Method for producing organosilicon compound

Abstract

To provide a method for producing an organosilicon compound that enables favorable control of the structure of the resulting organosilicon compound.SOLUTION: A method for producing an organosilicon compound includes a reaction step of subjecting a silane raw material, an organic halide containing two or more halogen substituents, and magnesium to a Grignard reaction in a mixed solvent containing ether-based and aromatic solvents.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an organosilicon compound.

Background Art

[0002] The Grignard reaction is widely used for the synthesis of various organic compounds as a carbon-carbon bond reaction. As the Grignard reagent in the Grignard reaction, an organomagnesium halide is used. Patent Document 1 discloses a method for producing such an organomagnesium halide and a method for producing an organosilicon compound by reacting the organomagnesium halide with a silicon compound. As the reaction solvent in the Grignard reaction, an organic solvent is usually used, and Patent Document 1 mentions an ether-based solvent as a preferred organic solvent.

[0003] The organosilicon compound obtained by the Grignard reaction as described above can be used in fields such as electronic materials and pharmaceutical precursors. Patent Document 2 discloses that the organosilicon compound obtained by the Grignard reaction can be used in applications such as electronic materials and pharmaceutical precursors. In such fields, controlling the structure of the obtained organosilicon compound is one of the important points. In particular, since silicon has multiple reaction points, it is important to control its molecular weight, structure, etc. Specifically, it is preferable that the structure represented by (-Si-R-Si-) of the obtained organosilicon compound is sufficiently developed. Here, R is an arbitrary organic group. Among them, carbosilane containing a silicon-carbon bond in the main skeleton (for example, R is CH2) is more difficult to synthesize compared to silicon whose main skeleton consists of a silicon-oxygen bond (for example, R is O), and the control of its structure is more important.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

[0005] However, when producing an organosilicon compound by the Grignard reaction, it has not been easy to control its structure, and there has been room for improvement. Therefore, an object of the present invention is to provide a method for producing an organosilicon compound capable of preferably controlling the structure of the obtained organosilicon compound. [Means for Solving the Problems]

[0006] As a result of intensive studies, the present inventors have found that when producing an organosilicon compound by the Grignard reaction, the above problems can be solved by carrying out the Grignard reaction in a mixed solvent containing an ether solvent and an aromatic solvent.

[0007] That is, the gist of the present invention is specifically as follows. <1>A method for producing an organosilicon compound, comprising a reaction step of subjecting a silane-based raw material, an organic halide having two or more halogen groups, and magnesium to a Grignard reaction in a mixed solvent containing an ether solvent and an aromatic solvent. <2>The method for producing an organosilicon compound according to <1>, wherein the silane-based raw material is an alkoxysilane. <3>The method for producing an organosilicon compound according to <1> or <2>, wherein the ether solvent is tetrahydrofuran. <4>The method for producing an organosilicon compound according to any one of <1> to <3>, wherein the aromatic solvent is at least one selected from the group consisting of toluene, benzene, ethylbenzene, o-xylene, m-xylene, and p-xylene. <5>The method for producing an organosilicon compound according to any one of <1> to <4>, wherein the volume ratio of the ether solvent to the aromatic solvent in the mixed solvent is 5 / 1 to 1 / 5. <6>The method for producing an organosilicon compound according to any one of <1> to <5>, wherein the organosilicon compound is a compound represented by the following formula (III).

Chemical formula

Advantages of the Invention

[0008] According to one embodiment of the present invention, there is provided a method for producing an organosilicon compound capable of preferably controlling the structure of the obtained organosilicon compound.

Modes for Carrying Out the Invention

[0009] Embodiments of the present invention will be described in detail below, but the present invention is not limited to these contents as long as the gist thereof is not exceeded. Further, the present invention can be arbitrarily modified and implemented within the scope not departing from the gist thereof.

[0010] In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, and "A~B" means A or more and B or less.

[0011] One embodiment of the present invention is a method for producing an organosilicon compound, which includes a reaction step of subjecting a silane-based raw material, an organic halide having two or more halogen groups, and magnesium to a Grignard reaction in a mixed solvent containing an ether solvent and an aromatic solvent.

[0012] <Silane-based raw material> The silane-based raw material can react with an organomagnesium halide (Grignard reagent), and there is no particular limitation as long as the desired organosilicon compound can be obtained, and known silane compounds can be used. For example, chlorosilane compounds such as dimethyldichlorosilane, methyltrichlorosilane, trimethylchlorosilane, methyldichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, and trichlorosilane can be mentioned. Also, the silane-based raw material may be an alkoxysilane, and among them, it may be an alkoxysilane represented by the following formula (I). Si(R 2 ) b (OR 3 ) 4-b (I) In the above formula (I), R 2 each independently represents a hydrogen atom or a monovalent organic group; R 3 each independently represents an alkyl group; and b represents an integer of 0 to 2.

[0013] R 2 is not particularly limited as long as it is each independently a hydrogen atom or a monovalent organic group, and may be a hydrogen atom or a monovalent hydrocarbon group, but from the viewpoint of reactivity, it is preferably a hydrogen atom. The monovalent organic group may have a linear structure, a branched structure, a ring structure (alicyclic structure and / or aromatic ring structure), or an unsaturated bond. R 2 The monovalent hydrocarbon group related to is not particularly limited, but from the viewpoint of reactivity, the carbon number of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.

