JP2002003529A - Method for producing silyl group-containing compound using supercritical carbon dioxide as reaction solvent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an effective process for hydrosilylation reaction using a harmless reaction solvent. SOLUTION: A method for producing a silyl group-containing compound is characterized by reacting (A) a hydrogenated silicon compound having specified structure with (B) an alkenyl group-containing compound in the presence of supercritical carbon dioxide using a group VIII metal-containing complex and/or metal salt of the same as a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrosilyl compound comprising a specific silicon hydride compound (hydrolyzable silane compound) and a compound having an alkenyl group (carbon-carbon unsaturated bond) using supercritical carbon dioxide as a reaction solvent. The present invention relates to a method for producing a silyl group-containing compound capable of effectively proceeding a chemical reaction.

[0002]

2. Description of the Related Art A reaction in which a silicon hydride compound having a Si--H group is added to an alkenyl group (carbon-carbon unsaturated bond) is generally called a hydrosilylation reaction. In the hydrosilylation reaction, a catalyst containing a Group VIII metal is effective in promoting the reaction, and many catalysts containing platinum in particular have high performance.

It is important to introduce a hydrolyzable silyl group such as a methoxysilyl group into a compound having an alkenyl group by a hydrosilylation reaction. By performing a hydrosilylation reaction between a compound having an alkenyl group (carbon-carbon unsaturated bond) and a compound represented by the general formula (1), a compound having a terminal having a hydrolyzable silyl group or the like can be obtained. it can. The hydrolyzable silyl group (Si-X) is a group that gives a silanol group (Si-OH) by a hydrolysis reaction. A siloxane bond (Si-O-Si) is provided by a condensation reaction (silanol condensation) between the hydrolyzable silyl group (Si-X) and the silanol group (Si-OH). It is possible to form a crosslinked product by increasing the molecular weight by a silanol condensation reaction between compounds. Therefore, a compound having a hydrolyzable silyl group at its terminal gives a crosslinked product by a hydrolysis reaction of the silyl group due to moisture in the air and a subsequent silanol condensation reaction with other compound molecules (Japanese Patent Application Laid-Open No. Sho 63). -6041). Such crosslinkable compounds include various sealing agents, adhesives, paints, coating agents,
It is useful as a raw material for molded articles and the like.

The above-mentioned hydrosilylation reaction has been industrialized for a long time, and has been widely used for producing polyorganosiloxane. The conventional reaction method is a very simple one.
The stirring reaction is performed at a temperature of about 0 ° C.

However, when the raw material used or the substance obtained by the hydrosilylation reaction is a high-viscosity liquid, stirring is difficult, so that a large amount of a plasticizer or a solvent is added or the reaction temperature is increased. It was necessary to lower the viscosity and promote the reaction.

A major problem known in the technical field utilizing this reaction is that the rate of the hydrosilylation reaction is reduced during the reaction due to the decrease in the activity of the catalyst during the reaction or the like. Is stopped. In particular, when the compound having an alkenyl group is a polymer compound, the viscosity of the reaction solution is extremely high, and a sufficient mixing state cannot be obtained by mixing with stirring, which may cause a reduction in the reaction rate.

[0007] The adverse effects of a decrease in the reaction rate and instability not only increase the time required for the reaction, but also relatively increase the ratio of side reactions, thereby reducing the selectivity of the desired hydrosilylation reaction. It also leads to things.

Although it is possible to accelerate the reaction by increasing the amount of the expensive Group VIII metal catalyst, it is difficult to solve the instability of the reaction rate, and it is difficult for the reaction product to remain in the reaction product. In some cases, the amount of catalyst to be used increases, which is not preferable for subsequent use. In particular, in the case of a hydrosilylation reaction of a polymer compound, it is difficult to remove black powder derived from the catalyst, so that there is a problem that the product becomes black and turbid.

It is also known to add oxygen in order to maintain the activity of the catalyst and promote the hydrosilylation reaction (Japanese Patent Laid-Open Nos. 5-213972 and 8-28333).
9). Further, there is a method of adding a substance for accelerating the hydrosilylation reaction. Effective substances that promote the reaction are also described in acetylene alcohols (JP-A-8-23156).
3), unsaturated secondary and tertiary alcohols (Japanese Unexamined Patent Publication No.
291181), tertiary alcohols (JP-A-8-333)
373), unsaturated ketones (JP-A-8-20883)
8), ene-unsaturated compounds (JP-A-9-2528)
1), a method of adding a sulfur compound (JP-A-11-080167) and the like are known. However, even if these additives are added, if the reaction system is a high-viscosity substance, oxygen and additives can be supplied to every corner of the reaction system only by a stirring method used in a normal process. Have difficulty.

