaktion wird der Ionenaustauscher abfiltriert und überschüssiges Wasser durch einen Strom getrockneter Luft ausgetragen.After the reaction has ended, the ion exchanger is filtered off and excess water is discharged through a stream of dried air.
Das Verfahren der WO00/63149 weist mehrere Nachteile auf:The method of WO00 / 63149 has several disadvantages:
Durch das Einblasen des Luftstroms in die Reaktionsmischung erfährt der Ionenaustauscher einen erhöhten Abrieb. Bei höheren Ansprüchen an die Reinheit des Produkts ist der Abrieb, der auch durch Filtration nicht vollständig zu entfernen ist, nicht tragbar. Die Methode, den Wassergehalt des Produkts durch Durchblasen getrockneter Luft zu reduzieren, führt zu nicht tragbaren Ausbeuteverlusten. In der Publikation wird nicht beschrieben, dass irgendwelche Maßnahmen zur Reduktion der Produktverluste ergriffen worden wären. Für einige Anwendungsfälle ist der Wassergehalt zu hoch. In der Offenlegung werden keine Methoden beschrieben, den Wassergehalt sicher und reproduzierbar einzustellen.By blowing the air stream into the reaction mixture, the ion exchanger experiences increased abrasion. With higher demands on the purity of the product, the abrasion, which cannot be completely removed by filtration, is not acceptable. The method of reducing the water content of the product by blowing dried air through it leads to unsustainable losses in yield. The publication does not describe that any measures to reduce product losses have been taken. The water content is too high for some applications. In the disclosure, no methods are described to set the water content safely and reproducibly.
WO00/63150 (Hydron Ltd.) beschreibt ebenfalls ein Verfahren zur Herstellung eines polymerisierbaren Diols durch die ionenaustauscherkatalysierte Umsetzung eines geschützten Glycerin-Derivats der Methacrylsäure unter Abspaltung von Aceton. Die dabei zwangsläufig als Nebenprodukt entstehende Methacrylsäure wird mit einem basischen Ionenaustauscher in einem zweiten Schritt abgefangen. Auch dieses Verfahren hat die folgenden Nachteile:WO00 / 63150 (Hydron Ltd.) also describes a process for the preparation of a polymerizable diol by the ion-exchange-catalyzed reaction of a protected glycerol derivative of methacrylic acid with the elimination of acetone. The methacrylic acid which is inevitably formed as a by-product is captured in a second step using a basic ion exchanger. This method also has the following disadvantages:
Durch zweimaligen Einsatz der Ionenaustauscher steigt der Anteil an Abrieb im Produkt. Der Wassergehalt des Produkts wird durch Durchleiten getrockneter Luft auf < 3 % eingestellt. Dieses Vorgehen ist mit Ausbeuteverlusten verbunden. Der Gehalt an Vernetzer (Glycerinmethacrylat) beträgt 0,8 %.Using the ion exchanger twice increases the amount of abrasion in the product. The water content of the product is adjusted to <3% by passing dried air through it. This procedure is associated with losses in yield. The content of crosslinking agent (glycerol methacrylate) is 0.8%.
Aufgabetask
Es bestanden also anhand des vorstehend diskutierten Standes der Technik die Aufgaben, ein Verfahren zur Herstellung von Glycerinmonomethacrylat (GMMA) zu entwickeln, das die im Stand der Technik vorhandenen Nachteile nicht mehr aufweist und insbesondere das Reaktionsgemisch thermisch so wenig wie möglich belastet, einen definierten, möglichst niedrigen Wassergehalt des Produkts besitzt, den lästigen Abrieb des Ionenaustauschers ohne umfangreiche Maßnahmen vermeidet, anstelle des batch-Verfahrens ein semi-kontinuierliches Verfahren darstellt, mit weniger als der im Stand der Technik üblichen Stabilisator-Menge auskommt, ein lagerstabiles Produkt ergibt, das sich nicht oder nur unwesentlich verfärbt, mit nicht toxischem Polymerisationsstabilisator im Produkt auskommt. Durch die erhöhte thermische Belastung entstehen darüber hinaus im Monomer vernetzend wirkende Verbindungen, die schon im Monomer