TW202246291A - Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane, and method for producing polysiloxane - Google Patents

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 hexafluoroisopropanol group and its manufacturing method. Also, one embodiment of the present invention relates to a polysiloxane polymerized from the silicon compound and a method for producing the same.

Polymer compounds containing siloxane bonds (hereinafter sometimes referred to as polysiloxane polymer compounds, or polysiloxane for short) benefit from their high heat resistance and transparency, and are used as coating materials and Sealing materials are used in the semiconductor field. Also, because of its high resistance to oxygen plasma, it can also be used as a material for the resist layer.

In order to use a polysiloxane polymer compound as a resist, it is required to be soluble in alkali such as an alkaline developer. As a method for making it soluble in an alkaline developing solution, a method for introducing an acidic group into a polysiloxane polymer compound may, for example, be mentioned. As such an acidic group, a phenolic group, a carboxyl group, a fluoromethanol group etc. are mentioned. However, it is known that when a polysiloxane polymer compound containing a phenolic group or a carboxyl group is used at a high temperature, transparency may deteriorate, coloring may occur, or heat resistance may deteriorate.

Patent Document 1 and Patent Document 2 disclose a polysiloxane polymer compound in which a fluoromethanol group as an acidic group is introduced into a polysiloxane polymer compound. The fluoromethanol group is, for example, a hexafluoroisopropanol group { 2-Hydroxy-1,1,1,3,3,3-fluoroisopropyl [-C(CF ₃ ) ₂ OH], hereinafter sometimes referred to as HFIP group}.

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 a HFIP group (R means an alkane with 1 to 3 carbons oxygen). The organosilicon compound is prepared by siliconizing a compound having a HFIP group represented by CH ₂ ═CH-CH ₂ -C(CF ₃ ) ₂ OH and a trialkoxysilane containing an alkoxy group with 1 to 3 carbons. Obtained by hydrogenation.

Patent Document 2 discloses a polymer compound, which is bonded via a straight-chain, branched, cyclic, or bridging cyclic divalent hydrocarbon group with 1 to 20 carbons on the main chain composed only of siloxane. A fluoromethanol group.

The organosilicon compound described in Patent Document 1 contains a vinyl bond (-CH ₂ -CH ₂ -) between the HFIP group and the silicon atom, and the polymer compound described in Patent Document 2 has a silicon bond between the HFIP group and the siloxane main chain. There are aliphatic hydrocarbon groups between the atoms.

[先前技術文獻] [專利文獻] In addition, Patent Document 3 and Patent Document 4 disclose a method for producing a HFIP-group-containing silicon compound (1) formed by directly bonding a HFIP group to a silicon atom, and a HFIP-group-containing compound obtained by (1) polymerization. The polysiloxane-containing polymer compound exhibits heat resistance higher than that of the polymer compound described in Patent Document 1 above. It is also disclosed that the HFIP group-containing polysiloxane polymer compound also has both transparency and alkali solubility. [chemical 1]

[Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-256503 [Patent Document 2] Japanese Patent Laid-Open No. 2002-55456 [Patent Document 3] Japanese Patent Laid-Open No. 2014-156461 [Patent Document 4] International Publication No. 2019/167770

[Problem to be solved by the invention]

For example, in the production steps of the HFIP group-containing silicon compound (1) described in Patent Document 3 and Patent Document 4, a compound containing halogen other than fluorine is used, so there is a possibility of obtaining a HFIP group-containing impurity containing halogen other than fluorine. Possibility of silicon compound (1). Generally, alkoxysilanes are used in electronic materials, so the content of halogen-containing impurities is required to be low.

The present inventors found that in the production methods of the HFIP group-containing silicon compound (1) described in Patent Document 3 and Patent Document 4, a specific halogenated silane compound was contained as one of the halogen-containing impurities, and found that by reducing the halogenated The content of the silane compound reduces the content of halogen-containing impurities and there is still room for improvement.

Therefore, the object of the present invention is to provide a silicon compound containing a HFIP group (hereinafter also referred to as an aromatic alkoxysilane containing a HFIP group) that reduces the content of a specific halosilane compound. Polysiloxane polymerized from a silicon compound and a method for producing the same. [Technical means to solve the problem]

The inventors of the present invention have conducted intensive research on a novel method for removing residual halogen-containing impurities in HFIP-containing alkoxysilanes. As a result, it was found that the halogen-containing impurities remaining in the HFIP group-containing alkoxysilane can be removed by performing the distillation operation after removing the high-boiling point components.

