JP2000159784A - Production of cyclic oligosiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cyclic oligosiloxane by which the gelatinization of a reaction system in the case or the like of carrying out a long term reaction under a condition of having a high catalyst content at high temperature, by reacting a polysiloxane in the presence of a metal alkoxide with an added specific additive. SOLUTION: (A) A linear or cyclic polysiloxane is heated in the presence of (B) a metal alkoxide in (C) an added at least one additive selected from an inert solvent, disiloxane or trisiloxanes, alcohols, a carboxylic acid ester or orthoesters of an alcohol each having >=140 deg.C boiling point to provide the objective practicably cyclic oligosiloxane. The component A is preferably a polysiloxane of formula I (R1 is a monovalent hydrocarbon; R2 is hydroxy group or the like; R3 is H or a monovalent hydrocarbon; R4 to R6 are each a monovalent hydrocarbon; k and l are each 0 or 1-1,000 with the proviso that they satisfy the equation 4<=m+n<=1,000) and/or formula II (m and n are each a number of 0 or 1-1,000 with the proviso that they satisfy the equation 4<=m+n<=1,000).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a compound represented by the following general formula (III):

[0002]

Embedded image And a method for producing a cyclic oligosiloxane represented by the formula:

[0003]

2. Description of the Related Art As a method for disproportionating polysiloxane, a method using an acidic or alkaline catalyst is generally known. However, the method using such an acidic or alkaline catalyst has severe reaction conditions and cannot be said to be advantageous for industrially stable production. As for the disproportionation method under neutral conditions, for example, the formation of cyclosiloxane by thermal decomposition of polysiloxane is known, but this method requires a very high temperature of about 300 ° C. It cannot be said to be an advantageous method for producing a stable product. In addition, a method using a transition metal catalyst is known as a disproportionation method under neutral conditions. However, this method requires the use of an expensive metal catalyst such as Pt and Pd, and also considers a cost viewpoint. This is not an industrially advantageous method.

[0004] Cyclic oligosiloxanes are used in the silicone industry as raw materials for the production of high molecular weight polysiloxanes. Further, cyclic oligosiloxanes containing Si—H groups are used as raw materials for producing room temperature cross-linkable silicone rubber used for sealants and the like in the silicone industry. The room temperature crosslinkable silicone rubber can be obtained by reacting a cyclic oligosiloxane containing a Si—H group with a polysiloxane containing a vinyl group in the presence of a platinum catalyst to cause crosslinking. Further, the cyclic oligosiloxane containing a Si-H group is also used as a raw material for producing an organic functional group-bonded oligosiloxane used as an adhesion promoter or the like. The organic functional group-bonded oligosiloxane is obtained by reacting a cyclic oligosiloxane containing a Si-H group with an organic group containing a vinyl group in the presence of a platinum catalyst.

[0005] As a method for producing a cyclic oligosiloxane, for example, a method in which a cyclic oligosiloxane is formed on silicon such as dimethyldichlorosilane.
A method of hydrolyzing and condensing organosilanes having one hydrolyzable group is generally known. However,
Under such hydrolysis-condensation reaction conditions, the reaction system becomes severe in an acidic condition, which is not advantageous for industrially stable production.

[0006] In the production of cyclic oligosiloxanes containing Si-H groups, in particular, the Si-H groups have very high reactivity under such acidic conditions and react with water or silanol groups coexisting in the reaction system. And the yield of the desired compound is low. In order to solve this problem, the following methods (a) and (b) have been proposed.

That is, (a) a method of hydrolyzing methyldichlorosilane in the presence of a mixed solvent of tetrahydrofuran and a hydrocarbon solvent (JP-A-6-80680); This is a method of hydrolyzing in the presence of butyl alcohol (JP-A-7-285974).

However, in the method (a), benzene must be used as a hydrocarbon solvent in order to obtain a cyclic oligosiloxane as a product with a high yield. This can be problematic when the method is industrially put into practical use. In addition, in the method (b), dichlorodisiloxane used as a raw material is not a raw material that is distributed as a general-purpose product. Therefore, in general, the availability of the raw material is a problem when the present technology is to be implemented. There is a problem in that general technology lacks versatility.

Further, the methods (a) and (b) are both based on the hydrolysis of chlorosilane, and at that time, hydrogen chloride is produced as a by-product, so that a small amount of hydrogen chloride is mixed in the product. It is known. However, when products containing hydrogen chloride are used for applications such as electronic materials, products containing ionic components such as chloride ions are not preferred from the viewpoint of electrode corrosion and the like. For this reason, products manufactured by such a method are not suitable for uses such as electronic materials, and their industrial utility value is reduced. Also,
Since both methods (a) and (b) carry out the reaction under strongly acidic conditions, not only the steps are complicated such as adjusting the pH in the subsequent steps, but also caution is required in handling the raw materials. There is also the problem of

As another method for producing a cyclic oligosiloxane, a method has been proposed in which a chain polysiloxane or a highly polymerized cyclic polysiloxane is reacted under various conditions in the presence of an acidic or alkaline catalyst.

