JP5062231B2 - Organosilicon resin having alcoholic hydroxyl group and method for producing the same - Google Patents

Description

The present invention relates to a novel organosilicon resin having an alcoholic hydroxyl group and a method for producing the same.
The organosilicon resin of the present invention is useful as a raw material for lithography materials and organic-inorganic hybrid materials.

(Organic silicon resin containing alcoholic hydroxyl group)
Various types of organosilicon resins containing alcoholic hydroxyl groups are known. Conventional organosilicon resins are obtained by introducing an alcoholic hydroxyl group into a polymeric organosilicon resin constituting a skeleton (for example, Patent Documents 1 to 4).

  Since these conventional organosilicon resins are obtained by a polymer reaction in which a specific reactive group in a polymer is reacted with a compound having an alcoholic hydroxyl group, it is difficult to precisely control the amount of alcoholic hydroxyl group introduced. Moreover, when raw materials remain after the completion of the polymer reaction, it is difficult to remove them and purify the organosilicon resin.

As a method for obtaining a silicon resin having an alcoholic hydroxyl group, a method of synthesizing an organosilicon resin having an alicyclic epoxide and then converting it to an organosilicon resin having a diol using an oxidation reaction (polymer reaction) has been reported. (For example, Patent Document 5).
Further, polymethylsilsesquioxane-related fine particles having an alcoholic hydroxyl group have also been reported (for example, Patent Document 6).

Since the organosilicon resin having an alcoholic hydroxyl group expresses an alkali-soluble group, it is useful as a raw material for a lithography material, an organic-inorganic hybrid material, and the like.
In addition, these resins easily react with the silylating agent, and thus can be used as raw materials for various functional materials.

  On the other hand, oxa-silacyclopentanes have been reported to be used as intermediates in organic synthesis (for example, Non-Patent Documents 1 and 2).

  In addition, since oxa-silacyclopentanes easily cause a ring-opening reaction by hydrolysis and give a hydroxyl group, basic research has been made (for example, Non-Patent Documents 3 to 4).

JP-A-8-231924 JP-A-9-176321 JP 2001-213963 A Japanese Patent Laid-Open No. 2003-146832 Japanese Patent Laid-Open No. 10-87834 JP-A-11-116682 JP 2003-149822 A

J. Org. Chem. 1997, 62, 4206 J. Org. Chem. 2002, 67, 2056 MakromolekulareChemie 1964, 73, 85 MakromolekulareChemie 1966, 97, 241

As described above, when an alcoholic hydroxyl group is introduced into an organosilicon resin, most reports use a polymer reaction, and precise control of the resin composition is very difficult.
In addition, alcoholic hydroxyl groups easily react with silanol remaining in the resin, and organosilicon resins having alcoholic hydroxyl groups are easily gelled.
The present inventors have made it an object to construct a stable organosilicon resin having an alcoholic hydroxyl group and a method for producing the same, which is easy to control the composition and does not change with time.

  The present invention relates to an organosilicon resin containing an alcoholic hydroxyl group.

［式中、Ｚは、水酸基が結合する炭素原子から遠い末端炭素原子Ｃ_Ｅが炭素−炭素不飽和結合を形成している炭素数２〜５のアルケニル基を示し、Ｒはメチル基または水素を示し、Ｍｅはメチル基を示す。］