(式(1)中，R ¹分別獨立地為氫原子、碳數1以上5以下之烷基、苯基、或碳數1以上10以下之氟烷基，R ²分別獨立地為氫原子、或碳數1以上5以下之烷基，n為1～5之整數，a為1以上3以下之整數，b為0以上2以下之整數，c為1以上3以下之整數，a＋b＋c＝4) [化3]

(式(2)中，R ^1a分別獨立地為氫原子、碳數1以上5以下之烷基、苯基、或碳數1以上10以下之氟烷基，R ^2a分別獨立地為氫原子、或碳數1以上5以下之烷基，X為氯原子、溴原子或碘原子，n為1～5之整數，aa為1以上3以下之整數，bb為0以上2以下之整數，cc為0以上2以下之整數，dd為1以上3以下之整數，aa＋bb＋cc＋dd＝4) One embodiment of the present invention provides a silicon compound, which includes a silicon compound represented by the following formula (1), a halosilane compound represented by the following formula (2), and a compound of the halosilane compound represented by the formula (2) The content is more than 0 mass ppm and 1000 mass ppm or less. [Chem 2]

(In formula (1), R ¹ are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of 1 to 10, and R ² are each independently a hydrogen atom, Or an alkyl group with a carbon number of 1 to 5, 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 an integer of 1 to 3, a+b+c=4) [Chem 3]

(In formula (2), R ^1a are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, phenyl, or a fluoroalkyl group with a carbon number of 1 to 10, and R ^2a are each independently a hydrogen atom, Or an alkyl group with a carbon number of 1 to 5, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer from 1 to 5, aa is an integer from 1 to 3, bb is an integer from 0 to 2, and cc is An integer between 0 and 2, dd is an integer between 1 and 3, aa+bb+cc+dd=4)

The upper limit of the content of the halosilane compound may be 100 mass ppm or less.

(與波浪線交叉之線段表示鍵結鍵) 所表示之基可為選自由下述式(2A)～(2D)所表示之基所組成之群中之一種以上。 [化5]

(各個與波浪線交叉之線段表示鍵結鍵) [Chemical 4] in formula (1) and formula (2)

(A segment intersecting with a wavy line represents a bonding bond) The group represented may be one or more kinds selected from the group consisting of groups represented by the following formulas (2A) to (2D). [chemical 5]

(Each line segment crossing the wavy line represents a bond bond)

aa can be 1.

dd can be 1.

R ^2a can be methyl or ethyl.

The halogenated silane compound may be a compound 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 methyl or ethyl.

When the content of the silicon compound (metasite) represented by the formula (1) containing the group represented by the formula (2A) is set as Xa mole, and When the content of the silicon compound (parasite) represented by the formula (1) containing the group represented by the formula (2B) is Ya mole, The following relationship can be satisfied: Ya/(Ya+Xa)<0.10.

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

(上述式(1)中，R ¹分別獨立地為氫原子、碳數1以上5以下之烷基、苯基、或碳數1以上10以下之氟烷基，R ²分別獨立地為氫原子、或碳數1以上5以下之烷基，n為1～5之整數，a為1以上3以下之整數，b為0以上2以下之整數，c為1以上3以下之整數，a＋b＋c＝4) [化7]

(上述式(2)中，R ^1a分別獨立地為氫原子、碳數1以上5以下之烷基、苯基、或碳數1以上10以下之氟烷基，R ^2a分別獨立地為氫原子、或碳數1以上5以下之烷基，X為氯原子、溴原子或碘原子，n為1～5之整數，aa為1以上3以下之整數，bb為0以上2以下之整數，cc為0以上2以下之整數，dd為1以上3以下之整數，aa＋bb＋cc＋dd＝4) One embodiment of the present invention provides a method for producing a silicon compound, which is characterized by comprising: a first distillation step, which contains at least a silicon compound represented by the following formula (1) and a silicon compound represented by the following formula (2): The mixture of halogenated silane compounds is distilled to recover the first mixture containing the silicon compound represented by the formula (1) and the components having a boiling point lower than the silicon compound represented by the formula (1); and a second distillation step for the first Distilling the first mixture comprising the silicon compound represented by formula (1) and components having a boiling point lower than the silicon compound represented by formula (1) obtained in step 1, and recovering the silicon compound represented by formula (1); and The content of the halogenated silane compound represented by formula (2) is 1000 mass ppm or less. [chemical 6]

(In the above formula ( ¹ ), R1 are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of ¹ to 10, and R2 are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 an integer of 1 to 3, a+b+c=4 ) [C7]

(In the above formula (2), R ^1a are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of 1 to 10, and R ^2a are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 to 3, bb is an integer of 0 to 2, cc is an integer from 0 to 2, dd is an integer from 1 to 3, aa+bb+cc+dd=4)

One embodiment of the present invention provides a polysiloxane, which is polymerized from any one of the above-mentioned silicon compounds.

