JP2000159783A - Production of cyclic oligosiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for practicably producing a cyclic oligosiloxane by which gelatinization of the reaction system is prevented in the case or the like of carrying out a long term reaction under a condition of having a large amount of a catalyst at high temperature, by heating a polysiloxane in the presence of a specific metal alkoxide. SOLUTION: (A) A linear or cyclic polysiloxane is heated in the presence of (B) a metal alkoxide of formula I (M is preferably a metal such as Al and Ti; Y1 is a 1-10C monovalent hydrocarbon; Y2 is a 1-10C monohydric alkoxy or the like; Y3 is a 1-6C monohydric alkoxy; s and t are each a number satisfying the equations 0<s<=2 or s=0 and 0<t<=2) to provide (C) the objective cyclic oligosiloxane. The component A is preferably a polysiloxane of formula II (R1 is a monovalent hydrocarbon; R2 is hydroxy or the like; R3 is H or a monovalent hydrocarbon, R4 to R6 are each a monovalent hydrocarbon; k and l are each a number of 0 or 1-1,000 with the proviso that they satisfy the equation 4<=k+1<=1,000) and/or formula III (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]

TECHNICAL FIELD The present invention relates to a compound represented by the following general formula (IV) used as a raw material in the silicone industry:

[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 the method (f), it is necessary to use a high-boiling disiloxane as an auxiliary material in addition to the main material. However, these special disiloxanes are not raw materials that are distributed as general-purpose products, and therefore generally lack the versatility of industrial technology in terms of obtaining raw materials when implementing the present technology. It is not an industrially advantageous method from the viewpoint of cost.

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.

[0017]

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.

[0018]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that the reaction can be carried out in the presence of a metal alkoxide having a valence substantially lower than divalent. The present inventors have found that cyclic oligosiloxanes can be produced, and have reached the present invention.

That is, the present invention relates to a method for producing a cyclic oligosiloxane comprising heating a linear or cyclic polysiloxane in the presence of a metal alkoxide, wherein the metal alkoxide has the following general formula (I):

[0020]

Embedded image (Wherein, Y ¹ represents a C 1-10 monovalent hydrocarbon group, and Y ² represents a C 1-10 monovalent alkoxy group or a C 1-15 monovalent alkylcarboxy group. Y ³ represents a same or different monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and s and t are 0 <s ≦ 2, s = 0 and 0
<T ≦ 2. A method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (Claim 1):

[0021]

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 a linear polysiloxane represented by the following general formula (III):

[0022]

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 (IV) is heated in the presence of a metal alkoxide.

[0023]

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. Wherein the metal alkoxide is represented by the following general formula (I):

[0024]

Embedded image (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. ), Wherein the k and m are each independently 0 or a number from 1 to 999, and the l and n are each independently The method for producing a cyclic oligosiloxane according to claim 2, wherein the number is 1 to 1000, the p is 0 or a number of 1 to 9 and the q is a number of 1 to 10 (claim 3). And k, l, m, n, p, and q are 5
≦ m + n ≦ 1000 and p + q <k + 1 and p + q <m
4. The method for producing a cyclic oligosiloxane according to claim 3, wherein the number satisfies + n, 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.
The method for producing a cyclic oligosiloxane according to any one of claims 1 to 5, wherein k, l, m, n, p, and q are k <l, m <n, and p <q. 5. The method for producing a cyclic oligosiloxane according to any one of claims 5 to 6 (claim 6).
6. The method for producing a cyclic oligosiloxane according to claim 3, wherein k = m = p = 0 (claim 7), wherein [1] the following general formula (V):

[0025]

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 (VI)

[0026]

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 (VII)

[0027]

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 (VIII)

[0028]

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). Wherein the polysiloxane component is heated in the presence of a metal alkoxide;

[0029]

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. Wherein the metal alkoxide is represented by the following general formula (I):

[0030]

Embedded image (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. A method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the following formula (Claim 8):

[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. A) a chain polysiloxane represented by the following general formula (VII):