［式中、Ｒ_１は、炭素数１〜３のアルキル基又はアルコキシル基を示し、Ｒ_２は炭素数１〜３のアルキル基を示し、複数のＲ_２は互いに同一でも異なっていてもよい。］

［式中、Ｚ’は、Ｚの炭素−炭素不飽和結合を飽和結合にし、Ｚの末端炭素原子Ｃ_ＥがＳｉ原子と結合する炭素数２〜５のアルキレン基を示し、Ｒはメチル基または水素を示し、Ｒ_１は炭素数１〜３のアルキル基又はアルコキシル基を示し、Ｒ_２は炭素数１〜３のアルキル基を示す。］ The present invention provides a stable organosilicon resin having an alcoholic hydroxyl group that can be easily controlled in composition and that does not change with time by using a cyclic organosilicon compound such as oxa-silacyclopentanes as a resin raw material. To do.
The organosilicon resin of the present invention is obtained by reacting an olefin represented by the following general formula (1) and an alkoxysilane represented by the following general formula (2) in the presence of a transition metal catalyst. A cyclic organosilicon compound represented by formula (3) (hereinafter abbreviated as cyclic organosilicon compound [3]) or a mixture of this and a polyfunctional alkoxysilane is hydrolyzed and condensed, and has an alcoholic hydroxyl group. It is an organosilicon resin.

[In the formula, Z represents an alkenyl group having 2 to 5 carbon atoms in which the terminal carbon atom _CE far from the carbon atom to which the hydroxyl group is bonded forms a carbon-carbon unsaturated bond, and R represents a methyl group or hydrogen. Me represents a methyl group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, R ₂ represents an alkyl group having 1 to 3 carbon atoms, and a plurality of R ₂ may be the same as or different from each other. ]

[In the formula, Z ′ represents a C2-C5 alkylene group in which the carbon-carbon unsaturated bond of Z is a saturated bond and the terminal carbon atom _{CE of} Z is bonded to the Si atom, and R is a methyl group or Represents hydrogen, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, and R ₂ represents an alkyl group having 1 to 3 carbon atoms. ]

Considering the ease of obtaining the raw material and the raw material cost, a desirable raw material compound is a cyclic organosilicon compound (hereinafter abbreviated as DESMBO) in which each substituent in the general formula (3) is as follows.
Z ′: ethylene group R: methyl group R ₁ : ethoxy group R ₂ : ethyl group By hydrolyzing and condensing this compound, the composition can be easily controlled and has a stable alcoholic hydroxyl group which does not change with time. A silicon resin can be easily obtained.

A preferred production method for obtaining the organosilicon resin of the present invention is a cyclic organosilicon compound [3] or a mixture of this and a polyfunctional alkoxysilane, while maintaining the concentration of the resulting polymer at 30% by mass or less. It is a method of hydrolysis and condensation in an organic solvent.
A preferred production method comprises the following four steps.
Step (1): A cyclic organosilicon compound [3] or a mixture composed of this and a polyfunctional alkoxysilane is hydrolyzed in an organic solvent, and after further adding an organic solvent, a dehydrating agent is added for dehydration.
Step (2): After filtering the dehydrating agent, the resin-terminated silanol is sealed with a silylating agent.
Step (3): After distilling off the solvent, an organic solvent and water are added, and the organosilicon resin having an alcoholic hydroxyl group is washed with water.
Step (4): A dehydrating agent is added to dehydrate the resin, and then the solvent is distilled off to obtain an organosilicon resin having an alcoholic hydroxyl group.

According to the present invention, a stable organosilicon resin having an alcoholic hydroxyl group, which is easy to control the composition and does not change with time, can be obtained.
According to the production method of the present invention, an organosilicon resin having an alcoholic hydroxyl group can be stably produced without any change in molecular weight while easily controlling the composition.

FIG. 1 is a ¹ H-NMR spectrum of the compound obtained in the Reference Example. FIG. 2 is a ¹³ C-NMR spectrum of the compound obtained in the reference example. FIG. 3 shows the ¹ H-NMR spectrum of the organosilicon resin obtained in Example 1. FIG. 4 shows the ¹³ C-NMR spectrum of the organosilicon resin obtained in Example 1. FIG. 5 shows the IR spectrum of the organosilicon resin obtained in Example 1.

