JP6225888B2 - Organopolysiloxane compound and method for producing the same - Google Patents

Description

  The present invention relates to a novel organopolysiloxane compound, particularly an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound and a method for producing the same.

Organopolysiloxane compounds having aliphatic unsaturated monovalent hydrocarbon groups on silicon atoms are useful as base polymers for addition-curable silicone compositions. Addition-curable silicone compositions cure to form silicone gels and silicone rubbers with excellent electrical properties, cold resistance, etc., so electrical and electronic parts, semiconductor device sealants, fillers or coating agents, light It is widely used as a semiconductor insulation coating protective agent. As the base polymer for addition-curable silicone compositions, organopolysiloxane compounds having vinyl groups on silicon atoms are mostly used, and silicone curing is achieved by hydrosilylation reaction with organohydrogen (poly) siloxane. Give things. However, the aliphatic unsaturated hydrocarbon group that can be originally applied to the hydrosilylation reaction is not limited to a vinyl group, and if it has an aliphatic carbon-carbon multiple bond as a partial structure, Application to the base polymer is theoretically possible.
For this reason, the novel base polymer used for an addition curable silicone composition is calculated | required.

  In addition, the following are mentioned as prior art documents relevant to the present invention.

Org. Biomol. Chem. , 2011, 9, 504

  The present invention has been made in view of the above circumstances, and is a novel organopolysiloxane compound applicable as a base polymer of an addition-curable silicone composition, particularly an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound and It aims at providing the manufacturing method.

The present inventors have made various studies in order to achieve the above object.
In this case, when a base polymer having at least one unit represented by the following general formula (b) is applied as a partial structure, it is due to the substituent effect of the triorganosilyl group substituted at the α-position on the vinyl group. Control of the curing reaction rate and improvement of the properties of the composition are expected.
(Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different.)

The simplest compound having two units of the above formula (b) as a partial structure is represented by the following formula (c).

(Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different.)

By using a compound represented by the above formula (c) as a raw material and applying a known equilibration reaction, an α, α-disubstituted terminal vinyl group-containing organo group having at least one unit represented by the following general formula (b) Polysiloxane compounds can be synthesized.
(Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different.)

When it is applied as the base polymer of an addition-curable silicone composition, it is possible to control the curing reaction rate and improve the properties of the composition by the substituent effect of the triorganosilyl group substituted at the α-position on the vinyl group. Be expected.
The compound represented by the formula (c) can be synthesized by the method described later.
And when applying the compound which has a unit shown by the said Formula (b) as a base polymer of an addition curable silicone composition, it shows by following General formula (2) which extended the siloxane unit in the said Formula (c) structure. Application of such an organopolysiloxane compound is effective, but no synthesis example of such an organopolysiloxane compound has been reported so far.

[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, and the sum of a, b and x represents an integer of 1 to 2,000. ]

  Therefore, as a result of further intensive studies, the present inventors have found that a novel organopolysiloxane that has at least one unit represented by the following general formula (1) as a partial structure and is linear or branched In the presence of an acidic or basic catalyst, a compound represented by the following general formula (3) and a compound represented by the following general formula (4) or the following general formula (5) An α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2), which can be produced by an equilibration reaction with a compound to be used, is preferably used as a base polymer of an addition-curable silicone composition. As a result, the present invention has been found.

Accordingly, the present invention are shown in the following alpha, providing α- disubstituted terminal vinyl group-containing organopolysiloxane compound, and a manufacturing method thereof.
[ 1 ]
An α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2).
[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, and the sum of a, b and x represents an integer of 1 to 2,000. ]
[ 2 ]
A terminal vinyl group-containing siloxane compound represented by the following general formula (4).
(Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different.)
[ 3 ]
Produced by an equilibration reaction between a compound represented by the following general formula (3) and a compound represented by the following general formula (4) or a compound represented by the following general formula (5) in the presence of an acidic or basic catalyst. A method for producing an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2):
[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, and the sum of a, b and x represents an integer of 1 to 2,000. R ²⁰ is a hydrogen atom, an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or the following general formula (a0)
And each R ²⁰ may be the same or different. R ³⁰ represents a group represented by the above formula (a0), and each R ³⁰ may be the same or different. m represents an integer of 3 to 20, and y represents 3 or 4. ]

The novel α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound of the present invention has a triorganosilyl group substituted at the α-position on the vinyl group when applied as a base polymer of an addition-curable silicone composition. Control of the curing reaction rate by the substituent effect, improvement of the properties of the composition, and the like are expected.
In addition, according to the method of the present invention, when applied as a base polymer of an addition-curable silicone composition, the curing reaction rate control and composition by the substituent effect of the triorganosilyl group substituted at the α-position on the vinyl group It is possible to stably produce an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound that is expected to improve the properties of the product.

