KR100528498B1 - A distillation and dropping apparatus - Google Patents

Abstract

The present invention relates to a hydrosilylation reaction method using a distillation-dropping reactor, and more specifically, it can support the cooler 30 and the compound (A) to be reacted, After distillation by heating, the cooled compound (A ') is introduced into the collector (20), and a mixture of compound (B) and compound (A'), which is added and injected into compound (A) in the reaction vessel (10), is introduced. A reaction vessel including an inlet port 60 connected to one end of the passage-type connecting portion to be connected therein, and connected to the opposite end of the inlet port 60 to support compound (B) and compound (A ′) to be reacted. And a coke 40 positioned between the collector 20 and the passage-type connection of the reaction vessel 10 as flow control means, so that distillation-dropping can occur simultaneously, in particular, in the hydrosilylation reaction. Significantly reduce the amount of catalyst used In addition, it is possible to reduce the amount of side reactions to produce a high conversion and to obtain a high yield of the target product, and relates to a hydrosilylation reaction method using a distillation-dropping reaction apparatus that can visually confirm the progress of the reaction.

Description

Hydrosilylation method using a distillation-dropping reactor {A distillation and dropping apparatus}

The present invention relates to a hydrosilylation reaction method using a distillation-dropping reactor, and more specifically, it can support the cooler 30 and the compound (A) to be reacted, After distillation by heating, the cooled compound (A ') is introduced into the collector (20), and a mixture of compound (B) and compound (A'), which is added and injected into compound (A) in the reaction vessel (10), is introduced. A reaction vessel including an inlet port 60 connected to one end of the passage-type connecting portion to be connected therein, and connected to the opposite end of the inlet port 60 to support compound (B) and compound (A ′) to be reacted. And a coke 40 positioned between the collector 20 and the passage-type connection of the reaction vessel 10 as flow control means, so that distillation-dropping can occur simultaneously, in particular, in the hydrosilylation reaction. Significantly reduce the amount of catalyst used In addition, it is possible to reduce the amount of side reactions to produce a high conversion and to obtain a high yield of the target product, and relates to a hydrosilylation reaction method using a distillation-dropping reaction apparatus that can visually confirm the progress of the reaction.

In general, hydrosilylation reactions are one of the most basic and precise methods for the preparation of organosilane compounds [Marciniec, B .; Gulinski, J .; Urbaniak, W .; Korenetka, ZW In Comprehensive Handbook on Hydrosilylation, 1990]. The discovery of hexachloroplatinic acid, known as a highly effective catalyst by Johh L. Speier of Dow Corning in 1957, was the starting point for a wide variety of applications of catalytic hydrosilylation reactions. The Karstedt's catalyst Pt ₂ {[(CH ₂ = CH ₂ ) Me ₂ Si] ₂ } ₃ , patented in 1973, is very attractive and widely used commercially [US Pat. No. 3,775,452, USA Patent 4,288,345, US Patent 4,421,903, US Patent 5,908,951]. In the case of using this catalyst, it is known that the reaction is almost completed when the catalyst level is maintained at about 5 to 50 ppm, but more sophisticated reaction conditions become an important issue (US Pat. No. 6,177,583). Pt / C catalysts are also widely applied as hydrosilylation catalysts, but have a disadvantage in that the reactivity is somewhat deteriorated. However, Pt / C catalysts are heterogeneous catalysts and thus can be applied to a continuous process (US Pat. No. 6,177,584, US Patent 6,100,408).

Hydrosilylation catalysts and process development are very important for the economic production of organosilane compounds. In particular, obtaining 3-chloropropyltrichlorosilane by addition reaction of allyl chloride and trichlorosilane is very important in preparing organosilane compounds [Deshchler, U .; Kleinshcmit, P .; Panster, P. Angew. Chem. Int. Ed. Engl. 1986, 25, 236.

In particular, the organosilane is a substance added when using a silica reinforcing agent and serves to improve various physical properties. In other words, when applied to the tread of the tire, it can save energy by reducing the rolling resistance, and it is possible to manufacture a safer tire because it has a feature of shortening the braking distance on a wet road or an ice road [a) Bayer, JT Rubber World 1998, 38 (b) Tisel, A. Rubber & Plastics News, 2001, 11 (c) Araki, S .; Yanagisawa, K. US Pat. No. 6,242,516]. Degussa Si-69 is well known as a commercial example of such a material. In order to prepare the silane coupling agent as described above, a hydrosilylation process is essential, but it is known that by-products such as the following Scheme 1 occur in this reaction.