The alkenyl group-containing polymer compound has a higher viscosity than the alkenyl group-containing low molecular weight compound, and has a low concentration of the alkenyl group with respect to the whole amount, so that the progress of the hydrosilylation reaction is slow. In the prior art, in order to solve this problem, a method of using a large amount of a solvent or a plasticizer as a solvent or increasing the temperature of the reaction solution to lower the viscosity of the reaction solution has been adopted. However, when a large amount of a solvent or a plasticizer is used, a cost for separating the solvent or the plasticizer after the completion of the reaction is required, and if the recovery of the solvent or the plasticizer is poor, an environmental load is increased. As for the method of increasing the reaction temperature, the heat cost is wasted, and there is a limit from the viewpoint of the heat resistance of the organic compound.

[0011] Supercritical fluids have promising potential for extraction and purification processes because they have a dissolving power near liquid and a diffusion coefficient close to gas. In particular, since supercritical carbon dioxide is easy to separate from products when returned to atmospheric pressure and is harmless, it has been put to practical use as a process for extracting and purifying fragrances, coffee and the like.

In recent years, a technique using a supercritical fluid as a reaction solvent has been reported at the research level (PG Jessop).
et. al, 1999, 99, 475), few processes have been put to practical use. In particular, when the reactant is a high molecular compound, the solubility of the high molecular compound in supercritical carbon dioxide is low, and therefore, there is little study as a reaction solvent. Further, it has been reported that a hydrosilylation reaction proceeds between supercritical carbon dioxide and a silicon hydride compound under conditions of 90 ° C. and 200 atm using a ruthenium-based catalyst (P.
G. FIG. Jessop et. al, 1999, 99, 47
5) There is no description of a hydrosilylation reaction between silicon hydride and another compound having an alkenyl group using supercritical carbon dioxide as a solvent.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to facilitate the mass transfer of a reactant in a hydrosilylation reaction, to promote the reaction effectively, and to make the reaction harmless and easy to separate from the target substance. It is to provide a method using a solvent.

[0014]

Means for Solving the Problems As a result of diligent studies conducted by the present inventors, the use of supercritical carbon dioxide as a reaction solvent facilitates the mass transfer of the reactants in the hydrosilylation reaction, and promotes the reaction. They have found that they can proceed effectively and completed the present invention.

That is, the present invention relates to (A) a compound represented by the general formula (1): R _a X _b H _c Si (1) wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl group or a triorganosiloxy group. When a is 2 or more, R may be the same or different, and X is a halogen, an alkoxy group, an acyloxy group or a hydroxyl group, and when b is 2 or more, X may be the same or different. a and b are integers of 0 to 3; c is an integer of 1 to 3; a + b + c = 4); and (B) a compound containing an alkenyl group, A complex containing a Group 8 metal in the presence of carbon dioxide and / or
Alternatively, the present invention relates to a method for producing a silyl group-containing compound, wherein a hydrosilylation reaction is performed using a metal salt as a catalyst.

In a preferred embodiment, the present invention relates to the method for producing a silyl group-containing compound described above, wherein the temperature of the supercritical carbon dioxide is 35 ° C. or more and 120 ° C. or less, and the pressure is 8 MPa or more.

As a further preferred embodiment, the present invention relates to the method for producing a silyl group-containing compound according to any one of the above, wherein a substance having a dielectric constant of 3 or less is used as a cosolvent.

In a further preferred embodiment, the present invention relates to the method for producing a silyl group-containing compound according to any one of the above, wherein the cosolvent is hexane.

In a further preferred embodiment, the complex and / or metal salt containing a Group VIII metal is chloroplatinic acid, a complex compound of chloroplatinic acid with an alcohol, aldehyde or ketone, a platinum-olefin complex, a platinum-olefin complex, One or two selected from a vinylsiloxane complex, a platinum-phosphine complex, a platinum-phosphite complex, a ruthenium-phosphine complex, a ruthenium-phosphite complex, and a solution in which these substances are dissolved in a solvent that does not react with these substances;
A method for producing a silyl group-containing compound according to any one of the above, which is a mixture of at least one kind.