As a method using an acidic catalyst, for example,
(C) A method of reacting a Si-H group-containing polysiloxane in the presence of water and activated clay (Section 54-13480)
And (d) a method in which methylhydrogenpolysiloxane is heated and reacted in the presence of an acid catalyst (Section 55)
JP-A-11697), (e) a method in which an organopolysiloxane is brought into contact with a heated fixed catalyst bed under reduced pressure to cause a reaction (JP-A-2-129192), and (f) a method of reacting methylhydrogenpolysiloxane. A method in which the reaction is carried out in the presence of a high-boiling organodisiloxane (JP-A-7-242678), and a method in which (g) an organohydrogenpolysiloxane is reacted in the presence of aluminum chloride (JP-A-7-316167). is there.

However, the method (c) has a large industrial problem that the reaction system is gelled because the Si—H group is highly reactive with water particularly in an acidic state, and is used industrially. In some cases there is a problem. In the methods (d) and (e), the reaction requires a very high temperature of 250 to 500 ° C., and there is a problem in industrial use.

In each of the methods (c) to (g), an acid catalyst is used. In particular, the method (g) uses a very acidic catalyst called aluminum chloride. In these methods, it is also not preferable to use an acidic catalyst in a system containing a Si—H group because the Si—H group is essentially unstable to water or the like under acidic conditions.
For example, when a small amount of water is mixed into the system from the raw material or from the air, Si-H reacts with the water to lower the yield of the cyclic oligosiloxane, which is a product. It may cause injuries. Therefore,
The methods (c) to (g) using an acidic catalyst are techniques having a problem in practicality from an industrial viewpoint of stable production.

As a method using an alkaline catalyst, for example, (h) a method using an alkali metal carbonate as a catalyst (Japanese Patent Publication No. 45-15036), and (ii) a method using an alkali metal silanolate as a catalyst (Japanese Patent Publication No. 33) -21
No. 49).

However, since all use an alkaline catalyst, not only the process becomes complicated such as adjusting the pH in the subsequent step as in the case of the acidic catalyst, but also caution is required in handling the raw materials. There is a problem in industrially stable production. Further, in a system containing a Si-H group, these methods cannot be applied substantially because the Si-H group is very unstable under alkaline conditions. Therefore, the methods (h) and (li) using an alkaline catalyst are techniques having problems in practicality from the industrial viewpoint of stable production, and are also techniques lacking in versatility.

In order to solve such a problem, it is possible to carry out the reaction under the simple conditions of neutral conditions and relatively low temperature by using raw materials which can be obtained at a low cost, and particularly in the case of a system containing a Si--H group. As a method for producing a cyclic oligosiloxane that does not involve gelation of the system and is practical when industrially practiced, the present inventor is characterized in that a linear or cyclic polysiloxane is heated in the presence of a metal alkoxide. And a method for producing a cyclic oligosiloxane. This reaction can be carried out substantially without gelation of the reaction system.However, when the reaction is carried out for a very long time at a high temperature under conditions with a large amount of catalyst, or at the very end of the reaction, Under such special circumstances, it has been found that there is still a problem that a part of the reaction residue is gelled.

On the other hand, there is disclosed a method of reacting polysiloxane in the presence of various acidic or alkaline catalysts and adding an inert solvent when producing a cyclic oligosiloxane. For example, (nu) a method using an acid such as sulfuric acid or phosphoric acid as a catalyst (Japanese Patent Application Laid-Open No. 8-109187), a method using (l) an alkali metal hydroxide or an alkali metal salt of silanol as a catalyst (Japanese Patent Publication No. 33-2149) No.
JP-B-35-4240, JP-A-50-10007
No. 5). All of them mention only the method using an acidic or alkaline catalyst, and do not mention the case where a neutral catalyst is used as in the present invention.

Further, a method of adding a disiloxane is also disclosed, for example, Japanese Patent Application Laid-Open No. Hei 7-242678. However, the catalyst used is sulfuric acid, phosphoric acid,
It mentions only a method using an acidic catalyst such as activated clay, but does not mention a method using a neutral catalyst as in the present invention.

Further, a method of adding an alcohol is also disclosed, for example, Japanese Patent Application Laid-Open Nos. 54-90120 and 8-176162. But,
As a catalyst to be used, only a method using an alkaline catalyst such as an alkali metal hydroxide is mentioned, but no description is made when a neutral catalyst is used as in the present invention.

[0020]

Therefore, according to the present invention, a reaction is carried out for a very long time at a high temperature under a condition of a large amount of a catalyst, while substantially not accompanied by gelation of the reaction system.
It is an object of the present invention to provide a method for producing a cyclic oligosiloxane which can suppress gelation of a reaction residue in a special situation such as the very end of the reaction and is more practical for industrial use.

[0021]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that an inert solvent having a boiling point of 140 ° C. or more, disiloxane or trisiloxanes, alcohols, and carboxylic acid esters of alcohols. It has been found that cyclic oligosiloxanes can be produced more practically by adding at least one or more additives selected from the group consisting of carboxylic acids and orthoesters.