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

One embodiment of the present invention provides a method for producing polysiloxane, which is to polymerize any one of the above-mentioned silicon compounds. [Effect of Invention]

According to the present invention, it is possible to provide a HFIP-group-containing silicon compound (HFIP-group-containing aromatic alkoxysilane) that reduces the content of a specific halogenated silane compound, its production method, and polymerize the HFIP-group-containing silicon compound The polysiloxane and its production method.

Hereinafter, the silicon compound (HFIP group-containing aromatic alkoxysilane) which is an embodiment of the present invention, its production method, polysiloxane and its production method will be described. However, the embodiments of the present invention should not be construed as being limited to the contents described in the embodiments and examples shown below. In addition, in this specification, the notation of "X-Y" in description of a numerical range means that X is more than Y and below Y unless otherwise specified.

In the notation of a group (atomic group) in this specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" refers not only to an alkyl group without a substituent (unsubstituted alkyl group), but also includes an alkyl group with a substituent (substituted alkyl group).

In this specification, "cyclic alkyl" includes not only monocyclic structures but also polycyclic structures. The same applies to "cycloalkyl".

In this specification, the hexafluoroisopropanol group represented by -C(CF ₃ ) ₂ OH may be referred to as "HFIP group".

The silicon compound according to one embodiment of the present invention includes: HFIP group-containing aromatic alkoxysilanes and halogenated silane compounds 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 HFIP group directly bonded to a silicon atom in the structure of the aromatic ring. [chemical 8]

In formula (1), R ¹ are 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. R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbons, and n is an integer of 1 to 5. a is an integer ranging from 1 to 3, b is an integer ranging from 0 to 2, c is an integer ranging from 1 to 3, and a+b+c=4.

所表示之基，n較佳為1或2，特佳為選自由下式(2A)～式(2D)所表示之基所組成之群中之一種以上。又，a較佳為1。再者，於上式及式(2A)～式(2D)中，與波浪線交叉之線段表示鍵結鍵。 [化10]

Among them, [Chemical 9] in the HFIP group-containing aromatic alkoxysilane represented by formula (1)

As for the groups represented, n is preferably 1 or 2, and particularly preferably at least one selected from the group consisting of groups represented by the following formula (2A) to formula (2D). Also, a is preferably 1. In addition, in the above formula and formula (2A) - formula (2D), the line segment which intersects with the wavy line represents a bond. [chemical 10]

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

R ² is preferably a straight-chain alkyl group having 1-4 carbons or a branched-chain alkyl group having 3-4 carbons, and all or part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. Specifically, R can use: methyl, ethyl, 1-propyl, ² -propyl, n-butyl, isobutyl, second butyl, third butyl, 2-fluoroethyl, 2 ,2,2-trifluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2 , 2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, etc., particularly preferably methyl or ethyl.

<Halogenated silane compound> The halogenated silane compound contained in the silicon compound of this invention is represented by following formula (2). As described below, the halogenated silane compound represented by the following formula (2) is preferably not included in the silicon compound of the present invention, but in the production process of the HFIP group-containing aromatic alkoxysilane (1), the raw material Or the side reactants may contain halogen and/or halogen compounds, so it is difficult to make the content of the halosilane compound in the silicon compound of the present invention 0 mass ppm. The silicon compound of the present invention is characterized in that the content of the halogenated silane compound represented by the following formula (2) is unprecedentedly reduced. [chemical 11]

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

所表示之基，n可為1或2，尤其是可為選自由下式(2A)～式(2D)所表示之基所組成之群中之一種以上。又，aa可為1。再者，於上述式及式(2A)～式(2D)中，與波浪線交叉之線段表示鍵結鍵。 [化13]

Among them, regarding [Chemical 12] in the halogenated silane compound represented by the formula (2)

In the group represented, n may be 1 or 2, and in particular may be at least one selected from the group consisting of groups represented by the following formula (2A) to formula (2D). Also, aa may be 1. In addition, in the said formula and formula (2A) - a formula (2D), the line segment which intersects with a wavy line represents a bond. [chemical 13]

In one embodiment, dd can 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 carbons or a branched alkyl group having 3 to 4 carbons, and all or part of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. Specifically, examples of R ^2a include methyl, ethyl, 1-propyl, 2-propyl, n-butyl, isobutyl, second-butyl, third-butyl, and 2-fluoroethyl. , 2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl , 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, etc., especially methyl or ethyl.

