WO2022168735A1

WO2022168735A1 - Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane, and method for producing polysiloxane

Info

Publication number: WO2022168735A1
Application number: PCT/JP2022/003177
Authority: WO
Inventors: 友大片村; 惇也中辻; 豊杉田; 祐梨及川; 一広山中
Original assignee: セントラル硝子株式会社
Priority date: 2021-02-05
Filing date: 2022-01-27
Publication date: 2022-08-11
Also published as: TW202246291A; KR20230142534A; JPWO2022168735A1; CN116802186A

Abstract

Provided are: a silicon compound (HFIP group-containing aromatic alkoxysilane) containing an HFIP group and containing a reduced amount of a specific halogenated silane compound; a method for producing the same; a polysiloxane obtained by polymerizing the silicon compound which contains the HFIP group; and a method for producing the same. Provided is a silicon compound containing a silicon compound represented by formula (1) and a halogenated silane compound represented by formula (2), wherein the content of the halogenated silane compound represented by formula (2) is greater than 0 ppm by mass and no greater than 1,000 ppm by mass.

Description

Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane and method for producing polysiloxane

One embodiment of the present invention relates to a silicon compound containing a hexafluoroisopropanol group and a method for producing the same. Alternatively, one embodiment of the present invention relates to a polysiloxane obtained by polymerizing the silicon compound and a method for producing the same.

Polymer compounds containing siloxane bonds (hereinafter sometimes referred to as polysiloxane polymer compounds or simply polysiloxane) are used in the field of semiconductors as coating materials and sealing materials, taking advantage of their high heat resistance and transparency. in use. It is also used as a resist layer material due to its high resistance to oxygen plasma.

In order to use a polysiloxane polymer compound as a resist, it must be soluble in an alkali such as an alkaline developer. As a means for making the polysiloxane polymer soluble in an alkaline developer, an acidic group may be introduced into the polysiloxane polymer compound. Such acidic groups include phenol groups, carboxyl groups, fluorocarbinol groups, and the like. However, it is known that polysiloxane polymer compounds containing a phenol group or a carboxyl group may cause deterioration in transparency, coloration, etc., or poor heat resistance when used at high temperatures.

A fluorocarbinol group, which is an acidic group, such as a hexafluoroisopropanol group {2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [-C(CF ₃ ) ₂ OH], hereinafter sometimes referred to as an HFIP group}, are disclosed in Patent Documents 1 and 2.

Patent Document 1 discloses a method for producing an organosilicon compound (R ₃ Si—CH ₂ —CH ₂ —CH ₂ —C(CF ₃ ) ₂ OH) having an HFIP group (R has 1 to 3 carbon atoms). alkoxy group). The organosilicon compound is obtained by hydrosilylating a compound having an HFIP group represented by CH ₂ ═CH—CH ₂ —C(CF ₃ ) ₂ OH and a trialkoxysilane containing an alkoxy group having 1 to 3 carbon atoms. can get.

In Patent Document 2, a fluorocarbinol group is bonded to a main chain consisting only of siloxane via a linear, branched, cyclic or bridged cyclic divalent hydrocarbon group having 1 to 20 carbon atoms. Polymeric compounds are disclosed.

The organosilicon compound described in Patent Document 1 contains an ethylene bond ₍ --CH.sub.2--CH.sub.2--) between the HFIP group and the silicon atom, and the polymer compound described in Patent Document ₂ contains the HFIP group and the siloxane main chain. An aliphatic hydrocarbon group is interposed between the silicon atoms of .

Further, Patent Documents 3 and 4 disclose a method for producing an HFIP group-containing silicon compound (1) in which an HFIP group and a silicon atom are directly bonded, and an HFIP group-containing polysiloxane polymer obtained by polymerizing (1). The compound is disclosed, and it is shown that the polysiloxane polymer compound exhibits higher heat resistance than the polymer compound described in Patent Document 1. It is also disclosed that the HFIP group-containing polysiloxane polymer compound has both transparency and alkali solubility.

JP-A-2004-256503 JP-A-2002-55456 JP 2014-156461 A International Publication No. 2019/167770

For example, in the manufacturing process of the HFIP group-containing silicon compound (1) described in Patent Documents 3 and 4, since a compound containing halogen other than fluorine is used, the HFIP group containing impurities containing halogen other than fluorine is used. Silicon-containing compound (1) may be obtained. In general, in order to use alkoxysilanes for electronic material applications, it may be required that the content of halogen-containing impurities be low.