polymerisieren und zu einem unerwünschten Viskositätsanstieg führen, der das Monomer nicht verkäuflich werden lässt. Darüber hinaus führen schon kleinere Anteile an Vernetzern im Monomer zu Eigenschaftsänderungen im Polymer, die ebenfalls unerwünscht sind. Die erhöhte thermische Belastung während des Herstellungsverfahrens ist daher möglichst gering zu halten.On the basis of the prior art discussed above, there were therefore the tasks of developing a process for the production of glycerol monomethacrylate (GMMA) which no longer has the disadvantages present in the prior art and, in particular, has as little thermal impact on the reaction mixture as possible, a defined, has the lowest possible water content of the product, avoids the annoying abrasion of the ion exchanger without extensive measures, is a semi-continuous process instead of the batch process, requires less than the amount of stabilizer customary in the prior art, and results in a storage-stable product not discolored or only slightly discolored, with a non-toxic polymerization stabilizer in the product. The increased thermal stress also creates crosslinking compounds in the monomer, which polymerize in the monomer and lead to an undesirable increase in viscosity that does not make the monomer salable. In addition, even small amounts of crosslinkers in the monomer lead to changes in the properties of the polymer, which are also undesirable. The increased thermal load during the manufacturing process must therefore be kept as low as possible.
Gelöst wird die Aufgabe durch ein Verfahren zur Herstellung von Verbindungen der Formel IThe object is achieved by a process for the preparation of compounds of the formula I.
R3 R4 O R1 I I II IR 3 R 4 OR 1 II II I
R2 - C - Am - C - (CR5R6)n - O - C - C = CH2 (I) I I OH OHR 2 - C - A m - C - (CR 5 R 6 ) n - O - C - C = CH 2 (I) II OH OH
wobei gilt:where:
R1 H oder CH3 R 1 H or CH 3
A = (CH2), wobei m die Werte 0 oder 1 annehmen kann,A = (CH 2 ), where m can have the values 0 or 1,
R2"6 = können gleich oder verschieden sein und die Bedeutungen annehmen OH, H, aliphatischer oder aromatischer Kohlenwasserstoff, wie beispielsweise Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, tertiär-Butyl, Pentyl, Hexyl, Cyclopentyl, Cyclohexyl, Methylcyclohexyl, Isobornyl, Heptyl, Octyl, substituierte Kohlenwasserstoffreste, wie beispielsweise Hydroxyethyl, 2-(N,N-Dimethylamino)ethyl, 2-(N,N- Dimethylamino)propyl, 2-Hydroxypropyl, 2-Hydroxyethyl, 2- Ethyl hexyl, iso-Octyl, n kann die Werte 0, 1 oder 2 annehmen,R 2 "6 = may be the same or different and assume the meanings OH, H, aliphatic or aromatic hydrocarbon, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclohexyl , Isobornyl, heptyl, octyl, substituted hydrocarbon radicals, such as Hydroxyethyl, 2- (N, N-dimethylamino) ethyl, 2- (N, N-dimethylamino) propyl, 2-hydroxypropyl, 2-hydroxyethyl, 2-ethylhexyl, iso-octyl, n can have the values 0, 1 or 2 accept,
dadurch gekennzeichnet, dass man Verbindungen der Formel IIcharacterized in that compounds of the formula II
R3 R4 O R1 I I II IR 3 R 4 OR 1 II II I
R2 - C - Am - C - (CR5R6)n - O - C - C = CH2 (II)R 2 - C - A m - C - (CR 5 R 6 ) n - O - C - C = CH 2 (II)
O O \ / C R 77 \ R 88 OO \ / CR 7 7 \ R 8 8
wobei R1, R2, R3, R4, R5, R6, A, m und n die oben angegebenen Bedeutungen haben und R7 und R8 gleich oder verschieden sein können und die Bedeutungen Methyl, Ethyl oder Propyl annehmen können, mit Wasser in geringen Mengen an einem sauren Ionenaustauscher im Festbett umsetzt und die entstandene Verbindung IIIwhere R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A, m and n have the meanings given above and R 7 and R 8 can be the same or different and can have the meanings methyl, ethyl or propyl , reacted with water in small amounts on an acidic ion exchanger in a fixed bed and the resulting compound III
R7 R8 C = O (III)R 7 R 8 C = O (III)