The silicon compound of the present invention mainly includes HFIP-containing aromatic alkoxysilane represented by formula (1). In one embodiment, the content of the halogenated silane compound represented by formula (2) is more than 0 mass ppm and is 1000 mass ppm or less. Preferably, the upper limit of the content of the halogenated silane compound represented by the formula (2) is 100 mass ppm or less. In the silicon compound of the present invention, the less the content of the halogenated silane compound represented by the formula (2), the better, it can be 0 mass ppm, but in the production step of the HFIP-containing aromatic alkoxysilane (1) , The raw materials or side-reactants may contain halogen and/or halogen compounds, so it is difficult to make the content of the halosilane compound in the silicon compound of the present invention 0 mass ppm. In addition, the detection limit may be set as a lower limit from a technical point of view for detecting the halide silane compound. For example, 10 mass ppm can be set as the lower limit. In this specification, the content of the halosilane compound represented by formula (2) is measured using gas chromatography.

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

In the silicon compound of the present invention, the concentration of halide ions may be 0 mass ppm. As mentioned above, it is difficult to make the concentration of halide ions 0 in the manufacturing process using halogen compounds. Furthermore, based on the method used to detect the concentration of halide ions From the point of view of the technical level, the detection limit can be set as the lower limit. For example, 0.1 mass ppm can be set as the lower limit. In this specification, the halide ion concentration can be determined by selecting the best measurement method according to the measurement sample. A measurement sample in which the silicon compound of the present invention is a solid, and a measurement sample containing the silicon compound of the present invention and a water-insoluble organic solvent are measured using ion chromatography. Also, the measurement sample containing the silicon compound or polysiloxane of the present invention and a water-soluble organic solvent, for example, the measurement sample containing a reaction solvent used in the production method of polysiloxane described below uses silver chloride ratio Turbidimetric measurement.

In one embodiment, when the halide ion concentration is measured 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. 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 measurement sample containing the organic solvent The weight (g) of the above-mentioned measurement sample except the halide ion derived from the organic solvent (g) was obtained (hereinafter referred to as the halide ion amount (1)). 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. It is believed that the amount of halide ions (1) obtained above comes from the silicon compound, so the halide ion concentration (ppm) of the silicon compound can be calculated from the amount of halide ions (1) and the mass (g) of the silicon compound in the measured sample .

In one embodiment, when the content of the silicon compound (metasite) represented by the formula (1) containing the group represented by the formula (2A) is set as Xa mole, and the content of the silicon compound (metasite) represented by the formula (2B) is When the content of the silicon compound (para-body) represented by the formula (1) of the base is set as Ya mole, The following relationship can be satisfied: Ya/(Ya+Xa)<0.10.

The silicon compound according to the embodiment of the present invention is solid at room temperature (for example, 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 fluidity tends to be improved, which is preferable from the viewpoint of solid operability.

It is known that the meta-body and the para-body have different polymerization reactivity, and by satisfying the above relationship, the difference in polymerization reactivity can be suppressed. In particular, the smaller the value of the above relational expression, the more the variation in polymerization reactivity tends to be suppressed, which is preferable from the viewpoint of polymer quality and production stability.

[Manufacturing method of silicon compound] The method for producing the silicon compound of the present invention can be the method for producing the HFIP group-containing aromatic alkoxysilane (1), and is not particularly limited. A description of a typical manufacturing method is as follows.

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

[purification method] The synthesized HFIP group-containing aromatic alkoxysilane (1) contains halogen and/or halogen compounds generated in raw materials or side reactions. That is, since the above-mentioned halogen and/or halogen compound are contained in the silicon compound before purification, the halogenated silane compound represented by the formula (2) can be easily produced by performing the previous purification operation. Therefore, in the production method of the silicon compound of the present invention, in one embodiment, the following purification method is used.

The purification method in the present invention is characterized in that the halogen-containing impurities are reduced by the following steps: In the first step, the HFIP group-containing aromatic alkoxysilane represented by formula (1) is used in the distillation step, and the The mixture of HFIP-based aromatic alkoxysilane and components with a boiling point lower than the HFIP-containing aromatic alkoxysilane is recovered; then, the second step, which contains the HFIP-containing group obtained in the first step The mixture of the aromatic alkoxysilane and the components having a boiling point lower than the HFIP-containing aromatic alkoxysilane is again used in the distillation step to recover the HFIP-containing aromatic alkoxysilane. Hereinafter, the operation will be described in detail.