In the cyclic organosilicon compound represented by the general formula (3), a hydrosilylation reaction and a ring-closure condensation reaction (desorption) are performed on an olefin (1) having a hydroxyl group and an alkoxysilane (2) in the presence of a transition metal catalyst. It is synthesized by performing an alcohol reaction.
Since these reactions can be performed instantaneously, side reactions hardly occur and the target compound can be obtained with extremely high purity and high yield.

［式中、Ｚは、水酸基が結合する炭素原子から遠い末端炭素原子Ｃ_Ｅが炭素−炭素不飽和結合を形成している炭素数２〜５のアルケニル基を示し、Ｒはメチル基または水素を示し、メチル基が好ましく、Ｍｅはメチル基を示す。］ O Olefins having a hydroxyl group Olefins having a hydroxyl group are represented by the following general formula (1).

[In the formula, Z represents an alkenyl group having 2 to 5 carbon atoms in which the terminal carbon atom _CE far from the carbon atom to which the hydroxyl group is bonded forms a carbon-carbon unsaturated bond, and R represents a methyl group or hydrogen. And a methyl group is preferred, and Me represents a methyl group. ]

Preferred examples of olefins include 1-propen-3-methyl-3-ol, 1-butene-4-methyl-4-ol, 1-penten-5-methyl-5-ol, 1-hexene-6-methyl. -6-ol, 1-buten-3-methyl-3-ol, 1-penten-4-methyl-4-ol, 1-hexen-5-methyl-5-ol and 1-heptene-6-methyl-6 -There is an oar.
Among these, 1-butene-3-methyl-3-ol is most preferable because it is easy to obtain a raw material.
When a compound having no methyl group at the α-position of the hydroxyl group is used as the olefin (1), a large amount of by-products are generated, and the yield of the target compound is significantly reduced.

［式中、Ｒ_１は、炭素数１〜３のアルキル基又はアルコキシル基を示し、Ｒ_２は炭素数１〜３のアルキル基を示し、複数のＲ_２は互いに同一でも異なっていてもよい。］ ○ Alkoxysilanes The alkoxysilanes are represented by the following general formula (2).

[Wherein, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, R ₂ represents an alkyl group having 1 to 3 carbon atoms, and a plurality of R ₂ may be the same as or different from each other. ]

Preferred examples of alkoxysilanes include trimethoxysilane, triethoxysilane, tripropoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyldipropoxysilane, methoxydiethoxysilane, methoxydipropoxysilane, ethoxydipropoxysilane, Examples include methylmethoxyethoxysilane and methylmethoxypropoxysilane. Of these, triethoxysilane in which R ₁ is an ethoxy group and R ₂ is an ethyl group is most preferred.

○ Catalyst The olefins of the above general formula (1) and the alkoxysilane of the above general formula (2) are subjected to a hydrosilylation reaction and a ring-closing condensation reaction (dealcoholization reaction) in the presence of a transition metal catalyst.
The catalyst is not particularly limited as long as it is known to promote the hydrosilylation reaction, and preferred catalysts include those from Group 8 such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum. There are simple substance of group 10 metal, organometallic complex, metal salt, metal oxide and the like.
Usually, platinum-based catalyst is used, preferred platinum catalysts, chloroplatinic acid hexahydrate _{(H 2 PtCl 6 · 6H 2} O), cis-PtCl 2 (PhCN) 2, platinum carbon, divinyl siloxane Examples include coordinated platinum complexes (Pt-dvds). Ph represents a phenyl group.
The amount of the catalyst used is preferably 0.1 ppm to 1,000 ppm with respect to the olefin of the general formula (1).

○ Reaction conditions The preferred feed ratio of olefins (1) and alkoxysilane (2) is 110 to 120 moles of compounds having a low boiling point based on 100 moles of compounds having a high boiling point among these raw material compounds. It is a ratio to do.
This is to facilitate purification by distillation after synthesis.
Usually, since alkoxysilane (2) is a compound having a lower boiling point than olefins (1), alkoxysilane (2) is used in excess of olefins (1).
In addition, the reaction temperature control operation depends on the heating from the outside and the supply rate of the alkoxysilane, and thus cannot be generally determined. However, the reaction temperature is usually maintained in the range of 40 to 120 ° C. The relation reaction and the ring closure condensation reaction (dealcoholization reaction) can be continued smoothly.
The product obtained by the above reaction is further purified by appropriately removing unreacted raw materials by a purification step such as distillation, and can be easily made 90% or more pure.

