JPH03236393A - Silicone-modified phenol compound, production thereof and epoxy derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is H, phenyl, methyl, CF3CH2CH2 or vinyl; m is 3 or 4) and compound expressed by formula II and formula III (R2 and R3 are R1; p is integer of >=1). EXAMPLE:Tris[(p-hydroxyphenyl)dimethylsilyloxy]phenylsilane. USE:Usable as a raw material for polyfunctional silicon-modified epoxy resin capable of providing a cured product having high mechanical strength and stiffness and improved heat resistance, raw material for synthetic resin having characteristics such as heat resistance, cold resistance and flexibility which silicone has and reactive modifier and photoresist. PREPARATION:For example, a silanol compound expressed by formula IV (R4 is allyl, alkyl ether compound or pyranyl compound) is reacted with a substituted halogenated silane compound expressed by formula V (X is halogen) and the resultant compound expressed by formula VI is subjected to deprotecting reaction to provide the compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to novel polyfunctional silicone-modified phenol compounds, methods for producing them, and novel polyfunctional silicone-modified epoxy resins derived therefrom. be.

The phenol compound developed in the present invention can be used as a raw material for a synthetic resin having properties such as heat resistance, cold resistance, and flexibility of silicone.

Since the epoxy resin used in the present invention is polyfunctional, it is expected to provide a cured product that has higher mechanical strength and toughness than a bifunctional type, and has improved heat resistance and the like. Furthermore, since the silicone content increases, it is thought that the properties of silicone are more highly expressed.

[Conventional technology]

The bisphenol compound currently used in large quantities in synthetic resins is bisphenol A. A wide variety of synthetic resins have been developed from bisphenol A, but in recent years, not only bifunctional types but also polyfunctional types have been attracting attention in search of more advanced properties. For example, glycicylamine type tetrafunctional epoxy resin has great expectations as a high-performance material, and therefore various polyfunctional synthetic resin monomers including this are being developed.

The present inventors have disclosed a method for synthesizing 1,3-bis(p-hydroxyphenyl)-1,1,3,3-tetramethyldisiloxane in Japanese Patent Application No. 1983-269336 and Japanese Patent Application No. 1-23732. and its derivation into an epoxy resin by reaction with epichlorohydrin. This method gives only a bifunctional product, but a trifunctional or higher functional silicone-modified phenol compound is required for the base of the polyfunctional silicone-modified epoxy resin. Furthermore, when a pyranyl compound as described in Japanese Patent Application No. 63-269336 is used as a retainer, during the isolation and purification of a silicone-modified phenol compound,
There are some inconveniences in removing protecting groups, and a method to improve this is desired.

[The problem that the invention aims to solve! ! ] The present invention uses a silanol derivative represented by formula (IV) obtained by a conventional method to react a substituted halogenated silane compound in the presence of an organic amine compound, and then removes the protecting group. The object of the present invention is to obtain a polyfunctional silicone-modified phenol compound that could not be obtained by the method described above, as well as to provide a method for producing the same and a polyfunctional silicone-modified epoxy resin derived therefrom.

Furthermore, the present invention also shows that allyl groups can be used as protective groups in addition to those used in conventional methods, and are more effective than conventional methods.

[Means to solve the problem]

The present invention provides polyfunctional silicone-modified phenol compounds represented by the following (1), (II), and (DI) and methods for producing them, as well as the following (V), (VI),
It relates to the polyfunctional silicone-modified epoxy resin shown by (■).

(1) Using the silanol compound of formula (IV) synthesized by (III) (V) as a raw material, it is reacted with a substituted halogenated silane compound to form a siloxane compound, followed by a deprotection reaction. The basic idea is to do the basics.

(Vl) (VI!) [Formula (1), (II), (DI), (V),
In (Vl) and (■), R1, Rt and R8 are hydrogen,
phenyl group, methyl group, ChCHzCFIg- group and vinyl group, which may be the same or different from each other.
m is 3 or 4. P is an integer of 1 or more.

) Formula (I), (II), (I[[), (V
), (VT) and (■) are produced by the method disclosed by the present inventors in Japanese Patent Application No. 63-269336 (IV> (R is an allyl group, an alkyl ether The method for synthesizing the compounds represented by formulas (1), (II), and (I[[) will be described in detail.

The combination of the compounds of formula (1) or the reaction formula below is followed.

×: For the reaction of halogen (f)-(A) (1-A), a substituted halogenated silane compound and an organic amine compound are charged into a reaction vessel equipped with a cooling device, a stirring device, and a dropping device, and a predetermined amount of the formula The silanol compound (IV) was added dropwise. Various substituted halogenated silane compounds can be used and are not particularly limited.