In a further preferred embodiment, the complex and / or metal salt containing a Group VIII metal is chloroplatinic acid, a complex compound of chloroplatinic acid with an alcohol, aldehyde or ketone, a platinum-olefin complex, a platinum-olefin complex, One or two selected from a vinylsiloxane complex, a platinum-phosphine complex, a platinum-phosphite complex, a ruthenium-phosphine complex, a ruthenium-phosphite complex, and a solution in which these substances are dissolved in a solvent that does not react with these substances;
The present invention relates to the method for producing a silyl group-containing compound according to any one of the above, which is a colloidal solution of a complex containing a Group VIII metal and / or a metal salt obtained by reacting a mixture of at least two species with silicon hydride.

In a more preferred embodiment, (A) the silicon hydride compound represented by the general formula (1) is selected from methyldichlorosilane, dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, and triethoxysilane. The present invention relates to the method for producing a silyl group-containing compound according to any one of the above, which is one or more compounds.

In a further preferred embodiment, the amount of the catalyst for hydrosilylation reaction is such that the number of moles of the eighth metal is 10 ^-6 times to 10 ^-3 times the number of moles of the alkenyl group in the compound (B). The present invention relates to the method for producing a silyl group-containing compound according to any one of the above, which is a double value.

In a further preferred embodiment, (B) the compound containing an alkenyl group is one or more organic compounds selected from polyisobutylene, polyacryl, polybutene, hydrogenated polybutene, polypropylene oxide and polyorganosiloxane. The present invention relates to the method for producing a silyl group-containing compound according to any one of the above, which is a polymer.

In a further preferred embodiment, the compound (D) containing an alkenyl group has a molecular weight of 500 to 300.
The present invention relates to the method for producing a silyl group-containing compound according to any one of the above, which is an organic polymer having an average alkenyl group of 1.0 or more in one molecule.

As a further preferred embodiment, the present invention relates to any one of the above-mentioned methods for producing a silyl group-containing compound in which oxygen is present in a reaction vessel.

In a further preferred embodiment, the number of moles of oxygen in the reaction vessel is 5% with respect to the number of moles of alkenyl groups.
The present invention relates to the method for producing a silyl group-containing compound according to any of the above.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments for carrying out the present invention will be described in detail.

The carbon dioxide used in the present invention is a carbon dioxide at a temperature (31.1 ° C.) exceeding the critical point and a pressure (7.38 MPa), and is generally called supercritical carbon dioxide. The supercritical carbon dioxide used in the present invention can be used as long as it has a temperature and a pressure higher than the critical point. However, if the reaction temperature is low, the reaction rate of the hydrosilylation reaction becomes slow. Therefore, the reaction temperature is preferably 35 ° C. or more. Conversely, if the temperature is too high, the compound having an alkenyl group may be thermally decomposed, and carbon dioxide and the silicon hydride compound may directly react as described above (PG Jessop e).
t. al, 1999, 99, 475), the reaction is preferably performed at 120 ° C. or lower, more preferably at 90 ° C. or lower. On the other hand, if the pressure is too low, the density of the supercritical carbon dioxide is small and the function as a solvent is weakened. Therefore, the pressure is preferably 8 MPa or more.

In the present invention, supercritical carbon dioxide mainly works as a reaction solvent. When the compound having an alkenyl group is a high molecular compound, it is difficult to completely dissolve the high molecular compound in supercritical carbon dioxide, but the low molecular weight of the high molecular compound is swollen to promote the reaction. Can be done. Further, when it is desired to increase the solubility of the compound having an alkenyl group in supercritical carbon dioxide, it is preferable to use an appropriate cosolvent. For example, a low-polarity organic substance having a dielectric constant of 3 or less such as hexane, heptane, benzene, xylene, and toluene is preferably used. For unknown reasons, hexane is a particularly effective co-solvent for accelerating the hydrosilylation reaction. The use amount of the co-solvent is not particularly limited, but when used in a large amount, the effect of the present invention using harmless carbon dioxide as a solvent is reduced, and therefore 500 parts by weight or less based on 100 parts by weight of the compound having an alkenyl group. It is preferably 200 parts by weight or less. In addition, since these cosolvents are more soluble in supercritical carbon dioxide or liquefied carbon dioxide than a polymer compound having an alkenyl group, the pressure is reduced after the reaction is completed, or new carbon dioxide is passed through the reaction system. Thereby, it can be easily separated and washed, and can be reused.