[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 (X)

[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 ≦ wherein the metal alkoxide is represented by the following general formula (I):

[0034]

Embedded image (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. The method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (Claim 9), wherein R ¹ , R ⁴ , R ⁵ , R ⁷ , R ⁸ ,
^10. The cyclic oligosiloxane according to claim 8, wherein R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are a methyl group, R ² and R ⁶ are a hydroxyl group or a methyl group, and R ³ is a hydrogen atom or a methyl group. The method for producing a cyclic oligosiloxane according to any one of claims 1 to 10, wherein M in the general formula (I) is Al, Ti, Zr, Sn, Zn, or Mg. (Claim 11) The method for producing a cyclic oligosiloxane according to any one of Claims 1 to 10, wherein M in the general formula (I) is Al.
The method according to any one of claims 1 to 12, wherein the cyclic oligosiloxane produced under reduced pressure is distilled off.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The chain represented by the general formula R ¹ a chain polysiloxane represented by (II), R ¹ and Formula chain polysiloxane represented by the general formula (V) (VII) 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, preferably methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, vinyl,
A phenyl group is exemplified, and a methyl group and a phenyl group are more preferred. Most preferred is a methyl group.

The chain represented by the general formula (II) chain polysiloxanes R ² represented by the general formula (V) a chain-like polysiloxane of R ² and the general formula represented (VII) 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 .

[0038] Formula (II) represented by chain polysiloxanes of R ³ and the formula of the linear polysiloxane represented by (V) 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 general formula (II)
Kisane's R^Four, R⁶And a ring represented by the general formula (III)
R of polysiloxane^Four, R⁶Represented by the general formula (IV)
R of cyclic oligosiloxane^Four, R⁶, The general formula (V)
R of the linear oligosiloxane represented by^Four, The general formula (V
R of the cyclic polysiloxane represented by I)^Five, The general formula
Chain polysiloxane R represented by (VII)⁹, The general formula
R of the cyclic polysiloxane represented by (VIII)¹¹The said one
R of the cyclic oligosiloxane represented by the general formula (IX) ^Four,
R^Five, R⁹, R¹¹And a ring represented by the general formula (X)
Oligosiloxane R ^Four, R⁹Is monovalent substituted or unsubstituted
And an example is the aforementioned R.¹Is the same as Ma
In addition, R of the above general formulas (II), (III) and (IV)^Four, R⁶You
And the general formulas (V), (VI), (VII), (VIII),
R of (IX), (X)^Four, R^Five, R⁹, R¹¹Repeats each
It may be the same or different for each unit.

The chain polysilyl represented by the general formula (II)
Kisane's R^FiveA cyclic policy represented by the general formula (III)
Roxan's R^FiveAnd a ring represented by the general formula (IV)
R of linear oligosiloxane^FiveRepresented by the general formula (VII)
R of the chain polysiloxane^Ten, Represented by the general formula (VIII)
Of the cyclic polysiloxane to be¹²In the general formula (IX)
R of the cyclic oligosiloxane represented^Ten, R¹²And said
R of the cyclic oligosiloxane represented by the general formula (X)^TenIs
A monovalent substituted or unsubstituted hydrocarbon group,
Examples of groups include alkyl groups, cycloalkyl groups,
Nil group, cycloalkenyl group or aryl group
No. Of these, preferably a methyl group, ethyl
Group, CH_TwoCH_TwoX¹A substituted alkyl group represented by (where
Say X¹Represents a halogen atom, a cyano group, a phenyl group,
Coxy group, alkylcarbonyl group, alkoxycarbonyl
Represents a monovalent organic group such as ), CH_TwoCH (CH_Three)
X^TwoA substituted alkyl group represented by the formula (X^TwoIs haloge
Atom, phenyl group, alkylcarbonyl group, alkoxy
Represents a monovalent organic group such as a cyclocarbonyl group. ), CH _TwoC
H_TwoCH_TwoX^ThreeA substituted alkyl group represented by the formula (X^Three
Is a halogen atom, a hydroxyl group, a substituted or unsubstituted alcohol
Represents a monovalent organic group such as a xy group. ), Vinyl group, phenyl
And the like. Further, the compounds represented by the general formulas (II) and (II)
R of I) and (IV)^FiveAnd the aforementioned general formulas (VII) and (VII
R of I), (IX), (X)^Ten, R¹²Are simply repeated
It may be the same or different for each position.