[Pre-distillation (first distillation step)] In the present invention, the HFIP group-containing aromatic alkoxysilane is distilled (pre-distillation) as the first distillation step to remove high boiling point components. When the precision distillation (main distillation) is directly performed without pre-distillation (in the case of the previous purification operation), the halogenated silane compound represented by the formula (2) is produced as a by-product. It is speculated that the reason is that the residual high-boiling halogen-containing impurities in the HFIP-containing aromatic alkoxysilane are decomposed by the heat of distillation. At this time, the generated hydrogen halide and alkoxy (Si-OR ² ) exchange reaction to generate the above-mentioned by-products. Although the above thermal decomposition reaction is relatively slow, it continues to occur during distillation, so it is difficult to completely separate the halogenated silane compound as a halogen-containing impurity from the HFIP-containing aromatic alkoxysilane.

On the other hand, by pre-distillation, the mixture containing the HFIP group-containing aromatic alkoxysilane and components having a boiling point lower than the HFIP group-containing aromatic alkoxysilane can be recovered and removed as a still residue Halogen-containing impurities with high boiling points that cause thermal decomposition. By distilling and purifying the distillation fraction obtained in this operation again, the halogenated silane compound is separated from the aromatic alkoxysilane containing HFIP group, and the halogen-containing impurities can be reduced.

The method of pre-distillation is not particularly limited. In addition to simple distillation, multi-stage distillation of repeated simple distillation or batch distillation and continuous distillation with rectification tower can be used. In addition, in the case of high boiling point compounds, it can be Thin film distillation or the like is used. The optimal distillation temperature in distillation varies greatly depending on the type of HFIP group-containing aromatic alkoxysilane (1) to be purified, and it is preferably carried out within the range of 100°C to 200°C. If the temperature is too high, there is a possibility that 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 preferably performed at 0.01 to 101 kPa (atmospheric pressure).

In the present invention, after performing the above-mentioned pre-distillation, the obtained distillation fraction is distilled again, thereby reducing the halogen-containing impurities. At this time, the halogen-containing impurities contained in the pre-distilled distillation fraction are mainly halogenated silane compounds (2) that are by-produced during the pre-distillation. Therefore, the halogenated silane compound (2) can be removed before the formal distillation. As such a removal process, reprocessing with the alcohol (so-called HOR ² ) corresponding to OR ² in formula (1), washing with water, etc. are mentioned, for example.

[Main distillation (2nd distillation step)] Then, the main distillation is carried out as the second distillation step to recover the HFIP group-containing aromatic alkoxysilane (1) and remove the halosilane compound (2). There are no special restrictions on the method of formal distillation. In addition to simple distillation, multi-stage distillation with repeated simple distillation or batch distillation or continuous distillation with rectification tower can be used, or in the case of high boiling point compounds, it can be used thin film distillation etc. Among them, from the viewpoint of separation from the halosilane compound (2), batch distillation or continuous distillation equipped with a rectification column is preferable. The optimal distillation temperature in the formal distillation is also different from the pre-distillation according to the type of HFIP group-containing aromatic alkoxysilane (1) used for purification, and it is preferably between 100°C and 200°C within the range, more preferably within the range of 100°C to 180°C. The pressure during the formal distillation is the same as that during the pre-distillation, and there is no special limitation. It is better to adjust it according to the boiling point of the aromatic alkoxysilane containing HFIP groups. ) to carry out formal distillation.

[polysiloxane] The polysiloxane of the present embodiment is a polysiloxane polymerized from the above-mentioned silicon compound of the present invention, and has at least one siloxane bond. The production method of polysiloxane is known, for example, the method described in patent document 3 or patent document 4 can be referred to and synthesize|combined.

Specifically, after the above-mentioned silicon compound of the present invention is taken into the reaction vessel, water for hydrolyzing the above-mentioned silicon compound of the present invention, an acid catalyst for polycondensation reaction, and a reaction solvent are added to the reactor, and then , Stir the reaction solution at room temperature or under heating to carry out hydrolysis and polycondensation reactions, thereby obtaining the polysiloxane polymer compound containing HFIP groups of the present invention.

The reaction solvent may be any solvent as long as it can dissolve the raw material compound, and the solvent may be a water-soluble or water-insoluble organic solvent, for example, an alcohol-based solvent or an ether-based solvent. The water-soluble organic solvent in the present invention refers to an organic solvent whose solubility in water is greater than 50 g/L, and the water-insoluble organic solvent refers to an organic solvent whose solubility in water is less than 50 g/L. As water-soluble organic solvents, for example: lower alcohols, lower ethers, lower ketones, and lower esters, etc., specifically, for example: methanol (solubility in water: optional mixing), ethanol (solubility in water: optional mixing ), 1-propanol (solubility in water: mix freely), isopropanol (solubility in water: 1000 g/L), 1-butanol (solubility in water: 77 g/L), Diethyl ether (solubility in water: 60 g/L), acetonitrile (solubility in water: 1000 g/L), tetrahydrofuran (solubility in water: mix freely), N,N-dimethylformyl Amine (solubility in water: optional mixture), N-methyl-2-pyrrolidone (solubility in water: optional mixture), etc. As the non-water-miscible solvent, can exemplify: hydrocarbon, or higher ether, higher ketone etc., specifically can exemplify: toluene (solubility in water: 0.526 g/L), diisopropyl ether (solubility in water: 11 g/L), and methyl tertiary butyl ether (solubility in water: 42 g/L), etc.