1 is a ¹ H-NMR spectrum of 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane. It is a ¹³ C-NMR spectrum of 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane. 2 is a ¹ H-NMR spectrum of an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound obtained in Example 7. 4 is a GPC curve of the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound obtained in Example 7.

  Hereinafter, the method for producing the organopolysiloxane compound of the present invention, particularly the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound and the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound will be described in more detail. However, the present invention is not limited to these.

Organopolysiloxane Compound The novel organopolysiloxane compound of the present invention has at least one unit represented by the following general formula (1) as a partial structure, and is either linear or branched It is what.
[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, and b represents an integer of 0 to 1,999. ]

  This organopolysiloxane compound is characterized in that it has a vinyl group on the terminal silicon atom in which the α-position on the vinyl group is substituted with a triorganosilyl group. If such an organopolysiloxane compound is applied as the base polymer of an addition-curable silicone composition, the curing reaction rate can be controlled by the substituent effect of the triorganosilyl group substituted at the α-position on the vinyl group. An improvement in properties of the composition is expected.

R ¹ in the above formula (1) is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and preferably has a hydrogen atom or a substituent. A monovalent saturated aliphatic hydrocarbon group, a monovalent unsaturated aliphatic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent (an aromatic heterocyclic ring) More preferably, a hydrogen atom, a monovalent saturated aliphatic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, particularly preferably, It is a monovalent saturated aliphatic hydrocarbon group which may have a substituent.

  Specific examples of the monovalent saturated aliphatic hydrocarbon group which may have a substituent include linear chains such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Branched alkyl groups such as alkyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group and neopentyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, chloromethyl group and 3-chloropropyl group , 3,3,3-trifluoropropyl groups, halogen-substituted alkyl groups such as bromopropyl groups, etc., having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. .

  Specific examples of the monovalent unsaturated aliphatic hydrocarbon group which may have a substituent include alkenyl groups such as ethenyl group, 1-methylethenyl group and 2-propenyl group, ethynyl group and 2-propynyl group. An alkynyl group or the like has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms.

Specific examples of the monovalent aromatic hydrocarbon group which may have a substituent include aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and 2-phenylethyl group, α, α, α -It has 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 carbon atoms, such as a halogen-substituted aryl group such as a trifluorotolyl group and a chlorobenzyl group.
Among these, R ¹ is preferably a methyl group, an ethyl group, a 3,3,3-trifluoropropyl group, or a phenyl group, and more preferably a methyl group, an ethyl group, or a phenyl group.

R ² in the above formula (1) is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
(Wherein R ¹ and R ⁴ are the same as above. X represents an integer of 0 to 1,998, preferably an integer of 0 to 1,800, more preferably an integer of 0 to 1,500.)
Preferably a hydrogen atom, a monovalent saturated aliphatic hydrocarbon group which may have a substituent, a monovalent unsaturated aliphatic hydrocarbon group which may have a substituent, a substituent And a monovalent aromatic hydrocarbon group (including an aromatic heterocycle) and a group represented by the formula (a) are preferable, and a hydrogen atom or a substituent may be more preferable. A monovalent saturated aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group which may have a substituent, a group represented by the formula (a), particularly preferably a monovalent saturated aliphatic which may have a substituent A hydrocarbon group, a group represented by the formula (a).

  Specific examples of the monovalent saturated aliphatic hydrocarbon group which may have a substituent include linear chains such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Branched alkyl groups such as alkyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group and neopentyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, chloromethyl group and 3-chloropropyl group , 3,3,3-trifluoropropyl groups, halogen-substituted alkyl groups such as bromopropyl groups, etc., having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. .

  Specific examples of the monovalent unsaturated aliphatic hydrocarbon group which may have a substituent include alkenyl groups such as ethenyl group, 1-methylethenyl group and 2-propenyl group, ethynyl group and 2-propynyl group. An alkynyl group or the like has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms.

  Specific examples of the monovalent aromatic hydrocarbon group which may have a substituent include aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and 2-phenylethyl group, α, α, α -It has 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 carbon atoms, such as a halogen-substituted aryl group such as a trifluorotolyl group and a chlorobenzyl group.

Specific examples of the group represented by the formula (a) include those shown below.