kontinuierlich aus dem Reaktionsmedium entfernt und das Produkt mit Tocopherol-Derivaten gegen Polymerisation und Verfärbung stabilisiert. Ein günstiges Verhältnis von Verbindung II zu Wasser liegt zwischen 1 :1 und 1 :3. Sehr gute Ergebnisse werden bei einem Verhältnis von 1 :1 ,1 und 1:2,5 erzielt. Eine besondere Ausgestaltung der Erfindung sieht die Verwendung bei einem Verhältnis von 1 :1 ,2 bis 1 :2 vor. Ganz besonders zweckmäßig erweist sich ein Verhältnis von 1 :1 ,5. Bei allen voran stehenden Angaben wird der im Ionenaustauscher befindliche Wasseranteil mit einbezogen.continuously removed from the reaction medium and the product stabilized with tocopherol derivatives against polymerization and discoloration. A favorable ratio of compound II to water is between 1: 1 and 1: 3. Very good results are achieved with a ratio of 1: 1, 1 and 1: 2.5. A special embodiment of the invention provides use at a ratio of 1: 1, 2 to 1: 2. A ratio of 1: 1, 5 proves to be particularly useful. The water content in the ion exchanger is included in all of the above.
Im Rahmen der Erfindung wird bevorzugt eine Tocopherolverbindung zur Lager- und Farbstabilisierung von ethylenisch ungesättigten Monomeren verwendet.In the context of the invention, a tocopherol compound is preferably used for the storage and color stabilization of ethylenically unsaturated monomers.
Bei den im Sinne der Erfindung verwendbaren Tocopherolverbindungen handelt es sich um in 2-Stellung mit einem 4,8,12-Trimethyltridecyl-Rest substituierte Chroman-6-ole (3,4-Dihydro-2H-1-benzopyran-6-ole). Zu den erfindungsgemäß vorzugsweise einsetzbaren Tocopherolen gehören alpha-Tocopherol, beta- Tocopherol, gamma-Tocopherol, delta-Tocopherol, zeta2-Tocopherol und eta- Tocopherol, alle der vorgenannten Verbindungen jeweils in der (2R, 4'R,8'R)- Form, sowie alpha-Tocopherol in der (aÜ-rac)-Form. Bevorzugt sind alpha- Tocopherol in der (2R, 4'R,8'R)-Form (Trivialname: RRR-alpha-Tocopherol) sowie das synthetische racemische alpha-Tocopherol (all-rac-alpha- Tocopherol). Hiervon wiederum ist letztgenanntes aufgrund des relativ niedrigen Preises besonders interessant.The tocopherol compounds which can be used in the context of the invention are chroman-6-oles (3,4-dihydro-2H-1-benzopyran-6-ole) substituted in the 2-position with a 4,8,12-trimethyltridecyl radical. , To the present invention is preferably usable tocopherols to alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, and eta tocopherol zeta2-tocopherol, all of the aforementioned compounds each belonging to the (2 R, 4 'R, 8' R) - Form, as well as alpha-tocopherol in the (aÜ-rac) form. Alpha- tocopherol are preferred in the (2 R, 4 'R, 8'R) -form (common name: RRR-alpha-tocopherol) as well as the synthetic racemic alpha-tocopherol (all-rac-alpha-tocopherol). Of these, the latter is particularly interesting due to the relatively low price.
Die Menge an Tocopherolverbindung, die zur Lager- und Farbstabilisierung von grundstabilisierten Monomeren anwendbar ist, kann je nach Monomer und gewünschter Effizienz über einen weiten Bereich differieren. Für viele Einsatzbereiche sind Mengen von bis zu 1000 ppm, bezogen auf die Monomermasse ausreichend. Häufig genügen schon sehr geringe Zusatzmengen von 10 ppm, um eine erkennbare Verbesserung der Lager- und Farbstabilisierung zu erzielen. Sollte man weniger als 10 ppm einsetzen, so ist jedoch eine wesentliche Lager- und Farbstabilisierung im Allgemeinen nicht wahrnehmbar. Ein günstiger Bereich für die zuzusetzende Menge liegt daher zwischen 10 und 1000 ppm an Tocopherolverbindung bezogen auf die Monomermasse. Sehr gute Ergebnisse werden im Zugabebereich 50 bis 800 ppm erzielt. Eine besondere Ausgestaltung der Erfindung sieht die Verwendung in einer Menge von 100 bis 600 ppm vor. Ganz besonders zweckmäßig werden etwa 500 ppm Tocopherolverbindung verwendet.The amount of tocopherol compound which can be used for the storage and color stabilization of stabilized monomers can vary over a wide range depending on the monomer and the desired