DE102013214830A1 - Process, apparatus and their use for the preparation of acryloxy and methacryloxypropyltrialkoxysilanes - Google Patents

Abstract

The present invention relates to a special method, a particularly advantageous device and their use for the preparation of pure organosilanes with unsaturated organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyltrialkoxysilan, in particular of 3-methacryloxypropyltrimethoxysilane (MEMO), by hydrosilylation of allyl or allyl methacrylate with Trialkoxysilane in the presence of a homogeneous Pt (IV) catalyst and a special stabilizer system and distillative workup of the crude product, wherein the pure product via a targeted side decrease, which takes place under temperature and pressure control from the rectification column wins.

Description

The present invention relates to a special method and a device or system suitable for this purpose and their use for a particularly gentle production of acryloxy and methacryloxypropyl-trialkoxysilanes by hydrosilylation of allyl acrylate or allyl methacrylate with a Hydrogentrialkoxysilan in the presence of a homogeneous Pt catalyst system and using a stabilizer system.

Organic silicon compounds (organosilanes) having unsaturated organic radicals such as acryloxyalkyltrialkoxysilane or methacryloxyalkyltrialkoxysilane are important chemical substances with an extremely broad field of application. They are used, for example, in very large quantities in the production of paints or as an additive in the production of sizes for glass fibers.

It has long been known to prepare acrylic or methacryloxypropyltrialkoxysilanes from alkali acrylate or alkali methacrylate and haloalkyltrialkoxysilane, for example potassium methacrylate and 3-chloropropyltrimethoxysilane in the presence of a phase transfer catalyst (cf. EP 0 437 653 B1 . EP 0 708 081 A2 ) (hereinafter also referred to as phase transfer catalysis method (PTC method) or "salt method" or "salt route"). The disadvantage of this process is the by-product formation of alkali metal halide, for example potassium chloride, in a stoichiometric amount. It must be laboriously separated from the target product, processed and disposed of, which is associated with high costs.

It is also known that in the production of acrylic or 3-methacryloxypropyltrialkoxysilanes the so-called "popcorn polymerization" (US Pat. EP 0 437 653 B1 . EP 0 483 480 A1 . EP 0 708 081 A2 ) can occur, which can lead to an immediate blockage of the plant or unit. In order to minimize this risk as far as possible, the most widely used polymerization inhibitors (hereinafter also referred to as stabilizers for short) and stabilizer combinations are recommended in the prior art, depending on the process.

EP 0 437 653 B1 teaches the use of N, N'-diphenyl-p-phenylenediamine (DPPD) in the "salt process" to reduce the risk of "popcorn polymerization" of acrylic or methacryloxypropyltrialkoxysilanes.

Out EP 0 708 081 A2 such as EP 0 483 480 A1 are the use of N, N'-disubstituted p-quinonediimines and N, N'-diphenyl-p-phenylenediamine in the respective process steps in the "salt process" refer to the risk of "popcorn polymerization" of acrylic or Methacryloxypropyltrialkoxysilanen after Possibility to avoid. Furthermore, in said process, 2,6-di-tert-butyl-4-methylphenol (Jonol) can be used, in particular after the fractional distillation work-up for the subsequent stabilization of the product.

DE 102 58 982 B3 discloses a four-step process for working up a crude product fraction containing an acryloxy- or methacryloxyalkyl-group-containing organosilane using a very elaborate array of five columns and deriving the crude product from the "salt process".

EP 0 702 016 A2 teaches acrylic or methacryloxypropyltrialkoxysilanes containing tertiary amine to increase pH and improve storage stability.

The "salt process" with its individual process steps is clearly different from the alternative hydrosilylation process from the perspective of the chemist and is generally not comparable.

In the DE 38 32 621 C1 are disclosed to improve the stabilization of acrylsilanes prepared by the process of hydrosilylation of allyl methacrylate by means of trialkylsilanes in the presence of H ₂ PtCl ₆ as catalyst, the use of N, N'-disubstituted p-phenylenediamines and hindered phenols, wherein the Diamines in the distillative workup of the crude acrylic silanes stabilize the swamp and the volatile phenols stabilize the vapor phase. The technical implementation of this method provides for the addition of the stabilizers before or after completion of the synthesis steps.

EP 0 707 009 B1 discloses hydrosilylation of an allyl ester with a hydrogen silane in the presence of a homogeneous Pt (II) catalyst. Stabilizer systems used are 2,6-di-tert-butylphenol and triphenylphosphane or 2,6-di-tert-butylphenol and triethylamine or phenylphosphine or 2,6-di-tert-butylphenol alone. In carrying out this process, either a mixture of hydrogen silane, stabilizer system and Pt (II) catalyst or one of allyl ester, stabilizer system and Pt (II) catalyst initially charged, the mixture is heated and the missing component for the reaction, ie the allyl ester or the hydrogen silane added dropwise. Further, in the reaction, air is introduced into the reaction mixture.

WO 2008/017554 A1 discloses a hydrosilylation process wherein a mixture of allylmethyl methacrylate, N, N'-diphenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, an acetonic solution of H ₂ PtCl ₆ .6H ₂ O and hydrogentrimethoxysilane fed to a preheated microreactor under pressure, where reacted and worked up the product mixture by means of thin film or short path evaporator.

It was an object of the present invention to provide a further possibility for the preparation of acryloxy- and methacryloxypropyl-trialkoxysilanes by hydrosilylation of allyl acrylate or methyl methacrylate with a hydrogentrialkoxysilane in the presence of a homogeneous Pt catalyst system and using a stabilizer system; in particular, MEMO was a concern in large-scale quantities and manufacture in a suitable facility as cost-effective, safe, trouble-free and consistent and high quality.