(Wherein x is the same as above)

Among these, R ² is a methyl group, an ethyl group, a 3,3,3-trifluoropropyl group, a phenyl group, or a group represented by the above formula (a), wherein R ⁴ is a methyl group And more preferably a methyl group, an ethyl group, a phenyl group, or a group represented by the above formula (a), wherein R ⁴ is a methyl group.

R ³ in the above formula (1) is a group represented by the above formula (a). Specific examples of the group represented by the formula (a) include the same groups as those represented by the formula (a) exemplified for R ² above. The R ^3, among these, the groups represented by the above formula (a), R ⁴ is a methyl group.

R ⁴ in the above formula (1) is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, preferably a monovalent saturated aliphatic group which may have a substituent. A hydrocarbon group, a monovalent unsaturated aliphatic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group (including an aromatic heterocycle) which may have a substituent, and more. Preferably, the monovalent saturated aliphatic hydrocarbon group which may have a substituent, the monovalent aromatic hydrocarbon group which may have a substituent, particularly preferably, the monovalent which may have a substituent It is a saturated aliphatic hydrocarbon group.

  Specific examples of the monovalent saturated aliphatic hydrocarbon group which may have a substituent include linear chains such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Branched alkyl groups such as alkyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group and neopentyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, chloromethyl group and 3-chloropropyl group , 3,3,3-trifluoropropyl groups, halogen-substituted alkyl groups such as bromopropyl groups, etc., having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. .

  Specific examples of the monovalent unsaturated aliphatic hydrocarbon group which may have a substituent include alkenyl groups such as ethenyl group, 1-methylethenyl group and 2-propenyl group, ethynyl group and 2-propynyl group. An alkynyl group or the like has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms.

  Specific examples of the monovalent aromatic hydrocarbon group which may have a substituent include aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and 2-phenylethyl group, α, α, α -It has 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 carbon atoms, such as a halogen-substituted aryl group such as a trifluorotolyl group and a chlorobenzyl group.

Among these, R ⁴ is preferably a methyl group, an ethyl group, a 3,3,3-trifluoropropyl group or a phenyl group, more preferably a methyl group, an ethyl group or a phenyl group, and particularly preferably a methyl group. It is.

a is an integer of 1 to 2,000, preferably an integer of 10 to 1,800, more preferably an integer of 20 to 1,500. When a exceeds 2,000, the viscosity becomes high and handling becomes difficult. b is an integer of 0 to 1,999, preferably an integer of 0 to 1,000, more preferably an integer of 0 to 100. When b exceeds 1,999, the viscosity becomes high and handling becomes difficult.
In addition, each repeating unit may be couple | bonded at random.

As an organopolysiloxane compound having at least one unit represented by the above formula (1) as a partial structure of an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound and being either linear or branched May include an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2).
(Wherein R ^{1 to} R ⁴ , a, b are the same as above, and the sum of x in formula (a) contained as a, b and R ² or R ³ is an integer of 1 to 2,000. is there.)

  When such an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound is applied as the base polymer of the addition-curable silicone composition, the triorganosilyl group substituted at the α-position on the vinyl group. Control of the curing reaction rate by the substituent effect and improvement of the properties of the composition are expected further.

R ¹ in the formula (2) can be exemplified by the same as R ¹ of the above-mentioned formula (1), among these, a methyl group, an ethyl group, a 3,3,3-trifluoropropyl Group and phenyl group are preferable, and methyl group, ethyl group and phenyl group are more preferable.

R ² in the formula (2) can be exemplified by the same as R ² of the above-mentioned formula (1), among these, a methyl group, an ethyl group, a 3,3,3-trifluoropropyl Of the groups, phenyl groups, or groups represented by the above formula (a), those wherein R ⁴ is a methyl group are preferred, more preferably a methyl group, an ethyl group, a phenyl group, or the above formula (a). Of the groups, R ⁴ is a methyl group.

R ³ in the formula (2) in may be exemplified by the same as R ³ of the above formula (1), among these, the groups represented by the above formula (a), R ⁴ is Those which are methyl groups are preferred.

R ⁴ in the formula (2) in may be exemplified by the same as R ⁴ of the above-mentioned formula (1), among these, a methyl group, an ethyl group, a 3,3,3-trifluoropropyl Group and phenyl group are preferred, methyl group, ethyl group and phenyl group are more preferred, and methyl group is particularly preferred.

A and b in the formula (2) are the same as a and b in the formula (1) described above. In the formula (2), the sum of x in the formula (a) contained as a, b and R ² or R ³ is an integer of 1 to 2,000, preferably an integer of 10 to 1,800, more preferably. Is an integer from 20 to 1,500. If the sum of a, b and x exceeds 2,000, the viscosity becomes high, and the handleability may be difficult.
In addition, each repeating unit may be couple | bonded at random.

