WO2005044828A1

WO2005044828A1 - Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group

Info

Publication number: WO2005044828A1
Application number: PCT/JP2004/016445
Authority: WO
Inventors: Katsuhiko Komuro; Hiroshi Suzuki
Original assignee: Toagosei Co., Ltd.
Priority date: 2003-11-07
Filing date: 2004-11-05
Publication date: 2005-05-19
Also published as: KR20060111489A; KR101097570B1; JP4470886B2; JP5062231B2; JPWO2005044828A1; KR20110070928A; TW200519120A; JP2010013653A; TWI341842B; KR101064063B1

Abstract

[PROBLEMS] Disclosed is a production method wherein synthesis of a cyclic organic silicon compound similar to oxa-silacyclopentanes is completed in a single-step reaction. Also disclosed are an organic silicon resin having an alcoholic hydroxyl group which has long-term stability and whose composition is easily controlled, and a method for producing such an organic silicon resin. [MEANS FOR SOLVING PROBLEMS] A cyclic organic silicon compound represented by the formula (3) below is produced by reacting an olefin represented by the formula (1) below and an alkoxysilane represented by the formula (2) below in the presence of a transition metal catalyst. (In the above formula, Z represents an alkenyl group having 2-5 carbon atoms wherein the terminal carbon atom forms a C=C bond, R represents a methyl group or a hydrogen, and Me represents a methyl group.) (In the above formula, R1 represents an alkyl group or an alkoxyl group having 1-3 carbon atoms, and R2 represents an alkyl group having 1-3 carbon atoms.) (In the above formula, Z' represents an alkylene group having 2-5 carbon atoms.) An organic silicon resin having an alcoholic hydroxyl group is obtained by hydrolyzing and condensing the organic silicon compound represented by the above formula (3) or a mixture of the organic silicon compound and a multifunctional alkoxysilane.

Description

Specification

Method for producing cyclic organic gayne compound, gayne-based resin having alcoholic hydroxyl group, and method for producing same

Technical field

The present invention relates to a method for producing a cyclic organic silicon compound, and more particularly, to a method for producing an alkoxysilane having a hydroxyl group protected by an organic substituent.

The present invention also relates to a novel organic gay resin having an alcoholic hydroxyl group and a method for producing the same.

The organic gay resin of the present invention is useful as a raw material such as a material for lithography and an organic-inorganic hybrid material. Background art

[0002] (Cyclic organic gay compound)

Many compounds are known as halogenosilanes and alkoxysilanes having protected alkali-soluble groups. As a protected soluble group

And carboxyl groups, catechol (for example, Patent Document 1, Patent Document 2), or protected hydroxyl groups in alcohol.

Halogenosilanes and alkoxysilanes having a soluble group are useful as raw materials for lithography materials and organic-inorganic hybrid materials.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-224949

Patent Document 2: Japanese Unexamined Patent Application Publication No. 200 2-3 3 8583

[0004] However, the method known so far as a method for producing a halogenosilane or an alkoxysilane having a soluble group is a method utilizing a multi-step synthesis reaction. Not suitable.

On the other hand, as a cyclic organosilicon compound having a hydroxyl group protected by an organic group,

Oxa-silacyclopentanes are known (for example, Non-Patent Document 1, Non-Patent Document 2). [0005] Non-Patent Document 1: J. Org. Chem. 1997, 62, 4206-4207

Non-Patent Document 2: J. Org. Chem. 2002, 67, 2056-2064

[0006] It is known that oxa-silacyclopentanes easily cause a ring-opening reaction by hydrolysis to give a gay resin having an alcoholic hydroxyl group (for example, Non-Patent Document 3 Non-Patent Document 4).