The object has been achieved according to the features of claims 1, 2 and 13. The present subclaims, in conjunction with the independent claims, disclose preferred embodiments of the present invention.

• – die Reaktions- und die Rektifikationseinheit sowie optional die Vakuumeinheit der Produktionsanlage, wie sie beispielsweise – aber nicht ausschließlich – der idealisierten Darstellung in 1 zu entnehmen ist, mit einem Inertgas spült, bevorzugt mit getrocknetem Stickstoff, der beispielsweise mit Hilfe eines Trocknungsmittels, wie Silicagel oder durch Ausfrieren von Feuchtigkeit (Wasserfeuchte) getrocknet werden kann,
• – anschließend 2,6-Di-tert.-butyl-4-methylphenol, Allylacrylat, N,N’-Diphenyl-p-phenylendiamin und eine acetonische Lösung von H₂PtCl₆ × 6H₂O oder 2,6-Di-tert.-butyl-4-methylphenol, Allylmethacrylat, N,N’-Diphenyl-p-phenylendiamin und eine acetonische Lösung von H₂PtCl₆ × 6H₂O in den Reaktor, welcher vorzugsweise mit Rührvorrichtung, Heizung bzw. Kühlung einschließlich Temperaturmessung und -regelung und Rückflusskondensation ausgestattet ist, gibt und
• – das vorgelegte Gemisch vorzugsweise unter Rühren auf Reaktionstemperatur erhitzt,
• – anschließend Trialkoxysilan, vorzugsweise Hydrogentrimethoxysilan (TMOS), unter Zeit- und Temperaturkontrolle direkt in das vorgelegte Gemisch dosiert, d. h. die Zuführung für das Trialkoxysilan in den Reaktor ist erfindungsgemäß unterhalb der Flüssigkeitsoberfläche der Mindestfüllmenge für das Reaktionsgemisch orientiert,
• – das Reaktionsgemisch nachreagieren läßt,
• – Leichtsieder bzw. flüchtige Bestandteile, d. h. Bestandteile des Reaktionsgemischs bzw. Rohprodukts, die einen höheren Siedepunkt besitzen als das Zielprodukt, zumindest anteilig aus dem so erhaltenen Reaktions- bzw. Produktgemisch abtrennt und
• – anschließend das so erhaltene Rohprodukt in die Rektifikationseinheit überführt und destillativ aufarbeitet.

Thus, it has surprisingly been found that pure organosilanes with unsaturated organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyltrialkoxysilan advantageous by hydrosilylation of allyl acrylate or allyl methacrylate with trialkoxysilane in the presence of a homogeneous Pt (IV) catalyst and 2,6-di-tert. -butyl-4-methylphenol (Jonol) and N, N'-diphenyl-p-phenylenediamine (DPPD) as stabilizers in comparatively simple, economical, ie cost-effective, and very gentle to the product in large quantities with particularly high and consistent quality and in good Yield and selectivity can be produced by specifically carrying out the following steps in the present process:

• - The reaction and the rectification unit and optionally the vacuum unit of the production plant, as for example - but not exclusively - the idealized representation in 1 can be taken with an inert gas flushes, preferably with dried nitrogen, which can be dried, for example by means of a drying agent such as silica gel or by freezing of moisture (water moisture),
• - Then 2,6-di-tert-butyl-4-methylphenol, allyl, N, N'-diphenyl-p-phenylenediamine and an acetone solution of H ₂ PtCl ₆ × 6H ₂ O or 2,6-di-tert .-Butyl-4-methylphenol, allyl methacrylate, N, N'-diphenyl-p-phenylenediamine and an acetonic solution of H ₂ PtCl ₆ .6H ₂ O in the reactor, which is preferably equipped with stirrer, heating or cooling, including temperature measurement and regulation and reflux condensation is equipped, and
• The mixture initially heated to the reaction temperature with stirring,
• Then trialkoxysilane, preferably hydrogentrimethoxysilane (TMOS), metered directly into the initially introduced mixture under time and temperature control, ie the feed for the trialkoxysilane into the reactor is oriented below the liquid surface of the minimum fill quantity for the reaction mixture,
• - reacting the reaction mixture,
• - low boilers or volatile constituents, ie components of the reaction mixture or crude product, which have a higher boiling point than the target product, at least partially separated from the thus obtained reaction or product mixture and
• - Then transferred the crude product thus obtained in the rectification unit and worked up by distillation.

In particular, 3-methacryloxypropyltrimethoxysilane (MEMO) can thus be advantageously prepared, wherein MEMO produced according to the invention is characterized in the context of a quality test in that it remains clear when diluted with water and also no yellowing occurs.

The method according to the invention, including its preferred embodiments, can advantageously be carried out in a production plant as claimed in claim 1 and / or in the idealized representation according to FIG 1 can be seen.

In addition, the production plant specially developed for the advantageous implementation of the present method, despite comparatively low acquisition costs and low technical complexity, surprises by a largely safe and trouble-free operation.