That is, the present invention relates to a method for producing a cyclic oligosiloxane comprising heating a chain or cyclic polysiloxane in the presence of a metal alkoxide, wherein (A) an inert solvent having a boiling point of 140 ° C. or more; B) Boiling point 14
A disiloxane or trisiloxane at 0 ° C or higher,
It is characterized by adding at least one additive selected from (C) alcohols having a boiling point of 140 ° C. or higher, and (D) carboxylic acid esters or orthoesters of alcohols having a boiling point of 140 ° C. or higher. A method for producing a cyclic oligosiloxane (Claim 1), which comprises the following general formula (I)

[0023]

Embedded image (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² is a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ^{4 to} R ⁶ are the same or different monovalent substituted or Represents an unsubstituted hydrocarbon group, k and l are each independently 0 or a number from 1 to 1000, and k and l represent numbers satisfying 4 ≦ k + 1 ≦ 1000. ) And / or the following general formula (II)

[0024]

Embedded image (Wherein, R ^{4 to} R ⁶ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, m and n are each independently 0 or a number from 1 to 1000, and m and n
Represents a number satisfying 3 ≦ m + n ≦ 1000. Wherein the cyclic polysiloxane represented by the general formula (III) is heated in the presence of a metal alkoxide.

[0025]

Embedded image (Wherein, R ^{4 to} R ⁶ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, p and q each independently represent a number of 0 or 1 to 10, and p and q represent 3
≤p + q≤10. In the process for producing a cyclic oligosiloxane represented by the formula (A):
(B) disiloxanes or trisiloxanes having a boiling point of 140 ° C. or higher, (C) alcohols having a boiling point of 140 ° C. or higher, (D) carboxylic acid esters or orthoesters of alcohols having a boiling point of not less than Is a method for producing a cyclic oligosiloxane (Claim 2), wherein at least one additive selected from those having a temperature of 140 ° C. or higher is added. 999, and l and n are each independently a number of 1 to 1000, and p is 0 or a number of 1 to 9, and q is 1 to 1.
The method for producing a cyclic oligosiloxane according to claim 2, wherein the number is 0 (claim 3), wherein the k, l, m, n, p,
q is 5 ≦ m + n ≦ 1000 and p + q <k + 1 and p +
4. The method for producing a cyclic oligosiloxane according to claim 3, wherein q <m + n is satisfied, wherein R ¹ , R ⁴ and R ⁶ are a methyl group, R ² is a hydroxyl group or a methyl group, 5. The method for producing a cyclic oligosiloxane according to claim 2, wherein ³ is a hydrogen atom or a methyl group (claim 5), wherein the k, l, m, n, p, q
Is a method for producing a cyclic oligosiloxane according to any one of claims 2 to 5, wherein k <l, m <n, and p <q (claim 6), wherein k = m = p = 0. The method for producing a cyclic oligosiloxane according to any one of claims 3 to 5 (claim 7), wherein [1] the following general formula (IV):

[0026]

Embedded image (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group. And k represents a number of 4 to 1000. ) And / or the following general formula (V)

[0027]

Embedded image (Wherein, R ⁵ represents the same or different monovalent substituted or unsubstituted hydrocarbon group, and 1 represents a number of 4 to 1,000). And [2] the following general formula (VI)

[0028]

Embedded image (In the formula, R ⁶ represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ^{7 to} R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon group, and m represents 4 to 1000.
Represents the number of And / or the linear polysiloxane represented by
Or the following general formula (VII)

[0029]

Embedded image (Wherein, R ¹¹ and R ¹² represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, and n represents a number of 4 to 1,000). And heating the polysiloxane component in the presence of a metal alkoxide.

[0030]

Embedded image (Wherein, R ⁴ , R ⁵ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent the same or different monovalent substituted or unsubstituted hydrocarbon groups,
p, q, r, and s are numbers from 0 to 9, and p, q, r,
s represents a number that satisfies 3 ≦ p + q + r + s ≦ 10, 1 ≦ p + q, and 1 ≦ r + s. (C) a disiloxane or trisiloxane having a boiling point of 140 ° C. or higher, and (C) an alcohol having a boiling point of 140 ° C. or higher. And (D) a method for producing a cyclic oligosiloxane, comprising adding at least one additive selected from carboxylic acid esters or orthoesters of alcohols having a boiling point of 140 ° C. or higher. Claim 8) and the following general formula (IV)

[0031]

Embedded image (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group. And k represents a number of 4 to 1000. ) And a linear polysiloxane represented by the following general formula (VI)

[0032]

Embedded image (In the formula, R ⁶ represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ^{7 to} R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon group, and m represents 4 to 1000.
Represents the number of And the linear polysiloxane represented by the formula (1) is heated in the presence of a metal alkoxide.
The following general formula (IX)

[0033]

Embedded image (Wherein, R ⁴ , R ⁹ and R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, p and r are numbers from 1 to 9, and p and r are 3 ≦ (a) a method satisfying p + r ≦ 10), wherein (A) an inert solvent having a boiling point of 140 ° C. or more,
(B) disiloxanes or trisiloxanes having a boiling point of 140 ° C or higher, (C) alcohols having a boiling point of 140 ° C or higher,
(D) A method for producing a cyclic oligosiloxane, comprising adding at least one additive selected from carboxylic esters or orthoesters of alcohols having a boiling point of 140 ° C. or higher. Item 9), wherein R ¹ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ ,
^{10. The} method for producing a cyclic oligosiloxane according to claim 8, wherein R ¹⁰ , R ¹¹ , and R ¹² are methyl groups, R ² and R ⁶ are hydroxyl groups or methyl groups, and R ³ is a hydrogen atom or a methyl group. (Claim 10) wherein the metal alkoxide is an aluminum alkoxide, a titanium alkoxide, a zirconium alkoxide, a tin alkoxide, or a zinc alkoxide.
The method for producing a cyclic oligosiloxane according to any one of claims 1 to 10, wherein the metal alkoxide is an aluminum alkoxide (claim 12).
Wherein the cyclic oligosiloxane produced under reduced pressure is distilled off to produce the cyclic oligosiloxane according to any one of claims 1 to 12 (claim 13).