efficiency. For many areas of application, quantities of up to 1000 ppm, based on the monomer mass, are sufficient. Very small additions of 10 ppm are often sufficient to achieve a noticeable improvement in storage and color stabilization. If you use less than 10 ppm, however, a significant storage and color stabilization is generally not noticeable. A favorable range for the amount to be added is therefore between 10 and 1000 ppm of tocopherol compound based on the Monomer mass. Very good results are achieved in the range of 50 to 800 ppm. A particular embodiment of the invention provides for use in an amount of 100 to 600 ppm. About 500 ppm of tocopherol compound are very particularly advantageously used.
Die Schreibweise (Meth)acryl umfaßt Methacryl, Acryl und Mischungen aus beiden.The notation (meth) acrylic includes methacrylic, acrylic and mixtures of both.
Verfahrensbeschreibungprocess Description
Die Hydrolyse von Isopropylidenglycerinmethacrylat (IPGMA) zu Glycerinmonomethacrylat (GMMA) wurde in einer Laboranlage untersucht. Das Fließbild der Anlage ist in Figur 1 zu sehen.The hydrolysis of isopropylidene glycerol methacrylate (IPGMA) to glycerol monomethacrylate (GMMA) was investigated in a laboratory facility. The flow diagram of the plant can be seen in FIG. 1.
Befüllung: Der Sumpf (4) einer Trennkolonne (3) wird mit 500 g IPGMA befüllt, welches mit Hydrochinonmonomethylether grundstabilisiert ist.Filling: The bottom (4) of a separation column (3) is filled with 500 g IPGMA, which is stabilized with hydroquinone monomethyl ether.
Unter Grundstabilisierung wird die in der (Meth)acrylatchemie allgemein übliche Stabilisierung von Monomeren oder Monomergemischen mit Hydrochinonen, wie beispielsweise Hydrochinonmonomethylether, 4-Methyl-2,6-di-tert- butylphenol, 2,4-Dimethyl-6-tert-butylphenol, Phenothiazin, N- Nitrosophenylhydroxylamin, Diethylhydroxylamin, 2,6-Di-tert-butyl-alpha- (dimethylamino)-p-cresol oder 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1 -oxyl (rad.) (z.B. TEMPOL® ) oder aus Mischungen der vorgenannten Verbindungen verstanden. Die eingesetzte Menge an Stabilisator beträgt für jede Einzelsubstanz beispielsweise 35 ppm. Die Grundstabilisierung wird vor der Reaktion zugesetzt. Im Fall, dass die Monomere mit der oben beschriebenen Grundstabilisierung versetzt werden, beträgt die nach der Reaktion als Lagerstabilisator zugesetzte Tocopherol-Menge 10-1000 ppm, bezogen auf die Monomermenge. Ohne Grundstabilisierung der Monomere beträgt die nach der Reaktion als Lagerstabilisator zugesetzte Tocopherol-Menge 100 - 600 ppm.Basic stabilization is the stabilization of monomers or monomer mixtures with hydroquinones, such as, for example, hydroquinone monomethyl ether, 4-methyl-2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, which is generally customary in (meth) acrylate chemistry, Phenothiazine, N-nitrosophenylhydroxylamine, diethylhydroxylamine, 2,6-di-tert-butyl-alpha- (dimethylamino) -p-cresol or 4-hydroxy-2,2,6,6-tetramethylpiperidin-1 -oxyl (rad.) ( eg TEMPOL®) or from mixtures of the aforementioned compounds. The amount of stabilizer used is, for example, 35 ppm for each individual substance. The basic stabilization is added before the reaction. In the event that the monomers are mixed with the basic stabilization described above, the amount of tocopherol added as a storage stabilizer after the reaction is 10-1000 ppm, based on the amount of monomer. Without basic stabilization of the monomers, the amount of tocopherol added as a storage stabilizer after the reaction is 100-600 ppm.