In the present invention, since the content rate of the halogenated silane represented by the formula (2) contained in the HFIP group-containing aromatic alkoxysilane represented by the formula (1) is reduced, by polymerizing these, it is possible to Polysiloxanes with lower halogen content are obtained. In one embodiment, the concentration of halide ions in polysiloxane is 1000 mass ppm or less. [Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

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

[Gas Chromatography (GC)] Regarding solid or solution samples, the purity of the silicon compound and the content of the chlorosilane compound equivalent to formula (2) in the silicon compound were determined using a gas chromatograph manufactured by Shimadzu Corporation, trade name Shimadzu GC -2010, using capillary column DB1 (60 mm×0.25 mmϕ×1 μm) as the column for determination.

[Determination of chloride ion] In this example, chloride ions were determined as halogens.

[Ion Chromatography] A measurement sample in which the silicon compound of the present invention is a solid and a measurement sample containing the silicon compound of the present invention and a water-insoluble organic solvent are measured using ion chromatography. Chloride ion measurement by ion chromatography is to add methyl tertiary butyl ether and ultrapure water to the measurement sample, stir, and inject the water layer into an ion chromatograph (DIONEX) manufactured by Thermo Fisher Scientific Co., Ltd. (registered trademark) AQUION), for measurement. The column system uses Dionex (registered trademark) Ion Pac AS22.

[Silver Chloride Turbidimetry] A sample containing the silicon compound or polysiloxane of the present invention and a water-soluble organic solvent is measured by the silver chloride nephelometric method using silver nitrate. The above-mentioned silver chloride turbidimetric method can be performed in accordance with JISB8224:2016. Furthermore, use nitric acid with a mass fraction of 60% specified in JIS K 8541 as nitric acid, use 1.2 mol/L silver nitrate aqueous solution as silver nitrate aqueous solution, add methanol to the measurement sample, adjust to a uniform sample, and measure The sample was measured at a wavelength of 335 nm.

[Molecular weight determination] The molecular weight of the polymer was measured by GPC (Gel Permeation Chromatograph, gel permeation chromatography) using a gel permeation chromatograph (manufactured by Tosoh Co., Ltd., HLC-8320GPC), and the weight average was calculated in terms of polystyrene. Molecular weight (Mw).

[Synthesis Example 1] Add 360 g (1.70 mol) of phenyltrichlorosilane and 5.70 g (0.0425 mol) of aluminum chloride into a 1 L autoclave with a stirrer. 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 stirring was continued for 12 hours. After the reaction was completed, configure a thermometer, a mechanical stirrer, and a Dairy reflux tube, transfer the reaction solution to a glass reaction device with a capacity of 3 L replaced by a dry nitrogen atmosphere, stir the contents of the flask and heat it to 60°C. Then nitrogen gas was introduced, and 376 g (8.16 mol) of absolute ethanol was added dropwise over 3 hours using a drip pump to carry out alkoxylation reaction while removing hydrogen chloride. Subsequently, the excess ethanol was distilled off using a decompression pump. By washing the resulting mixture with water, 611 g of a mixture containing 3-(2-hydroxyl-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene was obtained ( GC area%: 1-3 substitution body (meta body) = 86.7%, 1-4 substitution body (para body) = 3.7%, triethoxyphenylsilane = 5.3%, others: 4.3%). In the resulting mixture, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)- For chlorodiethoxysilylbenzene (ie, 10 mass ppm below the detection limit), the chloride ion concentration was 1.4 ppm.

[Example 1] The 3-(2-hydroxyl-1,1,1,3,3,3-hexafluoroisopropyl)-triethyl-1 Simple distillation of 200 g of the mixture of oxysilylbenzenes yielded 190 g of 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilyl Benzene (meta-body: GC purity 88.2%), 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-body: GC purity 3.9%), 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilylbenzene (detected by GC: 20 mass ppm ) fraction. By using a distillation apparatus with 15 distillation stages, the obtained fractions were subjected to precise distillation at a distillation temperature of 143-146°C and a reduced pressure of 0.2 kPa to obtain 144 g (yield 72%) of 3-( 2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (Metasite: GC purity 99.4%), 4-(2-Hydroxy-1, 1,1,3,3,3-Hexafluoroisopropyl)-triethoxysilylbenzene (Para: GC purity 0.5%). 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilane as a chlorosilane compound represented by formula (2) was not detected by GC phenylbenzene (that is, 10 mass ppm below the detection limit), and the chloride ion concentration was 0.3 ppm.