Non-Patent Document 3: MakromolekulareChemie 1964, 73, 85

Non-Patent Document 4: MakromolekulareChemie 1966, 97, 241

[0007] (Organic gay resin containing alcoholic hydroxyl group)

Various organic gay resins containing alcoholic hydroxyl groups are known

. A conventional organic gay resin is obtained by introducing an alcoholic hydroxyl group into a polymer organic gay resin constituting a skeleton (for example, Patent Document 1 ^ 4) Patent Document 1: Japanese Patent Laid-Open No. 8- No. 231 924

Patent Document 2: JP-A-9-176321

Patent Document 3: JP 2001-213963 A

Patent Document 4: JP 2003-146832A

[0008] Since these conventional organic gay resins are obtained by a polymer reaction in which a specific reactive group in a polymer reacts with a compound having an alcoholic hydroxyl group, the introduction amount of the alcoholic hydroxyl group can be precisely determined. If the raw materials remain after the completion of the high molecular reaction, it is difficult to remove them and purify the organic gay resin.

[0009] As a method for obtaining a gay resin having an alcoholic hydroxyl group, an organic gay resin having an alicyclic epoxide is synthesized, and then an oxidation reaction (polymer reaction) is used to convert the organic gay resin having a diol into an organic gay resin having a diol. Conversion methods have also been reported (eg,

Patent Document 5).

Patent Document 5: JP-A-10-87834 Further, polymethylsilsesquioxane-based fine particles having an alcoholic hydroxyl group have been reported (for example, Patent Document 6). Patent Document 6: Japanese Patent Application Laid-Open No. Hei 1-11-1681

[0010] An organic gay resin having an alcoholic hydroxyl group is useful as a raw material for a lithography material, an organic-inorganic hybrid material, etc. because it exhibits an alkali-soluble group.

Patent Document 7: Japanese Patent Application Laid-Open No. 2003-149822 In addition, these resins can easily react with a silylating agent, and thus can be used as raw materials for various functional materials.

[0011] On the other hand, oxa-silacyclopentanes have been reported to be used as intermediates in organic synthesis.

Non-Patent Document 1: J.0rg. Chem. 1997, 62, 4206

Non-Patent Document 2: J. Org. Chem. 2002, 67, 2056

[0013] Furthermore, oxa-silacyclopentanes easily cause a ring-opening reaction by hydrolysis to give a hydroxyl group, and thus basic research has been conducted.

Non-Patent Document 3: MakromolekulareChemie 1964, 73, 85

Non-Patent Document 4: MakromolekulareChemie 1966, 97, 241

Disclosure of the invention

Problems to be solved by the invention

[0014] Oxa-silacyclopentanes are useful as various organic synthetic intermediates, reactants, and resin raw materials because they generate an alcoholic hydroxyl group by performing a ring opening reaction.

However, synthesis of oxa-silacyclopentanes usually requires at least two steps of 1) hydrosilation of olefins with hydrosilane and 2) ring-closure reaction. Requires two or more reaction steps.

[0015] The present invention provides a process for synthesizing a cyclic organosilicon compound having a structure similar to that of oxa-silacyclopentanes by completing the reaction in a one-step reaction to obtain a target compound with high purity and high yield. The task is to provide a law.

As described above, when introducing an alcoholic hydroxyl group into an organic gay resin, most reports use a polymer reaction, and precise control of the resin composition is not possible. It has always been difficult.

In addition, the alcoholic hydroxyl group easily reacts with silanol remaining in the resin, and the organic gay resin having the alcoholic hydroxyl group easily gels.

Another object of the present invention is to construct an organic gay resin having an alcoholic hydroxyl group which is easy to control the composition and does not change with time, and a method for producing the same. Means for solving the problem

[0017] The present invention relates to Invention 1 (hereinafter abbreviated as Invention 1) relating to a method for producing a cyclic organic gayne compound and Invention 2 (hereinafter referred to as Invention 2) relating to an organic gay resin containing an alcoholic hydroxyl group. Abbreviated).

The production method of the present invention 1 is characterized 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. This is a method for producing a cyclic organic gay compound represented by the following general formula (3).