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the inert solvent having a boiling point of 140 ° C. or more as the component (A), various solvents having no chemical reactivity with a metal alkoxide, a hydrosilyl group, or the like can be used. Specific examples of the solvent include nonane, decane, dodecane, octadecane, aliphatic saturated hydrocarbons such as decahydronaphthalene, decene, decadiene, aliphatic unsaturated hydrocarbons such as dipentene, mesitylene, diethylbenzene, cumene, diphenyl, Tetrahydronaphthalene, diphenylbenzene (and its hydride), 2,2'-dimethylbibenzyl, aromatic hydrocarbons such as cyclohexylbenzene, oils such as mineral oil, halogenated hydrocarbons such as dichlorobenzene, diphenyl ether, Examples thereof include ethers such as diethylene glycol diethyl ether and diethylene glycol dibutyl ether, and ketones such as acetophenone. These solvents may be used alone or in a mixture.

Among these, those having compatibility with the raw materials are preferable from the viewpoint of a high gelling suppressing effect.

The amount of the catalyst to be used is not particularly limited, but is preferably from 10 to 200 parts by weight, more preferably from 50 to 100 parts by weight, based on the starting material, from the viewpoint of high gelling suppressing effect and high reaction efficiency. Is used.

The used solvent can be recovered by distillation after the completion of the reaction and reused.

As the component (B), various disiloxanes or trisiloxanes having a boiling point of 140 ° C. or more can be used. Specific examples include hexaethyldisiloxane, 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyl Trisiloxane and 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane. These disiloxanes or trisiloxanes may be used alone or as a mixture.

The amount of the disiloxane or trisiloxane used is not particularly limited, but is preferably 0.1 to 20 parts by weight based on the raw material, from the viewpoint of high gelation suppressing effect and high reaction efficiency. Preferably 1
To 10 parts by weight are used.

Various alcohols having a boiling point of 140 ° C. or more, which is the component (C), can be used. Specific examples include hexanol, octanol, 2-
Examples thereof include aliphatic alcohols such as ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, and cyclohexyl alcohol, and aromatic alcohols such as benzyl alcohol, phenethyl alcohol, and 3-phenyl-1-propanol. These alcohols may be used alone or in a mixture.

The amount of the alcohol used is not particularly limited, but is preferably 0.1 to 20 with respect to the raw material, from the viewpoint of high gelation suppressing effect and high reaction efficiency.
Parts by weight, more preferably 0.5 to 10 parts by weight, are used.

As the carboxylic acid esters or orthoesters of the component (D), alcohols having a boiling point of 140 ° C. or higher, various types can be used. Specific examples include esters or orthoesters of alcohols such as formic acid, acetic acid, propionic acid, and benzoic acid, which are shown as examples of the component (C). These carboxylic esters or orthoesters may be used alone or as a mixture.

The amount of the carboxylic acid ester or the ortho ester is not particularly limited, but is preferably 0.1 to 20 parts by weight based on the raw material, from the viewpoint of high gelation suppressing effect and high reaction efficiency. And more preferably 0.5 to 10 parts by weight.

The above-mentioned solvent or additive is preferably one having a boiling point higher than that of the cyclic oligosiloxane to be obtained by the reaction, in order to make the reaction proceed efficiently. Those having a boiling point higher by 10 ° C. or more at normal pressure than the boiling point of the oligosiloxane are more preferable.

The solvent or additive may be added in its entirety before or after the start of the reaction. However, in order to improve the efficiency of the reaction, part or all of the solvent used is successively added during the reaction. Alternatively, they may be added all at once.

The chain represented by the general formula R ¹ a chain polysiloxane represented by the formula (I), the general formula (IV) in a chain-like polysiloxane of R ¹ and the general formula represented (VI) R ⁷ and R ⁸ of the linear polysiloxane are a monovalent substituted or unsubstituted hydrocarbon group, and examples of the hydrocarbon group include a halogenated alkyl group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, Alternatively, an aryl group and the like can be mentioned. Of these, methyl, ethyl, propyl, isopropyl, n-butyl, s-
Examples thereof include a butyl group, a t-butyl group, a cyclohexyl group, a vinyl group and a phenyl group, and more preferably a methyl group and a phenyl group. Most preferred is a methyl group.

The chain represented by the general formula chain polysiloxanes R ² represented by the formula (I), the general formula (IV) in a chain-like polysiloxane of R ² and the general formula represented (VI) R ⁶ of the polysiloxane is a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, and examples of the monovalent substituted or unsubstituted hydrocarbon group are the same as those of R ¹ .

[0048] The general formula (I) represented by chain polysiloxanes of R ³ and the formula of the linear polysiloxane represented by (IV) R ³ is substituted or unsubstituted hydrogen atom or a monovalent a hydrocarbon group, examples of the substituted or unsubstituted monovalent hydrocarbon group are the same as the R ^1.