[Comparative example 1] By using a distillation device with 15 distillation stages, at a distillation temperature of 143-146°C and a reduced pressure of 0.1 kPa, the 3-(2-hydroxyl-1,1,1,3, 200 g of a mixture of 3,3-hexafluoroisopropyl)-triethoxysilylbenzene was subjected to precision distillation to obtain 146 g (yield 73%) of 3-(2-hydroxy-1,1, 1,3,3,3-Hexafluoroisopropyl)-triethoxysilylbenzene (Metasite: GC purity 99.2%), 4-(2-Hydroxy-1,1,1,3,3, 3-Hexafluoroisopropyl)-triethoxysilylbenzene (para: GC purity 0.4%). 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chlorodiethoxysilyl as a chlorosilane compound represented by formula (2) was detected by GC Benzene is 1700 ppm by mass, and the chloride ion concentration is 140 ppm.

If comparing Example 1 and Comparative Example 1, the 3-(2-hydroxyl-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilyl group represented by formula (1) The GC purity and yield of benzene (metasite) are roughly the same (the GC purity of Example 1 is 99.4% and the yield is 72%, and the GC purity of Comparative Example 1 is 99.2% and the yield is 73%). (2) The concentration of chlorosilane compounds and chloride ions represented in Example 1 is significantly lower than that obtained in Comparative Example 1.

In Example 1 and Comparative Example 1, the raw materials obtained in Synthesis Example 1 were used together, and it was clear that Example 1, which is within the scope of the present invention, is more effective as a method for reducing chlorine-containing impurities.

[Synthesis Example 2] Add 325 g (1.70 mol) of dichloro(methyl)phenylsilane and 5.70 g (0.0425 mol) of aluminum chloride into a 1 L autoclave with a stirrer. 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 stirring was continued for 12 hours. After the reaction was completed, configure a thermometer, a mechanical stirrer, and a Dairy reflux tube, transfer the reaction solution to a glass reaction device with a capacity of 3 L replaced by a dry nitrogen atmosphere, stir the contents of the flask and heat it to 60°C. Then nitrogen gas was introduced, and 251 g (5.44 mol) of absolute ethanol was added dropwise over 3 hours using a drip pump to carry out alkoxylation reaction while removing hydrogen chloride. Subsequently, the excess ethanol was distilled off using a decompression pump. By washing the resulting mixture with water, a compound containing 3-(2-hydroxyl-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene was obtained. Mixture 514 g (GC area%: 1-3 substitution body (meta body) = 79.9%, 1-4 substitution body (para body) = 6.2%, diethoxy (methyl) phenyl silane = 4.4% , Others: 9.5%). In the resulting mixture, 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)- Chloro(diethoxy)methylsilylbenzene (ie, 10 mass ppm less than the detection limit), the chloride ion concentration is 6.8 ppm.

[Example 2] By distilling at a temperature of 97 to 107°C and a degree of reduced pressure of 0.5 kPa, the 3-(2-hydroxyl-1,1,1,3,3,3-hexafluoroisopropyl)- Simple distillation of 200 g of the mixture of diethoxy(methyl)silylbenzene, using a distillation device with 15 stages of distillation, the distillation temperature is 103-106 ° C, and the degree of reduced pressure is 0.5 kPa. Distillation afforded 110 g (55% yield) of 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silane as a solid Phenylbenzene (Metasite: GC purity 99.9%), 4-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-diethoxy(methyl)silylbenzene (Para: GC purity 0.1%). 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-chloro(ethoxy) as a chlorosilane compound represented by formula (2) was not detected by GC For methylsilylbenzene (ie, 10 mass ppm below the detection limit), the chloride ion concentration was 9.3 ppm.

