JPS59213728A - Manufacture of silicone compound - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable silicone compound capable of affording coating film of high heat and chemical resistance through the irradiation of radiation or viscible light, by the reaction between each specific organopolysiloxane and unsaturated compound. CONSTITUTION:The objective compound can be obtained by the reaction, while stirring at room temperature, between (A) an organopolysiloxane of formula I (R is phenyl or alkyl, n is 2-100) (pref. a hydroxy-terminated ladder organopolysiloxane with a polymerization degree 5-10) and (B) an unsaturated compound of formula II [X is H or (halogen-substituted) phenyl; Y is H, methyl, or ethyl] as a terminal functional group-introducing reagent, so that pref. one chlorosilane group in the component (B) is made to react with are hydroxyl group in the component (A).

Description

[Detailed description of the invention] The present invention relates to a novel method for producing silicone compounds.

That is, formula (1): (wherein, R is a phenyl group or an alkyl group, and n is 2 to 1
(representing an integer of 00) and the organopolysilxane represented by the formula (2): (wherein, A photopolymerizable silicone compound is produced by reacting with an unsaturated compound, which is a terminal functional group-introducing reagent represented by (indicated by group).

The organopolysiloxane used in the present invention has the formula (1)
It is an organopolysiloxane with terminals represented by
In formula (1), R represents a methyl group, an ethyl group, a propyl group, a phenyl group, or the like.

The organopolysiloxane can be obtained, for example, by hydrolyzing phenyltrichlorosilane or alkyltrichlorosilane, but it can also be synthesized with any molecular weight by using a condensation catalyst such as potassium hydroxide or ram as necessary. be done.

In the present invention, in formula (1), n is an integer from 2 to 100, but if n is 1, the organopolysiloxane will not have a ladder structure, and if n exceeds 1oo, the number of reaction points per weight will decrease. The resulting silicone compound has poor photopolymerizability.

The unsaturated compound used in the present invention is represented by the formula (8) as shown in the formula (2): (wherein, This reagent for introducing a terminal functional group has in its structure a photosensitive group represented by a methyl group or an ethyl group and an ao silane group represented by the formula (4).

The unsaturated compound is an acrylic acid represented by formula (5): (in the formula, or a hydrogen atom, a phenyl group, or a phenyl group substituted with a hydrogen atom, and Y represents a hydrogen atom, a methyl group, or an ethyl group) Allyl is expressed by the formula (6
): It is synthesized by hydrosilylation using dimethylchlorosilane as shown in the reaction formula: In this reaction, allyl groups are preferentially hydrosilylated.

Examples of the allyl acrylate represented by formula (5) include allyl acrylate, allyl methacrylate, and allyl cinnamate.

The human tetrasilyl reaction of allyl acrylate shown in the above reaction formula can be carried out using a platinum black catalyst in the presence of hyde tetraquinone as a polymerization inhibitor, and the formation of unsaturated compounds can be observed by MR spectroscopy.

The production method of the present invention is to react an organopolysiloxane represented by formula (1) with an unsaturated compound represented by formula (2) at a ratio of one human tetraxyl group of the former to one chlorosilane of the latter. After mixing, leave at room temperature for 6 hours ff! By stirring and silylating the terminal hydroxyl group of the organopolysiloxane, a silicone compound having an unsaturated bond at the terminal is obtained. The reaction proceeds quickly without a catalyst.

Solid organopolysiloxane is dissolved in a solvent and reacted as a uniform layer. Examples of such solvents include ketone solvents such as tetrahydrofuran, methyl ethyl ketone, and isobutyl ketone, and aromatic hydrocarbons such as benzene, toluene, and xylene. can give.

The silylation of the hydroxyl group is confirmed by the decrease in the absorption attributed to the human tetraxyl group in the reaction product R spectrum.

When the composition obtained by mixing the silicone compound, sensitizer, diluent, etc. thus obtained is irradiated with ultraviolet light or strong visible light, the silicone compound polymerizes and becomes heat resistant and chemical resistant. Forms an excellent film.

The present invention will be described in more detail below based on Examples, but the present invention is not limited to these Examples.

Reference Example 1 (Production of terminal-terminated phenyl ladder polysiloxane precursor) Phenyltricone (06H5S)
i(M3) 105-81i+ (0.5 mol) was dissolved in 200 cc of methyl isobutyl ketone.