• – eine Reaktionseinheit (1), wobei diese auf einem Reaktor (Rührkessel) (1) basiert und mit Rührvorrichtung (2) und Heizung, Kühlung, Temperaturmessung und -regelung (3) und Rückflusskondensation (7, 8, 9) und den Zuführungen (4) und (5) für Einsatzstoffe, wie Inertgas, Eduktkomponenten sowie Stabilisatoren und Katalysatorsystem, ausgestattet ist, dabei ist die Zuführung (5) unterhalb der Zuführung (4) angeordnet, sodass der Eintritt der Zuführung (5.1) in den Reaktor (1) unterhalb der Flüssigkeitsoberfläche der späteren Mindestfüllmenge für das Reaktionsgemisch (6.1) orientiert ist,
• – einer Rektifikationseinheit (16), wobei diese auf einer Rektifikationskolonne (16) basiert und mit Rührvorrichtung (17) und Heizung, Kühlung, Temperaturmessung und -regelung (18) und Rückflusskondensation (22, 23, 24) einschließlich Leichtsiederauslass (25) und zwei Bereichen mit Kolonnenpackungen (19, 20) und einer Seitenstromabnahme (26) im Mittelteil der Rektifikationskolonne (16), diese platziert oberhalb der Packung (19) und unterhalb der Packung (20), und weiter mit Kondensationseinheit mit Temperatur-/Druckmessung und -regelung (27) einschließlich Rückführung für flüchtige Bestandteile (28), d.h. Bestandteile bzw. Komponenten der vorliegenden Phase, welche einen niedrigeren Siedepunkt besitzen als das Zielprodukt, in die Rektifikationskolonne (16) oberhalb der Packung (20) und einer Austragsvorrichtung (29) für das Produkt (30) ausgestattet ist,
• – die Reaktionseinheit (1) und die Rektifikationseinheit (16) sind für die Überführung von Rohprodukt über die Einheiten (11) und (15) verbunden, wobei die Leitung (11) von der Einheit (8) ausgeht, in Leitung (15) übergeht, die in den unteren Teil der Rektifikationskolonne (16) unterhalb der Packung (19) und oberhalb der Einheiten (17) sowie (18) mündet, und
• – mindestens eine Einheit zur Druckminderung, -messung und -regelung (10) einschließlich einer damit verbundenen Einheit (13) für den Austrag flüchtiger Bestandteile bzw. Leichtsieder, wobei die Einheit (10) über die Einheiten (21) und (22) mit dem Kolonnenkopf der Rektifikationseinheit (16) sowie über Einheiten (12) und (11) mit dem Kopf (7, 8) der Reaktionseinheit (1) verbunden sind.

The subject of the present invention is thus a device - also referred to in the present specification as a production plant or plant briefly - for the preparation of pure organosilanes with unsaturated comprising organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyltrialkoxysilan by hydrosilylation

• A reaction unit ( 1 ), whereby these on a reactor (stirred tank) ( 1 ) and with stirring device ( 2 ) and heating, cooling, temperature measurement and control ( 3 ) and reflux condensation ( 7 . 8th . 9 ) and the feeders ( 4 ) and ( 5 ) for feedstocks, such as inert gas, educt components and stabilizers and catalyst system, is equipped, the feed ( 5 ) below the feeder ( 4 ) so that the entrance of the feeder ( 5.1 ) in the reactor ( 1 ) below the liquid surface of the later minimum filling quantity for the reaction mixture ( 6.1 ),
• A rectification unit ( 16 ), whereby these on a rectification column ( 16 ) and with stirring device ( 17 ) and heating, cooling, temperature measurement and control ( 18 ) and reflux condensation ( 22 . 23 . 24 ) including low boiler outlet ( 25 ) and two areas with column packs ( 19 . 20 ) and a side stream decrease ( 26 ) in the middle part of the rectification column ( 16 ), placed above the pack ( 19 ) and below the pack ( 20 ), and further with condensation unit with temperature / pressure measurement and control ( 27 ) including volatile expulsion ( 28 ), ie constituents or components of the present phase, which have a lower boiling point than the target product, in the rectification column ( 16 ) above the pack ( 20 ) and a discharge device ( 29 ) for the product ( 30 ) Is provided,
• The reaction unit ( 1 ) and the rectification unit ( 16 ) are used for the transfer of crude product through the units ( 11 ) and ( 15 ), the line ( 11 ) of the unit ( 8th ), in line ( 15 ), which enters the lower part of the rectification column ( 16 ) below the pack ( 19 ) and above the units ( 17 ) such as ( 18 ), and
• - at least one unit for pressure reduction, measurement and control ( 10 ) including an associated unit ( 13 ) for the discharge of volatile constituents or low boilers, the unit ( 10 ) about the units ( 21 ) and ( 22 ) with the column head of the rectification unit ( 16 ) as well as units ( 12 ) and ( 11 ) with the head ( 7 . 8th ) of the reaction unit ( 1 ) are connected.

The respective units or lines of the present system may also be provided with shut-off valves at required points in addition to control systems.

• – Reaktions- und Rektifikationseinheit der Produktionsanlage sowie optional den Anlagenteil zur Druckminderung mit einem Inertgas spült,
• – anschließend Allylacrylat, 2,6-Di-tert.-butyl-4-methylphenol, N,N’-Diphenyl-p-phenylendiamin und eine acetonische Lösung von H₂PtCl₆ × 6H₂O oder Allylmethacrylat, 2,6-Di-tert.-butyl-4-methylphenol, N,N’-Diphenyl-p-phenylendiamin und eine acetonische Lösung von H₂PtCl₆ × 6H₂O in den Reaktor gibt und
• – das vorgelegte Gemisch auf Reaktionstemperatur erhitzt,
• – anschließend Trialkoxysilan unter Zeit- und Temperaturkontrolle direkt in das vorgelegte Gemisch dosiert,
• – das Reaktionsgemisch nachreagieren läßt,
• – Leichtsieder zumindest anteilig aus dem so erhaltenen Reaktionsgemisch abtrennt und
• – das so erhaltene Rohprodukt in die Rektifikationseinheit überführt und destillativ aufarbeitet.