The chain polysilyl represented by the above general formula (I)
Kisane's R^Four, R⁶And the cyclic poly represented by the general formula (II)
R of siloxane^Four, R⁶Represented by the general formula (III)
R of cyclic oligosiloxane^Four, R⁶And the general formula (IV)
R of the linear oligosiloxane represented by^Four, The general formula
R of the cyclic polysiloxane represented by (V)^Five, The general formula
Chain polysiloxane R represented by (VI)⁹, The general formula
R of the cyclic polysiloxane represented by (VII)¹¹The said one
R of the cyclic oligosiloxane represented by the general formula (VIII) ^Four,
R^Five, R⁹, R¹¹And a ring represented by the general formula (IX)
Oligosiloxane R^Four, R⁹Is monovalent substituted or unsubstituted
And an example is the aforementioned R.¹Is the same as Ma
In addition, R in the above general formulas (I), (II) and (III)^Four, R⁶And
And the aforementioned general formulas (IV), (V), (VI), (VII), (VII
R of (I), (IX)^Four, R^Five, R⁹, R¹¹Is repeated for each
The units may be the same or different.

The chain polysilyl represented by the above general formula (I)
Kisane's R^FiveA cyclic policy represented by the general formula (II)
Roxan's R^FiveAnd a ring represented by the general formula (III)
R of linear oligosiloxane^FiveRepresented by the general formula (VI)
R of the chain polysiloxane^TenRepresented by the general formula (VII)
Of the cyclic polysiloxane to be¹²And the general formula (VIII)
R of the cyclic oligosiloxane represented by^Ten, R¹²And before
R of the cyclic oligosiloxane represented by the general formula (IX)^Ten
Is a monovalent substituted or unsubstituted hydrocarbon group;
Examples of elementary groups include alkyl groups, cycloalkyl groups,
Kenyl group, cycloalkenyl group, aryl group, etc.
Is mentioned. Of these, a methyl group and an ethyl group are preferred.
Group, CH_TwoCH_TwoX¹A substituted alkyl group represented by
X for¹Represents a halogen atom, a cyano group, a phenyl group,
Lucoxy group, alkylcarbonyl group, alkoxycarbo
Represents a monovalent organic group such as a nyl group. ), CH_TwoCH (C
H_Three) X^TwoA substituted alkyl group represented by the formula (X^TwoIs
Halogen atom, phenyl group, alkylcarbonyl group,
Represents a monovalent organic group such as a lucoxycarbonyl group. ), C
H _TwoCH_TwoCH_TwoX^ThreeA substituted alkyl group represented by
U X^ThreeIs a halogen atom, a hydroxyl group, a substituted or unsubstituted
Represents a monovalent organic group such as an alkoxy group. ), Vinyl group,
A phenyl group. Further, the above-mentioned general formulas (I) and (I
R of I) and (III)^FiveAnd the general formulas (VI), (VII),
R of (VIII) and (IX)^Ten, R¹²Is a repeating unit
Each may be the same or different.

Specific examples of the linear polysiloxane represented by the general formula (I) include Me ₃ SiO— (Me ₃ Si
O) _x -SiMe ₃ , Me ₃ SiO- (Ph ₂ SiO) _x-
SiMe ₃ , Me ₃ SiO— (MePhSiO) _x —Si
Me ₃ , Me ₂ PhSiO— (Me ₂ SiO) _x —SiMe
₂ Ph, MePh ₂ SiO- (Me ₂ SiO) _x -SiMe
_{Ph 2, Me 2 Si (OH} ) O- (Me 2 SiO) x -Si
Me ₂ (OH) Me ₃ SiO— (MeHSiO) _x —SiMe ₃ , Me ₂ P
_{hSiO- (MeHSiO) x -SiMe 2 Ph} , MeH
Si (OH) O- (MeHSiO) _x -SiMe (O
H) H, (where x represents a number of 4 to 1000, preferably 20 to 500, and more preferably 3
Represents a number from 5 to 200. _{) Me 3 SiO- (MeSi (CH} 2 CH 2 C 6 H 4 CH 3)
O) _5- (MeHSiO) ₅ -SiMe ₃ , MeHSi
(OH) O- (MeSi (CH 2 CH 2 C 6 H 4 CH 3)
O) _5- (MeHSiO) ₅ -SiMe (OH) H, Me
₃ SiO- (Me ₂ SiO) _x- (MeHSiO) _y -Si
Me ₃ , Me ₃ SiO— (MePhSiO) _x — (MeH
SiO) _y -SiMe ₃ , Me ₃ SiO- (MeSi (C
_{H 2 CH (CH 3) C} 6 H 5) O) x - (MeHSiO) y -
SiMe ₃ , Me ₃ SiO— (MeSi (CH ₂ CH ₂ CH
₂ (OCH ₂ CH ₂ ) _n OMe) O) _x- (MeHSiO) _y-
SiMe ₃ , (where x and y represent a number of 4 to 1000, preferably x + y represents a number of 20 to 500, more preferably x + y represents a number of 35 to 200, and n represents a number of Represents a number of 0 or 1 to 100, preferably represents a number of 1 to 20, more preferably 5 to 1
Represents the number 0. ) And the like.