The present inventors have found that a specific halogenated silane compound is contained as one of the halogen-containing impurities in the method for producing the HFIP group-containing silicon compound (1) described in Patent Documents 3 and 4, It has been found that there is room for improvement in reducing the content of halogen-containing impurities by reducing the content of the halogenated silane compound.

Therefore, in the present disclosure, a silicon compound containing an HFIP group in which the content of a specific halogenated silane compound is reduced (hereinafter also referred to as an HFIP group-containing aromatic alkoxysilane), a method for producing the same, and a silicon compound containing an HFIP group An object of the present invention is to provide a polysiloxane obtained by polymerizing a compound and a method for producing the same.

The present inventors diligently studied a new method for removing halogen-containing impurities remaining in the HFIP group-containing alkoxysilane. As a result, it was found that halogen-containing impurities remaining in the HFIP group-containing alkoxysilane can be removed by performing distillation again after removing high-boiling components by distillation.

One embodiment of the present invention includes a silicon compound represented by the following formula (1) and a halogenated silane compound represented by the following formula (2), wherein the halogenated silane compound represented by the formula (2) content is more than 0 ppm by mass and 1000 ppm by mass or less.

(In formula (1), R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R ² is each independently , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is 1 or more It is an integer of 3 or less, and a+b+c=4.)

(In formula (2), R ^1a is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R ^2a is each independently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, and aa is an integer of 1 to 3 , bb is an integer of 0 or more and 2 or less, cc is an integer of 0 or more and 2 or less, dd is an integer of 1 or more and 3 or less, and aa+bb+cc+dd=4.)

The upper limit of the content of the halogenated silane compound may be 100 ppm by mass or less.

in formula (1) and formula (2)

(A line segment that intersects with a wavy line represents a bond.)
The group represented by
It may be one or more selected from the group consisting of groups represented by the following formulas (2A) to (2D).

(The line segments intersecting the wavy lines represent bonds, respectively.)

aa may be 1.

dd may be 1.

R ^2a may be a methyl group or an ethyl group.

The halogenated silane compound is represented by formula (2) in which aa is 1, bb is 0, dd is 1 or 2, cc is 1 or 2, and R ^2a is a methyl group or an ethyl group. It may be a compound that is

The content of the silicon compound (meta form) represented by the formula (1) composed of the group represented by the formula (2A) is Xa mol,
When Ya mol is the content of the silicon compound (para-body) represented by the formula (1) composed of the group represented by the formula (2B),

Ya/(Ya+Xa)<0.10

may satisfy the relationship of

The halide ion concentration may be 100 ppm by mass or less.

One embodiment of the present invention distills a mixture containing at least a silicon compound represented by the following formula (1) and a halogenated silane compound represented by the following formula (2), and a first distillation step of recovering a first mixture containing a lower boiling point component than the silicon compound represented by the formula (1);
Distilling the first mixture containing the silicon compound represented by the formula (1) and a component with a boiling point lower than that of the silicon compound represented by the formula (1) obtained in the first step, ) and a second distillation step to recover the silicon compound represented by
Provided is a method for producing a silicon compound, characterized in that the content of the halogenated silane compound represented by formula (2) is 1000 ppm by mass or less.

(In the above formula (1), each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and each R ² is independently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is 1 It is an integer greater than or equal to 3 and less than or equal to 3, and a + b + c = 4.)

(In the above formula (2), each R ^1a is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R ^2a is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is 1 to 3 an integer, bb is an integer of 0 or more and 2 or less, cc is an integer of 0 or more and 2 or less, dd is an integer of 1 or more and 3 or less, and aa+bb+cc+dd=4.)

One embodiment of the present invention provides a polysiloxane obtained by polymerizing any of the above silicon compounds.

The halide ion concentration may be 1000 ppm by mass or less.

An embodiment of the present invention provides a method for producing polysiloxane by polymerizing any of the above silicon compounds.

According to the present invention, a silicon compound containing a HFIP group (HFIP group-containing aromatic alkoxysilane) having a reduced content of a specific halogenated silane compound, a method for producing the same, and a silicon compound containing an HFIP group are polymerized. and a method for producing the same can be provided.

A silicon compound (HFIP group-containing aromatic alkoxysilane), a method for producing the same, polysiloxane, and a method for producing the same according to an embodiment of the present invention will be described below. However, the embodiments of the present invention should not be construed as being limited to the descriptions of the embodiments and examples shown below. In this specification, the notation "X to Y" in the explanation of the numerical range means X or more and Y or less, unless otherwise specified.