The complex containing a Group VIII metal used in the present invention
And / or metal salts are usually cobalt, nickel, lute
Ni, rhodium, palladium, iridium, platinum
(Platinum), and gold of these Group 8 metals
It is used as a complex with a genus salt or an organic compound. Ingredient
Physically, CoH_Two[Si (OC_TwoH_Five)_Three] (PP
h_Three)_Three, Ni (PPh_Three)_Four, Ni (CO)_Two(PP
h_Three)_Two, RhCl (PPh_Three)_Three, Rh_TwoCl_Two(C
_TwoH_Four)_Two, RhCl (CO) (PPh_Three)_Two, RhH (C
O) (PPh_Three)_Two, RhCl_Three・ XH_TwoO, Pd (PPh
_Three)_Four, Pd (PPh_Three)_Two, PdCl_Two(PPh_Three)_Two,
(PPh_Three)_TwoPdO_Two, RuH_Two(PCH_Three)_Four, RuC
l _Two(PCH_Three)_Four, RuH_Two(PPh_Three)_Four, RuCl
_Two(PPh_Three)_Four , Ir (CO) Cl (PPh_Three)_Two, I
rCO (H) (PPh_Three)_Three, IrHCl (SiR_Three)
(PPh_Three)_Two, [IrCl (COE)_Two]_Two, [IrCl
(COD)_Two]_Two, (However, COE is cis-cyclo
Octen, COD is 1,5-cyclotadi
ene) and the like, but chloroplatinic acid, chloroplatinic acid and
Complex compounds with alcohols, aldehydes, ketones, etc., white
Gold-olefin complex [for example, Pt (CH_Two= CH_Two)
_Two(PPh_Three), Pt (CH_Two= CH_Two)_TwoCl_Two], Platinum-
Vinylsiloxane complex [Pt @ (vinyl) Me_TwoS
iOSiMe_Two(Vinyl)}], Pt ｛Me (vi
nyl) SiO｝_Four], A platinum-phosphine complex [Ph
(PPh_Three)_Four, Pt (PBu_Three)_Four], Platinum-phosphite
Complex [Pt @ P (OPh)_Three｝_Four], Pt (CO
D)_Two, (COD) PtCl_TwoZero-valent or bivalent white such as
Gold-containing complexes, ruthenium-phosphine complexes, ruthenium
Mu-phosphite complexes are preferred. In particular, platinum-phosph
Quin complexes, platinum-vinylsiloxane complexes, ruthenium-
The phosphine complex is easy to dissolve in supercritical carbon dioxide,
It is more preferable because the reaction activity is relatively high. Also these
Solution of the above substances in a solvent that does not react with these substances
One or a mixture of two or more selected from
You. Supercritical carbon dioxide is a substance due to changes in pressure and temperature.
Since the solubility of the solvent changes drastically,
The use of the compound is subject to wider pressure and temperature conditions.
This is preferable in that the activity can be maintained.

A colloid catalyst (Lewis, J. American Chem.) Obtained by reacting a complex and / or metal salt containing these Group 8 metals with silicon hydride.
medical Soc. , 1990, 112, 5998).
Are also preferred because of their high reaction activity.

These complexes containing a Group VIII metal and / or metal salt and / or colloidal catalyst may be used alone or in combination of two or more. Further, in the present invention, it is preferable that handling is facilitated by dissolving and diluting a complex, a metal salt, or a metal colloid of a Group 8 metal in various solvents. Preferred solvents include, for example, hydrocarbon solvents such as benzene, toluene, xylene, hexane, and heptane, and halogenated hydrocarbons, ethers, and esters.

The amount of the catalyst for the hydrosilylation reaction of the present invention is not particularly limited, but usually, the Group VIII metal is used in an amount of 10 ^-1 to 10 ^-8 per 1 mol of the alkenyl group in the compound (B).
It is preferably used in moles, more preferably in the range of 10 ^-3 to 10 ^-6 mole. If the amount of the catalyst is less than 10 ^-8 mol, the hydrosilylation reaction may not proceed sufficiently. On the other hand, if the amount of the catalyst is more than 10 ^-1 mol, problems such as an increase in the cost of raw materials and mixing of the residue of the catalyst, such as coloring of the product and a decrease in transparency, occur.

The component (A) of the present invention, which is represented by the general formula (1): R _a X _b H _c Si (1) (where R is an alkyl group having 1 to 20 carbon atoms, an aryl group or a triorganosiloxy group) R is the same or different when a is 2 or more, X is a halogen, an alkoxy group, an acyloxy group or a hydroxyl group, and when b is 2 or more, X may be the same or different A and b are integers of 0 to 3, c is an integer of 1 to 3, and a + b + c = 4.) As the silicon hydride compound, a conventionally known compound can be used without particular limitation. Although possible, specifically, for example, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, halogenated silanes such as trimethylsiloxydichlorosilane, trimethoxysilane, triethoxysilane, Methoxymethyl silane, diethoxy methyl silane, methoxy dimethylsilane, dimethoxyphenyl silane, 1,
Alkoxysilanes such as 3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane, acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane, dimethylsilane, trimethylsiloxymethyl Silane, 1,1,3
Hydrosilanes having two or more Si-H bonds in a molecule such as 3-tetramethyldisiloxane and 1,3,5-trimethylcyclotrisiloxane, and alkenyloxysilanes such as methyldi (isopropenyloxy) silane are included. Among them, preferred are methyldichlorosilane, dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, triethoxysilane and the like. These silicon hydride compounds may be used alone or in combination of two or more.