Examples of the cyclic polysiloxane represented by the general formula (II) include:

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image (Here, x and y represent 0 or a number of 1 to 1000, preferably x + y represents a number of 4 to 100, more preferably x + y represents a number of 4 to 10, and n referred to here is Represents a number of 0 or 1 to 100, preferably 1
-20, more preferably 5-10. ) And the like.

Examples of the cyclic oligosiloxane represented by the general formula (III) include:

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image (Here, x and y represent 0 or a number of 1 to 10, and x
+ Y represents a number of 3 to 10. Preferably, x and y represent 0 or a number of 1 to 6, and x + y represents a number of 3 to 6. More preferably, x and y represent 0 or a number of 1 to 4, and x + y
Is 4. N is 0 or 1 to 100.
, Preferably 1 to 20, more preferably 5 to 10. ) And the like.

Specific examples of the linear polysiloxane represented by the general formula (IV) include Me ₃ SiO— (MeHSi
O) _x -SiMe ₃ , Me ₂ PhSiO- (MeHSi
O) _x -SiMe ₂ Ph, MeHSi (OH) O- (Me
HSiO) _x -SiMe (OH) H, Me ₃ SiO- (P
hHSiO) _x -SiMe ₃ , Me ₂ PhSiO- (Ph
HSiO) _x -SiMe ₂ Ph, MeHSi (OH) O-
(PhHSiO) _x -SiMe (OH) H, where x represents a number of 4 to 1000, preferably 20 to 50
It represents the number of 0, more preferably represents the number of 35 to 200. ) And the like.

Examples of the cyclic polysiloxane represented by the general formula (V) include:

[0062]

Embedded image

[0063]

Embedded image (Here, x represents a number of 4 to 1000, preferably represents a number of 4 to 100, and more preferably represents a number of 4 to 10).

Examples of the linear polysiloxane represented by the general formula (VI) include Me ₃ SiO— (Me ₂ SiO) _x
—SiMe ₃ , Me ₃ SiO— (Ph ₂ SiO) _x —SiM
_{e 3, Me3SiO- (MePhSiO) x} -SiMe 3,
Me ₂ PhSiO— (Me ₂ SiO) _x —SiMe ₂ Ph,
MePh ₂ SiO— (Me ₂ SiO) _x —SiMePh ₂ ,
_{Me 2 Si (OH) O- (} Me 2 SiO) x -SiMe
_{2 (OH), Me 3 SiO-} (MeSi (CH 2 CH 2 CH
_{2 (OCH 2 CH 2) n} OMe) O) x -SiMe 3 (x here represents the number of 4 to 1000, preferably 20 to 50
Represents a number of 0, more preferably represents a number of 35 to 200, and n represents a number of 0 or 1 to 100, preferably represents a number of 1 to 20, more preferably 5 to 10 Represents the number of ) And the like.

Specific examples of the cyclic polysiloxane represented by the general formula (VII) include:

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image (Here, x represents a number of 4 to 1,000, preferably represents a number of 4 to 100, more preferably represents a number of 4 to 10, and n represents 0 or a number of 1 to 100. And preferably represents a number of 1 to 20, and more preferably represents a number of 5 to 10).

The formula (VIII) and the formula (I
Examples of the cyclic oligosiloxane represented by X) include:

[0071]

Embedded image

[0072]

Embedded image (Where x and y represent numbers from 1 to 9 and x + y is from 3 to
Represents the number 10. Preferably, x and y represent a number of 1 to 5, and x + y represents a number of 3 to 6. More preferably x, y
Represents the number of 1 to 3d, and x + y is 4. In addition, n represents 0 or a number of 1 to 100, preferably a number of 1 to 20, and more preferably a number of 5 to 10. ) And the like.

The metal alkoxide used in the present invention is, for example, a compound represented by the following general formula (X)

[0074]

Embedded image (In the formula, R ¹ is a monovalent substituted or unsubstituted hydrocarbon group. Examples of the hydrocarbon group are the same as R ¹ in the above general formula (I), and Y ¹ and Y ² have the same number of carbon atoms. 1 to 8 alkyl groups, aryl groups or alkoxy groups, M is a divalent to tetravalent metal element, and r and s are 0, 1, 2,
3, 4 and r + s is 2 to 4). Of these, M is preferably Al, Ti, Z
Metal alkoxides of r, Sn, Zn and Mg are used, more preferably metal alkoxides of M being Al, Ti and Zr, and most preferably aluminum alkoxides.