In the notation of a group (atomic group) in this specification, a notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituents and those having substituents. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

As used herein, the "cyclic alkyl group" includes not only monocyclic structures but also polycyclic structures. The same applies to a "cycloalkyl group".

In this specification, a hexafluoroisopropanol group represented by —C(CF ₃ ) ₂ OH is sometimes referred to as “HFIP group”.

A silicon compound according to one embodiment of the present invention includes an HFIP group-containing aromatic alkoxysilane and a halogenated silane compound, which will be described below.

<HFIP Group-Containing Aromatic Alkoxysilane>
The HFIP group-containing aromatic alkoxysilane (silicon compound) used in the present invention is represented by the following general formula (1) and has a structure in which the HFIP group and silicon atoms are directly bonded to an aromatic ring.

In formula (1), each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms. Each R ² is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1-5. a is an integer of 1 or more and 3 or less, b is an integer of 0 or more and 2 or less, c is an integer of 1 or more and 3 or less, and a+b+c=4.

Among these, in the HFIP group-containing aromatic alkoxysilane represented by formula (1)

In the group represented by, n is preferably 1 or 2, and particularly preferably at least one group selected from the group consisting of groups represented by the following formulas (2A) to (2D). Moreover, as for a, 1 is preferable. In the above formulas and formulas (2A) to (2D), line segments intersecting with the wavy lines represent bonds.

R ¹ is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group.

R ² is preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and all or part of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. may be Specifically, R ² includes methyl group, ethyl group, 1-propyl group, 2-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2 , 2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group and the like can be used, and methyl group or ethyl group is particularly preferable.

<Halogenated silane compound>
The halogenated silane compound contained in the silicon compound according to the present invention is represented by the following formula (2). As will be described later, the halogenated silane compound represented by the following formula (2) is preferably not included in the silicon compound according to the present invention. Halogens and/or halogen compounds may be contained as raw materials or by-reactants, so it is difficult to reduce the content of halogenated silane compounds in the silicon compound according to the present invention to 0 mass ppm. The silicon compound according to the present invention is characterized in that the content of the halogenated silane compound represented by the following formula (2) is lower than ever before.

In formula (2), R ^1a is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R ^2a is each independently and , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is an integer of 1 or more and 3 or less, bb is an integer of 0 or more and 2 or less, and cc is an integer of 0 or more and 2 or less. and dd is an integer of 1 or more and 3 or less, and aa+bb+cc+dd=4.

Among these, in the halogenated silane compound represented by formula (2)

For the group represented by n may be 1 or 2, particularly one or more selected from the group consisting of groups represented by the following formulas (2A) to (2D) good too. Also, aa may be 1. In the above formulas and formulas (2A) to (2D), line segments intersecting with the wavy lines represent bonds.

In one embodiment, dd may be 1.

R ^1a may be an alkyl group having 1 to 5 carbon atoms, especially a methyl group.

R ^2a may be a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and all or part of the hydrogen atoms in the alkyl group are fluorine atoms. may be replaced with Specifically, R ^2a includes a methyl group, ethyl group, 1-propyl group, 2-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2 , 2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, and the like, and particularly methyl group or ethyl group.

The silicon compound according to the present invention mainly contains an HFIP group-containing aromatic alkoxysilane represented by formula (1), and in one embodiment, the content of the halogenated silane compound represented by formula (2) is 0 mass. ppm and not more than 1000 mass ppm. Preferably, the upper limit of the content of the halogenated silane compound represented by formula (2) is 100 mass ppm or less. In the silicon compound according to the present invention, the content of the halogenated silane compound represented by formula (2) is preferably as small as possible, and may be 0 ppm by mass. Halogens and/or halogen compounds may be included as raw materials or by-reactants in the process, so it is difficult to reduce the content of the halogenated silane compound in the silicon compound according to the present invention to 0 mass ppm. Moreover, from a technical point of view for detecting a halogenated silane compound, the detection limit may be the lower limit. For example, the lower limit may be 10 mass ppm. In this specification, the content of the halogenated silane compound represented by formula (2) shall be measured using gas chromatography.

In one embodiment, the silicon compound according to the present invention preferably has a halide ion concentration of 100 ppm by mass or less. In this specification, the halide ions to be measured are evaluated as halide ions including the halogen contained in the halogenated silane compound represented by formula (2). The halide ions to be measured are chloride, bromide or iodide ions.