[0018] [Formula 1]

[In the formula, Z represents an alkenyl group having 25 carbon atoms in which a terminal carbon atom C remote from the carbon atom to which the hydroxyl group is bonded forms a carbon-carbon unsaturated bond, and R is a methyl group or Me represents hydrogen, and Me represents a methyl group. ] [0020] [Formula 2]

[Wherein, R represents an alkyl group or an alkoxyl group having 13 carbon atoms, and R represents

12 represents an alkyl group having a prime number of 13, and a plurality of Rs may be the same or different from each other. ]

[0022] [Formula 3]

[In the formula, Z ′ represents an alkylene group having 25 carbon atoms in which the carbon-carbon unsaturated bond of z is a saturated bond, the terminal carbon atom C of Z is bonded to a Si atom, and R is a methyl group or Represents hydrogen, R represents an alkyl group having 13 carbon atoms or an alkoxyl group, and R represents an alkyl group having 13 carbon atoms. ]

In the present invention 2, the use of a cyclic organic gayne compound such as oxa-silacyclopentane as a resin raw material allows easy control of the composition and stable alcoholic hydroxyl groups with no change over time. To provide an organic gay resin having The organic gay resin of the present invention 2 comprises a cyclic organic gay compound represented by the above general formula (3) (hereinafter, abbreviated as a cyclic organic gay compound [3]), or a polyfunctional alkoxysilane Is an organic gay resin having an alcoholic hydroxyl group obtained by hydrolyzing and condensing a mixture of the above.

[0024] In view of the availability of raw materials and the cost of raw materials, a desirable raw material compound is a cyclic organic gayne compound (hereinafter abbreviated as DESMBO) in the above general formula (3) in which each substituent is as follows. It is.

Z ': ethylene group

R: methyl group

R: ethoxy group

1

R: ethyl group

2

By hydrolyzing and condensing this compound, it is easy to control the composition, and it is possible to easily obtain a stable silicone resin having an alcoholic hydroxyl group which does not change with time.

[0025] A preferred production method for obtaining the organic gay resin of the present invention 2 is to prepare a cyclic organosilicon compound [3] or a mixture thereof with a polyfunctional alkoxysilane at a polymer concentration of 30%. This is a method in which hydrolysis and condensation are performed in an organic solvent while maintaining the concentration at not more than mass%.

A preferred production method comprises the following four steps.

Step (1): In an organic solvent, the cyclic organic gayne compound [3] or a mixture of the cyclic organic gayne compound and the polyfunctional alkoxysilane is hydrolyzed, and after adding an organic solvent, a dehydrating agent is added to dehydrate.

Step (2): After filtering the dehydrating agent, the silanol at the terminal of the resin is sealed with a silylating agent.

Step (3): After distilling off the solvent, an organic solvent and water are added to form an alcoholic hydroxyl group. The organic gay resin to be washed with water.

Step (4): After adding a dehydrating agent and dehydrating the resin, the solvent is distilled off to obtain an organic gay resin having an alcoholic hydroxyl group. The invention's effect

According to the present invention 1, a cyclic organic gayne compound having an alcoholic hydroxyl group and an alkoxyl group protected by an organic substituent can be synthesized by a one-step reaction.

According to the method of the present invention 1, a side reaction can be suppressed, and a target cyclic organosilicon compound can be obtained with high purity and high yield.

When producing oxa-silacyclopentanes, high purity products of 98% or more can be easily obtained.

Since the cyclic organosilicon compound obtained by the present invention 1 has an alkoxysilyl group, it reacts with another organic gay compound (including a polymer) to form a lithiloxane bond, Coupling reaction with the silanol group in it is possible.

Further, the cyclic organosilicon compound obtained according to the present invention 1 easily undergoes ring opening by a hydrolysis reaction to generate an alcoholic hydroxyl group, and the alcoholic hydroxyl group functions as an alkali-soluble group and a crosslinkable group. That is, it functions as a multi-reactive gay compound having a gay functional and a protected carbon functional group. Therefore, the cyclic organic gayne compound obtained by this production method is useful as an intermediate for organic synthesis, a raw material for resin synthesis, a modifier for resin, and a surface treatment agent for inorganic compounds.