More specifically, aluminum triethoxide, aluminum triisopropoxide, aluminum tributoxide, aluminum tributoxide, aluminum diisopropoxy second butoxide, aluminum diisopropoxyacetylacetonate, aluminum diethanol Butoxyacetylacetonate, aluminum diisopropoxyethylacetoacetate, aluminum disecondary butoxyethylacetoacetate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, aluminum acetylacetonate bisethylacetoacetate, titanium tetraethoxy , Titanium tetraisopropoxide, titanium tetrabutoxide, titanium diisopropoxybisacetylacetonate, Tanji isopropoxybis ethyl acetoacetate, titanium tetra 2-ethylhexyl oxide, titanium diisopropoxy bis (2-ethyl-1,
3-hexanediolate), titanium dibutoxy bis (triethanol aminate), zirconium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetramethoxide, zirconium tributoxide monoacetylacetonate, zirconium dibutoxide bisacetylacetonate, zirconium Butoxide trisacetylacetonate, zirconium tetraacetylacetonate, zirconium tributoxide monoethylacetoacetate, zirconium dibutoxide bisethylacetoacetate, zirconium butoxide trisethylacetoacetate, zirconium tetraethylacetoacetate, dibutyltin diacetate, dibutyltin diacetate Octoate, dibutyltin dilaurate, dibutyltin bisacetyl Acetonate, dibutyltin bisethylacetoacetate, tin (II) diacetate, tin (II) dioctoate, tin (II) dilaurate, tin (II) bisacetylacetonate, tin (II) bisethylacetoacetate, zinc diacetate, magnesium Diacetate, magnesium dimethoxide, magnesium diethoxide and the like. In addition, annular 1, 3, 5-
Triisopropoxycyclotrialuminoxane, a partial hydrolyzate of the metal alkoxide, and the like can also be used. Of these, aluminum triisopropoxide, aluminum trisecondary butoxide, aluminum diisopropoxyethyl acetoacetate, and aluminum disecondary are preferable from the viewpoints of reactivity and industrial availability.
Butoxyethyl acetoacetate, aluminum trisacetylacetonate, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide are used. Most preferred is aluminum triisopropoxide.

These metal alkoxides may be used alone or in any combination.

These catalysts may be supported on various carriers such as zeolite by methods such as adsorption and fusion.

The amount of the metal alkoxide to be used in the present invention can be variously selected according to the reaction rate, but is generally 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.01 to 5 parts by weight, based on the starting polysiloxane. 0.01 to 1 part by weight can be used.

The reaction temperature in the present invention may be any temperature at which the reaction proceeds. Generally, a temperature of 60 to 300 ° C. is used. In order to suppress a side reaction and promote the reaction efficiently, the reaction temperature is 100 to 200 ° C. Is preferred.

The reaction of the present invention can be carried out at normal pressure or under reduced pressure. However, it is preferable to carry out the reaction under reduced pressure in order to proceed with the reaction efficiently at a relatively low temperature by sequentially distilling the product. . In this case, the reaction can be performed under reduced pressure of, for example, 10 to 300 mmHg.

Although the present invention can be practiced even when a small amount of an alkoxysilane is present as an additive, the greater the amount of the alkoxysilane added, the lower the yield of the target cyclosiloxane, and the lower the practicality.

In the reaction of the present invention, after the raw material polysiloxane and the metal alkoxide are mixed and heated and reacted, the product can be purified by distillation or the like, or the reaction can be performed while the product is sequentially distilled off during the progress of the reaction. You can also. In order to suppress a side reaction, it is desirable to carry out the reaction while sequentially distilling out the product. When distilling off the product, a rectification column such as various packed columns can be used as necessary. When a rectification column is used, the purity of the product can be increased.

A method of adding the starting polysiloxane to the reaction residue obtained in the present reaction to carry out a further reaction, or simultaneously adding the starting polysiloxane while distilling off the cyclic oligosiloxane as a reaction product. , It is also possible to carry out the reaction semi-batch or continuously.

In the reaction of the present invention, a low molecular weight cyclic oligosiloxane can be produced from a high molecular weight chain or cyclic polysiloxane, but conversely, a low molecular weight compound can be converted into a high molecular weight compound. .

Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

[0086]

EXAMPLE 1 Me ₃ SiO— (MeHSiO) ₄₀ —Si was placed in a 100 mL flask equipped with a thermometer, a magnetic stirrer, and a reflux condenser.
30 g of trimethylsilylpolymethylhydrogensiloxane at both ends represented by Me ₃ and ₃ g of aluminum triisopropoxide were added, and 30 g of dodecane was further added as a solvent.
Heated in an oil bath. When the state of the reaction solution was observed over time, the viscosity gradually increased, but the reaction system did not gel even after 5 hours. Comparative Example When the same operation was performed in the same manner as in Example 1 except that the solvent was not added, the entire reaction system gelled after 3 hours.

[0087]

According to the present invention, when the reaction is carried out for a very long time at a high temperature under the condition of a large amount of the catalyst, or at the very end of the reaction, the reaction is substantially not accompanied by gelation. Gelation of the reaction residue in special situations such as
The cyclic oligosiloxane can be produced in a more practical manner when industrially practiced.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4H039 CA92 CH20 4H049 VN01 VP10 VQ02 VQ20 VQ79 VQ87 VR11 VR21 VR42 VS02 VS20 VS79 VT05 VT06 VT08 VT09 VT10 VT10 VT40 VU20 VV01 VV02 VV03 VV05 CA02V02VV02VV02

Claims (13)