Vorreaktion: Der Sumpfinhalt wird bei Versuchsstart unter Umgebungsdruck mit Hilfe einer Zahnradpumpe von oben auf eine temperierte (40 °C) wasserfeuchte lonenaustauscher-Festbettschüttung (z. B. von Fa. Dow Chemical, Typ: Dowex M-31 ) (1 , 2) gepumpt. Das im Ionenaustauscher befindliche Wasser reagiert mit IPGMA unter Bildung von GMMA und Aceton. Anschließend gelangt die Reaktionsmischung über eine Trennkolonne - Aceton wird hierin aus der Reaktionsmischung abdestilliert (6) - wieder in den Sumpf zurück, wo sie erneut zum Festbett gepumpt wird (Kreislauffahrweise).Preliminary reaction: At the start of the experiment, the sump contents are placed under ambient pressure with the aid of a gear pump from above onto a tempered (40 ° C) water-moist ion exchanger fixed bed (e.g. from Dow Chemical, type: Dowex M-31) (1, 2) pumped. The water in the ion exchanger reacts with IPGMA to form GMMA and acetone. The reaction mixture then passes through a separation column - acetone is distilled out of the reaction mixture (6) - back into the sump, where it is pumped again to the fixed bed (recycle mode).
Hauptreaktion: Nach einer gewissen Zeit (ca. 30 min) wird direkt vor der Festbettschüttung (5) eine bestimmte Menge Wasser (ca. 45 g) mit Hilfe einer Pumpe in einem gewissen Zeitintervall (ca. 1 h) zudosiert. Gleichzeitig wird der Druck im Reaktionskreislauf auf ca. 150 mbar abgesenkt, um möglichst vollständig Aceton zu entfernen.Main reaction: After a certain time (approx. 30 min), a certain amount of water (approx. 45 g) is metered in with a pump in a certain time interval (approx. 1 h) directly before the fixed bed (5). At the same time, the pressure in the reaction circuit is reduced to approximately 150 mbar in order to remove acetone as completely as possible.
Nachreaktion: Anschließend wird der Druck stufenweise weiter auf ca. 20 mbar reduziert, um Restmengen an Aceton und überschüssiges Wasser zu entfernen. Nach einem gewissen Zeitintervall (ca. 2 h) wird die Anlage abgefahren und das fertige Reaktionsprodukt aus Sumpf und Festbettschüttung abgelassen. Post-reaction: The pressure is then gradually reduced to approx. 20 mbar in order to remove residual amounts of acetone and excess water. After a certain time interval (approx. 2 h), the plant is shut down and the finished reaction product from the sump and the fixed bed is discharged.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
Nr. BezeichnungNo.
1 Ionenaustauscher1 ion exchanger
2 Temperiermantel2 tempering jacket
3 Trennkolonne3 separation column
4 Sumpf4 swamp
5 Wasserzulauf5 water inlet
6 Aceton-/Wasser-Destillat6 acetone / water distillate
Die Tabelle zeigt die Ergebnisse der Trübungsmessung. Die Trübungsmessungen werden mit dem Labortrübungsmessgerät Modell 2100AN der Fa. Hach durchgeführt. Es misst Trübungen von 0 bis 10.000 NTU (Nephelometrische Trübungseinheiten; entspricht It. Definition Trübungseinheiten Formazin = TE/F). Das Messgerät entspricht der Norm EN 270 27 (ISO 7027). Der Formazin Standard ist in der 13. Ausgabe (1971 ) Standard Methods of the Examination of Water and Wastewater, herausgegeben von AWWA (American Waterworks Association) definiert.The table shows the results of the turbidity measurement. The turbidity measurements are carried out with the laboratory turbidity meter Model 2100AN from Hach. It measures turbidity from 0 to 10,000 NTU (nephelometric turbidity units; corresponds to the definition of turbidity units formazin = TE / F). The measuring device corresponds to the standard EN 270 27 (ISO 7027). The Formazin Standard is defined in the 13th edition (1971) Standard Methods of the Examination of Water and Wastewater, published by AWWA (American Waterworks Association).
Die zu messende Probe wird in die Messküvette gefüllt. Diese wird anschließend mit einem fusselfreien Tuch abgerieben und außen wird ein dünner Film Silikonöl aufgetragen. Nach einsetzen des Filtermoduls in das Messgerät, wird die Küvette eingesetzt und der Trübungswert bestimmt. HQME = Hydrochinonmonomethylether The sample to be measured is filled into the measuring cell. This is then rubbed off with a lint-free cloth and a thin film of silicone oil is applied on the outside. After inserting the filter module into the measuring device, the cuvette is inserted and the turbidity value is determined. HQME = hydroquinone monomethyl ether