[0014] R 3 is not particularly limited as long as it is each independently an alkyl group, and the alkyl group may have a linear structure or a branched structure. It is preferable that all of the plurality of R 3 are the same. R 3The alkyl group related thereto is not particularly limited, but from the viewpoint of reactivity, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.

[0015] b is not particularly limited as long as it is an integer of 0 to 2, but from the viewpoint of reactivity, it is preferably 1 (that is, trialkoxysilane).

[0016] Specific examples of the dialkoxysilane include, for example, dimethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, vinyldimethoxysilane, phenyldimethoxysilane, dimethyldimethoxysilane, methylethyldimethoxysilane, or diethyldimethoxysilane and other dimethoxy-based silanes; diethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butyldiethoxysilane, vinyldiethoxysilane, phenyldiethoxysilane, dimethyldiethoxysilane, methylethyldiethoxysilane, or diethyldiethoxysilane and other diethoxy-based silanes; or dipropoxysilane, methyldipropoxysilane, ethyldipropoxysilane, butyldipropoxysilane, vinyldipropoxysilane, phenyldipropoxysilane, dimethyldipropoxysilane, methylethyldipropoxysilane, or diethyldipropoxysilane and other dipropoxy-based silanes and the like. Specific examples of the trialkoxysilane include, for example, trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, or phenyltrimethoxysilane and other trimethoxy-based silanes; triethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, or phenyltriethoxysilane and other triethoxy-based silanes; tripropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, vinyltripropoxysilane, or phenyltripropoxysilane and other tripropoxy-based silanes and the like. Examples of the tetraalkoxysilane include, specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

[0017] The usage amount of the silane-based raw material is not particularly limited. For example, from the viewpoint of reactivity, the total usage amount (mol) of the silane-based raw material with respect to the total usage amount (L) of the mixed solvent described later in the reaction step is preferably 0.10 mol / L or more, more preferably 0.30 mol / L or more, still more preferably 0.50 mol / L or more, and particularly preferably 0.70 mol / L or more. Also, from the viewpoint of the solubility of the reaction product, it is preferably 6.0 mol / L or less, more preferably 4.0 mol / L or less, still more preferably 3.0 mol / L or less, and particularly preferably 2.0 mol / L or less. In the description of the reaction step, the "total usage amount" means the total usage amount of the target substance used throughout the reaction. For example, when a solution in which an organic halide is dissolved in a solvent is dropped into a solvent in which magnesium is dispersed to carry out the reaction, the total usage amount of the solvent is the sum of the amount of the solvent in the solvent in which magnesium is dispersed and the amount of the solvent in the solution in which the silane-based raw material and the organic halide are dissolved in the solvent. When a solution in which an organic halide is dissolved in a solvent is dropped into a solvent in which magnesium is dispersed to carry out the reaction, the total usage amount of the solvent is the sum of the amount of the solvent in the solvent in which magnesium is dispersed and the amount of the solvent in the solution in which the silane-based raw material and the organic halide are dissolved in the solvent.

[0018] <Organic halide having two or more halogen groups> The organic halide having two or more halogen groups according to the present embodiment (hereinafter, also simply referred to as "organic halide") is not particularly limited as long as it has two or more halogen groups. The organic halide may be used alone or in combination of two or more.

[0019] The organic halide can be represented by the following formula (II). R 1 X a (II) In the above formula (II), R 1represents an a-valent organic group; X each independently represents a halogen atom; a represents an integer of 2 or more. The valence of this organic group is determined by the number of X atoms to which it is bonded. For example, if the number of X atoms is 2, it is divalent, and if the number of X atoms is 3, it is trivalent. These organic groups may also have substituents within the range where the effects of the present invention can be obtained.

[0020] Although details will be described later, for example, when a in the above formula (II) is 2, the organic halide has two halogen groups, and by reacting with magnesium, X-R 3 -Mg-X, a Grignard reagent represented by, is formed. Then, the Grignard reagent reacts with a silane-based raw material to produce an organosilicon compound having a structure represented by (-Si-R 3 -X). At this time, the terminal X reacts with magnesium to form a Grignard reagent of (-Si-R 3 -Mg-X), and then reacts with another silane-based raw material molecule to produce an organosilicon compound having a structure represented by (-Si-R 3 -Si-). On the other hand, when the reaction of the Grignard reagent of (-Si-R 3 -Mg-X) with the silane-based raw material does not proceed and is quenched by a molecule having an active proton, such as a water molecule or methanol, it will have a terminal structure represented by (-Si-R 3 -H), and the desired structure of (-Si-R 3 -Si-) may not develop sufficiently.

[0021] R 1 is not particularly limited as long as it is an a-valent organic group. For example, it may be an a-valent hydrocarbon group, which may have a linear structure, a branched structure, a ring structure (alicyclic structure and / or aromatic ring structure), or an unsaturated bond. R 1 The hydrocarbon group related to is not particularly limited, but from the viewpoint of reactivity, the number of carbon atoms of the hydrocarbon group is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 6.

[0022] X is not particularly limited as long as each is independently a halogen atom, and may be any of a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. From the viewpoint of reactivity, a chlorine atom or a bromine atom is preferred, and a bromine atom is more preferred.