[Example 3] 3-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta Para-form: GC purity 99.4%), 4-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-form: GC purity 0.5% ) mixture (chloride ion concentration = 2.5 ppm) 30 g (74 mmol) was added 4.2 g (233 mmol) of water, 0.2 g (3 mmol) of acetic acid, stirred at 75 ° C for 24 hours to obtain HFIP containing Based 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 the polysiloxane polymer compound, the polycondensation reaction may also be performed using a reaction solvent as described above. It was confirmed that 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (meta-position) synthesized separately by the method described in Example 1 Para-form: GC purity 99.4%), 4-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (para-form: GC purity 0.5% ) mixture (chloride ion concentration = 2.5 ppm) 28 g, add 12 g of ethanol as a reaction solvent, after making a 70% by mass ethanol solution (chloride ion concentration is 1.7 ppm), it can be the same as in Example 3 Sequentially obtain polysiloxane macromolecules. GPC measurement was carried out after the reaction, and the result was Mw=1850, and the chloride ion concentration was 2.7 ppm.

[Example 5] Similarly, it was confirmed that 3-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene synthesized separately by the method described in Example 1 (Meta-form: GC purity 99.4%), 4-(2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-triethoxysilylbenzene (Para-form: GC Purity 0.5%) mixture (chloride ion concentration=2.5 ppm) 28 g, add the toluene of 12 g as reaction solvent, after making the toluene solution of 70 mass % (chloride ion concentration is 1.0 ppm), can be with embodiment 3. Obtain polysiloxane polymer in the same order. GPC measurement was carried out after the reaction, and the result was Mw=1620, and the chloride ion concentration was 1.6 ppm.

Claims (13)

A silicon compound comprising a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2), wherein the content of the halosilane compound represented by the above formula (2) is more than 0 mass ppm And it is 1000 mass ppm or less, [Chem. 1]

(In the above formula ( ¹ ), R1 are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of ¹ to 10, and R2 are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 an integer of 1 to 3, a+b+c=4 ) [Chem 2]

(In the above formula (2), R ^1a are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of 1 to 10, and R ^2a are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 to 3, bb is an integer of 0 to 2, cc is an integer ranging from 0 to 2, dd is an integer ranging from 1 to 3, aa+bb+cc+dd=4). The silicon compound according to claim 1, wherein the upper limit of the content of the above-mentioned halogenated silane compound is 100 mass ppm or less. Such as the silicon compound of claim 1, wherein [Chemical 3] in the above formula (1) and the above formula (2)

(The line segment intersecting with the wavy line represents the bonding bond) The base represented is one or more selected from the group consisting of the bases represented by the following formulas (2A) to (2D), [Chem. 4]

(Each segment intersecting the wavy line represents a bonding bond). The silicon compound according to claim 1, wherein aa above is 1. The silicon compound according to claim 1, wherein the above-mentioned dd is 1. The silicon compound according to claim 1, wherein the above R ^2a is methyl or ethyl. Such as the silicon compound of claim 1, wherein the above-mentioned halogenated silane compound is the above-mentioned formula in which the above-mentioned aa is 1, the above-mentioned bb is 0, the above-mentioned dd is 1 or 2, the above-mentioned cc is 1 or 2, and the above-mentioned R ^2a is methyl or ethyl (2) The compound represented. The silicon compound according to Claim 3, wherein the content of the silicon compound (metasite) represented by the above formula (1) containing the group represented by the above formula (2A) is Xa mole, and When the content of the silicon compound (parasite) represented by the above formula (1) containing the group represented by the above formula (2B) is Ya mole, the following relationship is satisfied: Ya/(Ya+Xa)<0.10. The silicon compound according to claim 1, wherein the halide ion concentration is 100 mass ppm or less. A method for producing a silicon compound, characterized by comprising: a first distillation step of distilling 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) , recovering the first mixture comprising the silicon compound represented by the formula (1) and the components having a boiling point lower than the silicon compound represented by the formula (1); 1 The mixture is distilled to recover the silicon compound represented by formula (1); and the content of the halogenated silane compound represented by formula (2) is 1000 mass ppm or less, [Chemical 5]

(In the above formula ( ¹ ), R1 are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of ¹ to 10, and R2 are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 an integer of 1 to 3, a+b+c=4 ), [Chem.6]

(In the above formula (2), R ^1a are each independently a hydrogen atom, an alkyl group with a carbon number of 1 to 5, a phenyl group, or a fluoroalkyl group with a carbon number of 1 to 10, and R ^2a are each independently a hydrogen atom , or an alkyl group with a carbon number of 1 to 5, 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 to 3, bb is an integer of 0 to 2, cc is an integer ranging from 0 to 2, dd is an integer ranging from 1 to 3, aa+bb+cc+dd=4). A polysiloxane polymerized from the silicon compound according to any one of claims 1 to 9. The polysiloxane according to claim 11, wherein the halide ion concentration is 1000 ppm by mass or less. A method for producing polysiloxane, which is to polymerize the silicon compound according to any one of claims 1 to 9.