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Verbindungen der Formel I,1. Process for the preparation of compounds of the formula I,
R3 R4 O R1 I I II I R2-C-Am-C-(CR5R6)n-0-C-C = CH2 (I) I I OH OHR 3 R 4 OR 1 II II IR 2 -CA m -C- (CR 5 R 6 ) n -0-CC = CH 2 (I) II OH OH
wobei gilt:where:
R1 H oder CH3 A = (CH2), wobei m die Werte 0 oder 1 annehmen kann, R2"5 = können gleich oder verschieden sein und die Bedeutungen annehmen OH, H, aliphatischer oder aromatischer Kohlenwasserstoff, wie beispielsweise Methyl, Ethyl, Propyl, Isopropyl, (usw.). n kann die Werte 0, 1 oder 2 annehmen,R 1 H or CH 3 A = (CH 2 ), where m can have the values 0 or 1, R 2 "5 = can be the same or different and have the meanings OH, H, aliphatic or aromatic hydrocarbon, such as methyl, Ethyl, propyl, isopropyl, etc. n can be 0, 1 or 2,
dadurch gekennzeichnet, dass man Verbindungen der Formel IIcharacterized, that compounds of formula II
R3 R4 O R1 I I II I R2 - C - Am - C - (CR5R6)n - O - C - C = CH2 (II)R 3 R 4 OR 1 II II IR 2 - C - A m - C - (CR 5 R 6 ) n - O - C - C = CH 2 (II)
wobei R1, R2, R3, R4, R5, R6, A, m und n die oben angegebenen Bedeutungen haben und R7 und R8 gleich oder verschieden sein können und die Bedeutungen Methyl, Ethyl oder Propyl annehmen können, mit Wasser in geringen Mengen (Verhältnis Verbindung (II) zu Wasser zwischen 1 :1 und 1 :3) an einem sauren Ionenaustauscher im Festbett umsetzt und die entstandene Verbindung III where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A, m and n have the meanings given above and R 7 and R 8 can be the same or different and can have the meanings methyl, ethyl or propyl , reacted with water in small quantities (ratio of compound (II) to water between 1: 1 and 1: 3) on an acidic ion exchanger in a fixed bed and the compound III
R7 Rö C = O (III) kontinuierlich aus dem Reaktionsmedium entfernt.R 7 R ö C = O (III) continuously removed from the reaction medium.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man mit Tocopherol-Derivaten gegen Polymerisation und Verfärbung stabilisiert.2. The method according to claim 1, characterized in that stabilized with tocopherol derivatives against polymerization and discoloration.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man mit Tocopherol in einer Menge von 10 ppm - 1000 ppm, bezogen auf die Monomermischung stabilisiert. 3. The method according to claim 1, characterized in that stabilized with tocopherol in an amount of 10 ppm - 1000 ppm, based on the monomer mixture.
4. Verwendung der nach einem der vorstehenden Ansprüche erhältlichen Monomermischung zur Herstellung von Kontaktlinsen.4. Use of the monomer mixture obtainable according to one of the preceding claims for the production of contact lenses.
5. Verwendung der nach einem der vorstehenden Ansprüche erhältlichen Monomermischung zur Herstellung von wasserlöslichen Polymerisaten. 5. Use of the monomer mixture obtainable according to one of the preceding claims for the production of water-soluble polymers.
EP04741212A 2003-10-24 2004-07-22 Method for producing polymerisable polyhydroxy compounds Withdrawn EP1675815A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10349972A DE10349972A1 (en) 2003-10-24 2003-10-24 Production of triol mono(meth)acrylate, e.g. glycerol monomethacrylate for use in contact lens production, involves hydrolytic cleavage of an alkylidene-ether derivative with water on an acid ion exchange resin
PCT/EP2004/008182 WO2005047227A1 (en) 2003-10-24 2004-07-22 Method for producing polymerisable polyhydroxy compounds