Organic amine compounds act as hydrochloric acid scavengers and include primary amines, secondary amines, and tertiary amines, but primary amines and secondary amines have the risk of reacting with hydrogen bonded to nitrogen. Therefore, a tertiary amine is preferable, and the tertiary amine is trimethylamine.

Triethylamine, tributylamine, etc. can be used, but are not particularly limited.

After the dropwise addition is completed, the reaction temperature is heated to a predetermined temperature and reacted for a predetermined time.The reaction temperature can be from 0°C to 120°C, and the reaction time varies depending on the reaction temperature. In the case of 100°C, about 2 to 8 hours is appropriate.

After the reaction was completed, the reaction solution was poured into ice water, and the solution was neutralized with acid. After neutralization, the organic phase was separated and washed with water. The desired product can be obtained by evaporating the solvent and purifying the residue. Monosilanol or disilanol can also be isolated by adjusting the charging ratio of the silanol compound of formula (IV) and the substituted halogen compound. Although the acid used for neutralization is not particularly limited, in the present invention, a lN hydrochloric acid aqueous solution was mainly used in the experiments. Regarding the purification of the residue,
Although not necessary, this can be done using a silica gel column.

The reaction (I-B) is a mineral acid! This can be carried out using an acid, a metal complex catalyst, or the like.

A metal complex catalyst is mainly used when deprotecting an allyl group. The compound synthesized in (1-A), the catalyst, and the promoter are charged in a predetermined ratio into a reaction vessel equipped with a nitrogen purging device and a dropping device, and an active hydrogen compound is added dropwise thereto.

This is heated to a predetermined temperature to carry out a reaction. After the reaction is complete,
Pour into ice water and neutralize with acid. Thereafter, extraction with a solvent and washing with water are performed, and the solvent is further evaporated to obtain the target product. The reaction temperature is from room temperature to about 120°C, and if the active hydrogen compound to be added has a low boiling point, it is necessary to use an autoclave. Although the acid used for neutralization is not particularly limited, in the present invention, a 1N aqueous hydrochloric acid solution was mainly used in the experiments. The catalyst is a metal complex catalyst such as palladium, platinum, nickel, etc. For example, PdC1z, PdC
Iz(PPt+3)z, Pd(PPh3)4゜Pd(
OCOCHs)z, PtC1! (PPh3)2. P
Examples include t(PPh3)4 (PPhs indicates triphenylphosphine.

The co-catalyst functions to enhance the ability of the catalyst, and includes, for example, Ph0Na, PPha, and the like. A cocatalyst is not always necessary, and in some cases the reaction proceeds smoothly even without its use. The active hydrogen compound is not particularly limited, but includes, for example, amine compounds such as diethylamine, butylagon, and aniline, alcohol compounds such as methanol and ethanol, phenols, and carbonyl compounds having active hydrogen.

A mineral acid or an organic acid is used in the reaction (1-B) mainly when deprotecting a pyranyl compound or an alkyl ether compound. The compound synthesized in reaction (1-A) and alcohol are placed in an Erlenmeyer flask, and an acid is added to this. After stirring for a predetermined time and at a predetermined temperature, the reaction solution is dissolved in a solvent and washed with water to remove the acid. Thereafter, the solvent is evaporated to obtain the desired product.

The synthesis of formula (II) followed the reaction formula below.

X: Halogen Formula (II-A) is reacted by charging the silanol compound (IV) to the substituted halogenated silane compound in such a ratio that the product is monosilanol. Other than that, the synthesis was carried out according to the synthesis of (IA).

2 (It-B) can be obtained by two methods: a two-step method in which the compound obtained by formula (It-A) is condensed with an acid and then deprotected, and a one-step method in which condensation and deprotection are simultaneously performed with an acid. can be done.

The two-step method is when the protecting group is an allyl group, and after condensation with an acid in an alcohol solution, deprotection is performed according to a method using a metal complex catalyst to obtain the desired product. The one-stage method is when the protecting group is a pyranyl compound or an alkyl ether compound, and the desired product is obtained by simultaneously carrying out condensation and deprotection in an alcohol solution. Each method is based on the metal complex catalyst method disclosed in Japanese Patent Application No. 63-269336 and the present invention.

The compound P-1 in formula (III) was synthesized according to the following reaction formula.

The reaction formula below was followed.

0 formula (I[[-B) was prepared according to the method of formula (1-A) except that 2(I[[-A) was charged in an amount of 2 equivalents to the disubstituted halogenated silane compound. The deprotection reaction is carried out using a mineral acid, an organic acid, or a metal complex catalyst.
Obtain the desired object.

