JPH06279466A - Cyclotrisiloxane and its production - Google Patents

Abstract

(57) [Summary] [Structure] General formula: [In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and each is an alkyl group having 1 to 3 carbon atoms, and X is a cyclohexyl group or a formula: —C _n A cyclotrisiloxane represented by H _{2n + 1} (where n represents an integer of 4 to 15). [Effect] It is useful as an intermediate for producing silicone oil and silicone rubber, and the obtained silicone oil and silicone rubber have excellent lubricity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cyclotrisiloxane useful as a raw material for silicone oils and elastomers used in greases, cosmetics, sealing materials, paints, various rubber materials and the like, and a method for producing the same.

[0002]

2. Description of the Prior Art U.S. Pat. No. 4,898,958 describes a general formula:

[Chemical 4] [In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10, which} may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms, and Rf is —C _a F _{2a +. 1} (where a is 3
Represents an integer of ~ 10),

[Chemical 5] (Here, q represents an integer of 1 to 5), or

[Chemical 6] (Wherein q is as described above) and X is -O-.
Or -CH ₂ - represents, where, n when X is -O- 3
In the formula, m is an integer of 0 to 2, and when X is —CH ₂ —, n is 0 and m is 1]. It is described that this compound is suitable for producing a silicon polymer having excellent heat resistance, chemical resistance and weather resistance, and has a small surface energy.

However, the below-mentioned cyclotrisiloxane provided by the present invention has not been heretofore known.

[0004]

The object of the present invention is to develop novel cyclotrisiloxanes, more particularly C _{4-in the} molecule.
It is to provide a cyclotrisiloxane having a C ₁₅ alkyl group.

[0005]

The present invention provides a compound represented by the general formula (1):

[Chemical 7] [In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and may be substituted or unsubstituted 1 to
Is an alkyl group of 3, X is a cyclohexyl group or a formula:
A cyclotrisiloxane represented by the formula _: —C _n H _{2n + 1} (where n represents an integer of 4 to 15).

In the general formula (1), R ¹ , R ² , R ³ ,
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group and an isopropyl group, and a methyl group is particularly preferable. These alkyl groups may be substituted with a halogen atom such as fluorine or chlorine. Also, represented by X −
Since an alkyl group of C _n H _{2n + 1} is n = 4 to 15, for example, a linear alkyl group such as a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and a pentadecyl group, Examples thereof include branched alkyl groups such as an isobutyl group, an isopentyl group, an isooctyl group, and a 2-ethylhexyl group. Preferred as X is a cyclohexyl group and an alkyl group having 4 to 12 carbon atoms.

Production Method The cyclotrisiloxane of the present invention can be produced , for example, by the general formula (2)
:

[0008]

[Chemical 8] (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above), and a general formula (3):

[0009]

[Chemical 9] It is obtained by reacting dichlorosilane represented by the formula (wherein R ⁵ and X are as described above) in the presence of a catalyst.

As the catalyst used in the above reaction, a basic nitrogen-containing organic compound is suitable. Examples of the basic nitrogen-containing organic compound include amine compounds such as triethylamine and dimethylamine, aromatic amine compounds such as dimethylaniline, and pyridine. The amount of these catalysts added is preferably 1 to 6 mol, and more preferably 2 to 3 mol, per 1 mol of dichlorosilane of the general formula (3). The reaction temperature is preferably 0 to 100 ° C, more preferably 30 to 70 ° C.

The above-mentioned production method can be carried out, for example, by separately preparing a solution of the above-mentioned two kinds of compounds and then adding these solutions to a solution containing a catalyst to react them. At this time, the solvent that dissolves the disiloxane diol of the general formula (2) is preferably a polar organic solvent, and preferable examples include, for example, methyl ethyl ketone, methyl isobutyl ketone, ketones such as acetone, and esters such as ethyl acetate. And so on. Further, the solvent of dichlorosilane of the general formula (3) is an organic solvent, preferably,
Examples thereof include aromatics such as toluene, xylene and benzene, and ketones such as methyl isobutyl ketone.