In the silicon compound according to the present invention, the halide ion concentration may be 0 mass ppm, but as described above, it is difficult to make the halide ion concentration 0 due to the production process using a halogen compound, From a technical point of view for detecting halide ion concentration, the detection limit may be the lower limit. For example, the lower limit may be 0.1 mass ppm. In the present specification, the halide ion concentration can be determined by an optimum measuring method depending on the sample to be measured. A measurement sample in which the silicon compound of the present invention is solid and a measurement sample containing the silicon compound of the present invention and a water-insoluble organic solvent are measured using ion chromatography. Alternatively, a measurement sample containing the silicon compound or polysiloxane of the present invention and a water-soluble organic solvent, for example, a measurement sample containing a reaction solvent used in the method for producing polysiloxane described later, is measured using a silver chloride nephelometry. shall be

In one embodiment, when measuring the halide ion concentration in a solution containing a silicon compound, the halide ion concentration of the silicon compound of the present invention can be calculated from the halide ion concentration of a measurement sample containing an organic solvent. can. For example, the halide ion concentration (ppm) obtained by subtracting the halide ion concentration (ppm) of the organic solvent from the halide ion concentration (ppm) of the measurement sample containing the organic solvent, and the weight (g) of the measurement sample containing the organic solvent , the halide ion amount (g) of the measurement sample excluding the halide ions derived from the organic solvent (hereinafter referred to as halide ion amount (1)) can be obtained. Also, the mass (g) of the silicon compound in the measurement sample containing the organic solvent can be obtained from the concentration (% by mass) of the measurement sample containing the organic solvent and the weight (g) of the measurement sample containing the organic solvent. The amount of halide ions (1) obtained above is considered to be derived from the silicon compound. Concentration (ppm) can be calculated.

In one embodiment, the content of the silicon compound (meta-body) represented by formula (1) composed of the group represented by formula (2A) is Xa mol, composed of the group represented by formula (2B) When the content of the silicon compound (para-body) represented by the formula (1) is Ya mol,

Ya/(Ya+Xa)<0.10

may satisfy the relationship of

The silicon compound according to the embodiment of the present invention is solid at room temperature (eg, 20°C), and by satisfying the above relationship, the fluidity of the solid can be improved. In particular, the smaller the value of the above relational expression, the more the fluidity tends to be improved, which is preferable from the viewpoint of handling of solids.

It is known that the meta isomer and the para isomer have different polymerization reactivity, and by satisfying the above relationship, it is possible to suppress variations in polymerization reactivity. In particular, the smaller the value of the above relational expression, the more likely it is that variation in polymerization reactivity will be suppressed, which is preferable from the viewpoint of polymer quality and production stability.

[Method for producing silicon compound]
The method for producing the silicon compound according to the present invention is not particularly limited, and the method for producing the HFIP group-containing aromatic alkoxysilane (1) can be used. A typical manufacturing method is described below.

The compound represented by general formula (1) is known, and can be synthesized by referring to the methods described in Patent Document 3 and Patent Document 4, for example.

[Purification method]
The synthesized HFIP group-containing aromatic alkoxysilane (1) contains halogens and/or halogen compounds produced by raw materials and side reactions. That is, since the silicon compound in the state before purification contains the above halogens and/or halogen compounds, the halogenated silane compound represented by the formula (2) is likely to be produced when a conventional purification operation is performed. . Therefore, in one embodiment of the method for producing a silicon compound according to the present invention, the following purification method is used.

In the purification method of the present invention, the HFIP group-containing aromatic alkoxysilane represented by formula (1) is subjected to a distillation step, and the HFIP group-containing aromatic alkoxysilane and the A first step of recovering a mixture containing a boiling point component, and a mixture containing the HFIP group-containing aromatic alkoxysilane obtained in the following first step and a component with a boiling point lower than that of the HFIP group-containing aromatic alkoxysilane. is subjected to a distillation step again to perform a second step of recovering the HFIP group-containing aromatic alkoxysilane, thereby reducing halogen-containing impurities. The operation will be described in detail below.

[Pre-distillation (first distillation step)]
In the present invention, the HFIP group-containing aromatic alkoxysilane is subjected to distillation (pre-distillation) as the first distillation step for the purpose of removing high-boiling components. When direct precision distillation (main distillation) is performed without pre-distillation (in the case of conventional purification operations), the halogenated silane compound represented by formula (2) is produced as a by-product. This is because the high-boiling halogen-containing impurities remaining in the HFIP group-containing aromatic alkoxysilane are decomposed by the heat during distillation, and the hydrogen halide generated at that time undergoes an exchange reaction with the alkoxy group (Si—OR ² ). It is presumed that it was generated by waking up. Although the decomposition rate of the above thermal decomposition reaction is slow, it continues to occur during the distillation, making it difficult to completely separate the halogenated silane compound, which is a halogen-containing impurity, from the HFIP group-containing aromatic alkoxysilane.