It is known that when the platinum catalyst is subjected to hydrosilylation, platinum is converted into colloidal particles during the reaction, thereby decreasing the activity [Brook, M. A .; Ketelson, H. A .; LaRonde, F. J .; Pelton, R. Inorg. Chim Acata 1997, 264, 125]. Therefore, in the hydrosilylation reaction, it is very important to suppress the by-products as much as possible and to prevent the catalyst from being converted into inactive species, especially when hydrosilylation of allyl chloride with trichlorosilane.

Karstedt catalyst, which is a homogeneous catalyst, is known as a very active catalyst in hydrosilylation reaction, but has a disadvantage in that the selectivity is extremely low in a closed high pressure reactor and inactive in an atmospheric pressure reactor.

Accordingly, the inventors of the present invention have made efforts to solve the above problems, and when the reaction apparatus, the collector, the cooler, and the collector of the reactor are equipped with a coke to control the flow rate of the compound flowing into the reaction vessel is developed and used. The present invention has been found to solve the problem of low selectivity caused by the use of a closed high pressure reactor, and the problem of reduced activity caused by using an atmospheric pressure reactor, and also to significantly reduce the amount of catalyst used. It was.

Accordingly, an object of the present invention is to provide a novel distillation-dropping reaction apparatus having improved reactivity, which can maintain better selectivity and activity of a catalyst when applied to a hydrosilylation reaction.

It is another object of the present invention to provide a hydrosilylation reaction method using the novel distillation-dropping reactor.

The present invention is a reaction vessel (10) carrying a compound (A); A cooler 30 connected to an upper side of the reaction vessel 10; A collector (20) on which the compound (A ') cooled in the cooler (30) is dropped, and the compound (B) is supported; Hydrosilylation reaction is provided with a distillation-dropping reaction apparatus 100 composed of an inlet port 60 equipped with a coke 40 as a flow control means, while connecting the collector 20 and the reaction vessel 10 in communication. Performing, but distilling by heating the allyl chloride and the catalyst supported as the compound (A) in the reaction vessel 10 to 40 ~ 120 ℃; Allyl chloride (compound (A ')) cooled in the cooler (30) is collected dropwise in the collector 20, and mixed with trichlorosilane which is a compound (B) already added to the collector (20); The mixture (C) in which the allyl chloride of the compound (A ') and the trichlorosilane of the compound (B) is mixed is carried out through the inlet 60 at a rate of 2 to 4 ml / min per one mole of allyl chloride. It is introduced into the step is made of a step of reacting with each other, the reaction is characterized in that the trichlorosilane and allyl chloride distillate in the collector 20 takes place continuously.

The present invention will be described in detail as follows.

The present invention may support the cooler 30, the compound (A) to be reacted, the cooled compound (A ') is distilled by heating of the reaction vessel 10 is introduced into the collector 20 , A reaction vessel including an inlet port 60 connected to one end of a passage-type connecting portion into which a mixture of compound (B) and compound (A ′) into which the compound (A) is added and injected into the reaction vessel (10) is introduced; And a collector connected to the opposite end of the inlet 60 and capable of supporting the compound (B) and the compound (A ') to be reacted, and the collector 20 and the reaction vessel 10 as flow control means. The distillation-dropping can occur simultaneously by being composed of the coke 40 located between the passage-connected portions. In particular, when applied to the hydrosilylation reaction, the amount of side reactions can be reduced while the amount of the catalyst is dramatically reduced. High conversion yield The present invention relates to a distillation-dropping reactor capable of obtaining a stack and visually confirming whether the reaction proceeds.

When the present invention is described in detail based on the accompanying drawings and the hydrosilylation reaction when described as follows.

First, the reaction apparatus 100 of the present invention includes a reaction vessel 10. The reaction vessel 10 is connected to the cooler 30, may support allyl chloride and catalyst, and is cooled after distillation as the reaction vessel 10 is heated to enter the collector 20. The heating temperature of the reaction vessel 10 as described above may be heated to 40 to 120 ℃, in particular 60 to 90 ℃ is suitable, the reaction rate is lower when the heating temperature is less than 40 ℃, a lot of by-products above 120 ℃ Is generated.