[0023] a is not particularly limited as long as it is an integer of 2 or more, but from the viewpoint of reactivity, it is preferably 2 to 4, and more preferably 2 to 3.

[0024] Specific examples of the organic halide include, for example, dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,3-dichloro-2-methylpropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,3-dichlorocyclopentane, 1,6-dichlorohexane, dibromomethane, 1,3-dibromopropane, 1,3-dibromo-2-methylpropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,3-dibromocyclopentane, 1,6-dibromohexane, diiodomethane, 1,3-diiodopropane, 1,3-diiodo-2-methylpropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,3-diiodocyclopentane, or 1,6-diiodohexane and the like of alkyl halides; alkenyl halides; dihalogenated aryls such as 1,3-dichlorobenzene, α-chloro-4-chlorotoluene, 1,3-dibromobenzene, α-bromo-4-toluene, 1,3-diiodobenzene, or α-iodo-4-iodotoluene; and the like.

[0025] Since it is possible to obtain an organosilicon compound by using a silane-based raw material, an organic halide, and magnesium, the amount of the organic halide used is not particularly limited, but the appropriate usage ratio varies depending on the target reaction product. For example, when the silane-based raw material is alkoxysilane and all alkoxy groups are reacted, the alkoxy groups (ОR) contained in the entire alkoxysilane used 2) From the perspective of reactivity, the ratio of the total amount (mol) of halogen groups (X) contained in the entire organic halide used to the total amount (mol) of the compound of formula (0) is preferably 0.10 mol / mol or more, more preferably 0.20 mol / mol or more, still more preferably 0.40 mol / mol or more, and particularly preferably 0.50 mol / mol or more. From the perspectives of the concentration of the reaction solution and the cost of the raw material usage amount, it is preferably 20 mol / mol or less, more preferably 12 mol / mol or less, still more preferably 10 mol / mol or less, and particularly preferably 8.0 mol / mol or less. For example, when X mol of dialkoxysilane is used as the alkoxysilane and Y mol of alkyl monohalide is used as the organic halide, the above ratio is represented by Y / 2X mol / mol.

[0026] <Magnesium> The form of magnesium is not particularly limited, and it can be used in a known manner. In this specification, "magnesium" means magnesium atoms unless otherwise specified, and the magnesium atoms can exist, for example, in the form of metallic magnesium, magnesium salts, or ions. However, since the Grignard reaction is carried out using metallic magnesium, the magnesium used in the reaction contains at least metallic magnesium.

[0027] Since it is possible to obtain an organosilicon compound by using a silane-based raw material, an organic halide, and magnesium, the amount of metallic magnesium used is not particularly limited. For example, from the viewpoint of reaction efficiency, the ratio of the total amount (mol) of metallic magnesium used to the total amount (mol) of halogen groups (X) contained in the entire organic halide used is preferably 0.20 mol / mol or more, more preferably 0.40 mol / mol or more, still more preferably 0.50 mol / mol or more, particularly preferably 0.90 mol / mol or more, and even more preferably 1.0 mol / mol or more. For the convenience of post-treatment of the unreacted metallic magnesium remaining after completion of the reaction, it is preferably 50 mol / mol or less, more preferably 25 mol / mol or less, still more preferably 10 mol / mol or less, and particularly preferably 7.0 mol / mol or less.

[0028] <Other components> As reaction raw materials, components other than the above-mentioned silane-based raw material, organic halide, magnesium, and the mixed solvent described later (other components) may be included as long as the effects of the present invention are not impaired. For example, additives and the like may be included. The additive is not particularly limited as long as it can be dissolved in the mixed solvent described later. Typical examples include iodine, which is added for the purpose of accelerating the Grignard reaction.

[0029] <Mixed solvent> In the production method according to the present embodiment, the Grignard reaction is carried out under a mixed solvent containing an ether-based solvent and an aromatic-based solvent. The Grignard reaction is carried out. Usually, in the Grignard reaction, an organic solvent such as an ether-based solvent is used alone as a reaction solvent. This is known to have the effect of assisting the dissolution and stabilization of the Grignard reagent by forming a complex structure in which an ether-based solvent is coordinated when the Grignard reagent is generated from metallic magnesium and an organic halide. The inventors have found that by using a mixed solvent containing an ether solvent and an aromatic solvent as the reaction solvent, the structure of the resulting organosilicon compound changes. The reason for this is not clear, but it is presumed as follows. That is, when the above mixed solvent is used as the reaction solvent, the coexistence of the ether solvent and the aromatic solvent makes it easier for the Grignard reagent (organomagnesium halide) generated in the reaction system to dissociate from the stabilized complex, resulting in a more reactive state. Therefore, it is considered that the formation of the target (-Si-R-Si-) bond proceeds efficiently, and an organosilicon compound with a developed structure represented by (-Si-R-Si-) is generated. Here, R is an arbitrary organic group, such as a methylene group, an ethylene group, a propylene group, etc.

[0030] The ether solvent is not particularly limited and may be a known ether solvent used in the Grignard reaction. It may be a single ether solvent or may contain a plurality of ether solvents. Specific examples of the ether solvent include diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, etc. Among them, tetrahydrofuran is preferably used from the viewpoints of reaction control and ease of industrial availability.