[0028] According to the present invention 2, a stable organic gay resin having an alcoholic hydroxyl group, whose composition can be easily controlled and which does not change with time, can be obtained.

ADVANTAGE OF THE INVENTION According to the production method of the present invention 2, it is possible to stably produce an organic gay resin having an alcoholic hydroxyl group without a change in molecular weight while easily controlling the composition. Possible, best mode for carrying out the invention

[0029] The present invention 1 relates to a method for producing a cyclic organic gay compound represented by the above general formula (3). Hereinafter, the present invention 1 will be described in detail.

[0030] The cyclic organic silicon compound represented by the general formula (3) is obtained by subjecting a hydroxyl-containing olefin (1) and an alkoxysilane (2) to a hydrosilation reaction in the presence of a transition metal catalyst. It is synthesized by performing a ring-closing condensation reaction (dealcoholization reaction).

In the present invention 1, these reactions can be performed instantaneously, so that side reactions hardly occur, and the target compound can be obtained in extremely high purity and high yield.

[0031] Olefins having a hydroxyl group

Olefins having a hydroxyl group are represented by the following general formula (1).

[0032] [Formula 4]

[0033] In the formula, Z represents an alkenyl group having 25 carbon atoms in which a terminal carbon atom C far from the carbon atom to which the hydroxyl group is bonded forms a carbon-carbon unsaturated bond, and R is a methyl group Or, it represents hydrogen, preferably a methyl group, and Me represents a methyl group.

Preferred examples of olefins include 1-propene-3-methyl-3-ol, 1-butene-4-methyl-4-ol, 1-pentene-5-methyl-5-ol, 1-hexene- 6-methyl-6-ol, 1-butene-3-methyl-3 There are -ol, 1-penten-4-methyl-4-ol, 1-hexene-5-methyl-5-ol and 1-heptene-6-methyl-6-ol.

Of these, 1-butene-3-methyl-3-ol is most preferable because the raw material is easily obtained.

When a compound having no methyl group at the hydroxyl group is used as the olefins (1), a large amount of by-products are generated, and the yield of the target compound is significantly reduced.

[0034] 〇alkoxysilanes

The alkoxysilanes are represented by the following general formula (2).

[0035] [Formula 5]

12 represents an alkyl group having a prime number of 13, and a plurality of Rs may be the same or different from each other

2

No. ]

Preferred examples of the alkoxysilanes include trimethoxy silane, triethoxy silane, tripropoxy silane, methyl dimethoxy silane, methyl ethoxy silane, methyl dipropoxy silane, methoxy diethoxy silane, methoxy dipropoxy. Examples include silane, ethoxydipropoxysilane, methylmethoxyethoxysilane, and methylmethoxypropoxysilane. R is an ethoxy group and R is an ethyl group.

1 2

Is most preferred.

[0038] 〇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 in the presence of a transition metal catalyst. (Dealcoholization reaction).

The catalyst used in the present invention 1 is not particularly limited as long as it is known to promote the hydrolysis reaction. Preferred catalysts include cobalt, nickel, ruthenium, rhodium, palladium, and iridium. And metals such as platinum, platinum, and other metals belonging to Groups 8 to 10; organometallic complexes; metal salts; and metal oxides.

Usually, platinum-based catalysts are used. Preferred platinum-based catalysts include chloroplatinic acid hexahydrate (HPtCI-6H0), cis-PtCI (PhCN), platinum carbon, and divinyl chloride.

2 6 2 2 2

Platinum complexes (Pt-dvds) coordinated with loxane are exemplified. Ph represents a phenyl group.

The amount of the catalyst to be used is preferably 0.1 ppm to 1,000 ppm with respect to the olefins represented by the general formula (1).

〇Reaction conditions

The preferred charge ratio of the olefins (1) and the alkoxysilane (2) is such that, based on 100 moles of the compound having a high boiling point, 110 mol The ratio is 20 moles.