On the other hand, by performing pre-distillation, a mixture containing the HFIP group-containing aromatic alkoxysilane and a component with a boiling point lower than that of the HFIP group-containing aromatic alkoxysilane is recovered, and high boiling halogen-containing impurities that cause thermal decomposition are removed. It can be removed as boiler residue. The distillation fraction obtained by this operation is subjected to distillation purification again to separate the halogenated silane compound from the HFIP group-containing aromatic alkoxysilane, thereby reducing halogen-containing impurities.

There are no particular restrictions on the method of pre-distillation, and in addition to simple distillation, multi-stage distillation that repeats this, batch-type distillation equipped with a rectifying column, continuous distillation, and thin-film distillation for high-boiling compounds. is used. The optimum distillation temperature for distillation varies greatly depending on the type of the HFIP group-containing aromatic alkoxysilane (1) to be purified, but it is preferably in the range of 100°C to 200°C. If the temperature is too high, the yield may decrease due to thermal decomposition. More preferably, the pre-distillation is carried out in the range of 100°C to 180°C. The pressure during pre-distillation is not particularly limited, but it is preferably adjusted according to the boiling point of the HFIP group-containing aromatic alkoxysilane. Specifically, pre-distillation is performed at 0.01 to 101 kPa (atmospheric pressure). preferable.

In the present invention, the halogen-containing impurities are reduced by re-distilling the obtained distillation fraction after the pre-distillation. At this time, the main halogen-containing impurity contained in the distillation fraction of the pre-distillation is the halogenated silane compound (2) produced as a by-product during the pre-distillation. Therefore, the halogenated silane compound (2) may be removed before the main distillation. Examples of such a removal step include retreatment with alcohol corresponding to OR ² in formula (1) (so-called HOR ² ) and washing with water.

[Main distillation (second distillation step)]
Subsequently, as a second distillation step, main distillation is performed for the purpose of recovering the HFIP group-containing aromatic alkoxysilane (1) and removing the halogenated silane compound (2). There are no particular restrictions on the method of this distillation, and in addition to simple distillation, multi-stage distillation that repeats this, batch-type distillation/continuous distillation equipped with a rectification column, or thin-film distillation for high-boiling compounds. is used. However, from the viewpoint of separation from the halogenated silane compound (2), batch distillation or continuous distillation equipped with a rectifying column is preferred. The optimum distillation temperature in the main distillation varies greatly depending on the type of the HFIP group-containing aromatic alkoxysilane (1) to be purified, which is used in the same manner as in the pre-distillation. C. to 180.degree. C. is more preferable. The pressure during the main distillation is not particularly limited as in the pre-distillation, but it is preferably adjusted according to the boiling point of the HFIP group-containing aromatic alkoxysilane, specifically 0.01 to 101 kPa (atmospheric pressure). Preference is given to carrying out the main distillation.

[Polysiloxane]
The polysiloxane according to this embodiment is a polysiloxane obtained by polymerizing the silicon compound of the present invention, and has at least one or more siloxane bonds. Methods for producing polysiloxane are known, and can be synthesized with reference to the methods described in Patent Documents 3 and 4, for example.

Specifically, after collecting the silicon compound of the present invention in a reaction vessel, water for hydrolyzing the silicon compound of the present invention, an acid catalyst for advancing the polycondensation reaction, and a reaction solvent are added to the reactor. The HFIP group-containing polysiloxane polymer compound of the present invention is obtained by adding to the inside and then stirring the reaction solution at room temperature or while heating to allow hydrolysis and polycondensation reactions to proceed.

The reaction solvent may be any solvent that dissolves the raw material compound, and the solvent may be a water-soluble or water-insoluble organic solvent, such as an alcohol solvent or an ether solvent. The water-soluble organic solvent in the present invention is an organic solvent having a solubility in water of more than 50 g/L, and the water-insoluble organic solvent has a solubility in water of 50 g/L or less. An organic solvent. Examples of water-soluble organic solvents include lower alcohols, lower ethers, lower ketones, and lower esters. Specifically, methanol (solubility in water: optionally mixed), ethanol (solubility in water: arbitrarily mixed), 1-propanol (water solubility: arbitrarily mixed), isopropanol (water solubility: 1000 g/L), 1-butanol (water solubility: 77 g/L), diethyl ether (solubility in water: 60 g / L), acetonitrile (solubility in water: 1000 g / L), tetrahydrofuran (solubility in water: arbitrarily mixed), N,N-dimethylformamide (solubility in water : arbitrarily mixed), and N-methyl-2-pyrrolidone (solubility in water: arbitrarily mixed). Examples of water-insoluble solvents include hydrocarbons, higher ethers, and higher ketones. Specifically, toluene (solubility in water: 0.526 g/L), diisopropyl ether (solubility in water: 11 g/L), L), and methyl-t-butyl ether (solubility in water: 42 g/L).