[0031] The aromatic solvent is not particularly limited as long as it is miscible with the above ether solvent. Specifically, at least one aromatic solvent selected from the group consisting of toluene, benzene, ethylbenzene, o-xylene, m-xylene, and p-xylene is preferred. More preferably, it is at least one aromatic solvent selected from the group consisting of toluene and benzene. Regarding the aromatic solvent, a single aromatic solvent may be mixed with the ether solvent, or a plurality of aromatic solvents may be mixed.

[0032] The mixing method of each of the above solvents is not particularly limited. The aromatic solvent may be added to the reaction vessel after the ether solvent is first added, or the aromatic solvent may be added first, or the ether solvent and the aromatic solvent may be mixed in advance and then added to the reaction vessel.

[0033] Regarding the mixed solvent containing the above ether solvent and aromatic solvent, the mixing ratio of the ether solvent to the aromatic solvent (ether solvent / aromatic solvent) is preferably 5 / 1 to 1 / 5, more preferably 1 / 1 to 1 / 5, and particularly preferably 1 / 2 to 1 / 5 in terms of volume ratio. When the mixing ratio of the ether solvent to the aromatic solvent is within the above range, an organosilicon compound in which the structure represented by (-Si-R-Si-) is sufficiently developed can be obtained. Note that the above mixing ratio is the volume ratio after mixing all the raw materials to be subjected to the Grignard reaction.

[0034] <Organosilicon compound> The organosilicon compound produced by the production method according to the present embodiment is not particularly limited, but is, for example, a reaction product obtained by a reaction including a Grignard reaction, and examples thereof include at least one or more organosilicon compounds selected from the group consisting of alkoxysilane, silanol, and silicone having a coordinating functional group in the side chain.

[0035] Examples of silanol include polysiloxane compounds having a silanol group. These organosilicon compounds may be produced in a mode of producing two or more kinds.

[0036] More specifically, the production method according to the present embodiment can be suitably used in the production of an organosilicon compound represented by the following formula (III).

Chemical formula

[0037] The molecular weight of the organosilicon compound is not particularly limited. For example, it may be 200 or more, 300 or more, 400 or more in terms of the weight average molecular weight in terms of polystyrene, and may also be 1000 or less, 800 or less, 600 or less. The weight average molecular weight of the organosilicon compound can be measured by a known method using GPC (gel permeation chromatography). The measurement of the weight average molecular weight using GPC can be carried out using, for example, devices such as a high-speed GPC device HLC8220GPC or HLC8420GPC (both manufactured by Tosoh Corporation). In addition, tetrahydrofuran (without stabilizer, for GPC) can be used as the eluent, and the detailed analysis conditions can be the conditions shown in Table 1 below. In this case, the weight average molecular weight can be evaluated as a value converted based on the calibration curves prepared using standard polystyrene and p-t-butoxystyrene.

[0038]

Table 1

[0039] As the standard polystyrene used for preparing the calibration curve, for example, the standard polystyrene shown in Table 2 below (all manufactured by Tosoh Corporation) can be used.

[0040]

Table 2

[0041] In the examples described below, a high-speed GPC device HLC8220GPC (manufactured by Tosoh Corporation) was used as the GPC device, the standard polystyrene shown in Table 2 above was used, and the weight-average molecular weight of the obtained organosilicon compound was measured according to the above method including the conditions in Table 1 above.

[0042] Whether the structure represented by (-Si-R-Si-) of the organosilicon compound is sufficiently developed can be confirmed mainly by the following two methods. One is to calculate the ratio of the peak intensity indicating the (-Si-R-H) structure at the end to the peak intensity indicating the (-Si-R-Si-) structure in the molecular chain by using FT-IR (Fourier transform infrared spectroscopy). The other is the method using the above GPC, that is, the increase in the weight-average molecular weight. The method using FT-IR is specifically the following method.

[0043] <Method for Confirming (-Si-R-Si-) Structure> Taking the case where R is a methylene group as an example for explanation. The organosilicon compound to be measured is dissolved in an appropriate organic solvent, and the solution is dropped onto an IR measurement potassium bromide crystal card (manufactured by International Crystal Laboratories #7090), and then dried under room temperature vacuum for 30 minutes or more to prepare an analysis sample. Using an FT-IR device (Spectrum One (B) manufactured by PerkinElmer), a card without the measurement object is measured in advance as a blank, and then the analysis sample is measured. The measurement conditions are set as shown in Table 3.

[0044]

Table 3

[0045] The smaller the value of the above ratio, the more the formation of the (-Si-R) structure is suppressed, which means that the (-Si-R-Si-) structure is developed. That is, the elongation of the chain molecule having a chemically stable silicon-carbon bond as the main chain proceeds sufficiently, and since the (-Si-R) structure is small, the obtained organosilicon compound has stable properties that are physically and chemically difficult to decompose. The value of the above ratio is preferably 0.5 to 2.0, more preferably 0.5 to 1.5.

[0046] <Method for producing organosilicon compound> The method for producing an organosilicon compound according to the present embodiment is not particularly limited as long as the above mixed solvent is used as the reaction solvent, and other steps can be applied by known methods. As a specific example, the method is as follows.