Specific examples of the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the formula (2) include the following.

(Wherein, a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, x, x1, x2 represents an integer of 0 to 1,998, and a, b, x , X1 and x2 each represent an integer of 1 to 2,000.)

  The viscosity of the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound is not particularly limited, but the viscosity at 25 ° C. is preferably 10 to 1,000,000 mPa · s. More preferably, it is ~ 100,000 mPa · s. In the present invention, the viscosity can be measured with a rotational viscometer.

  The α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound of the present invention can be prepared, for example, by the following method for producing an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound.

Method for Producing α, α-Disubstituted Terminal Vinyl Group-Containing Organopolysiloxane Compound The α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound of the present invention is represented by the following general formula (3) in the presence of an acidic or basic catalyst. ) And a compound represented by the following general formula (4) or a compound represented by the following general formula (5).
(In the formula, R ^{1 to} R ⁴ are the same as described above. R ²⁰ and R ³⁰ will be described later. M represents an integer of 3 to 20, and y represents 3 or 4.)

  According to such a production method of the present invention, an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the above formula (2) can be produced, and further represented by the above formula (3). It is easy to adjust the polymerization degree by changing the molar ratio between the cyclic organosiloxane compound and the terminal vinylene group-containing organodisiloxane compound represented by the above formula (4) or the organosiloxane compound represented by the above formula (5). There is also excellent productivity.

The main raw material of the present invention includes a cyclic organosiloxane compound represented by the above formula (3).
R ¹ in the formula (3) can be exemplified by the same as R ¹ of the above-mentioned formula (1) and (2), among these, a methyl group, an ethyl group, 3,3,3 -A trifluoropropyl group and a phenyl group are preferable, and a methyl group, an ethyl group, and a phenyl group are more preferable.
M is an integer of 3-20, preferably an integer of 3-15, more preferably an integer of 3-10.

  Specific examples of the cyclic organosiloxane compound represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexaethylcyclotrisiloxane, and octaethylcyclohexane. Examples include tetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane.

Examples of the terminal raw material of the present invention include an α, α-disubstituted terminal vinyl group-containing organodisiloxane compound represented by the above formula (4).
R ¹ in the formula (4) in may be exemplified by the same as R ¹ of the above-mentioned formula (1) and (2), among these, a methyl group, an ethyl group, 3,3,3 -A trifluoropropyl group and a phenyl group are preferable, and a methyl group, an ethyl group, and a phenyl group are more preferable.

R ⁴ in the formula (4) in may be exemplified by the same as R ⁴ of the above-mentioned formula (1) and (2), among these, a methyl group, an ethyl group, 3,3,3 -A trifluoropropyl group and a phenyl group are preferable, and a methyl group, an ethyl group, and a phenyl group are more preferable.

  Specific examples of the α, α-disubstituted terminal vinyl group-containing organodisiloxane compound represented by the above formula (4) include 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl. Disiloxane, 1,1,3,3-tetraethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane, 1,1,3,3-tetraphenyl-1,3-bis [1- ( Trimethylsilyl) ethenyl] disiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (triethylsilyl) ethenyl] disiloxane, 1,1,3,3-tetraethyl-1,3-bis [1- (triethylsilyl) ethenyl] disiloxane, 1,1,3,3-tetraphenyl-1,3-bis [1- (triethylsilyl) ethenyl] disiloxane, 1,1,3,3-te Tramethyl-1,3-bis [1- (triphenylsilyl) ethenyl] disiloxane, 1,1,3,3-tetraethyl-1,3-bis [1- (triphenylsilyl) ethenyl] disiloxane, 1, Examples include 1,3,3-tetraphenyl-1,3-bis [1- (triphenylsilyl) ethenyl] disiloxane.

The compound of the above formula (4) can be produced by a hydrosilylation reaction of the following formula (4a) and formula (4b).

(In the formula, R ¹ and R ⁴ are the same as above.)

  In this case, a ruthenium catalyst such as pentamethylcyclopentadienyltris (acetonitrile) ruthenium (II) hexafluorophosphate, cyclopentadienyltris (acetonitrile) ruthenium (II) hexafluorophosphate is used for the hydrosilylation reaction. By using it, the compound of the above formula (4) can be obtained with high selectivity.

