JP3124910B2 - Cyclotrisiloxane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cyclotrisiloxane having a trimethylsiloxy group, which is useful as a starting material for synthesizing a silicone oil which can be used as a grease or a sealing material having excellent low-temperature properties. And its manufacturing method.

[0002]

2. Description of the Related Art Conventionally, as cyclotrisiloxane,
For example, the following general formula:

Embedded image Wherein R ³ is independently unsubstituted or substituted C 1 -C 1
X is a cyclohexyl group or an alkyl group represented by the following general formula: —C _n H _{2n + 1} (where n is an integer of 4 to 15). Is known (Japanese Unexamined Patent Publication No.
-279466). However, a cyclotrisiloxane having a trimethylsiloxy group bonded to a silicon atom constituting a ring is not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel cyclotrisiloxane having a trimethylsiloxy group bonded to a silicon atom constituting a ring and a method for producing the same.

[0004]

Means for Solving the Problems A first aspect of the present invention is the following general formula (1):

Embedded image (In the formula, R ^1, A alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an alkenyl group or (meth)
An acryloyloxypropyl group, and R ² is a methyl group or a phenyl group).

A second aspect of the present invention is the following formula (2):

Embedded image And a dichlorosilane represented by the following general formula (3): R ¹ R ² SiCl ₂ (3) (wherein R ¹ and R ² are the same as described above). The method for producing cyclotrisiloxane according to the general formula (1), wherein the reaction is performed in the presence of a hydrochloric acid scavenger.

Hereinafter, the present invention will be described in detail. Cyclotrisiloxane of cyclotrisiloxane present invention, the is represented by the general formula (1), wherein, R ¹ is A alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an alkenyl group or (meth) acryloyl An oxypropyl group, and R ² is a methyl group or a phenyl group. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group,
Alkyl groups having 1 to 12 carbon atoms such as isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the like. And more typical ones are methyl, ethyl, propyl, isopropyl, butyl, hexyl and octyl having 1 to 8 carbon atoms.

The aryl group for R ¹ includes, for example,
An aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group is exemplified, and a more typical example is a phenyl group having 6 to 12 carbon atoms, a tolyl group, and a naphthyl group. It is. Examples of the aralkyl group for R ¹ include aralkyl groups having 7 to 12 carbon atoms such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group. To benzyl group and phenylpropyl group.

The halogenated alkyl group for R ¹ includes, for example, chloromethyl group, 2-bromoethyl group,
Alkyl halides having 1 to 12 carbon atoms such as -chloropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group And more typical ones having 1 carbon atom
To 6, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-
Nonafluorohexyl group.

The alkenyl group for R ¹ includes, for example, an alkenyl group having 2 to 12 carbon atoms such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group and a cyclohexenyl group. And more typical ones having 2 to 6 carbon atoms
A vinyl group, an allyl group, and a hexenyl group.

[0010] In terms of excellent silicone oil low-temperature properties than Among these R ¹ can be obtained, methylation group, a vinyl group, a phenyl group is particularly preferred. Specific examples of the cyclotrisiloxane of the present invention are not particularly limited thereto, and include, for example, those represented by the following formula.

[0011]

Embedded image (Where Ph is a phenyl group)

A method for producing cyclotrisiloxane The production method of the present invention relates to a method for preparing a silanol group-containing organosiloxane represented by the above formula (2) and dichlorosilane represented by the above formula (3) in the presence of a hydrochloric acid scavenger. It is a method of reacting below. As the dichlorosilane, For example,
Di methyldichlorosilane, methyl ethyl dichlorosilane, methyl propyl dichlorosilane, methyl hexyl dichlorosilane, methyl octyl dichlorosilane, methyl decyl dichlorosilane, methyl dodecyl dichlorosilane, methylphenyl dichlorosilane, diphenyl dichlorosilane, methyl benzyl dichlorosilane, ( 2-phenylpropyl) methyldichlorosilane, (3,3,3-
(Trifluoropropyl) methyldichlorosilane, methylvinyldichlorosilane, (meth) acryloyloxypropylmethyldichlorosilane, phenyldichlorosilane, ethylphenyldichlorosilane, vinylphenyldichlorosilane and the like.