Uses The cyclotrisiloxane of the present invention easily undergoes ring-opening polymerization by using an alkali catalyst or an acid catalyst, so that it can be used in various known uses such as grease, cosmetics, sealing materials, paints and various rubber materials. It is useful as a raw material for the silicone oil and silicone elastomer used. The cyclotrisiloxane of the present invention is more specifically a cyclohexyl group or C ₄ bonded to a silicon atom in the molecule.
It has the following advantages for the alkyl group -C _15.

(1) Since the siloxane polymer obtained by polymerizing the cyclotrisiloxane of the present invention has excellent lubricity, it is useful for grease, cosmetics and the like. (2) The cyclotrisiloxane of the present invention has excellent compatibility with hydrocarbon solvents, and is useful as a raw material for paints and the like.

[0014]

Example 1 A mixed solution of methyl ethyl ketone (150 g), toluene (150 g) and triethylamine (107 g) was prepared (hereinafter referred to as liquid A). Separately, methylhexyldichlorosilane (100g)
Toluene (150 g) solution (hereinafter referred to as Solution B) and 1,1,
A solution of 3,3-tetramethyldisiloxane-1,3-diol (88 g) in methyl ethyl ketone (150 g) was prepared (hereinafter referred to as liquid C). Methylhexyldichlorosilane and 1,1,3,3-tetramethyldisiloxane-1, were added to Solution A heated to 50 ° C by adding Solution B and Solution C at the same dropping rate (1 ml / min). The 3-diol was reacted. After completion of dropping, the reaction solution was stirred for 30 minutes. The reaction solution was washed with water and then separated into an organic layer and an aqueous layer. The organic layer is distilled under reduced pressure, 91 ℃ / 10m
106 g of mHg fraction was obtained.

The results of elemental analysis, infrared absorption spectrum and NMR spectrum analysis of this product were as follows. From this result, it was confirmed that the produced compound was 1,1,3,3,5-pentamethyl-5-hexylcyclotrisiloxane, and the yield was 73%.

[0016]

Infrared absorption spectrum is shown in FIG. Characteristic absorption: 1020cm ^-1 : Si-O bond

¹ H-NMR spectrum (carbon tetrachloride solvent, internal standard chloroform) δ value (ppm) 0.13 to 0.50 (m, Si-CH ₃ , 15H) 1.00 to 1.17 (m, C-CH ₃ , 3H) 0.80 ~ 1.27 (m, CH ₂ , 10H)

Example 2 A mixed solution of methyl ethyl ketone (150 g), toluene (150 g) and triethylamine (75 g) was prepared (hereinafter referred to as liquid D). In addition, methyldodecyldichlorosilane (100
g) solution of toluene (150 g) (hereinafter referred to as solution E) and 1,
1,3,3-Tetramethyldisiloxane-1,3-diol (62g)
A methyl ethyl ketone (150 g) solution (hereinafter referred to as solution F) was prepared. By adding E liquid and F liquid at the same dropping rate (1 ml / min) to D liquid heated to 50 ° C, methylhexyldichlorosilane and 1,1,3,3-tetramethyldisiloxane-1,3- The diol was reacted. After the dropping was completed, this mixed solution was stirred for 30 minutes. The reaction solution was washed with water and then separated into an organic layer and an aqueous layer. The organic layer was distilled under reduced pressure to 146 ° C / 3
A 95 g fraction of mmHg was obtained.

The results of elemental analysis, infrared absorption spectrum and NMR spectrum analysis of the obtained product are as follows:
It was as follows. From this result, the produced compound was 1,
It was confirmed to be 1,3,3,5-pentamethyl-5-dodecylcyclotrisiloxane, and the yield was 72%.

[0021]

Infrared absorption spectrum is shown in FIG. Characteristic absorption: 1020cm ^-1 : Si-O bond

¹ H-NMR spectrum (carbon tetrachloride solvent, internal standard chloroform) δ value (ppm) 0.10 to 0.47 (m, Si-CH ₃ , 15H) 0.97 to 1.20 (m, C-CH ₃ , 3H) 1.23 ~ 1.83 (m, CH ₂ , 22H)

Example 3 Methyl ethyl ketone (250 g) and toluene (250 g) were placed in a four-necked flask having an internal volume of 3 liters, and triethylamine (167 g) was dissolved therein.