As a raw material which comprises the terminal and branched chain of this invention, the organosiloxane compound shown by the said Formula (5) is mentioned.
R ²⁰ in the above formula (5) is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a0)
(In the formula, R ¹ and R ⁴ are the same as above.)
And each R ²⁰ may be the same or different. R ²⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and examples thereof are the same as those described above for R ^2, and among these, a methyl group , An ethyl group, a 3,3,3-trifluoropropyl group, a phenyl group, or a group represented by the above formula (a0) is preferably one in which R ⁴ is a methyl group, more preferably a methyl group or an ethyl group. , A phenyl group, or a group represented by the above formula (a0), R ⁴ is a methyl group.
R ³⁰ in the above formula (5) is the above formula (a0), among which R ⁴ is preferably a methyl group.

The compound of the said Formula (5) can be obtained by reaction of the compound of the said Formula (4), and the compound of following formula (5i).
(In the formula, R ²⁰ is as described above. Y is 3 or 4, and OR ′ is an alkoxy group having 1 to 4 carbon atoms.)

In this case, the reaction is carried out by adding concentrated sulfuric acid at a temperature of about 0 to 25 ° C. in the presence of an alcohol such as methanol, and then converting the compound of formula (4) into
(In the formula, R ¹ and R ⁴ are the same as above.)
The compound of the formula (5) can be obtained by a reaction of generating an alkoxysilane of the formula (5i), a dehydration reaction with the formula (5ii), and a condensation reaction involving dealcoholization.

Specific examples of the organosiloxane compound represented by the above formula (5) include those shown below.

  The cyclic organosiloxane compound represented by the above formula (3) and the α, α-disubstituted terminal vinyl group-containing organodisiloxane compound represented by the above formula (4) or the organosiloxane compound represented by the above formula (5) The amount (ratio) used can be arbitrarily selected according to the degree of polymerization of the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the formula (2) designed as described above.

  The production method of the present invention uses an α, α-disubstituted terminal vinyl group-containing organodisiloxane compound represented by the above formula (4) or an organosiloxane compound represented by the above formula (5) as a terminal raw material. Except for the presence of an acidic or basic catalyst together with the cyclic organosiloxane compound represented by the formula (3), the reaction is carried out by a known equilibration reaction. The equilibration reaction can be performed, for example, at 10 to 180 ° C. without using a solvent, or may be performed using an appropriate solvent such as toluene or xylene.

  Examples of the acidic catalyst include sulfuric acid or trifluoromethanesulfonic acid, and examples of the basic catalyst include potassium hydroxide, sodium hydroxide, potassium siliconate, sodium siliconate, and the like. By using these catalysts, the equilibration reaction can proceed stably.

  In general, when an acidic catalyst such as sulfuric acid or trifluoromethanesulfonic acid is used as the catalyst, it is relatively low temperature, for example, 10 to 150 ° C., preferably 20 to 100 ° C. for 30 minutes to 12 hours, particularly 1 hour to The equilibration reaction is performed for 8 hours, and the acidic catalyst is used in a mass ratio of 1,000 to 100,000 ppm, preferably 10,000 to 100,000 ppm, based on the total organosiloxane compound.

On the other hand, when a basic catalyst such as potassium hydroxide, sodium hydroxide, potassium siliconate or sodium siliconate is used as the catalyst, it is relatively high temperature, for example, 50 to 180 ° C., preferably 80 to 160 ° C. for 1 hour to The equilibration reaction is carried out for 24 hours, particularly 2 hours to 12 hours, and the basic catalyst is used as a hydroxide in an amount of 1 to 1,000 ppm, preferably 10 to 500 ppm as a hydroxide with respect to the total organosiloxane compound. The
After completion of the reaction, the catalyst is neutralized and filtered, and then the filtrate is subjected to purification such as distillation, whereby the desired α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound can be obtained. .

According to the method for producing an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound of the present invention, as a typical example, the molecular composition of the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound to be produced is as follows. R ¹ ₂ SiO _2/2 units 0.05 to 99.90 mol%, R ² R ³ SiO _2/2 units 0 to 99.85 mol%, R ⁴ ₃ SiHC═CH (R ¹ ) ₂ SiO _1/2 Units 0.1 to 66.67 mol% (wherein R ^{1 to} R ⁴ are the same as those described above), and these siloxane units have the formula (3 By selecting the amount of the cyclic organosiloxane compound represented by formula (4), the α, α-disubstituted terminal vinyl group-containing organodisiloxane compound represented by formula (4) or the organosiloxane compound represented by formula (5) above. , Such molecular pairs α represented by the formula with (2), it is possible to obtain the α- disubstituted terminal vinyl group-containing organopolysiloxane compound. By using an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound having such a molecular structure as the base polymer of an addition-curable silicone composition, it is possible to control the curing reaction rate and improve the properties of the composition. Can be measured. The production method is useful in that an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound having a desired degree of polymerization can be easily produced.