Compound A supported on the reaction vessel 10 generally uses a slightly higher boiling point. In the case of hydrosilylation, the boiling point of allyl chloride is 46 ° C. The amount of use varies depending on the type of catalyst used. When the Karstedt catalyst is applied, 0.1 to 10 ppm can be used, and even 1 ppm can be used to obtain sufficient conversion and yield. 1% Pt / C may be used in the range of 1 to 100 ppm and at least 10 ppm should be used. 1% Pt / C shows nearly similar results when using a conventional open reactor or a distillation-dropping reactor according to the present invention. This phenomenon is presumed to be due to the fact that 1% Pt / C has no catalyst species to deteriorate because the catalyst is already adsorbed to carbon in colloidal particles. Karstedt's catalyst, on the other hand, is very different because it is believed that the presence of excess trichlorosilane causes the platinum atoms to coalesce into the colloid.

Compound B having a relatively lower boiling point than Compound A added to the reaction vessel 10 is added to the collector 20, and in the case of hydrosilylation reaction, trichlorosilane having a boiling point of 34 ° C. is added. The mixture of allyl chloride and the catalyst is distilled from the reaction vessel (10), cooled, introduced into the collector (20), mixed with trichlorosilane, and the flow rate is controlled by coke into the reaction vessel (10) along the inlet (60). It is continuously added and injected. The flow rate is adjusted differently according to the type of each compound, and when applied to hydrosilylation, it is about 5 to 50 ml / min per mole of allyl chloride added to the reaction vessel 10, and 10 to 20 ml / min has a desirable effect. In this case, if the flow rate is less than 5 ml / min, the solution inside the reaction vessel 10 located at the top of the reactor 100 overflows, and if the flow rate exceeds 50 ml / min, the dropping effect does not occur. There is a problem. Properly regulated flow rate is generated with the effect of raising the temperature of the bottom reaction vessel 10, in the case of the conventional open reactor temperature of the contents of 36 ℃ or distillation-dropping reaction apparatus 100 according to the present invention When introduced, since the temperature of the reactant may be increased to 40 ° C., the reactivity is further improved.

The present invention develops a new and unique distillation-dropping reactor that can dramatically increase the activity and selectivity of catalysts in hydrosilylation reactions, thereby reducing the catalyst usage to 1-10 ppm when using the existing Karsteds catalyst. In addition, 3-chloropropyltrichlorosilane, which is a key material in preparing an organosilane compound, can be obtained purely.

One of the features of the distillation-dropping reactor of the present invention is that as the reaction proceeds, the amount of solution in the upper collector 20 gradually decreases over time, and the amount of the collected solution disappears when the reaction is almost completed. By observing the progress of the reaction can be seen.

By introducing the distillation-dropping reaction apparatus 100 according to the present invention, the selectivity and the conversion rate are remarkably improved as compared with the conventionally used closed reactor or atmospheric pressure reactor. That is, by dropping trichlorosilane, the contact time of the catalyst and trichlorosilane is reduced, so that the H / Cl exchange reaction is reduced and the low boiling point trichlorosilane is relatively small in the lower reaction vessel 10. The conversion is improved because the reaction can proceed at temperature.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1 Hydrosilylation Reaction in the Distillation-Drop Reactor of the Present Invention

42 ml (0.5 mol) of allyl chloride and 5 µl (0.1 mol, Aldrich) of Karstedt's catalyst were loaded in the reaction vessel 10 of a 100 ml distillation-dropping reactor, and trichlorosilane was placed in the upper collector 20. 50 mL (0.5 mol) was added by syringe, and the bottom reaction vessel 10 was put in an 80 ° C oil bath. At this time, the coke 40 was adjusted so that trichlorosilane was introduced into the reaction vessel 10 at a rate of 1 to 2 ml / min. After the reaction, the mixture was cooled to room temperature to obtain a product in the bottom reaction vessel (10). The product weighed 97 g and obtained a purity of 95.2% and a yield of 86.2%.

Example 2 Hydrosilylation Reaction in the Distillation-Drop Reactor of the Present Invention

The hydrosilylation reaction was applied in the same manner as in Example 1, and the type and amount of catalyst used were shown in Table 1 below.