Specific examples of the chain polysiloxane represented by the general formula (II) 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 35 to 20.
Represents the number 0. _{) 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 (III) include:

[0043]

Embedded image

[0044]

Embedded image

[0045]

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 (IV) include:

[0047]

Embedded image

[0048]

Embedded image

[0049]

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 (V) 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 (VI) include:

[0052]

Embedded image

[0053]

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 (VII) include Me ₃ SiO— (Me ₂ SiO)
_{x -SiMe 3, Me 3 SiO- (} Ph 2 SiO) x -Si
_{Me 3, Me3SiO- (MePhSiO) x} -SiM
e ₃ , Me ₂ PhSiO— (Me ₂ SiO) _x —SiMe _{2
Ph, MePh 2 SiO- (Me2SiO)} x -SiMe
_{Ph 2, Me 2 Si (OH} ) O- (Me 2 SiO) x -Si
Me 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 a number from 20 to 500, more preferably from 35 to 20
Represents the number of 0, and n is 0 or 1 to 10
It represents the number of 0, preferably represents the number of 1 to 20, more preferably represents the number of 5 to 10. ) And the like.

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

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

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).

Formula (IX) and Formula (X)
Examples of the cyclic oligosiloxane represented by

[0061]

Embedded image

[0062]

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 has the following general formula (II)

[0064]

Embedded image (Wherein, Y ¹ represents a C 1-10 monovalent hydrocarbon group, and Y ² represents a C 1-10 monovalent alkoxy group or a C 1-15 monovalent alkylcarboxy group. Y ³ represents a same or different monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and s and t are 0 <s ≦ 2, s = 0 and 0
<T ≦ 2. ). Of these, M is preferably Al, Ti, Zr, Sn, Zn,
A metal alkoxide which is Mg is used, more preferably a metal alkoxide where M is Al, Ti or Zr, and most preferably an aluminum alkoxide is used.

To be specific, aluminum diisopropoxyacetylacetonate, aluminum
Butoxyacetylacetonate, aluminum diisopropoxyethyl acetoacetate, aluminum di-second
Butoxyethyl acetoacetate, titanium diisopropoxybisacetylacetonate, titanium diisopropoxybisethylacetoacetate, titanium dibutoxybisacetylacetonate, titanium dibutoxybisethylacetoacetate, titanium diisopropoxybis (2- Ethyl-1,3-hexanediolate), zirconium dibutoxide bisacetylacetonate, zirconium dibutoxide bisethylacetoacetate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin bisethylacetonate Acetate, tin (II) diacetate, tin (II) dioctoate, tin (II) dilaurate, tin (II) bisacetylacetonate, tin (II) bis Ethyl acetoacetate, zinc diacetate, magnesium diacetate, magnesium dimethoxide, magnesium diethoxide and the like.

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

The amount of the metal alkoxide to be used in the present invention can be variously selected according to the reaction rate. 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 to make the reaction proceed efficiently, the reaction temperature is 100 to 200 ° C. Is preferred.

The reaction of the present invention can be carried out under normal pressure or 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 off the product. . In this case, the reaction can be performed under reduced pressure of, for example, 10 to 300 mmHg.

In the reaction of the present invention, an appropriate solvent or additive can be used according to the purpose of further suppressing gelation. As the solvent, a solvent having no chemical reactivity with a metal alkoxide or a hydrosilyl group or the like and having a higher boiling point than the generated cyclic oligosiloxane 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 high gelling suppressing effect.

The amount of the catalyst used is not particularly limited, but is, for example, 10 to 200 parts by weight, more preferably 50 to 100 parts by weight, based on the raw material.