Publications (1)

Publication Number Publication Date
EP1675815A1 true EP1675815A1 (en) 2006-07-05

Family

ID=34485083

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04741212A Withdrawn EP1675815A1 (en) 2003-10-24 2004-07-22 Method for producing polymerisable polyhydroxy compounds

Country Status (9)

Country Link
US (1) US7342054B2 (en)
EP (1) EP1675815A1 (en)
JP (1) JP2007509849A (en)
KR (1) KR100859109B1 (en)
CN (2) CN1835907A (en)
CA (1) CA2535231A1 (en)
DE (1) DE10349972A1 (en)
RU (1) RU2006117545A (en)
WO (1) WO2005047227A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4957067B2 (en) * 2006-04-28 2012-06-20 日油株式会社 Method for producing urethane bond-containing diol (meth) acrylate compound
DE102007022521A1 (en) 2007-05-14 2008-11-20 Cognis Ip Management Gmbh Process for the preparation of diols
US8307300B1 (en) * 2008-05-13 2012-11-06 Google Inc. Content resizing and caching in multi-process browser architecture
US20220298131A1 (en) 2019-07-31 2022-09-22 Arkema France Method of making glycerol carbonate (meth)acrylate and curable compositions based thereon
WO2023058511A1 (en) 2021-10-06 2023-04-13 日油株式会社 Carbonate (meth)acrylate composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408693B1 (en) 1988-12-23 1993-11-10 BASF Aktiengesellschaft Mixtures of stabilizers for plastics
GB2348879B (en) 1999-04-16 2004-03-31 Hydron Ltd Process
GB2348878B (en) 1999-04-16 2004-02-18 Hydron Ltd Process
DE10131479B4 (en) * 2001-06-29 2005-05-19 Röhm GmbH & Co. KG Color stabilization of basic stabilized ethylenically unsaturated monomers, in particular basic stabilized hydroxyalkyl (meth) acrylates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005047227A1 *