The present invention further provides a process for the preparation of pure organosilanes having unsaturated organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyltrialkoxysilan, wherein allyl acrylate or allyl methacrylate with trialkoxysilane in the presence of a homogeneous Pt (IV) catalyst and Jonol and N, N'-diphenyl -p-phenylenediamine reacted as stabilizers in a reactor and the crude product thus obtained is worked up by distillation, which is characterized by

• - Reaction and rectification unit of the production plant and optionally the plant section for pressure reduction with an inert gas flushes,
• - Allyl acrylate, 2,6-di-tert-butyl-4-methylphenol, N, N'-diphenyl-p-phenylenediamine and an acetone solution of H ₂ PtCl ₆ × 6H ₂ O or allyl methacrylate, 2,6-di tert.-butyl-4-methylphenol, N, N'-diphenyl-p-phenylenediamine and an acetone solution of H ₂ PtCl ₆ .6H ₂ O are in the reactor and
• The mixture is heated to the reaction temperature,
• - Trialkoxysilane then metered directly into the initially introduced mixture with time and temperature control,
• - reacting the reaction mixture,
• - Low-boiling components at least partially separated from the reaction mixture thus obtained and
• - The crude product thus obtained is transferred to the rectification unit and worked up by distillation.

In the process according to the invention, allyl acrylate or allyl methacrylate is preferably added to hydrogentrialkoxysilane in a molar ratio of 0.9 to 1: 1.

It is further preferred in the process according to the invention that the two stabilizers Jonol and DPPD are used in a molar ratio of 0.5 to 1:10.

It is further preferred in the process according to the invention that the Pt (IV) catalyst is used with respect to the allyl acrylate or allyl methacrylate used in a molar ratio of Pt to allyl (meth) acrylate of 0.1 to 1: 10,000. For this purpose, the Pt (IV) catalyst is used advantageously as an acetone solution of H ₂ PtCl ₆ × 6H ₂ O, wherein the content of Pt salt in the acetone is preferably 0.05 to 0.2 mol Pt per 1 liter of acetone.

Thus, in the process according to the invention, the components allyl acrylate or allyl methacrylate, 2,6-di-tert-butyl-4-methylphenol, N, N'-diphenyl-p-phenylenediamine and acetone solution of H ₂ PtCl ₆ .6H ₂ O are added preferably individually or in admixture with the reactor and the mixture initially heated to the reaction temperature while stirring.

Furthermore, in the process according to the invention, it should be emphasized that the trialkoxysilane, preferably hydrogentrimethoxysilane (TMOS), is metered directly into the initially introduced (reaction) mixture in that the trialkoxysilane metering takes place below the liquid surface of the reaction mixture and the reaction mixture is stirred.

Furthermore, it is advantageous that in the process according to the invention the trialkoxysilane dosing is carried out within a period of 5 to 115 minutes, preferably 10 to 80 minutes, more preferably 15 to 60 minutes, most preferably from 20 to 40 minutes.

Suitably, in the process according to the invention, the reaction mixture is allowed to react for a further 15 to 120 minutes, preferably for 20 to 80 minutes, more preferably for 30 to 45 minutes, at the reaction temperature after completion of the trialkoxysilane dosing in order to achieve as complete a reaction as possible.

In the process according to the invention, the reaction temperature in the (reaction) mixture is suitably adjusted by temperature control to a temperature of <90 ° C., preferably <80 ° C., particularly preferably to 70 to 80 ° C.

The pure distillation of the crude product is preferably carried out in the process according to the invention by first the crude product obtained by the reaction by means of a distillation (so-called "bridge distillation") in an overhead phase, which Acryloxalkyltrialkoxysilan-containing or Methacryloxyalkyltrialkoxysilan-containing, and a Catalyst-containing phase containing the catalyst and higher-boiling components (also called high-boiling residue), separated and the preferably taken under stirring and reduced pressure overhead of the reaction unit phase transferred to the lower part of the rectification unit and a side (current) decrease, the advantageous, as particularly gentle to the product, takes place from the middle run of the rectification column, in the pure target product, preferably pure 3-methacryloxyalkyltrimethoxysilane, purified.

Suitably, the distillation steps are carried out in the reaction unit ("bridging distillation") and in the rectification unit (pure distillation), each with stirring.

Thus, in the process according to the invention, the "bridge distillation" is preferably carried out at a bottom temperature in the reaction unit starting at approx. 70 ° C ascending to 140 ° C and a reduced pressure of 2 to 0.9 mbar, particularly preferably at approx. 1 mbar, by, wherein the head temperature for the decrease of the crude product, which is transferred to the rectification column, preferably approx. 75 ° C at approx. 1 mbar.

In carrying out the purifying distillation is carried out as part of the process according to the invention, the side (stream) decrease from the rectification column preferably at 50 ° C to 85 ° C and a reduced pressure of approx. 0.8 falling to approx. 0.5 mbar, wherein the bottom temperature in the rectification column is preferably 120 ° C to 140 ° C.

In this case, the rectification column used in the process according to the invention, cf. also unit ( 16 ) in 1 , preferably at least with stirrer ( 17 ), Heating, cooling and temperature measurement and control ( 18 ), Column packs ( 19 . 20 ), preferably with metal Sulzer LAB-EX / Mat. no. 1.4404, column head ( 22 . 23 . 24 . 25 ) and side acceptance ( 26 . 27 . 28 . 29 equipped with a unit for pressure reduction (vacuum), measurement and control ( 10 . 21 . 22 ) connected. Thus, the present process can advantageously be carried out in a production plant according to claim 1, cf. also a in 1 illustrated and preferred embodiment of such a system.