The compound containing an alkenyl group as the component (B) of the present invention is a compound having a carbon-carbon unsaturated bond, and specifically, for example, ethylene, propylene, 1-butene, 1- Low molecular weight compounds containing alkenyl groups such as alpha-olefins such as hexene and octene, cyclohexene, trans-2-hexene, butadiene, decadiene and allyltrimethylsilane, for example, organic silicon-based main chain, hydrocarbon-based main chain, and halogenated carbon Alkenyl groups having a main chain component of a hydrogen-based main chain, a saturated hydrocarbon-based main chain, a polyacryl-based main chain, a polyether-based main chain, a polyester-based main chain, a polyamide-based main chain, or a polyimide-based main chain. Examples include molecular compounds, but are not limited thereto.

Among the polymer compounds having an alkenyl group (carbon-carbon unsaturated bond), particularly preferred are:
An alkenyl group-terminated polyorganosiloxane,
Mention may be made of polypropylene oxide and polyisobutylene. Further, polyacryl, polybutene, hydrogenated polybutene, or the like having an alkenyl group at the terminal may be used. These may be used alone or in combination of two or more.

The polyisobutylene having an alkenyl group at the terminal is, for example, polyisobutylene having a terminal chlorine and allyltrimethylsilane (JP-A-63-10500).
5) or a diene (JP-A-4-288309).

The compound containing an alkenyl group (carbon-carbon unsaturated bond) referred to in the present invention is preferably a high molecular compound because the silylated product obtained after the hydrosilylation reaction forms a high-strength condensate. . In particular, those having a number average molecular weight of 500 or more obtained by GPC measurement using a polystyrene gel column are preferable. However, if the molecular weight is too large, the viscosity is too high and operations such as stirring cannot be performed at all, and even if the hydrosilylation reaction is successful, the obtained material has no value as a material that is cross-linked and hardened by the condensation reaction. . Therefore, the number average molecular weight of the polymer compound containing an alkenyl group (carbon-carbon unsaturated bond) referred to in the present invention is preferably 30,000 or less.

Further, if the compound having an hydrolyzable silyl group obtained by hydrosilylation of a compound having an alkenyl group has an average of 1.0 or more hydrolyzable silyl groups in one molecule, the compound may be subjected to a condensation reaction. A high-strength crosslinked product can be formed. Therefore, the compound having an alkenyl group used in the present invention preferably has an average of 1.0 or more alkenyl groups in one molecule, more preferably contains 1.2 or more alkenyl groups, and more preferably 1.4. More preferably, it contains at least two alkenyl groups.

The hydrosilylation reaction referred to in the present invention is:
(A) is a component of the general formula (1): wherein _{R a X b H c Si (} 1) ( wherein, R is an alkyl group, an aryl group or a triorganosiloxy group having 1 to 20 carbon atoms, a is When R is 2 or more, R may be the same or different, X is a halogen, an alkoxy group, an acyloxy group or a hydroxyl group, and when b is 2 or more, Xs may be the same or different, and a and b are each different. An integer of 0 to 3 and c is an integer of 1 to 3 and a + b + c = 4). The alkenyl group-containing compound as the component (B) is mixed with supercritical carbon dioxide. In this method, a compound having a condensable reactive group is produced using a complex containing a Group 8 metal and / or a metal salt as a catalyst. The reaction method may be a batch type reaction method or a continuous type reaction method, but is preferably a continuous type in order to improve productivity. Each material of the hydrogen silicon compound represented by the general formula (1), the compound containing an alkenyl group, and the catalyst may be separately mixed with supercritical carbon dioxide and a cosolvent, or an appropriate combination of the raw materials may be mixed. After that, it may be mixed with supercritical carbon dioxide or a cosolvent. The compound containing an alkenyl group used in the present invention is often a high-molecular-weight, high-viscosity substance, and it is easier to handle the compound containing the co-solvent and the compound containing the alkenyl group in advance, which is preferable. . Generally, the diffusion rate of a substance is extremely high in supercritical carbon dioxide, so that a reaction process using carbon oxide as a reaction solvent supercritically does not require a powerful stirring device as in the case of using a normal solvent. However, in the present invention, high molecular weight,
Since a high-viscosity substance is used as a raw material, it is preferable to use a stirrer.