Also Published As

Publication number Publication date
WO2005047227A1 (en) 2005-05-26
US20060258830A1 (en) 2006-11-16
US7342054B2 (en) 2008-03-11
DE10349972A1 (en) 2005-05-25
CN101353304A (en) 2009-01-28
KR20060123185A (en) 2006-12-01
RU2006117545A (en) 2007-12-10
JP2007509849A (en) 2007-04-19
CA2535231A1 (en) 2005-05-26
CN1835907A (en) 2006-09-20
KR100859109B1 (en) 2008-09-18

Similar Documents

Publication Publication Date Title
DE69204384T2 (en) Method and composition for coating an optical fiber.
EP2294048B1 (en) Method for the production of (meth)acrylic esters
EP1465859A1 (en) Method for the continuous production of alkyl (meth)acrylates
DE102006008998A1 (en) Stabiliser mixture, especially for the production of alkoxypolyoxyalkylene (meth)acrylate, comprises a hydroquinone mono-ether, a phenolic antioxidant and a 2,2,6,6-tetra-substituted hydroxypiperidine derivative
DE60214446T2 (en) Hyperbranched fluorinated multifunctional alcohols and their derivatives
WO2021058263A1 (en) Silicone (meth)acrylates, process for their preparation and their use in curable compositions
EP3044200B1 (en) Method for post-treating polyol esters
WO2005047227A1 (en) Method for producing polymerisable polyhydroxy compounds
DE10355830A1 (en) Production of (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate for use e.g. in adhesives or paint, comprises transesterification of methyl methacrylate with glycerol carbonate using a metal 1,3-diketonate catalyst
DE10063175A1 (en) Process for the preparation of higher (meth) acrylic acid esters
DE2435509A1 (en) STABILIZED POLYACRYLIC ACID ESTERS AND THE PROCESS FOR THEIR PRODUCTION
DE10131479B4 (en) Color stabilization of basic stabilized ethylenically unsaturated monomers, in particular basic stabilized hydroxyalkyl (meth) acrylates
DE69218282T2 (en) Process for the preparation of octyl methoxy cinnamate
EP2297224B1 (en) Method for producing polyalkylene glycoldi(meth)acrylates
DE102006039245B3 (en) Making oxetane group-containing (meth)acrylate for use as a binder, e.g. in adhesives, paints or ink-jet ink, involves reacting ethoxylated trimethylol-propane-oxetane with (meth)acrylate using a zirconium catalyst
EP1650184B1 (en) Mixtures of N,N-Bis-(2-hydroxyalkyl)-4-toluidin, their preparation and use
EP1231202A2 (en) Transesterification of (meth)acrylates in presence of alkali metal cyanate containing mixed catalysts
EP4015498B1 (en) Method for the continuous production of acrylic acid n-butylester
DE102010000945A1 (en) Producing (meth)acrylic acid esters, comprises reacting (meth)acrylic acid or (meth)acrylate with an alcohol in presence of polymerization inhibitor e.g. a copper compound, where an organic nitrogen compound is added
EP3611236B1 (en) An aqueous, storage-stable composition containing n-benzyl substituted n- (2-aminoethyl)-3-aminopropylsiloxane-hydrochlorides, method for their preparation and their use
DE102007037140A1 (en) Process for the heterogeneously catalyzed esterification of (meth) acrylic acid with oxyalkylated polyols
EP1223159B1 (en) Preparation of asymmetrical (meth)acrylate crosslinking agents
WO2011003669A2 (en) Method and system for purifying reaction mixtures comprising polyalkylene glycol mono(meth)acrylate
DE4391060C2 (en) Reduction in the molecular weight of poly (tetramethylene ether) glycol
DE10118232A1 (en) 1,3 Diol compounds, useful as comonomers in dental applications, are prepared by hydrolysis of the corresponding ketal in the presence of an acid ion exchange medium in a polar solvent and water.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060111

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ROEHM GMBH

17Q First examination report despatched

Effective date: 20061025

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK ROEHM GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK ROEHM GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20090225