21 fitted with stirrer, condenser, thermometer and dropping funnel
Ion-exchanged water 11 was placed in a four-round flask and cooled in a water bath.

A hydrolysis reaction was carried out by gradually dropping the solution from a dropping funnel over a period of 4 hours.

Thereafter, stirring was continued for an additional 60 minutes at room temperature to complete the hydrolysis reaction.

Next, a ketone layer was separated from the two-layered reaction solution using a separatory funnel, and the ketone layer was washed several times with ion-exchanged water until it became neutral.The solvent was removed and the ketone layer was dried in a vacuum dryer for 15 minutes.
It was dried at 0'o for 1 hour.

The organopolysiloxane precursor thus obtained is a white powder, and its engineering R spectrum has a peak at 3400 am-1 assigned to Si-OH and a peak at 3400 am-1 that is assigned to Si-0-Si.
Pifuca 1 i 55cm-1 and I
That's it for Q45am-1! It was determined that the precursor had a ladder structure with a hydroxyl group at the end.

The molecular weight was approximately 1500.

Reference Example 2 (Production of terminally human tetraxyphenyl ladder polysiloxane) Precursor 10y obtained in Reference Example 1 and xylene 50c were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a thermometer.
After adding C and dissolving it uniformly, 0.3 g of ethyl tetraformate as a condensation catalyst was added and dissolved.

The homogeneous layer was reacted at 160°0 for 5 hours. Generation of carbon dioxide gas was observed during the reaction.

After the reaction was completed, the reaction mixture was allowed to cool and poured into 10 times the volume of methanol to precipitate the polymer. Aspirator-1
The 100'G teformer was then dried under reduced pressure using a rotary pump.

The yield was 8g and the molecular weight was 3000.

In the engineering R spectrum, the absorption attributed to 5i-OH is 3
40OCZII-1, and it was confirmed that the obtained polymer was a polyoxyphenyl ladder polysoxyxane with terminals.

Reference Example 6 (Manufacture of end group introduction reagent) 30 parts of allyl acrylate (parts by weight, the same applies hereinafter), 60 parts of dimethylchlorosilane, platinum black catalyst O, 1i, and fi were combined to form a pressure stopper and hydride tetraquinone O" 5 parts of toluene and 100 parts of toluene were placed in a three-necked flask and allowed to react at 100'a for 4 hours.The solvent was distilled off to obtain a product as a white powder.

No absorption attributed to 5i-R was observed in the R spectrum, indicating that hydrosilylation was complete.

Example 1 To a homogeneous solution of terminal hydroxyphenylene/l/ladder polysiloxane, r-acryloxypropyl dimethyl chloride 92
TH for the 2nd part? 15°cJ of a solution dissolved in 100 parts
The mixture was added dropwise over 60 minutes while stirring. After the dropwise addition was completed, the reaction was completed by stirring for an additional 30 minutes.

After adding 100 parts of hexane to the reaction mixture, it was washed several times. Further, the reaction mixture was dried over anhydrous sodium sulfate for a day and night, the solvent was removed under reduced pressure, and the desired silicone compound was obtained by drying under reduced pressure.

In the engineered R spectrum of the silicone compound, the absorption at 4400 cm -1 attributed to the hydroxyl group decreased, and a new absorption at 1720 am attributed to the carbonyl group was confirmed.

Example 2 Terminal hydroxymethyl ladder polysiloxane (polymerization degree 5
, the number of hydroxyl groups 4) A homogeneous solution of 15 parts dissolved in 500 parts of THP was heated to 15°C! Add dropwise over 40 minutes while stirring.
Ta. After the dropwise addition was completed, the reaction was completed by further stirring for 60 minutes. Thereafter, it was treated in the same manner as in Example 1 to obtain a silicone compound.

In the Sonoko R spectrum, the absorption attributed to the hydroxyl group decreased, and a new absorption attributed to the carbonyl group was confirmed.

Claims (1)

[Claims] (1) Formula (1): (wherein, R is a phenyl group or an alkyl group, n is 2 to 1
(representing an integer of 00) and the organopolysilxane represented by the formula (2): (wherein, Method for producing a silicone compound 0 characterized by reacting with an unsaturated compound which is a reagent for introducing a terminal functional group (representing an ethyl group)