Hydrolysis / Condensation of Cyclic Organosilicon Compound [3] Cyclic organosilicon compound [3] synthesized as described above is hydrolyzed under acid or basic conditions to form a skeleton of organosilicon resin. A hydroxyl group can be introduced into the resin skeleton.
The product obtained by hydrolysis / condensation is a polymer having the following repeating units.
That is, when R ₁ in the general formula (3) is an alkyl group having 1 to 3 carbon atoms, the repeating unit is the following [A],

上記一般式（３）におけるＲ_１が炭素数１〜３のアルコキシル基である場合、繰り返し単位は、下記［Ｂ］である。

When R ₁ in the general formula (3) is an alkoxyl group having 1 to 3 carbon atoms, the repeating unit is [B] below.

上記［Ａ］、［Ｂ］の何れの繰り返し単位も、環状有機ケイ素化合物［３］の環が開環して生成する水酸基を有する点に特徴がある。

Any of the above repeating units [A] and [B] is characterized in that it has a hydroxyl group formed by opening the ring of the cyclic organosilicon compound [3].

The organosilicon resin of the present invention is obtained by hydrolyzing and cocondensing a mixture of a cyclic organosilicon compound [3] and a polyfunctional alkoxysilane, in addition to hydrolyzing and condensing the cyclic organosilicon compound [3] alone. Including
Preferred polyfunctional alkoxysilanes include 3 to 4 functional alkoxysilanes, and those composed of an alkyl group having 1 to 3 carbon atoms and / or an alkoxy group having 1 to 3 carbon atoms are preferable. Preferred examples of the tri- or tetrafunctional alkoxysilane include triethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
A desirable ratio of the polyfunctional alkoxysilane is a ratio of 10 moles or less per mole of the cyclic organosilicon compound [3].
The preferred number average molecular weight of the organosilicon resin of the present invention is 1,000 to 1,000,000, and the preferred average molecular weight measured by GPC is 1,000 to 100,000.

Preferred acids include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid and the like.
Preferred bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, triethylamine, pyridine and the like.
The preferable amount of water used for the hydrolysis is not less than the theoretical amount, desirably 1.5 to 2 times the theoretical amount.
Examples of preferable organic solvents used at the time of hydrolysis include acetone, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, hexane, and the like. Also good.
Preferred molecular weight regulators include hexamethyldisiloxane, tetramethyldisiloxane, hexaphenyldisiloxane, hexavinyldisiloxane, tetraphenyldimethyldisiloxane, tetraisopropyldisiloxane and the like.

  Examples of the dehydrating agent after hydrolysis include anhydrous sodium sulfate, anhydrous magnesium sulfate and the like, and there is no particular limitation on the type as long as it has a dehydrating effect and does not contaminate the resin.

The resin-terminated silanol is sealed with a silylating agent. By sealing the resin-terminated silanol, an organosilicon resin having an alcoholic hydroxyl group that is stable over time can be constructed.
Preferred silylating agents include 1,1,1,3,3,3-hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, heptamethyldisilazane, 1,3-divinyl-1, 1,3,3-tetramethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, tris (trimethylsilyl) amine, bis (diethylamino) dimethylsilane, bis (dimethylamino) dimethylsilane, Examples include aminosilanes such as bis (dimethylamino) diphenylsilane, bis (dimethylamino) methylphenylsilane, trimethylsilanol, and t-butylaminotrimethylsilane, and chlorosilanes such as silanol, trimethylchlorosilane, dimethylchlorosilane, and phenylmethylchlorosilane. The Moreover, you may use together with bases, such as a triethylamine and a pyridine.