In the present invention, since the content of the halogenated silane represented by the formula (2) contained in the HFIP group-containing aromatic alkoxysilane represented by the formula (1) is reduced, it is possible to polymerize them. , a polysiloxane with a low halogen content can be obtained. In one embodiment, the halide ion concentration in the polysiloxane is 1000 mass ppm or less.

The present invention will be specifically described below with reference to examples, but the present invention is not limited by these examples.

Various analyzes in this example were performed by the methods shown below.

[Gas Chromatograph (GC)]
The purity of the silicon compound and the content of the chlorosilane compound corresponding to the formula (2) were measured using a gas chromatograph manufactured by Shimadzu Corporation under the trade name Shimadzu GC-2010, using a capillary column DB1 (60 mm × 0.25 mmφ × 1 µm ) was used for the measurement.

[Chloride ion measurement]
In this example, chloride ion was measured as the halogen.

[Ion chromatography]
A measurement sample in which the silicon compound of the present invention is solid and a measurement sample containing the silicon compound of the present invention and a water-insoluble organic solvent were measured using ion chromatography. Chloride ion measurement by ion chromatography was performed by adding methyl-t-butyl ether and ultrapure water to the measurement sample and stirring, and then the water layer was subjected to ion chromatography (DIONEX (registered trademark) AQUION) manufactured by Thermo Fisher Scientific Co., Ltd. was injected and measured. Dionex (registered trademark) Ion Pac AS22 was used for the column.

[Silver chloride nephelometry]
A sample containing the silicon compound or polysiloxane of the present invention and a water-soluble organic solvent was measured by a silver chloride nephelometry using silver nitrate. The silver chloride turbidimetric method can be performed according to JISB8224:2016. Nitric acid with a mass fraction of 60% specified in JIS K 8541 was used, and silver nitrate aqueous solution was 1.2 mol/L. Measurement was performed at a measurement wavelength of 335 nm.

[Molecular weight measurement]
The molecular weight of the polymer was measured by GPC using a gel permeation chromatograph (manufactured by Tosoh Corporation, HLC-8320GPC), and the weight average molecular weight (Mw) was calculated by polystyrene conversion.

[Synthesis Example 1]
360 g (1.70 mol) of phenyltrichlorosilane and 5.70 g (0.0425 mol) of aluminum chloride were added to a 1 L stirred autoclave. Then, after nitrogen substitution, 271 g (1.63 mol) of hexafluoroacetone was added over 5 hours while maintaining the internal temperature at 5 to 15° C., and then stirring was continued for 12 hours. After completion of the reaction, the reaction solution was transferred to a 3 L glass reactor equipped with a thermometer, a mechanical stirrer, and a Dimroth reflux tube and replaced with a dry nitrogen atmosphere, and the contents of the flask were heated to 60°C while stirring. Thereafter, 376 g (8.16 mol) of anhydrous ethanol was added dropwise using a dropping pump over 3 hours while nitrogen bubbling was performed, and an alkoxylation reaction was carried out while removing hydrogen chloride. After that, excess ethanol was distilled off using a vacuum pump. By washing the resulting mixture with water, 611 g of a mixture containing 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (GCarea%: 1-3 substituted (meta) = 86.7%, 1-4 substituted (para) = 3.7%, triethoxyphenylsilane = 5.3%, others: 4.3%) were obtained. . In the resulting mixture, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilylbenzene, which is the chlorosilane compound represented by formula (2), was analyzed by GC. The chloride ion concentration was 1.4 ppm.