  Synthesis Examples and Examples are shown below to specifically explain the present invention, but the present invention is not limited to the following Examples. In addition, about the compound obtained by the synthesis example and the Example, the viscosity and average molecular weight were measured, and the structural analysis was performed using the following apparatus.

[viscosity]
Measured at 25 ° C. using a Toki Sangyo TVB10 viscometer.

[Average molecular weight]
Measurement was performed using a Tosoh high-speed GPC apparatus HLC-8220GPC.
(Elution solvent: Toluene, flow rate: 0.3 ml / min, column oven temperature: 40 ° C., column: TSKgel superH2000, TSKgel superH3000, TSKgel superH4000, TSKgel superH5000, detector: RI)

[Structural analysis]
Structural analysis of the compound was performed using BRUKER nuclear magnetic resonance apparatus AVANCEIII HD NanoBay 400 MHz and PerkinElmer Fourier transform infrared spectroscopic analyzer Spectrum One.

First, 1,1,3,3-tetramethyl-1,3-represented by the following formula (6), which is a terminal raw material for the α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound of the present invention. Bis [1- (trimethylsilyl) ethenyl] -disiloxane was prepared.

[Synthesis Example 1]
Preparation of 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane In a 500 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel Then, 240 g of dehydrated dichloromethane and 0.458 g of pentamethylcyclopentadienyltris (acetonitrile) ruthenium (II) hexafluorophosphate were added and stirred at 25 ° C. Next, when stirring, 7.3 g (54 mmol) of 1,1,3,3-tetramethyldisiloxane and 8.9 g (91 mmol) of ethynyltrimethylsilane are dropped simultaneously, the reaction temperature rises to 30 to 32 ° C. did. After maintaining the reaction system for 2 hours, the reaction mixture is concentrated and distilled under reduced pressure to obtain the desired 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl as a colorless and transparent fraction. 10.2 g (68% yield) of siloxane was obtained. ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the obtained 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane are shown in FIGS. 1 and 2, respectively. It was.

[Synthesis Example 2]
Preparation of branched end materials (1)
Then, the compound represented by following formula (47) used as the branched terminal raw material of the alpha, alpha-disubstituted terminal vinyl group containing organopolysiloxane compound of this invention was prepared.
To a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 1,1,3,3-tetramethyl-1,3-bis [1 -(Trimethylsilyl) ethenyl] -disiloxane (33.0 g, 100 mmol), methyltrimethoxysilane (4.5 g, 33.1 mmol), and methanol (2.1 g) were added, and the mixture was cooled to 10 ° C. or lower with stirring. Subsequently, 0.65 g (6.63 mmol) of concentrated sulfuric acid was added dropwise with stirring while keeping the system at 10 ° C. or lower. Furthermore, a mixed solution of 1.1 g (61.1 mmol) of water and 1.1 g of methanol was added dropwise while keeping the system at 10 ° C. or lower. After the temperature of the system was raised to 25 ° C. and the reaction system was maintained for 1 hour, 2.4 g (133 mmol) of water was further added dropwise while maintaining the system at 25 ° C. or lower, and the reaction system was maintained for 3 hours. Thereafter, waste acid separation was performed, and washing with water was performed until the system became neutral. Subsequently, vacuum distillation was performed to obtain 12.0 g (yield 64%) of the branched end raw material represented by the above formula (47) as a colorless and transparent fraction.

[Synthesis Example 3]
Preparation of branched end materials (2)
Furthermore, the compound represented by following formula (49) used as the branched terminal raw material of the alpha, alpha-disubstituted terminal vinyl group containing organopolysiloxane compound of this invention was prepared.
To a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 1,1,3,3-tetramethyl-1,3-bis [1 -(Trimethylsilyl) ethenyl] -disiloxane 33.0 g 33.0 g (100 mmol), tetramethoxysilane 3.8 g (25.0 mmol) and methanol 2.1 g were added, and the mixture was cooled to 10 ° C. or lower with stirring. Subsequently, 0.65 g (6.63 mmol) of concentrated sulfuric acid was added dropwise with stirring while keeping the system at 10 ° C. or lower. Furthermore, a mixed solution of 1.1 g (61.1 mmol) of water and 1.1 g of methanol was added dropwise while keeping the system at 10 ° C. or lower. After the temperature of the system was raised to 25 ° C. and the reaction system was maintained for 1 hour, 2.4 g (133 mmol) of water was further added dropwise while maintaining the system at 25 ° C. or lower, and the reaction system was maintained for 3 hours. Thereafter, waste acid separation was performed, and washing with water was performed until the system became neutral. Subsequently, distillation under reduced pressure was performed to obtain 7.8 g (yield 44%) of the target branched terminal material represented by the above formula (49) as a colorless and transparent fraction.