In addition, the process according to the invention can be carried out continuously or batchwise.

In general, the preparation process according to the invention is carried out as follows, cf. especially 1 :
For this purpose, the system is flushed with inert gas, in particular the units ( 1 ) 4 ) 5 ) 7 ) 8th ) 9 ) 10 ) 11 ) 15 ) 16 ) 21 ) 22 ) ( 23 ) 24 ) 26 ) 27 ) 29 ) of the plant, so that the entire system thereafter essentially free of oxygen and water. The reaction unit ( 1 ) advantageous with stirring device ( 2 ), Heating / cooling including temperature measurement and control ( 3 ) and reflux condensation ( 7 . 8th . 9 ) fitted. Subsequently, the previously weighed components allyl acrylate or allyl methacrylate, Jonol, DPPD and an acetone solution of H ₂ PtCl ₆ × 6H ₂ O, which is previously prepared by dissolving Pt (IV) salt in acetone, in the reactor, stir Mixture and heated it to reaction temperature.

Thereafter, over a defined period of time and under temperature control, trialkoxysilane is metered directly into the reaction mixture presented, ie the trialkoxysilane is metered in in particular via feed ( 5 , see. especially 5.1 ) under the liquid surface ( 6.1 ) of the reaction mixture ( 6 ), and leaves the reaction mixture for some time, preferably with stirring and temperature control, to react. Then it is separated, suitably with stirring ( 2 ) and inclusion of units ( 3 . 7 . 8th . 11 . 12 . 10 . 13 ), the low boilers or volatile constituents, ie constituents of the reaction mixture or crude product which have a higher boiling point than the target product, at least partially from the reaction or product mixture thus obtained. Subsequently, the crude product thus obtained, suitably incorporating the units ( 2 . 3 . 7 . 8th . 10 . 11 . 15 ), transferred to a rectification unit (so-called "Brückendestillation") and worked up there by distillation. A phase remaining after the distillation of the bridge in the reactor, which contains the catalyst residue and higher-boiling components, so-called high-boiling residue, can be passed through a high boiler outlet, cf. also unit ( 14 ), are removed from the reactor. The rectification unit ( 16 ) for carrying out the purifying distillation of the crude product is suitably with stirrer ( 17 ), Heating, cooling and temperature measurement and control ( 18 ), Column packs ( 19 . 20 ), preferably of the type Metall-Sulzer LAB-EX / Material No .: 1.4404, head ( 22 . 23 . 24 . 25 ) and side acceptance ( 26 . 27 . 29 ), arranged in the middle run of the rectification column, and a compound ( 21 . 22 ) to the pressure reduction unit including pressure measurement and control ( 10 ) fitted. For purifying the crude product, the bottoms are ( 15.1 ) of the rectification column is suitably stirred and heated ( 17 . 18 ), preferably under reduced pressure ( 10 ) (Vacuum), and there is a side decrease, cf. also the units ( 10 . 21 . 22 . 15.1 . 17 . 18 . 26 . 27 . 28 . 29 ), from the middle run of the rectification column under temperature and pressure control to obtain the pure target product. Volatile components can be removed from the unit ( 27 ) via line ( 28 ) or about the units ( 22 . 23 . 24 ) returned to rectification or via unity ( 25 ) such as ( 22 . 21 . 10 . 13 ) are discharged. Thus, the process according to the invention can advantageously be carried out under an inert gas atmosphere for the production of MEMO, wherein the use of allyl methacrylate and TMOS as educt component is particularly preferred.

• – Reaktions- (1) und Rektifikationseinheit (16) der Anlage einschließlich der damit verbundenen Anlagenteile sowie Leitungen einschließlich Einheit (10) mit einem getrocknetem Stickstoff Inertgas spült
• – anschließend ein vorzugsweise gemeinsam eingewogenes Gemisch aus Allylmethacrylat, Jonol, DPPD und eine acetonische Lösung von H₂PtCl₆ × 6H₂O über Zuführung (4) in den Reaktor (1) gibt, welcher vorteilhaft mit einer Rührvorrichtung (2), Heizung/ Kühlung einschließlich Temperaturmessung und -regelung (3) und Rückflusskondensation (7, 8, 9) ausgestattet ist, oder zunächst ein gemeinsam eingewogenes Gemisch aus Jonol und Allylmethacrylat über Zuführung (4) in den Reaktor (1) gibt und nachfolgend unter Rühren (2) ein gemeinsam eingewogenes Gemisch aus DPPD und einer acetonischen Lösung von H₂PtCl₆ × 6H₂O über Zuführung (4) zugibt, und
• – das vorgelegte Gemisch (6) unter Rühren auf Reaktionstemperatur (3) erhitzt,
• – anschließend Trimethoxysilan innerhalb eine definierte Zeitspanne und unter Temperaturkontrolle über Zuführung (5) unter die Flüssigkeitsoberfläche (6.1) des Reaktionsgemischs (6) dosiert,
• – das Reaktionsgemisch (6) unter Rühren nachreagieren läßt,
• – Leichtsieder zumindest anteilig von dem so erhaltenen Reaktions- bzw. Produktgemisch aus dem Reaktor (1) unter Einsatz der Einheiten (2, 3, 7, 8, 11, 12, 10, 13) abtrennt und
• – anschließend das so erhaltene Rohprodukt über die Einheiten (7, 8, 11, 15) in eine Rektifikationseinheit (16) überführt, destillativ aufarbeitet und man das Produkt (30), reines 3-Methacryloxypropyltrimethoxysilan (MEMO), über die Seitenabnahme (26), (27), (29) aus dem Mittellauf der Rektifikationskolonne (16) unter Temperatur- und Druckkontrolle gewinnt.