[Example 1]
200 g of the mixture containing 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene obtained in Synthesis Example 1 was distilled at a temperature of 125 to 135°C under reduced pressure. Simple distillation was carried out at a degree of 1.2 kPa, and 190 g of 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta form: GC purity 88.2 %), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-isomer: GC purity 3.9%), 3-(2-hydroxy- A fraction consisting of 1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilylbenzene (detected by GC: 20 mass ppm) was obtained. The obtained fraction is subjected to precision distillation at a distillation temperature of 143 to 146 ° C. and a reduced pressure of 0.2 kPa using a distillation apparatus with 15 distillation stages to obtain 3-(2-hydroxy-1,1,1, 3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta form: GC purity 99.4%), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) 144 g (yield 72%) of -triethoxysilylbenzene (para-isomer: GC purity 0.5%) was obtained as a solid. 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilylbenzene, which is a chlorosilane compound represented by formula (2), was not detected by GC (i.e. , less than the detection limit of 10 mass ppm), and the chloride ion concentration was 0.3 ppm.

[Comparative Example 1]
For 200 g of the mixture containing 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene obtained in Synthesis Example 1, a distillation apparatus with 15 distillation stages was used. 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilyl by performing precision distillation at a distillation temperature of 143 to 146 ° C. and a reduced pressure of 0.1 kPa using Benzene (meta form: GC purity 99.2%), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para form: GC purity 0.4 %) was obtained as a solid (146 g (yield 73%)). 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilylbenzene, which is a chlorosilane compound represented by formula (2), was detected by GC and weighed 1700 mass. ppm and the chloride ion concentration was 140 ppm.

Comparing Example 1 and Comparative Example 1, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta compound ) has almost the same GC purity and yield (Example 1 has a GC purity of 99.4% and a yield of 72%, Comparative Example 1 has a GC purity of 99.2% and a yield of 73%), but the formula (2 ) and chloride ion concentrations in Example 1 were clearly lower than those in Comparative Example 1.

Since Example 1 and Comparative Example 1 both use the raw material obtained in Synthesis Example 1, Example 1, which is within the scope of the present invention, is more effective as a method for reducing chlorine-containing impurities. It became clear.

[Synthesis Example 2]
325 g (1.70 mol) of dichloro(methyl)phenylsilane and 5.70 g (0.0425 mol) of aluminum chloride were added to a 1 L stirred autoclave. Then, after nitrogen substitution, 271 g (1.63 mol) of hexafluoroacetone was added over 5 hours while maintaining the internal temperature at 5 to 15° C., and then stirring was continued for 12 hours. After completion of the reaction, the reaction solution was transferred to a 3 L glass reactor equipped with a thermometer, a mechanical stirrer, and a Dimroth reflux tube and replaced with a dry nitrogen atmosphere, and the contents of the flask were heated to 60°C while stirring. Thereafter, 251 g (5.44 mol) of anhydrous ethanol was added dropwise over 3 hours using a dropping pump while nitrogen bubbling was performed, and an alkoxylation reaction was carried out while removing hydrogen chloride. After that, excess ethanol was distilled off using a vacuum pump. By washing the resulting mixture with water, 514 g of a mixture containing 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene (GCarea %: 1-3 substituted (meta) = 79.9%, 1-4 substituted (para) = 6.2%, diethoxy(methyl)phenylsilane = 4.4%, others: 9.5% ). In the resulting mixture, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chloro(diethoxy)methylsilylbenzene, which is the chlorosilane compound represented by formula (2), It was not detected by GC (that is, less than the detection limit of 10 mass ppm), and the chloride ion concentration was 6.8 ppm.

[Example 2]
For 200 g of the mixture containing 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene obtained in Synthesis Example 2, a distillation temperature of 97 to 107 ℃, the degree of pressure reduction of 0.5 kPa, and the obtained fraction is again subjected to precision distillation at a distillation temperature of 103 to 106 ° C. and a degree of pressure reduction of 0.5 kPa using a distillation apparatus with 15 distillation stages. Thus, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene (meta form: GC purity 99.9%), 4-(2- Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene (para-isomer: GC purity 0.1%) was obtained as a solid (110 g, yield 55%). 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chloro(ethoxy)methylsilylbenzene, which is the chlorosilane compound represented by formula (2), was not detected by GC. (that is, less than the detection limit of 10 mass ppm), and the chloride ion concentration was 9.3 ppm.

[Example 3]
3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta form: GC purity 99.4% ), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-body: GC purity 0.5%) mixture (chloride ion concentration = 2 .5 ppm) 30 g (74 mmol), water 4.2 g (233 mmol), and acetic acid 0.2 g (3 mmol) were added and stirred at 75° C. for 24 hours to obtain an HFIP group-containing polysiloxane polymer compound. As a result of GPC measurement, Mw=1970 and the chloride ion concentration was 3.9 ppm.