This is to facilitate purification by distillation after synthesis.

Usually, the alkoxysilane (2) is a compound having a lower boiling point than the olefins (1), so that the alkoxysilane (2) is used in excess of the olefins (1).

In addition, since the control operation of the reaction temperature depends on external heating and the supply rate of the alkoxysilane, it cannot be determined unconditionally. However, usually, the reaction temperature is maintained in the range of 40 ° C to 120 ° C. The silylation reaction and the ring closure condensation reaction (dealcoholization reaction) can be smoothly continued.

The product obtained by the above reaction can be further purified by appropriately removing unreacted raw materials by a purification step such as distillation, so that the purity can be easily increased to 90% or more. [0040] Hydrolysis and Condensation of Cyclic Organic Gay Compound [3]

The cyclic organic gayne compound [3] synthesized as described above can be hydrolyzed under acid or basic conditions to form an organic gayne resin skeleton, and at the same time, introduce a hydroxyl group into the resin skeleton. it can.

The product of the hydrolysis-condensation is a polymer having the following repeating units.

That is, when R in the general formula (3) is an alkyl group having 13 carbon atoms,

1

The repeating unit is [A] below,

[0041]

When R in the general formula (3) is an alkoxyl group having 13 carbon atoms, the repeating unit is the following [B]. [0042] [Formula 7]

Each of the repeating units [A] and [B] is characterized in that it has a hydroxyl group generated by opening the ring of the cyclic organic gay compound [3].

[0043] The organic gayne resin of the present invention can be obtained by, in addition to hydrolyzing and condensing a cyclic organic gayne compound [3] alone, a mixture of a cyclic organic gayne compound [3] and a polyfunctional alkoxysilane. Including those obtained by hydrolysis and co-condensation.

Preferable polyfunctional alkoxysilanes include 34-functional alkoxysilanes, preferably those comprising an alkyl group having 13 carbon atoms and Z or an alkoxy group having 13 carbon atoms. Preferred trifunctional alkoxysilanes include, for example, triethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and the like.

A preferable ratio of the polyfunctional alkoxysilane is a ratio of not more than 10 mol per 1 mol of the cyclic organic gayne compound [3].

The preferred number average molecular weight of the organic gay resin of the present invention is 1 000 ^ 100 The preferred average molecular weight measured by GPC is 1,000,000.

[0044] 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 preferred amount of water used for the hydrolysis is greater than or equal to the stoichiometric amount, preferably 1.52 times the stoichiometric amount.

Preferred organic solvents used in the hydrolysis include acetone, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, hexane, and the like. You may use it. Preferred examples of the molecular weight modifier include hexamethyldisiloxane, tetramethyldisiloxane, hexaphenyldisiloxane, hexavinyldisiloxane, tetraphenyldimethyldisiloxane, and tetraisopropyldisiloxane.

[0045] Examples of the dehydrating agent after hydrolysis include anhydrous sodium sulfate and anhydrous magnesium sulfate. The type of the dehydrating agent is not limited as long as it has a dehydrating effect and does not contaminate the resin.

[0046] The resin-terminated silanol is sealed with a silylating agent. By sealing the silanol at the terminal of the resin, an organic gay resin having an alcoholic hydroxyl group which 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 1,1,3,3-tetramethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, tris (trimethylsilyl) amine, bis (ethylamino) dimethylsilane, bis (dimethylamino) ) Dimethylsilane, bis (dimethylamino) diphenylsilane, bis (dimethylamino) methylphenylsilane, trimethylsi Illustrative are aminosilanes such as lanol and t-butylaminotrimethylsilane, and chlorosilanes such as silanols, trimethylchlorosilane, dimethylchlorosilane and phenylmethylchlorosilane. Further, it may be used in combination with a base such as triethylamine or pyridine.

[0047] After sealing the terminal silanol in the glycerol resin obtained immediately after the hydrolysis-condensation, the solvent is distilled off under reduced pressure, an organic solvent is added, and the organic garlic resin is washed with water. Preferred examples of the organic solvent used for washing with water include acetone, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, and hexane. You may use it.