Two dropping funnels were attached to this flask, a solution of cyclohexylmethyldichlorosilane (150 g) dissolved in toluene (230 g) was placed in one dropping funnel, and 1,1,3,3- was added to the other dropping funnel. A solution of tetramethyldisiloxane-1,3-diol (133 g) dissolved in methyl ethyl ketone (230 g) was added.

Next, the triethylamine solution in the flask was added.
After the temperature was raised to 50 ° C., the dichlorosilane solution and the disiloxane diol solution were dropped from the two dropping funnels at almost the same dropping rate (about 1 ml / min) and reacted. After the dropping was completed, the reaction mixture was stirred for 30 minutes. The obtained reaction product was washed with water to remove the by-produced triethylamine hydrochloride, and the separated organic layer was distilled under reduced pressure to obtain 112 ° C./26 mm
The compound (158 g) was obtained as a fraction of Hg (yield 72
%). Next, this compound was subjected to elemental analysis and IR spectrum and NMR spectrum were measured, and the following results were obtained.

[0027] IR spectrum is shown in FIG. 1020 cm ^-1 : (Si-O) ¹ H-NMR spectrum (carbon tetrachloride solvent, internal standard
Chloroform) δ (ppm) 0.27~0.73: ( m, Si-CH 3, 15H) 1.20~1.40: (m, -CH 2 -, -CH-, 11H)

The compounds obtained from the above results are 1,1,3,
It was confirmed to be 3-pentamethyl-5-cyclohexylcyclotrisiloxane.

[0029]

The organosilicon compound of the present invention represented by the above general formula (1) has cyclohexyl group or C ₄ -C ₁₅ group in only one of the three silicon atoms forming the cyclotrisiloxane skeleton. It is a structural feature that an alkyl group is bonded, and it is considered that this brings various advantages.

This cyclotrisiloxane is, for example, KOH, similar to the conventionally known hexamethyltrisiloxane.
_{(N-C 4 H 9)} 4 POH, Li siliconate, an alkali catalyst such as K _{siliconate, H 2 SO 4, CF 3} SO 3
In the presence of an acid catalyst such as H, ring-opening polymerization is easily carried out to form a chain siloxane polymer. This chain-shaped siloxane polymer is used as a raw material for various silicone oils and silicone elastomers. In particular, the cyclotrisiloxane of the present invention can be polymerized using a catalyst having a low activity such as Li siliconate, so that it is possible to suppress the leveling as much as possible and suppress the formation of a high molecular cyclic substance. Siloxane polymers are useful as intermediates in oils that do not contain volatile small molecules.

For example, the silicone-based oil obtained by using the cyclotrisiloxane of the present invention as a starting material is expected to have improved lubricity in comparison with the conventional dimethyl silicone oil and the like, in relation to the above-mentioned characteristics of the molecular structure. To be done.

As described above, the cyclotrisiloxane of the present invention is useful as an intermediate raw material for the production of silicone oil and silicone rubber, which are known for various uses. In particular, it is useful for producing silicone oil and silicone rubber which are useful as materials such as grease, cosmetics, sealing materials, paints and rubber materials.

[Brief description of drawings]

1 is a chart of infrared absorption spectrum of cyclotrisiloxane obtained in Example 1. FIG.

2 is a chart of infrared absorption spectrum of cyclotrisiloxane obtained in Example 2. FIG.

3 is a chart of infrared absorption spectrum of cyclotrisiloxane obtained in Example 3. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Fukuda, Inventor Kenichi Fukuda, Matsuida-cho, Gunma Prefecture, Hitomi 1-10 Hitomi, Daiji 10 Shin-Etsu Chemical Co., Ltd. Silicon Electronic Materials Research Laboratory

Claims (2)

[Claims] 1. General formula (1): [In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different and may be substituted or unsubstituted 1 to
Is an alkyl group of 3, X is a cyclohexyl group or a formula:
A cyclotrisiloxane represented by the formula _: —C _n H _{2n + 1} (where n represents an integer of 4 to 15). 2. General formula (2): (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above) and a disiloxane diol represented by the general formula (3): The method for producing cyclotrisiloxane according to claim 1, which comprises reacting dichlorosilane represented by the formula (wherein R ⁵ and X are as described above) in the presence of a catalyst.