After the completion of the reaction, the used solvent can be recovered by distillation or the like and reused.

As an additive, disiloxane or trisiloxane can be used. As a specific example,
Hexaethyldisiloxane, 1,3-diphenyl-1,1,3,3-
Tetramethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyltrisiloxane, 1,3,
3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane and the like. 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, for example, 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on the raw material.

Alcohols can also be used as additives. Specific examples include aliphatic alcohols such as hexanol, octanol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, and cyclohexyl alcohol, and aromatic alcohols such as benzyl alcohol, phenethyl alcohol, and 3-phenyl-1-propanol. Is mentioned. These alcohols may be used alone or in a mixture.

The amount of the alcohol to be used is not particularly limited, but for example, 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on the raw material.

As additives, carboxylic acid esters or ortho esters of other alcohols can also be used. Specific examples include esters or orthoesters of alcohols exemplified as the alcohols that can be used as the additive, such as formic acid, acetic acid, propionic acid, and benzoic acid. These carboxylic esters or orthoesters may be used alone or as a mixture.

The amount of the carboxylic acid esters or orthoesters is not particularly limited, but is, for example, 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on the raw materials.
5 to 10 parts by weight are used.

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 present invention can be practiced even when a small amount of alkoxysilane is present as an additive other than the solvent. However, the greater the amount of alkoxysilane added, the lower the yield of the target cyclosiloxane, so that practicality is reduced. Lower.

In the reaction of the present invention, the raw material polysiloxane and the metal alkoxide can be mixed and heated to cause a reaction, and then the product can be purified by distillation or the like. 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.

Further, a reaction may be carried out by adding the raw material polysiloxane to the reaction residue obtained in the present reaction, or simultaneously adding the raw material 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 oligomer can be converted into a high-molecular-weight oligomer. .

[0086]

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.

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Claims (13)

[Claims] 1. A method for producing a cyclic oligosiloxane, comprising heating a linear or cyclic polysiloxane in the presence of a metal alkoxide, wherein the metal alkoxide has the following general formula (I): ## STR1 ## (Wherein, Y ¹ represents a C 1-10 monovalent hydrocarbon group, and Y ² represents a C 1-10 monovalent alkoxy group or a C 1-15 monovalent alkylcarboxy group. Y ³ represents a same or different monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and s and t are 0 <s ≦ 2, s = 0 and 0
<T ≦ 2. The method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (1). 2. A compound represented by the following general formula (II): (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 (III): (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. ) Is heated in the presence of a metal alkoxide, characterized by the following general formula (IV): (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. ) Wherein the metal alkoxide is represented by the following general formula (I): (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. The method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (1). 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] The following general formula (V): (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 (VI): (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 (VII): (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 (VIII): (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 (IX): (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. ), Wherein the metal alkoxide is represented by the following general formula (I): (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. The method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (1). 9. A compound represented by the following general formula (V): (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 (VII): (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 (X) (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 ≦ wherein the metal alkoxide is represented by the following general formula (I): (Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a monovalent alkoxy group having 1 to 10 carbon atoms or a monovalent alkylcarboxy group having 1 to 15 carbon atoms. R ³ and R ⁴ are the same or different and represent a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent alkoxy group having 1 to 6 carbon atoms, and m and n are 0 <m ≦ 2. Is there, m =
It represents a number satisfying 0 and 0 <n ≦ 2. The method for producing a cyclic oligosiloxane which is a metal alkoxide represented by the formula (1). 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 compound of the formula (I) wherein M is Al, Ti, Z
The method for producing a cyclic oligosiloxane according to any one of claims 1 to 10, wherein the method is r, Sn, Zn, or Mg. 12. The method for producing a cyclic oligosiloxane according to claim 1, wherein M in the general formula (I) is Al. 13. The method for producing a cyclic oligosiloxane according to claim 1, wherein the cyclic oligosiloxane produced under reduced pressure is distilled off.