The amount of the dichlorosilane used is usually 0.8 mol per mol of the silanol group-containing organosiloxane.
To 1.2 mol, preferably 0.9 to 1.0 mol.
The hydrochloric acid scavenger is not particularly limited as long as it forms a stable salt with hydrochloric acid, and examples thereof include amine compounds such as ammonia, dimethylamine, triethylamine and pyridine. The amount of the hydrochloric acid scavenger used is 2 to 3 mol, preferably 2 mol, per 1 mol of the dichlorosilane.
~ 2.5 mol. Although the reaction between the silanol group-containing organosiloxane and dichlorosilane proceeds without using a solvent, the use of a solvent enables the cyclotrisiloxane of the present invention to be obtained in good yield. The solvent is not particularly limited as long as it is a solvent compatible with the silanol group-containing organosiloxane and dichlorosilane. For example, ketones such as acetone and methyl ethyl ketone; diethyl ether, tetrahydrofuran, 1,
Organic solvents, such as ether solvents such as 4-dioxane; toluene; xylene; hexane, etc., can be used alone or in combination of two or more. The reaction temperature is preferably from 0 to 20 ° C., and by setting the temperature within this range, the reaction can proceed favorably. Reaction time, after charging the specified raw materials into the reaction vessel,
It may be about 10 minutes to 4 hours.

The thus obtained cyclotrisiloxane of the present invention is particularly useful as a starting material for synthesizing a silicone oil which can be used as a grease or a sealing material having excellent low-temperature properties.

[0015]

EXAMPLE 1 A four-necked flask was charged with 160 g (1.58 g) of triethylamine.
Mol) and 500 g of toluene and stirred to make them uniform. Next, the temperature of the contents of the flask is set to 0 to
While maintaining the temperature at 10 ° C., 250 g of the silanol group-containing organosiloxane represented by the above formula (2) was placed in the flask.
(0.79 mol) in 200 g of methyl ethyl ketone, and 102 g of dimethyldichlorosilane (0.1 g).
(79 mol) in 350 g of toluene was simultaneously added dropwise over 2 hours. After completion of the dropwise addition, the contents of the flask were stirred for 1 hour, and the obtained reaction mixture was washed with water.
Distillation under reduced pressure at (boiling point) /2.5 Torr gave 167 g of a colorless and transparent liquid reaction product (yield: 55%). This reaction product was analyzed by gas chromatography-mass spectrometry (hereinafter, GC-
As a result of ¹ H-NMR and IR absorption measurement, 1,3-bis (trimethylsiloxy) -1,3,3
It was confirmed to be 5,5-tetramethylcyclotrisiloxane. In addition, GC-MS analysis, IR absorption and ¹
The results of the H-NMR measurement are shown below, a GC-MS chart is shown in FIG. 1, an IR chart is shown in FIG. 2, and a ¹ H-NMR chart is shown in FIG. (GC-MS analysis) [M-CH ₃ ] ⁺ = 355 (IR absorption analysis) 1020 cm ^-1 : Si-O 1085 cm ^-1 : O-SiCH ₃ ( ¹ H-NMR measurement) δ 0.15 to 0.5 ppm (Si-CH ₃ 30H)

Example 2 A four-necked flask was charged with 202 g (2.0 mol) of triethylamine and 500 g of toluene and stirred to make them uniform. Next, the temperature of the contents of the flask was set to 0 to 1
While maintaining the temperature at 0 ° C., 314 g of a silanol group-containing organosiloxane represented by the above formula (2) (1.
(0 mol) in 100 g of toluene and a solution of 141 g (1.0 mol) of vinylmethyldichlorosilane in 250 g of toluene were simultaneously dropped over 2 hours. After completion of the dropwise addition, the contents of the flask were stirred for 30 minutes, and the obtained reaction mixture was washed with water, and was heated at 74 ° C. (boiling point) / 3.
A colorless and transparent liquid reaction product 156 was distilled under reduced pressure at Torr.
g was obtained (yield: 41%). The reaction product is GC-
As a result of MS analysis, ¹ H-NMR and IR absorption measurement, 1,
It was confirmed to be 3-bis (trimethylsiloxy) -1,3,5-trimethyl-5-vinylcyclotrisiloxane. GC-MS analysis, IR absorption and ¹ H-
The results of NMR measurement are shown below, and the IR chart is shown in FIG. (GC-MS analysis) [M-CH ₃ ] ⁺ = 367 (IR absorption analysis) 1020 cm ^-1 : Si-O 1085 cm ^-1 : O-SiCH ₃ 1595 cm ^-1 : Si-CH = CH ₂ ( ¹ H-NMR) _{measurement) δ0.15~0.5 ppm (Si-CH 3} 27H) δ5.5 ~5.8 ppm (Si-CH = CH 2 3H)

[0017]