[Claims] 1. A process for producing a cyclic oligosiloxane, comprising heating a chain or cyclic polysiloxane in the presence of a metal alkoxide, wherein (A) a boiling point of 140
(B) disiloxanes or trisiloxanes having a boiling point of 140 ° C. or higher; (C) alcohols having a boiling point of 140 ° C. or higher; (D) carboxylic acid esters or orthoesters of alcohols having a boiling point of Wherein at least one additive selected from those having a temperature of 140 ° C. or higher is added. 2. A compound represented by the following general formula (I): (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² is a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ^{4 to} R ⁶ are the same or different monovalent substituted or Represents an unsubstituted hydrocarbon group, k and l are each independently 0 or a number from 1 to 1000, and k and l represent numbers satisfying 4 ≦ k + 1 ≦ 1000. And / or the following general formula (II): (Wherein, R ^{4 to} R ⁶ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, m and n are each independently 0 or a number from 1 to 1000, and m and n
Represents a number satisfying 3 ≦ m + n ≦ 1000. Wherein the cyclic polysiloxane represented by the general formula (III) is heated in the presence of a metal alkoxide. (Wherein, R ^{4 to} R ⁶ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, p and q each independently represent a number of 0 or 1 to 10, and p and q represent 3
≤p + q≤10. In the process for producing a cyclic oligosiloxane represented by the formula (A):
(B) disiloxanes or trisiloxanes having a boiling point of 140 ° C. or higher; (C) alcohols having a boiling point of 140 ° C. or higher; Wherein at least one additive selected from those having a temperature of 140 ° C. or higher is added. 3. k and m are each independently 0 or a number from 1 to 999; l and n are each independently a number from 1 to 1000; and p is 0 or 1 to 9 3. The method for producing a cyclic oligosiloxane according to claim 2, wherein q is a number of 1 to 10. 4. 4. The apparatus according to claim 1, wherein said k, l, m, n, p, and q are 5 ≦ m + n.
4. The method for producing a cyclic oligosiloxane according to claim 3, wherein the number satisfies ≦ 1000 and p + q <k + 1 and p + q <m + n. 5. The cyclic oligosiloxane according to claim 2, wherein R ¹ , R ⁴ and R ⁶ are a methyl group, R ² is a hydroxyl group or a methyl group, and R ³ is a hydrogen atom or a methyl group. Manufacturing method. 6. The method for producing a cyclic oligosiloxane according to claim 2, wherein said k, l, m, n, p, and q satisfy k <l, m <n, and p <q. 7. The method for producing a cyclic oligosiloxane according to claim 3, wherein k = m = p = 0. [1] [1] The following general formula (IV): (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group. And k represents a number of 4 to 1000. And / or the following general formula (V): (Wherein, R ⁵ represents the same or different monovalent substituted or unsubstituted hydrocarbon group, and 1 represents a number of 4 to 1,000). And [2] the following general formula (VI): (In the formula, R ⁶ represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ^{7 to} R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon group, and m represents 4 to 1000.
Represents the number of And / or the linear polysiloxane represented by
Or the following general formula (VII): (Wherein, R ¹¹ and R ¹² represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, and n represents a number of 4 to 1,000). A polysiloxane component is heated in the presence of a metal alkoxide, characterized by the following general formula (VIII): (Wherein, R ⁴ , R ⁵ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent the same or different monovalent substituted or unsubstituted hydrocarbon groups,
p, q, r, and s are numbers from 0 to 9, and p, q, r,
s represents a number that satisfies 3 ≦ p + q + r + s ≦ 10, 1 ≦ p + q, and 1 ≦ r + s. (C) a disiloxane or trisiloxane having a boiling point of 140 ° C. or higher, and (C) an alcohol having a boiling point of 140 ° C. or higher. And (D) a method for producing a cyclic oligosiloxane, which comprises adding at least one additive selected from carboxylic acid esters or orthoesters of alcohols having a boiling point of 140 ° C. or higher. 9. A compound represented by the following general formula (IV): (Wherein R ¹ is a monovalent substituted or unsubstituted hydrocarbon group,
R ² represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ³ represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and R ⁴ represents a monovalent substituted or unsubstituted hydrocarbon group. And k represents a number of 4 to 1000. A) a chain polysiloxane represented by the following general formula (VI): (In the formula, R ⁶ represents a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, R ^{7 to} R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon group, and m represents 4 to 1000.
Represents the number of And the linear polysiloxane represented by the formula (1) is heated in the presence of a metal alkoxide.
The following general formula (IX) (Wherein, R ⁴ , R ⁹ and R ¹⁰ represent the same or different monovalent substituted or unsubstituted hydrocarbon groups, p and r are numbers from 1 to 9, and p and r are 3 ≦ a) satisfying p + r ≦ 10), wherein (A) an inert solvent having a boiling point of 140 ° C. or more,
(B) disiloxanes or trisiloxanes having a boiling point of 140 ° C or higher, (C) alcohols having a boiling point of 140 ° C or higher,
(D) A method for producing a cyclic oligosiloxane, comprising adding at least one additive selected from alcohol carboxylate esters and orthoesters having a boiling point of 140 ° C. or higher. 10. The R ¹ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R
^10, R ^11, R ¹² is a methyl group, R ^2, R ⁶ is hydroxyl group or a methyl group, R ³ is claim is a hydrogen atom or a methyl group 8
Alternatively, a method for producing the cyclic oligosiloxane according to claim 9. 11. The method for producing a cyclic oligosiloxane according to claim 1, wherein the metal alkoxide is an aluminum alkoxide, a titanium alkoxide, a zirconium alkoxide, a tin alkoxide, a zinc alkoxide, or a magnesium alkoxide. 12. The method for producing a cyclic oligosiloxane according to claim 1, wherein the metal alkoxide is an aluminum alkoxide. 13. The method for producing a cyclic oligosiloxane according to claim 1, wherein the cyclic oligosiloxane produced under reduced pressure is distilled off.