[Example 4]
In order to obtain a polysiloxane polymer compound, a reaction solvent can also be used for the purpose of advancing the polycondensation reaction as described above. 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta form: GC purity 99.4% ), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-body: GC purity 0.5%) mixture (chloride ion concentration = 2 .5 ppm) was added with 12 g of ethanol as a reaction solvent to obtain a 70% by mass ethanol solution (chloride ion concentration was 1.7 ppm), and then the same procedure as in Example 3 was performed to obtain a polysiloxane polymer. It could be confirmed. As a result of GPC measurement after the reaction, Mw=1850 and the chloride ion concentration was 2.7 ppm.

[Example 5]
Similarly, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta form: GC purity 99 .4%), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-body: GC purity 0.5%) mixture (chloride ion concentration = 2.5 ppm), 12 g of toluene was added as a reaction solvent to obtain a 70 mass% toluene solution (chloride ion concentration was 1.0 ppm), and then the same procedure as in Example 3 was performed to obtain a polysiloxane polymer. It was confirmed that As a result of GPC measurement after the reaction, Mw was 1620 and the chloride ion concentration was 1.6 ppm.

Claims

It contains a silicon compound represented by the following formula (1) and a halogenated silane compound represented by the following formula (2), and the content of the halogenated silane compound represented by the above formula (2) is 0 ppm by mass. more than 1000 mass ppm or less, a silicon compound.

(In the above formula (1), each R 1 is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and each R 2 is independently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is 1 It is an integer greater than or equal to 3 and less than or equal to 3, and a + b + c = 4.)

(In the above formula (2), each R 1a is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R 2a is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is 1 to 3 an integer, bb is an integer of 0 or more and 2 or less, cc is an integer of 0 or more and 2 or less, dd is an integer of 1 or more and 3 or less, and aa+bb+cc+dd=4.)
2. The silicon compound according to claim 1, wherein the upper limit of the content of said halogenated silane compound is 100 mass ppm or less.
in the above formula (1) and the above formula (2)

(A line segment that intersects with a wavy line represents a bond.)
The group represented by
3. The silicon compound according to claim 1, which is one or more selected from the group consisting of groups represented by the following formulas (2A) to (2D).

(The line segments intersecting the wavy lines represent bonds, respectively.)
The silicon compound according to any one of claims 1 to 3, wherein said aa is 1.
The silicon compound according to any one of claims 1 to 4, wherein said dd is 1.
The silicon compound according to any one of claims 1 to 5, wherein said R 2a is a methyl group or an ethyl group.
The halogenated silane compound is such that the aa is 1, the bb is 0, the dd is 1 or 2, the cc is 1 or 2 , and the R2a is a methyl group or an ethyl group. The silicon compound according to any one of claims 1 to 3, which is a compound represented by the formula (2).
The content of the silicon compound (meta-body) represented by the formula (1) composed of the group represented by the formula (2A) is Xa mol,
When Ya mol is the content of the silicon compound (para-body) represented by the formula (1) composed of the group represented by the formula (2B),

Ya/(Ya+Xa)<0.10

4. The silicon compound according to claim 3, characterized in that it satisfies the relationship:
The silicon compound according to any one of claims 1 to 8, which has a halide ion concentration of 100 mass ppm or less.
A mixture containing at least the silicon compound represented by the following formula (1) and the halogenated silane compound represented by the following formula (2) is distilled to obtain the silicon compound represented by the formula (1) and the formula ( 1) a first distillation step of recovering a first mixture containing a lower boiling point component than the silicon compound represented by;
a second distillation step of distilling the first mixture obtained in the first step to recover the silicon compound represented by formula (1);
A method for producing a silicon compound, characterized in that the content of the halogenated silane compound represented by formula (2) is 1000 mass ppm or less.

(In the above formula (1), each R 1 is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and each R 2 is independently, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is 1 It is an integer greater than or equal to 3 and less than or equal to 3, and a + b + c = 4.)

(In the above formula (2), each R 1a is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, and R 2a is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is 1 to 3 an integer, bb is an integer of 0 or more and 2 or less, cc is an integer of 0 or more and 2 or less, dd is an integer of 1 or more and 3 or less, and aa+bb+cc+dd=4.)
A polysiloxane obtained by polymerizing the silicon compound according to any one of claims 1 to 9.
12. The polysiloxane according to claim 11, which has a halide ion concentration of 1000 mass ppm or less.
A method for producing polysiloxane, comprising polymerizing the silicon compound according to any one of claims 1 to 9.