In the present invention, the gas phase portion of the reactor may be filled with only supercritical carbon dioxide, or an inert gas such as nitrogen or helium may coexist. In the hydrosilylation reaction, the coexistence of oxygen in the gas phase of the reactor can sometimes promote the hydrosilylation reaction. Therefore, also in the present invention, it is preferable to make oxygen coexist with carbon oxide supercritically in the gas phase portion of the reaction vessel. Generally, when performing a hydrosilylation reaction, it is considered that it is preferable that oxygen does not exist inside the reactor from the viewpoint of safety in handling a combustible substance.
However, since the supercritical carbon dioxide used in the present invention has a very high density, the amount of oxygen necessary for the hydrosilylation reaction is relatively small, and the risk of explosion and combustion is extremely small.
The concentration of oxygen in the reaction vessel varies depending on the substance used, but it is preferable that the number of moles of oxygen is 5% or more based on the number of moles of alkenyl groups. If the number of moles of oxygen is less than 5% of the number of moles of the alkenyl group, oxygen is consumed during the reaction, and the promotion of the reaction may be stopped, which is disadvantageous.

[0042]

EXAMPLES Next, the method of the present invention will be specifically described with reference to examples. However, the present embodiment does not limit the present invention. (Example 1) A main chain is a linear polypropylene oxide, and alkenyl groups (CH ₂ ＣＨCH—
CH (CH ₃ ) —) having a number average molecular weight of 25,000
A solution 1 was prepared by mixing 200 parts by weight of hexane with respect to 100 parts by weight of the polymer compound.

As shown in FIG. 1, a magnetic rotor and 3 g of the solution 1 were placed in a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of a platinum vinylsiloxane complex (a platinum concentration of 0.003 wt%) was added. And sealed. 500 m of dimethoxymethylsilane is placed inside a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves.
g (50 equivalents based on the alkenyl group), and one valve was connected to pressure vessel A. Apparatus The entire apparatus was placed in a thermostat, and the other valve of pressure vessel B was connected to a carbon dioxide supply pump. The temperature inside the container is 35 ° C while stirring the inside with a magnetic rotor by a magnetic stirrer.
After the temperature was increased, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane in the pressure vessel B were introduced into the pressure vessel A. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the two valves were closed. When handling a supercritical fluid, there is a risk that the pressure inside the reaction vessel may rise sharply due to a slight change in temperature. Therefore, the temperature inside the reaction vessel was always measured using a thermocouple during the reaction. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 1 shows the results. (Comparative Example 1) A magnetic rotor and the solution 1 described in the above Example 1 were placed in a stainless steel pressure-resistant container A having a capacity of 100 ml.
g, and 100 mg of a xylene solution of a platinum vinyl siloxane complex (a platinum concentration of 0.003 wt%) was added, followed by sealing. The entire apparatus was placed in a thermostat, heated to 35 ° C. while stirring with a magnetic rotor, and then the pressure vessel A was opened.
500 mg of dimethoxymethylsilane was added and sealed again. After 2 hours, the reaction was sampled and ¹ H-
The residual ratio of the alkenyl group in the polymer compound was measured using NMR. Table 1 shows the results.

[0044]