[0047] First, after adding raw materials such as magnesium, a mixed solvent, and a catalyst to a reaction vessel, a solution in which a silane-based raw material and an organic halide are dissolved in the mixed solvent is dropped to perform a Grignard reaction to obtain a reaction solution containing an organosilicon compound, an organic solvent, unreacted magnesium, and a by-produced magnesium salt (reaction step). Depending on the target product, other reactions may be performed before and after the Grignard reaction. For example, after synthesizing a halosilane by a Grignard reaction, an alkoxylation reaction may be subsequently performed to obtain a reaction solution containing an alkoxysilane, an organic solvent, and magnesium. An aqueous solution containing an acid may be mixed with the obtained reaction solution, stirred and allowed to stand, and separated into an organic phase and an aqueous phase (liquid separation step). Instead of performing the liquid separation step, a poor solvent may be added to precipitate a salt. Then, unnecessary components are removed by a known method such as filtration, and the target product is recovered. Furthermore, it may include a step (purification step) of adsorbing and removing impurities using activated carbon or an ion exchange resin.

[0048] In the Grignard reaction described in this specification, an organic halide (R 1 X a ; R 1 is an organic group, X is independently a halogen atom, and a is an integer of 2 or more) reacts with magnesium (Mg) to generate a Grignard reagent (for example, when a = 2, R 1 (X)MgX), and then the Grignard reagent reacts with a silane-based raw material (for example, alkoxysilane (Si(R 2 ) b (OR 3 ) 4-b ); R 2 is independently a hydrogen atom or a monovalent organic group, R 3 is independently an alkyl group, and b is an integer of 0 to 2), and at least a part of (OR 3 ) of the alkoxysilane is substituted with R 1 to form an organosilicon compound. Note that the reaction step only needs to include at least the treatment of the Grignard reaction, and may also include other treatments.

[0049] The method for performing the Grignard reaction is not particularly limited and can be performed by a known method. The reaction temperature for performing the Grignard reaction is not particularly limited, but from the viewpoint of promoting the reaction, it is preferably 0 °C or higher, more preferably 10 °C or higher, further preferably 20 °C or higher, particularly preferably 30 °C or higher. Also, from the viewpoint of the stability of the Grignard reagent, which is the first stage of the reaction, it is preferably 100 °C or lower, more preferably 80 °C or lower, and further preferably 60 °C or lower. Also, the reaction time for carrying out the Grignard reaction is not particularly limited. However, from the perspective of the heat removal efficiency of the Grignard reaction with a large calorific value, it is preferably 0.1 hour or more, more preferably 0.5 hour or more, still more preferably 1 hour or more. Also, from the perspective of synthesis efficiency, it is preferably 24 hours or less, more preferably 12 hours or less, still more preferably 8 hours or less, and particularly preferably 6 hours or less. Also, the atmosphere for carrying out the Grignard reaction is not particularly limited and it can be carried out in the air, but it is preferably carried out in an inert gas such as nitrogen gas or argon gas.

[0050] Hereinafter, as an example of the reaction step, an example in the case including a reaction treatment for synthesizing an alkoxylated organosilicon compound is shown, but it is not limited thereto.

[0051] Organic halides such as alkyl halides, aryl halides, or alkenyl halides (R 1 X a ; R 1 is an organic group, X is independently a halogen atom, a is an integer of 2 or more), a halogenated organosilane compound (SiR 2 b Y 4-c ; Y is independently a halogen atom, R 2 is independently a hydrogen atom or an organic group, c is an integer of 0 to 3), and magnesium are prepared and mixed. First, the organic halide reacts with magnesium to form a Grignard reagent (R 1 (X) a-1 MgX), and then the Grignard reagent reacts with the halogenated organosilane compound, and an organosilicon compound in which at least a part of Y of the halogenated organosilane compound is substituted with R 1 is formed.

[0052] The above reaction will be described more specifically while showing an example. For example, using R 1 X2 as the organic halide and SiR 2When using Y3, first, a Grignard reagent ( R 1 (X)MgX) is generated by the reaction of an organic halide with magnesium (Mg). Then, the Grignard reagent reacts with an organosilane halide compound, and at least a part of Y in the organosilane halide compound is replaced by R 1 to form an organosilicon compound having the structure shown in the following formula (1) (hereinafter, also referred to as compound (1)). Furthermore, a Grignard reagent (XMgR 1 Si(R 2 )(Y)2) is generated by the reaction of compound (1) with magnesium (Mg). Then, the reaction of the Grignard reagent with an organosilane halide compound or compound (1) is repeated multiple times to form an organosilicon compound having the structure shown in the following formula (2) (hereinafter, also referred to as compound (2)). In formula (2), n represents the number of repetitions and is an integer of 2 or more.

[0053]

Chemical formula

Chemical formula

[0054] When a halogen atom remains in the obtained organosilicon compound, when the organosilicon compound is mixed with an alcohol such as methanol, the remaining halogen-silicon moiety in the organosilicon compound reacts with methanol to form an alkoxylated organosilicon compound. For example, when the above compound (2) is reacted with an alcohol (R 3 OH; R 3 is an organic group), an alkoxylated organosilicon compound having the structure represented by the following formula (3) (hereinafter, also referred to as "compound (3)") is generated.