[Example 1]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 1
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 20.4 g (61.7 mmol) of siloxane and 0.34 g of 3 mass% potassium siliconate as potassium hydroxide were added and stirred at 150 ° C. for 8 hours. After allowing the system to cool to room temperature, 0.09 g (1.1 mmol) of ethylene chlorohydrin was added and stirred at 150 ° C. for 2 hours to neutralize the system. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (35) (viscosity: 38 mPa · s).

[Example 2]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 2
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 3.4 g (10.3 mmol) of siloxane and 0.30 g of 3 mass% potassium siliconate as potassium hydroxide were added and stirred at 150 ° C. for 8 hours. After allowing the system to cool to room temperature, 0.08 g (1.0 mmol) of ethylene chlorohydrin was added and stirred at 150 ° C. for 2 hours to neutralize the system. Thereafter, stripping was performed under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (36) (viscosity: 955 mPa · s).

[Example 3]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 3
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 1.4 g (4.2 mmol) of siloxane and 0.30 g of 3 mass% potassium siliconate as potassium hydroxide were added and stirred at 150 ° C. for 8 hours. After allowing the system to cool to room temperature, 0.08 g (1.0 mmol) of ethylene chlorohydrin was added and stirred at 150 ° C. for 2 hours to neutralize the system. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (37) (viscosity: 7,440 mPa · s).

[Example 4]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 4
To a 1 L four-necked flask equipped with a stirrer and a thermometer, 588 g (1987 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 2.8 g (8.5 mmol) of siloxane and 1.18 g of 3 mass% potassium siliconate as potassium hydroxide were added and stirred at 150 ° C. for 8 hours. After allowing the system to cool to room temperature, 0.30 g (3.7 mmol) of ethylene chlorohydrin was added and stirred at 150 ° C. for 2 hours to neutralize the system. Thereafter, stripping was performed under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (38) (viscosity: 76200 mPa · s).

[Example 5]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 5
To a 1 L four-necked flask equipped with a stirrer and a thermometer, 588 g (1987 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 1.4 g (4.2 mmol) of siloxane and 1.18 g of 3 mass% potassium siliconate as potassium hydroxide were added and stirred at 150 ° C. for 8 hours. After allowing the system to cool to room temperature, 0.30 g (3.7 mmol) of ethylene chlorohydrin was added and stirred at 150 ° C. for 2 hours to neutralize the system. Thereafter, stripping was performed under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (39) (viscosity: 993, 100 mPa · s).

[Example 6]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 6
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 20.4 g (61.7 mmol) of siloxane and 5.0 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 1.7 g of water was added and stirred for 30 minutes. Further, 75 mL of toluene and 100 mL of water were added to perform waste acid separation, followed by washing and washing until the system became neutral. Thereafter, stripping was performed under reduced pressure at 150 ° C./10 mmHg, and filtration under pressure was performed to obtain a colorless and transparent polymer represented by the following formula (40) (viscosity: 70 mPa · s).

[Example 7]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 7
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 3.4 g (10.3 mmol) of siloxane and 4.5 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 1.5 g of water was added and the mixture was stirred for 30 minutes. Further, 75 mL of toluene and 100 mL of water were added to separate the waste acid, followed by washing and washing until the system became neutral. Thereafter, stripping was carried out under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (41) (viscosity: 679 mPa · s). The ¹ H-NMR spectrum and GPC curve of the resulting α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound are shown in FIGS. 3 and 4, respectively.

[Example 8]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 8
To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 147 g (497 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 1.4 g (4.2 mmol) of siloxane and 4.5 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 1.5 g of water was added and the mixture was stirred for 30 minutes. Further, 75 mL of toluene and 100 mL of water were added to separate the waste acid, followed by washing and washing until the system became neutral. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (42) (viscosity: 6,540 mPa · s).