After sealing the terminal silanol in the silicon-based resin obtained immediately after hydrolysis and condensation, the solvent is distilled off under reduced pressure, the organic solvent is added, and the organic silicon resin is washed with water.
Examples of preferable organic solvents used in the water washing include acetone, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, hexane, and the like, which may be used alone or in combination of two or more. Good.
Although ultrapure water is generally used for washing with water, an acidic aqueous solution such as a hydrochloric acid aqueous solution, an alkaline aqueous solution such as a sodium hydroxide aqueous solution, a saturated sodium chloride aqueous solution, or the like may be used. The washing with water is preferably performed until the water layer becomes neutral.

  By dehydrating after washing with water and distilling off the solvent under reduced pressure, a stable organosilicon resin having an alcoholic hydroxyl group that is easy to control the composition and does not change with time can be obtained. Examples of the dehydrating agent used after washing with water include anhydrous sodium sulfate, anhydrous magnesium sulfate and the like, and there is no particular limitation on the type as long as it has a dehydrating effect and does not contaminate the resin.

Hereinafter, the present invention will be specifically described by way of examples.
[Reference example]
A reactor (flask) equipped with a cooling tube, a dropping funnel and a magnetic stir bar was charged with 1-butene-3-methyl-3-ol (30 g, 348 mmol) in a reactor (flask) and stirred. Triethoxysilane (62.9 g, 383 mmol) was charged into the dropping funnel. Triethoxysilane (11.2 mL) charged in the dropping funnel is poured into the flask, and the oil bath is set at 80 ° C. When the internal temperature reaches 70 ° C., a 0.1 MPt-dvds xylene solution (13 μL, 0.0013 mmol) is placed in the flask to initiate the reaction. The reaction was continued, and it was confirmed by gas chromatography that the amount of ethanol produced by the ring closure reaction reached the amount expected from the raw material. After completion of the reaction, a colorless and transparent liquid (58.2 g) was obtained by distillation under reduced pressure (boiling point: 13300 Pa, 117-120 ° C., yield: 82%. A purity of 98% or more was confirmed by measurement by gas chromatography).

The colorless transparent liquid was subjected to ¹ H-NMR measurement at 270 MHz, and the spectrum shown in FIG. 1 was obtained. The δ value and its attribution are shown in Table 1. It was confirmed that the compound thus obtained had the following structure.

^{When 13} C-NMR was measured, the spectrum of FIG. 2 was obtained.
The δ value and its attribution are shown in Table 2. It was confirmed that the compound thus obtained had the following structure.

[Example 1]
(Synthesis of organosilicon resin)
A reactor equipped with a dropping funnel and a magnetic stir bar was charged with DESMBO (49 g, 240 mmol), methyltriethoxysilane (78.6 g, 441 mmol), hexamethyldisiloxane (19.5 g, 120 mmol), and acetone (91 g). did. A 1.5 wt% aqueous hydrochloric acid solution (37.4 g) was charged into the dropping funnel and slowly dropped. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours. Subsequently, after diisopropyl ether (200 g) was added, anhydrous magnesium sulfate was added and dehydrated for 2 hours. Anhydrous magnesium sulfate is filtered off, hexamethyldisilazane (38.7 g, 240 mmol) is slowly added with stirring, and after stirring at room temperature for 2 hours, the solvent is distilled off under reduced pressure. After washing with methyl ethyl ketone (200 g) and 1N-hydrochloric acid aqueous solution, washing with water is repeated until the aqueous layer becomes neutral. After dehydration with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain an organosilicon resin (73.3 g, 89%).
When this organic silicon resin was subjected to ¹ H-NMR measurement at 270 MHz, a spectrum shown in FIG. 3 was obtained.
The δ value and its attribution are shown in Table 3. It was confirmed that the compound thus obtained had the following structure.