[0055]

Chemical formula

[0056] In the reaction for producing the above compound (3), hydrogen halide (HY) is generated simultaneously with the production of the alkoxylated organosilicon compound.

[0057] The mixed solvent used in the reaction for obtaining the above compounds (1) and (2) is a mixed solvent of an ether-based solvent and an aromatic-based solvent as described in the section of <Mixed Solvent>.

[0058] Also, when alcohol is reacted to obtain the above compound (3) and hydrogen halide is generated, it is finally desirable to neutralize it, and it is preferable to add triethylamine, trimethylamine, sodium hydrogen carbonate, or a basic compound. Among these, triethylamine is more preferable.

[0059] The conditions for the reaction for obtaining the above compound (1) and the reaction for obtaining compound (2) are not particularly limited. For example, the reaction temperature may be 0 to 60°C, or 30 to 45°C, etc., and the reaction time may be 1 to 6 hours, or 1 to 4 hours, etc. Also, the conditions for the reaction of the above formula (3) are not particularly limited. For example, the reaction temperature may be 0 to 60°C, or 15 to 30°C, etc., and the reaction time may be 1 to 6 hours, or 1 to 2 hours, etc.

[0060] The present inventors further focused on the fact that the above compound (3) can also be synthesized by the following method. The following method is a method for synthesizing and purifying compound (3) by reacting an alkoxysilane, and an organic halide with magnesium. Hereinafter, the above method is also referred to as the first method, and the following method is also referred to as the second method. Regarding the number of reaction steps for synthesizing compound (3), since the second method has fewer steps than the first method, the second method is easier to react in a batch system, and there is a possibility of reducing the manufacturing cost.

[0061] Organic halides such as alkyl halides, aryl halides, or alkenyl halides (R 1 X a ;R1 is an organic group, X is independently a halogen atom, a is an integer of 2 or more), alkoxysilane (SiR 2 c (OR 3 ) 4-b ; R 2 is a hydrogen atom or an organic group, R 3 is independently a hydrogen atom or an organic group, b is an integer from 0 to 2), and magnesium (Mg) are prepared and mixed. First, the organic halide reacts with magnesium to form a Grignard reagent (R 1 (X)MgX), and then the Grignard reagent reacts with the alkoxysilane, and a part of OR 3 of the alkoxysilane is replaced by R 1 to form compound (3).

[0062] The above reaction will be described more specifically with an example. For example, when R 1 X2 is used as the organic halide and Si(R 2 )(OR 3 )3 is used as the silane compound, first, a Grignard reagent (R 1 (X)MgX) is formed by the reaction of the organic halide with magnesium (Mg), and then the Grignard reagent reacts with a specific alkoxysilane, and at least a part of (OR 3 ) of the alkoxysilane is replaced by R 1 to form an organosilicon compound having the structure shown in the following formula (4) (hereinafter also referred to as compound (4)). Furthermore, a Grignard reagent (XMgR 1 Si(R 2 )(OR 3 )2) is formed by the reaction of compound (4) with magnesium (Mg), and then the above compound (3) is formed by repeating the reaction of the Grignard reagent with the alkoxysilane or compound (4) a plurality of times. [Chemical formula]

[0063] In addition, in the above-described second method as well, a mixed solvent of an ether-based solvent and an aromatic-based solvent, which was described in the section of the <mixed solvent> above, is used in the same manner as the reaction for obtaining the above-described compound (1) and compound (2).

[0064] The reaction conditions in the above-described second method are not particularly limited. For example, the reaction temperatures for the reactions to obtain compound (4) and compound (3) may both be 0 to 60°C, or 30 to 45°C, etc., and the total reaction time for the reactions to obtain compound (4) and compound (3) may be 1 to 6 hours, or 1 to 2 hours, etc.

[0065] The production method according to this embodiment may include other steps such as another reaction step, a filtration step, a liquid separation step, a water washing step, a dehydration step, a concentration step, a UV treatment step, an adsorbent treatment step, etc., in addition to the above-described reaction steps. Specifically, for example, after adding water and an acid catalyst to the reaction solution of the target product containing an alkoxy group recovered by the above-described method and performing a hydrolysis and polycondensation reaction, liquid separation may be further performed by the method according to this embodiment. Next, after removing the acid catalyst, dehydration is performed by a known method, impurities such as organic lead are decomposed by UV treatment, and further impurities are removed by adsorbent treatment by a known method to obtain the target product (organosilicon compound).

[0066] The hydrolysis and polycondensation reaction is not particularly limited and can be performed by a known method according to the final target product. Examples of the acid catalyst include oxalic acid.

[0067] By performing liquid separation on the reaction solution obtained in the reaction step, impurities in the liquid can be removed. The method of liquid separation is not particularly limited. For example, by bringing the liquid into contact with water or an acid and then removing the aqueous layer, impurities can be removed. When using water, a dilute acid such as nitric acid or hydrochloric acid may be further used to increase the solubility of components such as lead components in water. When using a dilute acid, the concentration of the acid may be, for example, 0.001 to 1.0 mol / L, etc. When performing liquid separation treatment, the organic phase containing the organosilicon compound is treated as the above composition or reaction solution.