Example 4 10 g (128 mmol) of pyridine and 50 g of toluene were charged into a four-necked flask, and the mixture was stirred to make them uniform. Next, while maintaining the temperature of the contents of the flask at 0 to 10 ° C., 20 g (64 mmol) of the silanol group-containing organosiloxane represented by the above formula (2) is placed in the flask.
Was dissolved in 50 g of toluene, and 16.1 g (64 mmol) of diphenyldichlorosilane was added to 50 g of toluene.
The solution dissolved in g was dropped simultaneously over 30 minutes. After completion of the dropwise addition, the contents of the flask were stirred for 15 minutes, the obtained reaction mixture was washed with water, and distilled under reduced pressure at 150 ° C. (boiling point) / 1 Torr to obtain 20 g of a colorless and transparent liquid reaction product (yield). : 65%). As a result of GC-MS analysis, ¹ H-NMR and IR absorption measurement, this reaction product was found to be 1,3-bis (trimethylsiloxy) -5,5-diphenyl-1,
It was confirmed to be 3-dimethylcyclotrisiloxane. Incidentally, GC-MS analysis, IR absorption and ¹ H-NM
The results of the R measurement are shown below.

(GC-MS analysis) [M] ⁺ = 494 (IR absorption analysis) 1020 cm ^-1 : Si-O 1085 cm ^-1 : O-SiCH ₃ ( ¹ H-NMR measurement) δ 0.2 to 0.8 ppm _{(Si-CH 3 24H) δ7.3~7.8} ppm (Si-C 6 H 5 10H)

Example 5 The 1,3-bis (trimethylsiloxy) -1,1 obtained in Example 1 was placed in a four-necked flask purged with dry nitrogen gas.
3,5,5-tetramethylcyclotrisiloxane 30 g
(80 mmol) and 100 g of tetrahydrofuran. Next, the contents of the flask were maintained at 0 to 10 ° C,
Lithium trimethylsilanolate 0.96 in the flask
g (10 mmol) was added while stirring the contents of the flask, and then aging was performed for 10 minutes. Next, 1.3 g of trimethylchlorosilane was added to the flask, and the contents of the flask were stirred for 30 minutes to stop the reaction. After washing the obtained reaction product with water, the solvent was distilled off to obtain a colorless and transparent silicone oil (80% yield). Differential thermal analysis (DSC) was performed on the obtained silicone oil to evaluate low-temperature characteristics of the silicone oil. Table 1 shows the results. As a control, a differential thermal analysis (DS) of dimethylpolysiloxane represented by the following formula: Me (Me ₂ SiO) ₈₅ SiMe ₃
The low temperature characteristics according to C) were evaluated. The results are also shown in Table 1.

[0021]

[Table 1]

(Evaluation) The control dimethylpolysiloxane had a melting point peak of -39 ° C. and -51 ° C. by differential thermal analysis.
° C. On the other hand, the silicone oil obtained from the cyclotrisiloxane of the present invention has no melting point peak, exhibits fluidity without solidifying from room temperature to a low temperature range, and has extremely excellent low-temperature characteristics.

[0023]

The cyclotrisiloxane of the present invention is a novel compound and is useful as a starting material for synthesizing a silicone oil having excellent low-temperature properties. Therefore, according to the present invention, it is possible to obtain a grease, a sealing material, and the like having excellent low-temperature characteristics.

[Brief description of the drawings]

FIG. 1 is a GC-MS chart of the cyclotrisiloxane obtained in Example 1.

FIG. 2 is an IR chart of the cyclotrisiloxane obtained in Example 1.

FIG. 3 shows the results of the cyclotrisiloxane obtained in Example 1.
It is a < ¹ > H-NMR chart.

FIG. 4 is an IR chart of the cyclotrisiloxane obtained in Example 2.

──────────────────────────────────────────────────続 き Continuation of front page (56) References Organomet. Chem. , 377 (1989) pp. 9-17. Organomet. Chem. , 314 (1986) p39-45 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7/21 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The following general formula (1): (In the formula, R ^1, A alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an alkenyl group or (meth)
An acryloyloxypropyl group, and R ² is a methyl group or a phenyl group). (2) The following formula (2): In a silanol-containing organosiloxane represented by the following general formula ^{(3): R 1 R 2} SiCl 2 (3) ( In the formula, R ^1, A alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, Alkenyl group or (meth)
The method for producing cyclotrisiloxane according to claim 1, wherein dichlorosilane represented by an acryloyloxypropyl group and R ² is a methyl group or a phenyl group) is reacted in the presence of a hydrochloric acid scavenger.