^１３Ｃ−ＮＭＲの測定を行ったところ、第４図のスペクトルを得た。
δ値とその帰属は第４表のとおりであった。これにより得られた化合物は、下記構造であることが確認できた。

^{When 13} C-NMR was measured, the spectrum of FIG. 4 was obtained.
The δ value and its attribution were as shown in Table 4. It was confirmed that the compound thus obtained had the following structure.

ＩＲの測定を行ったところ、第５図のスペクトルを得た。
３４００ｃｍ^−１にＯ−Ｈ伸縮振動が観測され、アルコール性水酸基の存在が確認された。

As a result of IR measurement, the spectrum of FIG. 5 was obtained.
O-H stretching vibration was observed at 3400 cm ^−1, and the presence of an alcoholic hydroxyl group was confirmed.

(Stability test)
Propylene glycol methyl ether acetate containing 0.5 wt% water was prepared as a solvent. The organosilicon resin prepared in Example 1 was dissolved in a solvent at a concentration of 10 wt% to prepare a sample. This sample was allowed to stand at 60 ° C. for 3 days and the change in molecular weight was followed. The results are shown in Table 5.

分子量変化が無く、安定な有機ケイ素樹脂であることを確認した。

It was confirmed that the organosilicon resin was stable and had no change in molecular weight.

[Comparative Example 1]
(When resin end silanol is not sealed)
In a reactor equipped with a dropping funnel and a magnetic stirring bar, 1,1-diethyl-5,5-dimethyl-1-sila-2-oxacyclopentane (49 g, 240 mmol), methyltriethoxysilane (78.6 g, 441 mmol) , Hexamethyldisiloxane (19.5 g, 120 mmol) and acetone (91 g) were charged and stirred. A 1.5 wt% aqueous hydrochloric acid solution (37.4 g) was charged into the dropping funnel and slowly dropped. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours. When the solvent was distilled off under reduced pressure, gelation occurred.

  The organosilicon resin having an alcoholic hydroxyl group of the present invention is useful as a raw material for lithography materials and organic-inorganic hybrid materials.

Claims (4)

It is represented by the following general formula (3) obtained by reacting the olefins represented by the following general formula (1) and the alkoxysilane represented by the following general formula (2) in the presence of a transition metal catalyst. An organosilicon resin having an alcoholic hydroxyl group, which is obtained by hydrolyzing and condensing a cyclic organosilicon compound or a mixture of this and a polyfunctional alkoxysilane.

[In the formula, Z represents an alkenyl group having 2 to 5 carbon atoms in which the terminal carbon atom _CE far from the carbon atom to which the hydroxyl group is bonded forms a carbon-carbon unsaturated bond, and R represents a methyl group or hydrogen. Me represents a methyl group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, R ₂ represents an alkyl group having 1 to 3 carbon atoms, and a plurality of R ₂ may be the same as or different from each other. ]

[In the formula, Z ′ represents a C2-C5 alkylene group in which the carbon-carbon unsaturated bond of Z is a saturated bond and the terminal carbon atom _{CE of} Z is bonded to the Si atom, and R is a methyl group or Represents hydrogen, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group, and R ₂ represents an alkyl group having 1 to 3 carbon atoms. ]   The organosilicon resin having an alcoholic hydroxyl group according to claim 1, wherein after the condensation, the resin-terminated silanol is sealed with a silylating agent.   While maintaining the density | concentration of the polymer to produce | generate the mixture which consists of a cyclic | annular organosilicon compound represented by General formula (3) of Claim 1 or this and polyfunctional alkoxysilane at 30 mass% or less, in an organic solvent A method for producing an organosilicon resin having an alcoholic hydroxyl group, characterized by hydrolysis and condensation.   The method for producing an organosilicon resin having an alcoholic hydroxyl group according to claim 3, wherein the resin-terminated silanol is sealed with a silylating agent after the condensation.

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