[Table 1] From the results in Table 1, it can be seen that by using supercritical carbon dioxide as a reaction solvent and hexane as a cosolvent, the hydrosilylation reaction proceeds, and the residual ratio of alkenyl groups decreases. Further, it can be seen that the method of the present invention accelerates the reaction and reduces the residual alkenyl group, as compared with the case where only hexane is used as a solvent without using supercritical carbon dioxide. (Example 2) A magnetic rotor and 3 g of the solution 1 used in Example 1 were put in a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of platinum vinylsiloxane complex (a platinum concentration of 0.003 wt%) was added. And sealed. 500 m of dimethoxymethylsilane is placed inside a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves.
g (50 equivalents based on the alkenyl group), and one valve was connected to pressure vessel A. The entire apparatus was placed in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 70 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were put inside the pressure vessel A. Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the two valves were closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 2 shows the results. (Example 3) A magnetic rotor and 3 g of the solution 1 used in Example 1 were placed in a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of a platinum vinylsiloxane complex (platinum concentration 0.003 wt%) was added. And sealed. 500 m of dimethoxymethylsilane is placed inside a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves.
g (50 equivalents based on the alkenyl group), and one valve was connected to pressure vessel A. The entire apparatus was placed in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 90 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were mixed inside the pressure vessel A. Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the two valves were closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 2 shows the results. (Example 4) A magnetic rotor and 3 g of the solution 1 used in Example 1 were put into a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of a platinum vinyl siloxane complex (a platinum concentration of 0.003 wt%) was added. And sealed. 20 mg of dimethoxymethylsilane in a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves
(2 equivalents based on the alkenyl group), and one valve was connected to pressure vessel A. The entire apparatus was placed in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 90 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were mixed inside the pressure vessel A. Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the valve was closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 2 shows the results. (Example 5) A magnetic rotor and 3 g of the solution 1 used in Example 1 were placed in a stainless steel pressure-resistant container A having a capacity of 100 ml, and 100 mg of a xylene solution of platinum-vinylsiloxane complex (a platinum concentration of 0.003 wt%) was added. And sealed. 20 mg of dimethoxymethylsilane in a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves
(2 equivalents based on the alkenyl group), and one valve was connected to pressure vessel A. The whole apparatus was put in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 90 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were mixed inside Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 8 MPa, and the valve was closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 2 shows the results.

[0045]

[Table 2] From the results in Tables 1 and 2, the temperature was 35 ° C. or more, and the pressure was 8M.
It was shown that the hydrosilylation reaction proceeds using supercritical carbon dioxide of Pa or more. (Example 6) A magnetic rotor and 3 g of the solution 1 used in Example 1 were put into a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of a platinum vinylsiloxane complex (a platinum concentration of 0.003 wt%) was added. did. After the air in the pressure vessel A was removed using a vacuum pump, nitrogen gas was introduced into the vessel. In addition, add 500 nitrogen gas into the container.
The mixture was circulated at a rate of ml / min for 10 minutes, and the inside of the pressure-resistant container A was replaced with nitrogen. 500 mg of dimethoxymethylsilane (2 equivalents per alkenyl group) was sealed in a small pressure-resistant container B (capacity: about 1 ml) which can be closed with two valves, and one valve was connected to the pressure-resistant container A. The entire apparatus was placed in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 90 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were mixed inside the pressure vessel A. Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the valve was closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 3 shows the results. (Example 7) A magnetic rotor and 3 g of the solution 1 used in Example 1 were put into a stainless steel pressure vessel A having a capacity of 100 ml, and 100 mg of a xylene solution of a platinum vinylsiloxane complex (a platinum concentration of 0.003 wt%) was added. did. After the air in the pressure vessel A was removed using a vacuum pump, nitrogen gas was introduced into the vessel. In addition, add 500 nitrogen gas into the container.
The mixture was circulated at a rate of ml / min for 10 minutes, and the inside of the pressure-resistant container A was replaced with nitrogen. 20 mg of dimethoxymethylsilane (2 equivalents per alkenyl group) is sealed in a small pressure-resistant container B (capacity is about 1 ml) that can be sealed with two valves,
One valve was connected to pressure vessel A. The entire apparatus was placed in a thermostat, and the other valve of the pressure vessel B was connected to a carbon dioxide supply pump. After the temperature inside the vessel was raised to 90 ° C. while stirring the inside with a magnetic rotor, two valves attached to the pressure vessel B were opened, and carbon dioxide and dimethoxymethylsilane inside the pressure vessel B were mixed inside the pressure vessel A. Was introduced. Carbon dioxide was supplied until the pressure in the pressure vessel A became 18 MPa, and the valve was closed. After 2 hours, the reaction product was sampled, and the residual ratio of the alkenyl group in the polymer compound was measured using ¹ H-NMR. Table 3 shows the results.

[0046]

[Table 3] The results in Table 3 show that in the present method using supercritical carbon dioxide as a solvent, the hydrosilylation reaction proceeds even when oxygen does not exist in the reaction system. However, comparing the results in Tables 2 and 3, it was shown that even in the present method using supercritical carbon dioxide as a solvent, the presence of oxygen in the reaction system effectively promotes the hydrosilylation reaction. .

[0047]

According to the method of the present invention, the hydrosilylation reaction can be advanced using harmless supercritical carbon dioxide as a solvent, and the reaction can be accelerated as compared with the case where the reaction is carried out at normal pressure. In the present invention, the solvent can be easily removed by returning to normal pressure.