Ultrapure water is generally used for water washing, but an acidic aqueous solution such as a hydrochloric acid aqueous solution, an alkaline aqueous solution such as a sodium hydroxide aqueous solution, or a saturated sodium chloride aqueous solution may be used. Washing with water is preferably performed until the aqueous layer becomes neutral.

By dehydrating after washing with water and distilling off the solvent under reduced pressure, it is possible to obtain a stable organic gay resin having an alcoholic hydroxyl group, whose composition can be easily controlled and which does not change with time. Examples of the dehydrating agent to be used after washing with water include anhydrous sodium sulfate and anhydrous magnesium sulfate. The type of the dehydrating agent is not particularly limited as long as it has a dehydrating effect and does not contaminate the resin. Example

Hereinafter, the present invention will be described specifically with reference to Examples.

[Example 1]

A reactor (flask) provided with a cooling tube, a dropping funnel, and a magnetic stirrer was placed in an oil bath, and 1-butene-3-methyl-3-ol (30 g, 348 mmol) was charged and stirred. Triethoxysilane (62.9 g, 383 mmol) was charged into the dropping funnel. The 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, add 0.1 MPt-dvds xylene solution (13 to 0.0013 mmol) to the flask to start the reaction. 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 materials. After completion of the reaction, a colorless and transparent liquid (58.2 g) was obtained by reduced pressure distillation (boiling point: 13300 Pa, 117-120 ° C. Yield: 82%. Purity of 98% or more was confirmed by gas chromatography. ).

The colorless transparent liquid was subjected to ¹ HN MR measurement at 270 MHz.

The spectrum shown in Fig. 1 was obtained. The δ values and their assignments are as shown in Table 1. The compound thus obtained was confirmed to have the following structure.

[Table 1]

[0052] [Formula 8]

5) 6)

H ₃ CH ₂ CO 〇CH ₂ CH

1)

[0053] ¹³ C-NMR was measured, and the spectrum shown in Fig. 2 was obtained.

The S values and their assignments are shown in Table 2. The compound thus obtained was confirmed to have the following structure.

[Table 2]

Measurement method δ (f) pm)

l ³ c 3.88 1)

NMR 18.1 6 6)

29. 70 3)

37.43 2)

59.7 9 5)

76.2 5 4)

[0055] [Formula 9]

5) 6)

[Comparative Example 1] Synthesis was performed in the same manner as in Example 1, except that aryl alcohol was used in place of 2-methyl-3-buten-2-ol. As a result, 10 or more by-products were obtained, and the compound could not be purified (purity of 30% was confirmed by gas chromatography).

Hereinafter, the present invention 2 will be specifically described with reference to examples.

[Example 2]

(Synthesis of organic gay resin)

A reactor equipped with a dropping funnel and a magnetic stirrer was charged with DESMBO (49 g, 240 mmol), methyltriethoxysilane (78.6 g, 441 mmol), hexamethyldisiloxane (19.5 g, 120 mmol), and acetone (91 g). Stirred. A 1.5 wt% hydrochloric acid aqueous solution (37.4 g) was charged into the dropping funnel, and the solution was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours. Subsequently, diisopropyl ether (200 g) was added, and anhydrous magnesium sulfate was added, followed by dehydration for 2 hours. The anhydrous magnesium sulfate is filtered off, hexamethyldisilazane (38.7 g, 240 mmol) is slowly added with stirring, and the mixture is stirred at room temperature for 2 hours, and the solvent is distilled off under reduced pressure. Methyl ethyl ketone (200 g) and a 1N-hydrochloric acid aqueous solution are added, and the mixture is washed. The washing 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 organic gay resin (73.3 g, 89%).

The organic gay resin was measured for ¹ HN MR at 270 MHz, and the spectrum shown in FIG. 3 was obtained.

Table 3 shows the S values and their attributions. The compound thus obtained was confirmed to have the following structure.