The synthesis of the compound p-2 in formula (m) is as follows:
I-C) is for a disubstituted halogenated silane compound,
The product was charged twice so that it became monosilanol, and the formula (1-
It was carried out according to method A).

The compound obtained by formula (III-C) was condensed with an acid according to formula (1-D) and deprotected to obtain the target product. Each method is described in the previously shown patent application No. 63-2693.
The method was based on the metal complex catalyst method already explained in No. 36 and the present invention.

The compound of formula (III) with p≧3 was synthesized according to the following reaction formula.

(l×) (I I I )-(E) (III)-(F) Dimethylsiloxane cyclic The tetramer (D4) was subjected to ring-opening insertion polymerization, and the terminal portion of the polymer was subjected to a deprotection reaction to obtain the desired product. Ring-opening insertion polymerization was carried out in the absence of a solvent using a catalyst. As the polymerization catalyst, strong basic compounds such as hydroxyammonium salts, potassium hydroxide, and sodium hydroxide can be used, and are not particularly limited. If necessary, it is also possible to use promoters such as crown ethers.

Next, methods for synthesizing epoxy resins represented by (V), (VT), and (■) will be explained. This reaction is carried out in the same manner as the reaction between phenol and epichlorohydrin shown in formula (■) below. The desired product is obtained by reacting polyfunctional silicone-modified phenol compounds (I), (II), and (DI) with epichlorohydrin in the presence of an alkali. The details are as shown in the method for synthesizing a bifunctional silicone-modified epoxy resin presented by the present inventors in Japanese Patent Application No. 1-23732, and the process is carried out in accordance therewith.

Neutralized with normal aqueous hydrochloric acid solution. The organic phase was separated and washed with water. The solvent was evaporated and purified to obtain 41.8 g of the desired product.

The structure was confirmed by NMR and IR.

Example 2 [Example] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 In a 300-inch three-necked flask, 10.58 g of phenyltrichlorosilane and 15.15 g of ) ethylamine were added.

) Retriene 10 (1+d) was taken. To this, 37.8 g of p-pyranyloxyphenyldimethylsilanol dissolved in 100 rd of toluene was added dropwise at room temperature.

After the dropwise addition was completed, the reaction was heated to about 100°C for 6 hours.After the reaction was completed, the reaction mixture was poured into ice water, and p-allyloxyphenyldimethylsilanol was added instead of p-pyranyloxyphenyldimethylsilanol. The reaction was carried out in the same manner as in Example 1 using 2 g to obtain 36.1 g of the target product.

The structure was confirmed by NMR and IR.

Example 3 8.5% tetrachlorosilane in a 100d three-necked flask
g, triethylamine 20.2 g, ) toluene 100 d was taken. To this, p-allyloxyphenyldimethylsilanol 4 dissolved in 100 m of toluene was added.
1.6 g was added dropwise at room temperature.

After the dropwise addition was completed, the mixture was heated to about 100°C and reacted for 6 hours.

After the reaction was completed, the reaction mixture was poured into ice water and neutralized with a 1N aqueous hydrochloric acid solution. The organic phase was separated and washed with water. The solvent was evaporated and purified to obtain 41.0 g of the desired product.

The structure was confirmed by NMR and IR.

Example 4 (1) When tris((p-pyranyloxyphenyl)dimethylsilyluoquine)phenylsilane was used.

In a 200-mL Erlenmeyer flask, 15.0 g of tris((p-pyranyloxyphenyl)dimethylsilyloxyphenylsilane) and 150 d of ethanol were added.

0.06 g of P-toluenesulfonic acid was taken and reacted at room temperature for 4 hours. After the reaction was completed, ethyl ether was added and the mixture was washed with brine. After that, the solvent is evaporated and the target product is removed in 11.1
I got g.

(2) When tris((p-allyloxyphenyl)dimethylsilyloxyphenylsilane is used).

In a 100 af three-necked flask, 10.0 g of Tris[(P-allyloxyphenyl)dimethylsilyloxyphenylsilane, PdCl1 [PPt+sl
t O, 058 g and sodium phenoxide 0.02
I took 4 g'c.

12.1 g of diethylamine was added dropwise to this at room temperature.

After the dropwise addition was completed, the reaction was carried out at 85° C. for 12 hours under nitrogen. After the reaction was completed, the reaction mixture was poured into ice water, and the solution was neutralized with a 1N aqueous hydrochloric acid solution. The organic phase was extracted with ethyl ether and washed with water. Thereafter, the solvent was evaporated to obtain 9.45 g of the target product.