[Brief description of the drawings]

FIG. 1 is a sectional view of a reaction apparatus using supercritical carbon dioxide as a reaction solvent.

[Explanation of symbols]

 1. 1. Stainless steel pressure vessel A Magnetic rotor 3. Solution 1 4. 4. Xylene solution of platinum vinyl siloxane complex Valve 6. Pressure vessel B 7. 7. dimethoxymethylsilane 8. Carbon dioxide pressurization pump Magnetic stirrer 10. thermocouple

Continued on the front page F-term (reference) 4H039 CA92 CF10 4H049 VN01 VP01 VQ12 VQ21 VR22 VR32 VR42 VS12 VS21 VT16 VT17 VT25 VT30 VV02 VV19 VW02 VW32 4J005 AA03 BD08 4J035 BA01 CA01M CA13U CA14A01A01 CA25A01B HC79

Claims (12)

[Claims] (A) General formula (1): R _a X _b H _c Si (1) (wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl group or a triorganosiloxy group, and a Is 2 or more, R may be the same or different, X is a halogen, an alkoxy group, an acyloxy group or a hydroxyl group, and when b is 2 or more, X may be the same or different. Is an integer of 0 to 3; c is an integer of 1 to 3; a + b + c = 4); and (B) a compound containing an alkenyl group, A complex containing a Group 8 metal in the presence and / or
Alternatively, a method for producing a silyl group-containing compound, comprising performing a hydrosilylation reaction using a metal salt as a catalyst. 2. The temperature of supercritical carbon dioxide is 35 ° C. or higher,
The method for producing a silyl group-containing compound according to claim 1, wherein the temperature is 120 ° C or lower and the pressure is 8 MPa or higher. 3. The method for producing a silyl group-containing compound according to claim 1, wherein a substance having a dielectric constant of 3 or less is used as a cosolvent. 4. The method for producing a silyl group-containing compound according to claim 3, wherein the cosolvent is hexane. 5. The complex containing a Group 8 metal and / or a metal salt is chloroplatinic acid, a complex compound of chloroplatinic acid and an alcohol, aldehyde or ketone, platinum-olefin complex, platinum-vinylsiloxane complex, platinum -A phosphine complex, a platinum-phosphite complex, a ruthenium-phosphine complex, a ruthenium-phosphite complex, and one or a mixture of two or more selected from a solution in which these substances are dissolved in a solvent that does not react with these substances. A method for producing the silyl group-containing compound according to claim 1. 6. The complex containing a Group 8 metal and / or a metal salt is chloroplatinic acid, a complex compound of chloroplatinic acid and an alcohol, aldehyde or ketone, a platinum-olefin complex, a platinum-vinylsiloxane complex, or platinum. -A phosphine complex, a platinum-phosphite complex, a ruthenium-phosphine complex, a ruthenium-phosphite complex, and a mixture of one or more selected from a solution in which these substances are dissolved in a solvent that does not react with these substances; The method for producing a silyl group-containing compound according to any one of claims 1 to 4, which is a colloidal solution of a complex and / or metal salt containing a Group VIII metal obtained by reacting the compound with silicon halide. 7. (A) The silicon hydride compound represented by the general formula (1) is one of compounds selected from methyldichlorosilane, dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, and triethoxysilane. Or the method for producing a silyl group-containing compound according to any one of claims 1 to 6; 8. The amount of the catalyst for hydrosilylation reaction added is:
No. 8 relative to the number of moles of the alkenyl group in the compound (B).
2. The method according to claim 1, wherein the number of moles of the metal is 10 ^-8 to 10 ^-1 times.
8. The method for producing a silyl group-containing compound according to any one of items 1 to 7. 9. The alkenyl group-containing compound (B) is one or more organic polymers selected from polyisobutylene, polyacryl, polybutene, hydrogenated polybutene, polypropylene oxide, and polyorganosiloxane. Item 10. The method for producing a silyl group-containing compound according to any one of Items 1 to 8. 10. The compound according to claim 1, wherein the compound (D) having an alkenyl group is an organic polymer having a number average molecular weight of 500 to 30,000 and containing an average of 1.0 or more alkenyl groups in one molecule. 10. The method for producing a silyl group-containing compound according to any one of items 1 to 9. 11. The method according to claim 1, wherein oxygen is present in the reaction vessel.
11. The method for producing a silyl group-containing compound according to any one of items 10 to 10. 12. The method for producing a silyl group-containing compound according to claim 1, wherein the number of moles of oxygen in the reaction vessel is 5% or more based on the number of moles of alkenyl group.