[0058] [Table 3] Titration method δ (ppra)

0, 1 1)

NM 0.6 2)

one two Three)

1. 5 4)

2. S 5)

[0059] [Formula 10]

3);

Five) ? ^H 3 4) 2) I

HO-C-CH2CH2——Si—;

C IH,!

^{As a result of 13} C-NMR measurement, the spectrum shown in FIG. 4 was obtained.

The S values and their assignments are as shown in Table 4. The compound thus obtained was confirmed to have the following structure.

[Table 4]

Measurement method J »

1, 3 1)

NMR 7.1 2 2)

28, 54 3)

36-8 β 4)

7 1.29 5) [0061]

When IR was measured, the spectrum shown in FIG. 5 was obtained.

340 OcnT ¹ OH stretching vibration was observed in the presence of an alcoholic hydroxyl group has been confirmed.

[Example 3]

(Stability test)

Propylene glycol methyl ether acetate containing 0.5 wt% of water was prepared as a solvent. The organic gay resin prepared in Example 1 was dissolved in a solvent at a concentration of 10 wt% to prepare a sample. This sample was left at 60 ° C for 3 days, and the change in molecular weight was monitored. Table 5 shows the results.

[0063] [Table 5]

No change in molecular weight and confirmed to be a stable organic gay resin <

[Comparative Example 2] (When the silanol at the resin end is not sealed)

In a reactor equipped with a dropping funnel and a magnetic stirrer, 1,1-dimethyl-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 was slowly dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours. The solvent was distilled off under reduced pressure to gel. Industrial applicability

The production method of the present invention 1 is useful as a technique for inexpensively producing a cyclic organic gay compound having an alcoholic hydroxyl group and an alkoxyl group protected by an organic substituent.

The cyclic organosilicon compound obtained by the present invention 1 is useful as a resist raw material used in lithography. The organic gay resin having an alcoholic hydroxyl group of the present invention 2 is useful as a raw material for lithography materials and organic-inorganic hybrid materials. Brief Description of Drawings

FIG. 1 is a ¹ H-NMR spectrum of the compound obtained in Example 1.

FIG. 2 is a ¹³ C-NMR spectrum of the compound obtained in Example 1.

FIG. 3 shows a ¹ H-NMR spectrum of the organic gay resin obtained in Example 1.

FIG. 4 shows a ¹ -NMR spectrum of the organic gay resin obtained in Example 1.

[5] Figure 5 shows the IR scan Bae spectrum of organic Gay fluororesin obtained in Example 1 _c

Claims

Claims [1] The following general formula, characterized 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 method for producing a cyclic organic gay compound represented by the formula (3).

[Formula 1]

[In the formula, z represents an alkenyl group having 25 carbon atoms in which the terminal carbon atom c 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 Me represents a methyl group. ]

[Chemical 2]

[Wherein, R represents an alkyl group or an alkoxyl group having 13 carbon atoms, R represents an alkyl group having 13 carbon atoms, and a plurality of Rs may be the same or different. ]

[Formula 3]

[Wherein, Z, represents a carbon-carbon unsaturated bond of Z as a saturated bond, a terminal carbon atom C of Z represents an alkylene group having 25 carbon atoms bonded to a Si atom, and R represents a methyl group or Represents hydrogen, and R represents an alkyl group or an alkoxyl group having 13 carbon atoms.

1

And R represents an alkyl group having 13 carbon atoms. ]

2

[2] An organic gayne resin having an alcoholic hydroxyl group, obtained by hydrolyzing and condensing a cyclic organic gayne compound represented by the above general formula (3) or a mixture thereof with a polyfunctional alkoxysilane.

[3] The cyclic organic gayen compound represented by the general formula (3) according to claim 1 or a mixture thereof and a polyfunctional alkoxysilane, while maintaining the concentration of the produced polymer at 30% by mass or less. A method for producing an organic gay resin having an alcoholic hydroxyl group, comprising hydrolyzing and condensing in an organic solvent.