[0068] The temperature at which the liquid is brought into contact with water is not particularly limited, and it may be appropriately set at a temperature at which the organosilicon compound and the organic solvent are stable, such as 0 to 30°C.

[0069] The UV treatment step is not particularly limited either, and it can be carried out by irradiating ultraviolet rays by a known method. Generally, the reaction solution after the Grignard reaction may contain impurities such as organic lead derived from the raw materials. Since the bond between the lead atom and the carbon atom in the organic lead compound can be cleaved by irradiation with ultraviolet rays, the amount of the organic lead compound in the target product can be reduced.

[0070] The wavelength of the ultraviolet rays is not particularly limited, but from the viewpoint of efficiently removing the organic lead compound, 210 to 350 nm is preferable, 220 to 320 nm is more preferable, and 240 to 300 nm is even more preferable. At wavelengths of 350 nm or more, since there is no absorption derived from the organic lead compound, the reaction hardly occurs, and thus the removal effect of the organic lead compound tends to decrease. When the liquid contains an organic compound that is not desired to be removed, at short wavelengths of less than 210 nm, side reactions due to the absorption of the organic compound tend to occur easily.

[0071] The ultraviolet irradiation dose is defined by the integrated light quantity, and the integrated light quantity is not particularly limited, but it may be appropriately adjusted according to the content of the organic lead compound in the liquid, and it is preferably 0.1 to 100 J / cm 2 and more preferably 1 to 80 J / cm 2 and even more preferably 10 to 60 J / cm 2 The integrated light quantity can be obtained by multiplying the intensity of the ultraviolet rays by the irradiation time. Therefore, it is preferable to appropriately set the intensity of the ultraviolet rays to be irradiated and the irradiation time so that the integrated light quantity falls within the above range.

[0072]

[0073] ​The device for irradiating ultraviolet rays is not particularly limited as long as it uses a light source that emits ultraviolet rays, and an ultraviolet fluorescent lamp, a mercury lamp, a deuterium lamp, an ultraviolet LED, or an ultraviolet laser can be used. - Etc. can be used.

[0074] The method of irradiating ultraviolet rays is not particularly limited, and it is sufficient to irradiate the liquid with ultraviolet rays. However, from the viewpoint of efficiency, it is preferable to use a quartz container or the like with high ultraviolet transmittance as the container for containing the liquid and irradiate the container with ultraviolet rays.

[0075] When the irradiation step is adopted, the liquid may contain the following components in order to enhance the effect of ultraviolet irradiation. Examples of the components that can enhance the effect of ultraviolet irradiation include photosensitizers such as benzophenone, anthracene, or camphorquinone. In addition, when an organolead compound has a polymerizable group such as a (meth)acrylic group, a vinyl group, or an epoxy group, a polymerization inhibitor such as dibutylhydroxytoluene or benzoquinone may be added. The content of these components in the liquid is not particularly limited and may be appropriately determined in consideration of the desired effect. For example, if it is a photosensitizer, it may be 1 to 50% by mass, and if it is a polymerization inhibitor, it may be 1 to 50% by mass.

[0076] The adsorbent treatment step is not particularly limited, and a known method can be adopted. When a component intended to be taken into the liquid is contained, it is also possible to adsorb and remove impurities in the liquid by bringing the liquid containing the component and impurities such as lead components into contact with an adsorbent. As the adsorbent for removing impurities, ion exchange resins, chelate resins, activated carbon, and synthetic adsorbents used in known metal treatments can be used.

[0077] Activated carbon may be in any form such as granular, powdered, or fibrous, and the raw material may be derived from natural products such as coconut shells or from synthetic resins. It is preferable to perform heat-vacuum drying at 150 to 250 °C as a pretreatment. In the treatment using activated carbon, both batch treatment and column treatment can be applied. In batch treatment, specifically, 1 to 15% by mass of activated carbon is added to the liquid, and after stirring and shaking at a liquid temperature of 0 to 30 °C for 0.5 to 48 hours, the activated carbon is removed by filtration to obtain a liquid with reduced impurities. In column treatment, specifically, after filling activated carbon with an organic solvent in which an organic compound is dissolved in a cylindrical container such as PTFE, PFA, or glass, the liquid is passed through at a liquid temperature of 0 to 30 °C to obtain a liquid with reduced impurities.

[0078] As the ion exchange resin, a cation exchange resin can be used, and any cation exchange resin such as a strongly acidic, weakly acidic, gel type, or porous type can be used. Chelating resins can be those known to be used in metal treatment, and specific examples include iminodiacetic acid type, nitrilotriacetic acid type, ethylenediaminetetraacetic acid type, diethylenetriaminepentaacetic acid type, or triethylenetetraminehexaacetic acid type. Synthetic adsorbents may be of polystyrene type or polymethacrylic acid type, and specific examples include styrene-divinylbenzene copolymer, ethylstyrene-divinylbenzene copolymer, or methyl methacrylate-ethylene glycol dimethacrylate copolymer. Those in which the benzene ring of styrene is substituted with a halogen such as bromine may also be used. As a pretreatment for ion exchange resins, chelating resins, or synthetic adsorbents, it is preferable to treat them by a known method and then replace the solvent in the resin with a solvent that may be contained in the liquid. In the treatment of a liquid containing impurities with an ion exchange resin, chelating resin, or synthetic adsorbent, both batch treatment and column treatment can be applied, and specifically, a liquid with reduced impurities can be obtained by the same operation as the above activated carbon treatment.