[Example 9]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 9
To a 1 L four-necked flask equipped with a stirrer and a thermometer, 588 g (1987 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 2.8 g (8.5 mmol) of siloxane and 17.7 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 5.9 g of water was added and stirred for 30 minutes. Further, 250 mL of toluene and 300 mL of water were added to perform waste acid separation, followed by washing and washing until the system became neutral. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (43) (viscosity: 70,900 mPa · s).

[Example 10]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 10
To a 1 L four-necked flask equipped with a stirrer and a thermometer, 588 g (1987 mmol) of octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 1.4 g (4.2 mmol) of siloxane and 17.7 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 5.9 g of water was added and stirred for 30 minutes. Further, 250 mL of toluene and 300 mL of water were added to perform waste acid separation, followed by washing and washing until the system became neutral. Thereafter, stripping was performed under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (44) (viscosity: 989, 100 mPa · s).

[Example 11]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 11
In a 500 mL four-necked flask equipped with a stirrer and a thermometer, 203 g (497 mmol) of octaethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] diethyl 3.4 g (10.3 mmol) of siloxane and 6.2 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 2.1 g of water was added and stirred for 30 minutes. Further, 100 mL of toluene and 150 mL of water were added to perform waste acid separation, and then washing and washing were performed until the system became neutral. Thereafter, stripping was carried out under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (45) (viscosity: 1,770 mPa · s).

[Example 12]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 12
In a 500 mL four-necked flask equipped with a stirrer and a thermometer, 270 g (497 mmol) of 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,1,3, 20.4 g (61.7 mmol) of 3-tetramethyl-1,3-bis [1- (trimethylsilyl) ethenyl] disiloxane and 8.7 g of concentrated sulfuric acid were added and stirred at room temperature for 3 hours. Subsequently, 2.9 g of water was added and stirred for 30 minutes. Further, 150 mL of toluene and 200 mL of water were added to perform waste acid separation, and then washing and washing were performed until the system became neutral. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (46) (viscosity: 2,620 mPa · s).

[Example 13]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 13
In a 500 mL four-necked flask equipped with a stirrer and a thermometer, 295 g (997 mmol) of octamethylcyclotetrasiloxane, 6.8 g (12 mmol) of a siloxane compound represented by the following formula (47), and 9.1 g of concentrated sulfuric acid are placed. And stirred at room temperature for 3 hours. Subsequently, 3.0 g of water was added and stirred for 30 minutes. Further, 150 mL of toluene and 200 mL of water were added for waste acid separation, followed by washing and washing until the system became neutral. Thereafter, stripping was carried out under reduced pressure at 150 ° C./10 mmHg, followed by pressure filtration to obtain a colorless and transparent polymer represented by the following formula (48) (viscosity: 4,820 mPa · s).

[Example 14]
Preparation of α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound 14
In a 500 mL four-necked flask equipped with a stirrer and a thermometer, 295 g (997 mmol) of octamethylcyclotetrasiloxane, 6.8 g (12 mmol) of a siloxane compound represented by the following formula (49), and 9.1 g of concentrated sulfuric acid are placed. And stirred at room temperature for 3 hours. Subsequently, 3.0 g of water was added and stirred for 30 minutes. Further, 150 mL of toluene and 200 mL of water were added for waste acid separation, followed by washing and washing until the system became neutral. Thereafter, stripping was performed at 150 ° C./10 mmHg under reduced pressure, and pressure filtration was performed to obtain a colorless and transparent polymer represented by the following formula (50) (viscosity: 5,770 mPa · s).

Claims (3)

An α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2).
[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, and the sum of a, b and x represents an integer of 1 to 2,000. ] A terminal vinyl group-containing siloxane compound represented by the following general formula (4).
(Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different.) Produced by an equilibration reaction between a compound represented by the following general formula (3) and a compound represented by the following general formula (4) or a compound represented by the following general formula (5) in the presence of an acidic or basic catalyst. A method for producing an α, α-disubstituted terminal vinyl group-containing organopolysiloxane compound represented by the following general formula (2):
[Wherein, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ¹ may be the same or different. R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or the following general formula (a)
And each R ² may be the same or different. x represents an integer of 0 to 1,998. R ³ represents a group represented by the above formula (a), and each R ³ may be the same or different. R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and each R ⁴ may be the same or different. a represents an integer of 1 to 2,000, b represents an integer of 0 to 1,999, and the sum of a, b and x represents an integer of 1 to 2,000. R ²⁰ is a hydrogen atom, an optionally substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or the following general formula (a0)
And each R ²⁰ may be the same or different. R ³⁰ represents a group represented by the above formula (a0), and each R ³⁰ may be the same or different. m represents an integer of 3 to 20, and y represents 3 or 4. ]