In particular, one can perform the inventive method for an advantageous production of MEMO so that one

• - reaction ( 1 ) and rectification unit ( 16 ) of the installation, including the associated plant components, as well as lines including unit ( 10 ) is flushed with a dried nitrogen inert gas
• Followed by a mixture of allyl methacrylate, ionol, DPPD and an acetone solution of H ₂ PtCl ₆ .6H ₂ O, preferably weighed together, via feed ( 4 ) in the reactor ( 1 ), which advantageously with a stirring device ( 2 ), Heating / cooling including temperature measurement and control ( 3 ) and reflux condensation ( 7 . 8th . 9 ), or first a jointly weighed mixture of Jonol and allyl methacrylate via feed ( 4 ) in the reactor ( 1 ) and subsequently with stirring ( 2 ) a collectively weighed mixture of DPPD and an acetone solution of H ₂ PtCl ₆ .6H ₂ O via feed ( 4 ), and
• - the mixture submitted ( 6 ) with stirring to reaction temperature ( 3 ) heated,
• - then trimethoxysilane within a defined period of time and under temperature control via supply ( 5 ) under the liquid surface ( 6.1 ) of the reaction mixture ( 6 ),
• The reaction mixture ( 6 ) is allowed to react with stirring,
• Low boilers at least proportionally from the reaction or product mixture thus obtained from the reactor ( 1 ) using the units ( 2 . 3 . 7 . 8th . 11 . 12 . 10 . 13 ) and disconnects
• - then the crude product thus obtained via the units ( 7 . 8th . 11 . 15 ) into a rectification unit ( 16 ), worked up by distillation and the product ( 30 ), pure 3-methacryloxypropyltrimethoxysilane (MEMO), via the lateral decrease ( 26 ) 27 ) 29 ) from the middle run of the rectification column ( 16 ) wins under temperature and pressure control.

Thus, in the process according to the invention, the so-called "bridging distillation" can advantageously be carried out at a bottom temperature ( 6 ) in the reaction unit ( 1 ) starting at approx. 70 ° C rising to 140 ° C and a reduced pressure of 2 to 0.9 mbar ( 1 . 8th . 10 ), particularly preferably at approx. 1 mbar, with the head temperature ( 8th ) for the removal of the crude product which enters the rectification column ( 16 . 15.1 ), preferably approx. 75 ° C at approx. 1 mbar. In carrying out the purifying distillation ( 15.1 . 16 . 27 . 30 ) leads in the context of the method according to the invention the sides (current) decrease ( 26 ) out the rectification column ( 16 ) preferably at 50 ° C to 85 ° C and a reduced pressure ( 16 . 10 . 26 . 27 ) of approx. 0.8 falling to approx. 0.5 mbar, whereby the bottom temperature ( 15.1 ) in the rectification column ( 16 ) is preferably 120 ° C to 140 ° C.

The process according to the invention can be carried out batchwise or continuously.

Likewise, the subject of the present invention is the use of a system according to the invention, cf. Claim 1 and 1 for the preparation of 3-methacryloxypropyltrimethoxysilane (MEMO) by hydrosilylation of allyl methacrylate with trimethoxysilane in the presence of a homogeneous Pt catalyst and a stabilizer system and distillative workup of the crude product, whereby the pure product ( 30 ) via a targeted page decrease ( 26 ) 27 ) 29 ), which under temperature and pressure control from the rectification column ( 16 ), wins.

Thus, by the process according to the invention in a plant according to the invention in comparatively simple, economical, d. H. cost-effective, and particularly gentle to the product, in particular producing 3-methacryloxypropyl-trimethoxysilane (MEMO) in large quantities with particularly high and consistent quality in good yield and selectivity, wherein the system according to the invention is characterized by a largely safe and trouble-free operation. Thus, MEMO produced according to the invention remains clear, in particular as part of a quality test when diluted with water, and no yellowing occurs during this process.

The following example is intended to illustrate the invention without limiting it:

Example:

Synthesis of 3-methacryloxypropyltrimethoxysilane (MEMO):

Starting Materials: 3.50 kg 13 mol N, N'-diphenyl-p-phenylenediamine (DPPD) 0.20 kg 1 mol Jonol 0.90 l 0.09 mol [Pt] H ₂ PtCl ₆ × 6H ₂ O dissolved in acetone, 369.80 kg 2930 mol allyl methacrylate 393.20 kg 3210 mol Trimethoxysilane (TMOS)

Reaction:

 [Catalyst]

• (CH ₃ O) ₃ SiH + CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH = CH ₂ CHCH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

TMOS allyl methacrylate MEMO 122.20 g / mol 126.16 g / mol 248.36 g / mol

Execution:

First, under an inert gas atmosphere (dried nitrogen), Jonol (stabilizer) and allyl methacrylate (starting material component) were charged, and then DPPD (stabilizer) and the acetone H ₂ PtCl ₆ solution (homogeneous catalyst system) were added. The batch was heated to 75 ° C with stirring. Thereafter, a total of 393.2 kg of trimethoxysilane (TMOS) (further (educt component) was added to the liquid surface of the mixture or reaction mixture introduced.) The temperature of the reaction was maintained at about 70-80 ° C. during the trimethoxysilane metering trimethoxysilane was added over a period of 40 minutes, after which the reaction mixture was held at 75 ° C for an additional 45 minutes.