The compounds obtained by both methods were measured by NMR and IR, respectively, and it was confirmed that they were the same compound and had the desired structure.

Example 5 Tris((p-hydroxyphenyl)dimethylsilyloxy)phenylsilane 5 was placed in a 300 m four-bottle flask.
．． 0g + Take 150g of epichlorohydrin and add 80
The temperature was adjusted to reflux at °C. A solution of 1.09 g of sodium hydroxide dissolved in the same amount of water was slowly added dropwise to this.

After the dropwise addition was completed, the mixture was reacted for 1 hour while being dehydrated and refluxed. After the reaction was completed, epichlorohydrin was sufficiently removed and dissolved in toluene. After thoroughly washing this with water, toluene was removed to obtain 5.59 g of the desired product.

The structure was confirmed by NMR and IR, and the molecular weight was confirmed by GPC. The epoxy equivalent was 280 equiv/g (theoretical value 258 equiv/g).

Example 6 P-pyranyloxyphenyldimethylsilanol 25
．． 2 g was added dropwise with O'C.

After the dropwise addition was completed, the mixture was returned to room temperature and reacted for 2 hours.

After the reaction was completed, the reaction solution was poured into ice water and neutralized with 1N aqueous hydrochloric acid solution. After extraction with ethyl ether and washing with water, the solvent was evaporated to obtain 27.5 g of the desired product.

The structure was confirmed by NMR and IR.

Example 7 The synthesis reaction was carried out according to Example 4 (1) to obtain the target product.

The structure was confirmed by NMR and IR.

Example 8 Precepts.

Dimethyldichlorolane 6 in a 200 m 2 tube flask
．． 45 g,) 11.11 g of diethylamine and 5 THF
Take 0af, dissolve it in 50d of THF and add bis[(
p-pyranyloxyphenyl)dimethylsilyloxy]
Phenylsilanol and isopropanol were placed in an Erlenmeyer flask, 5% of the total amount of hydrochloric acid was added, and the mixture was allowed to react at room temperature for 4 hours.

After the reaction was completed, the product was dissolved in a solvent, washed with water, and the solvent was evaporated to obtain the desired product.

The structure was confirmed by NMR and TR.

〔Effect of the invention〕

The polyfunctional silicone-modified phenol compound of the present invention is a novel compound. Furthermore, we have developed a new method for producing polyfunctional silicone-modified phenol compounds that could not be obtained by the acid condensation method previously employed in the production of bifunctional silicone-modified phenol compounds. By performing epoxidation using these phenolic compounds as raw materials, we were able to obtain a novel multifunctional silicone-modified epoxy resin.

The above compounds can of course be used as raw materials for other synthetic resins, and can also be used for special purposes such as reactive modifiers containing silicone and photoresists.

Procedural amendment (voluntary) Flat Bottom 2pm March 23rd

Claims (7)

[Claims] (1) A polyfunctional silicone-modified phenol compound represented by formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 is hydrogen, phenyl group, methyl group, CF_3C
They are a H_2CH_2- group and a vinyl group. m is 3 or 4. ) (2) A polyfunctional silicone-modified phenol compound represented by formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (R_1 is hydrogen, phenyl group, methyl group, CF_3C
They are a H_2CH_2- group and a vinyl group. ) (3) A silicone-modified phenol compound represented by formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R_2 and R_3 are hydrogen, phenyl group, methyl group,
They are a CF_3CH_2CH_2- group and a vinyl group, and they may be the same or different from each other. p is an integer of 1 or more. ) (4) The polyfunctional silicone-modified phenol compound according to claim 1, 2 or 3, characterized in that a siloxane bond is created using the silanol compound of formula (IV) and a substituted halogenated silane compound as raw materials, and a deprotection reaction is performed. manufacturing method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (R_4 is an allyl group, an alkyl ether compound, and a pyranyl compound) (5) A polyfunctional silicone-modified epoxy resin represented by formula (V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (R_1 is hydrogen, phenyl group, methyl group, CF_3C
They are a H_2CH_2- group and a vinyl group. m is 3 or 4. ) (6) A multifunctional silicone-modified epoxy resin represented by formula (VI). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) (R_1 is hydrogen, phenyl group, methyl group, CF_3C
They are a H_2CH_2- group and a vinyl group. ) (7) A silicone-modified epoxy resin represented by formula (VII). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) (R_2 and R_3 are hydrogen, phenyl group, methyl group,
They are a CF_3CH_2CH_2- group and a vinyl group, and they may be the same or different from each other. p is an integer of 1 or more. )