Substrate / Catalyst Hours (h) % Conversion CPTCS ³⁾ (%) PTCS ⁴⁾ (%) % Selectivity Example 1 ¹⁾ 1,000,000 18 95.8 86.2 1.2 90 Example 2 ²⁾ 100,000 15 82.2 77.6 2 94.4 1) Karstedt Catalyst 2) 1% Pt / C 3) 3-chloropropyltrichlorosilane 4) 3-propyltrichlorosilane

Comparative Examples 1-3: Hydrosilylation Reaction in Closed Reactor

In a 50 ml sealed reactor, 8.4 ml (0.1 mol) of allyl chloride, 10 ml (0.1 mol) of trichlorosilane and 10.64 mg (0.04 mmol) of catalyst PtCl ₂ were added and reacted at 80 ° C. for 2 hours, followed by cooling to room temperature. In a closed reactor, the hydrosilylation reaction is represented by the following Scheme 2. The weight of the contents is 21 g and analyzed by GC is shown in Table 2 below. In the same manner, using 0.2 g of 1% Pt / C and 10 µl of Karstedt's catalyst, the results are shown in Table 2 below.

catalyst Substrate / Catalyst % Conversion CPTCS (%) PTCS (%) Comparative Example 1 PtCl ₂ 2,500 75.8 61.6 14.3 Comparative Example 2 1% Pt / C 10,000 79 63.4 15 Comparative Example 3 Karstedt 100,000 78 56.4 22.7  The GC column used Supelco 60 m x 0.32 μm.

Comparative Examples 4 to 5: hydrosilylation reaction in an open reactor

A 100 mL three-necked reactor was equipped with a cooler and a thermometer, and 42 ml (0.5 mol) of allyl chloride, 5 µl of Karstedt's catalyst (0.1 mol, Aldrich), and 50 ml (0.5 mol) of trichlorosilane were added at 80 캜. Reaction at After the reaction for 25 hours the temperature of the contents was 56 ℃ and cooled to room temperature to give a 99 g solution.

Analysis of the solution gave a conversion of 75.2% and a yield of 70%. The conversion and yields are shown in Table 3 by the same procedure using 1% Pt / C 10 mg.

catalyst Substrate / Catalyst Hours (h) % Conversion CPTCS (%) PTCS (%) % Selectivity Comparative Example 4 1% Pt / C 100,000 15 85 78 2.4 92 Comparative Example 5 Karstedt 1,000,000 25 75.2 70 0.2 93.1

As described above, when the distillation-dropping reactor according to the present invention is applied to the hydrosilylation reaction, 3-chloropropyltrichloro, which is the main product even at 1 ppm when the Karstedt catalyst is generally known to be most effective, is used. Lossilane can be obtained in a yield of 86.2%. When the 3-chloropropyltrichlorosilane prepared as described above is used for the production of Si-69, a silane coupler for a tire, there is an excellent economic effect.

As described above, the hydrosilylation reaction method using the distillation-dropping reaction apparatus according to the present invention can control the dropping flow rate, it is possible to perform an efficient distillation and dropping reaction because the progress of the reaction is visually revealed, Applying this to hydrosilylation can minimize the by-products and improve the conversion rate.

That is, even if the same catalyst is used, the reactivity and selectivity are remarkably improved by using the distillation-dropping reactor according to the present invention. There is an effect that can be given dramatically.

1 is a schematic view showing one embodiment of the distillation-dropping reactor according to the present invention.

[Description of Symbols for Main Parts of Drawing]

100: reactor 10: reaction vessel

20: collector 30: cooler

40: coke 60: inlet

Claims (2)

delete A reaction vessel (10) carrying the compound (A); A cooler 30 connected to an upper side of the reaction vessel 10; A collector (20) on which the compound (A ') cooled in the cooler (30) is dropped, and the compound (B) is supported; Hydrosilylation reaction is provided with a distillation-dropping reaction apparatus 100 composed of an inlet port 60 equipped with a coke 40 as a flow control means, while connecting the collector 20 and the reaction vessel 10 in communication. But do Distilling the allyl chloride and the catalyst supported as compound (A) in the reaction vessel (10) by heating to 40 to 120 ℃; Allyl chloride (compound (A ')) cooled in the cooler (30) is collected dropwise in the collector 20, and mixed with trichlorosilane which is a compound (B) already added to the collector (20); The mixture (C) in which the allyl chloride of the compound (A ') and the trichlorosilane of the compound (B) is mixed is carried out through the inlet 60 at a rate of 2 to 4 ml / min per one mole of allyl chloride. ) Flows into and reacts with each other, The reaction is a hydrosilylation reaction method using a distillation-dropping reactor, characterized in that continuously occurs until the trichlorosilane and allyl chloride distillate in the collector 20 disappears.