After completion of the reaction, a gas chromatographic analysis of the crude product obtained was carried out according to a standard method familiar to the expert for GC analyzes, wherein helium and a "30 m HP1 column" were used as the carrier gas. The resulting gas chromatogram of the crude product had a content of 84.7% (GC area percent) of 3-methacryloxypropyltrimethoxysilane (MEMO). This crude product was worked up by distillation.

The workup was carried out under pressure and temperature control via a reaction with the part [see. 1 :( 1 ) 8th )] associated "bridge distillation" [cf. 1 :( 1 ) / ( 10 ) above ( 7 ) 11 ) 12 ) 13 ) such as ( 7 ) 11 ) 15 ) to ( 16 )] with subsequent purifying distillation [see. 1 :( 16 ) such as ( 22 ) 21 ) 10 )] via a distillation unit with overhead [cf. 1 :( 22 ) 23 ) 24 ) 25 )] and lateral acceptance [cf. 1 :( 26 ) 27 ) 28 ) 29 )] for the pure product [cf. 1 :( 30 )]. The pure product 3-methacryloxypropyltrimethoxysilane (MEMO, pure) obtained by distillation has a purity of 99.3% (GC area%) according to GC analysis.

LIST OF REFERENCE NUMBERS

1

 Reactor with reflux condensation and for "bridge distillation" (also called reaction unit for short)

2

Agitation / mixing device

3

Heating / cooling with temperature measurement and control

4

Feed for inert gas (N ₂ ) and the components allyl (meth) acrylate, Jonol, DPPD and acetonic H ₂ PtCl ₆ solution

5

Feed for trialkoxysilane and inert gas (N ₂ )

5.1

Dosing of trialkoxysilane under the liquid surface of the reaction mixture

6

Reaction mixture or crude product

6.1

Surface of the liquid reaction mixture or crude product

7

 Volatile component for reflux distillation or bridge distillation

8th

 Reflux condensation

9

 Return for condensate

10

Unit for pressure reduction (vacuum), measurement and control

11

 Volatile phase supply to units (12) and (15) (bridge distillation)

12

 Line for pressure reduction / regulation and removal of volatile components / low boilers

13

 Discharge line for volatile constituents / low boilers

14

 Discharge for residue / high boilers

14.1

 Discharge for residue / high boilers

15

 Feed for crude product in the rectification column

15.1

 column bottom

16

 Rectification unit (rectification column) for purifying distillation

17

Agitation / mixing device

18

Heating / cooling with temperature measurement and control

19

column packing

20

column packing

21

 Line for pressure reduction / regulation

22

 Line for pressure reduction / regulation and overhead distillation and discharge low boilers

23

Column head with temperature / pressure measurement and acceptance control

24

Recycling of condensed components

25

Removal of volatile components / low boilers

26

Side flow sampling under T / p control

27

Condensation unit with temperature / pressure measurement and control

28

Return of volatiles

29

product discharge

30

pure product

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0437653 B1 [0003, 0004, 0005]
• EP 0708081 A2 [0003, 0004, 0006]
• EP 0483480 A1 [0004, 0006]
• DE 10258982 B3 [0007]
• EP 0702016 A2 [0008]
• DE 3832621 C1 [0010]
• EP 0707009 B1 [0011]
• WO 2008/017554 A1 [0012]

Claims (14)