Example

[0079] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. 。

[0080] <Example 1> In a dried 1 L three-necked glass flask, a mixed solvent consisting of 195.6 g of tetrahydrofuran and 294.4 g of toluene, and 32.7 g of magnesium particles were weighed. While stirring with a mechanical stirrer, a mixed solution consisting of 106.7 g of tetrahydrofuran, 129.2 g of 1,3-dibromopropane, and 78.2 g of trimethoxysilane was gradually added dropwise using a dropping tube. Since the solution exothermed during the addition, the dropping rate was adjusted to keep the temperature of the reaction solution at 30 °C while cooling the flask in a water bath, and the addition was carried out over 100 minutes to conduct a Grignard reaction. At the end of the addition, the volume ratio of tetrahydrofuran to toluene in the reaction solvent was 1:1. After the addition was completed, the temperature of the water bath was raised, and the reaction solution was heated to 55 - 60 °C and reacted for 3 hours, and then cooled to room temperature to obtain a reaction solution. Next, diisopropyl ether, which is a poor solvent for the by-product salt, was added to the obtained reaction solution, and after thorough stirring, it was filtered to remove the white magnesium salt, which is the by-product salt, to obtain a solution of the crude product. This solution was concentrated by distilling off the solvent and additional diisopropyl ether was added repeatedly. After further precipitating the magnesium salt, it was filtered again to remove most of the by-product salt. Furthermore, well-dried activated carbon (granular Shirasagi KL, manufactured by Osaka Gas Chemical Co., Ltd.) was added to this filtrate, and shaking was carried out for 3 hours using a mix rotor. Then, the activated carbon was removed by filtration, and a solution containing the organosilicon compound represented by formula (5) was recovered.

Chemical formula

[0081] <Example 2> The Grignard reaction was carried out in the same manner as in Example 1 except that the amount of the mixed solvent was adjusted so that the volume ratio of tetrahydrofuran to toluene after the dropping was completed was 1:5, and the organosilicon compound represented by the formula (5) was recovered. The obtained organosilicon compound was subjected to molecular weight measurement by GPC and analysis by FT-IR. The results are shown in Table 4.

[0082] <Example 3> The Grignard reaction was carried out in the same manner as in Example 1 except that a mixed solvent composed of tetrahydrofuran and benzene (volume ratio of tetrahydrofuran to benzene after the dropping was completed: 1:1) was used as the mixed solvent, and the organosilicon compound represented by the formula (5) was recovered. The obtained organosilicon compound was subjected to molecular weight measurement by GPC and analysis by FT-IR. The results are shown in Table 4.

[0083] <Comparative Example 1> The Grignard reaction was carried out in the same manner as in Example 1 except that tetrahydrofuran alone was used as the solvent instead of the mixed solvent, and the organosilicon compound represented by the formula (5) was recovered. The obtained organosilicon compound was subjected to molecular weight measurement by GPC and analysis by FT-IR. The results are shown in Table 1.

[0084] <Comparative Example 2> The Grignard reaction was carried out in the same manner as in Example 1 except that a mixed solvent composed of tetrahydrofuran and cyclohexane (volume ratio of tetrahydrofuran to cyclohexane after the dropping was completed: 1:1) was used as the solvent. Although heat was generated, the solution after the post-treatment was subjected to molecular weight measurement by GPC and analysis by FT-IR, but the target organosilicon compound and peaks corresponding thereto were not detected. The results are shown in Table 4.

[0085]

Table 4

[0086] As is clear from the above experimental results, by producing an organosilicon compound by the production method according to the present embodiment, the structure of the obtained organosilicon compound can be suitably controlled, and an organosilicon compound with a small (-Si-R) / (-Si-R-Si-) can be produced. The organosilicon compound produced by the production method according to the present embodiment can be used in fields such as electronic materials and pharmaceutical raw materials.

Claims

1. A method for producing an organosilicon compound, comprising a reaction step of subjecting a silane-based raw material, an organic halide having two or more halogen groups, and magnesium to a Grignard reaction in a mixed solvent containing an ether-based solvent and an aromatic-based solvent.

2. The method for producing an organosilicon compound according to claim 1, wherein the silane-based raw material is an alkoxysilane.

3. The method for producing an organosilicon compound according to claim 1, wherein the ether-based solvent is tetrahydrofuran.

4. The method for producing an organosilicon compound according to claim 1, wherein the aromatic-based solvent is at least one selected from the group consisting of toluene, benzene, ethylbenzene, o-xylene, m-xylene, and p-xylene.

5. The method for producing an organosilicon compound according to claim 1, wherein the volume ratio of the ether-based solvent to the aromatic-based solvent in the mixed solvent is 5 / 1 to 1 / 5.

6. The method for producing an organosilicon compound according to any one of claims 1 to 5, wherein the organosilicon compound is a compound represented by the following formula (III). 【Chemical 1】 In formula (III), R １ represents an organic group, and R ２ each independently represents a hydrogen atom or a monovalent organic group, R ３ each independently represents an alkyl group, and n is an integer of 2 or more.

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