Device for the preparation of pure organosilanes with unsaturated organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyl-trialkoxysilane by hydrosilylation comprising - a reaction unit ( 1 ), whereby these on a reactor (stirred tank) ( 1 ) and with stirring device ( 2 ) and heating, cooling, temperature measurement and control ( 3 ) and reflux condensation ( 7 . 8th . 9 ) and the feeders ( 4 ) and ( 5 ) is equipped for feedstocks, while the feeder ( 5 ) below the feeder ( 4 ) so that the entrance of the feeder ( 5.1 ) in the reactor ( 1 ) below the liquid surface of the later minimum filling quantity for reaction mixture ( 6.1 ), - a rectification unit ( 16 ), whereby these on a rectification column ( 16 ) and with stirring device ( 17 ) and heating, cooling, temperature measurement and control ( 18 ) and reflux condensation ( 22 . 23 . 24 ) including low boiler outlet ( 25 ) and two areas with column packs ( 19 . 20 ) and a side stream decrease ( 26 ) in the middle part of the rectification column ( 16 ), placed above the pack ( 19 ) and below the pack ( 20 ), and further with condensation unit with temperature / pressure measurement and control ( 27 ) including volatile expulsion ( 28 ) in the rectification column ( 16 ) above the pack ( 20 ) and a discharge device ( 29 ) for product ( 30 ), - the reaction unit ( 1 ) and the rectification unit ( 16 ) are used for the transfer of crude product through the units ( 11 ) and ( 15 ), the line ( 11 ) of the unit ( 8th ), in line ( 15 ), which enters the lower part of the rectification column ( 16 ) below the pack ( 19 ) and above the units ( 17 ) such as ( 18 ), and - at least one unit for pressure reduction, measurement and control ( 10 ) including an associated unit ( 13 ) for the discharge of volatile constituents or low boilers, the unit ( 10 ) about the units ( 21 ) and ( 22 ) with the column head of the rectification unit ( 16 ) as well as units ( 12 ) and ( 11 ) with the head ( 7 . 8th ) of the reaction unit ( 1 ) are connected. A process for the preparation of pure organosilanes having unsaturated organic radicals from the series Acryloxyalkyl- or Methacryloxyalkyl-trialkoxysilane, wherein allyl acrylate or allyl methacrylate with trialkoxysilane in the presence of a homogeneous Pt (IV) catalyst and Jonol and N, N'-diphenyl-p-phenylenediamine as Stabilizers implemented in a reactor and the crude product thereby obtained is worked up by distillation, characterized in that - rinsing reaction and rectification unit of the production plant and optionally the plant part for pressure reduction with an inert gas, - then allyl acrylate, 2,6-di-tert. butyl-4-methylphenol, N, N'-diphenyl-p-phenylenediamine and an acetone solution of H ₂ PtCl ₆ × 6H ₂ O or allyl methacrylate, 2,6-di-tert-butyl-4-methylphenol, N, Add N'-diphenyl-p-phenylenediamine and an acetone solution of H ₂ PtCl ₆ .6H ₂ O into the reactor; and - heat the initially charged mixture to the reaction temperature, - connect - Trialkoxysilane metered directly into the initially introduced mixture with time and temperature control, - the reaction mixture can be allowed to react, - low-boiling components are at least partly separated off from the reaction mixture thus obtained and - subsequently the crude product thus obtained is transferred to the rectification unit and worked up by distillation. A method according to claim 2, characterized in that the components allyl acrylate or allyl methacrylate, 2,6-di-tert-butyl-4-methylphenol, N, N'-diphenyl-p-phenylenediamine and acetone solution of H ₂ PtCl ₆ × 6H ₂ O singly or in a mixture in the reactor and the mixture initially stirred during heating to reaction temperature. Process according to Claim 2 or 3, characterized in that the trialkoxysilane, preferably hydrogentrimethoxysilane (TMOS), is metered directly into the initially charged (reaction) mixture by passing the trialkoxysilane metering under the liquid surface of the reaction mixture and stirring the reaction mixture. A method according to any one of claims 2 to 4, characterized in that one carries out the Trialkoxysilandosierung within a period of 5 to 115 minutes. A method according to any one of claims 2 to 5, characterized in that the reaction mixture after completion of Trialkoxysilandosierung another 15 to 120 minutes keeps at temperature and allowed to react. Method according to at least one of claims 2 to 6, characterized in that adjusting the reaction temperature in the reaction mixture by controlling the temperature to a temperature of <90 ° C. Process according to claims 2 to 7, characterized in that the pure distillation of the crude product is carried out by first the crude product obtained after the reaction by means of a distillation in an overhead phase which Acryloxalkyltrialkoxysilan-containing or Methacryloxyalkyltrialkoxysilan-containing, and separating a catalyst-containing phase containing the catalyst and higher-boiling components, transferring the overhead phase into the rectification unit and recovering the pure target product by taking a side draw from the middle run of the rectification column. Method according to one of claims 2 to 8, characterized in that one carries out the distillation steps in the reaction unit ("Brückendestillation") and in the rectification unit (pure distillation) each with stirring. Method according to one of claims 2 to 9, characterized in that one carries out the process under an inert gas atmosphere. Method according to one of claims 2 to 10, characterized in that one carries out the process continuously or discontinuously. Method according to one of claims 2 to 11, characterized in that one carries out the method in a plant according to claim 1. Process according to at least one of the preceding claims, characterized in that - reaction ( 1 ) and rectification unit ( 16 ) of the installation, including the associated plant components, as well as lines including unit ( 10 ) is flushed with a dried nitrogen inert gas - then a preferably weighed together mixture of allyl methacrylate, Jonol, DPPD and an acetone solution of H ₂ PtCl ₆ × 6H ₂ O via feed ( 4 ) in the reactor ( 1 ), which advantageously with a stirring device ( 2 ), Heating / cooling including temperature measurement and control ( 3 ) and reflux condensation ( 7 . 8th . 9 ), or first a jointly weighed mixture of Jonol and allyl methacrylate via feed ( 4 ) in the reactor ( 1 ) and subsequently with stirring ( 2 ) a collectively weighed mixture of DPPD and an acetone solution of H ₂ PtCl ₆ .6H ₂ O via feed ( 4 ), and - the mixture submitted ( 6 ) with stirring to reaction temperature ( 3 ), then trimethoxysilane within a defined period of time and under temperature control via feed ( 5 ) under the liquid surface ( 6.1 ) of the reaction mixture ( 6 ), - the reaction mixture ( 6 ) can be postreacted with stirring, - low boilers, at least proportionally, from the reaction or product mixture thus obtained from the reactor ( 1 ) using the units ( 2 . 3 . 7 . 8th . 11 . 12 . 10 . 13 ) and - then the crude product thus obtained via the units ( 7 . 8th . 11 . 15 ) into a rectification unit ( 16 ), worked up by distillation and the product ( 30 ), pure 3-methacryloxypropyltrimethoxysilane (MEMO), via the lateral decrease ( 26 ) 27 ) 29 ) from the middle run of the rectification column ( 16 ) wins under temperature and pressure control. Use of a plant according to claim 1 for the preparation of 3-methacryloxypropyltrimethoxysilane (MEMO) by hydrosilylation of allyl methacrylate with trimethoxysilane in the presence of a homogeneous Pt catalyst and a stabilizer system and distillative work-up of the crude product, whereby the pure product ( 30 ) via a targeted page decrease ( 26 ) 27 ) 29 ), which under temperature and pressure control from the rectification column ( 16 ), wins.

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