JP2599313B2 - Siloxane compound having tetrahydrophthalic anhydride group and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel siloxane compound having a structure in which tetrahydrophthalic anhydride groups are bonded to both ends of a siloxane chain, and a method for producing the same.

[0002]

2. Description of the Related Art Two [2- (1,3-
Butadienyl)] group is a known compound (ie, a compound having a structure in which maleic anhydride is added to a bis-substituted-1,3-butadienylsilane derivative) (JP-A-61-205285). Gazette). However,
Each of the silicon atoms at both ends of the siloxane skeleton [2
A compound having a structure in which maleic anhydride is added to a siloxane compound to which a-(1,3-butadienyl)] group is bonded has not yet been known.

[0003]

Therefore, according to the present invention, each of the silicon atoms at both ends of the siloxane skeleton has [2-
An object of the present invention is to provide a compound having a structure in which maleic anhydride is added to a siloxane compound to which a (1,3-butadienyl)] group is bonded, and a method for producing the same.

[0004]

According to the present invention SUMMARY OF], general formula [1]:

Embedded image (Wherein, R is a substituted or unsubstituted C 1 -C 1)
And each R may be the same group or different groups. N is 0 to 10
It is an integer of 0. ) Is provided.

Novel siloxane compound The novel siloxane compound of the present invention has the general formula [1] described above, that is,

Embedded image It is represented by As is apparent from this general formula, the siloxane compound of the present invention has tetrahydrophthalic anhydride groups at both ends of the molecule and is bonded to that of the silicon atom at the end of the siloxane chain [2- (1,3- Butadienyl)] group to which maleic anhydride is added.

In the general formula [1], the group R represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, a lower alkyl group, a lower alkenyl group, an aryl group and the like as typical examples. Some or all of the hydrogen atoms bonded to the carbon atoms may be replaced by halogen atoms or the like. Specifically, examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a group in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom. Examples thereof include a vinyl group, an allyl group, a butenyl group, and a group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom.Examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group, and the like. Examples thereof include groups in which part or all of the hydrogen atoms are substituted with halogen atoms. A plurality of these groups R may be all the same or different from each other. Furthermore, n
Represents an integer of 0 to 100.

In the present invention, a typical siloxane compound is, for example, a compound represented by the following general formula [3]:

Embedded image (Wherein, R is the same as above). Representative examples of R in the general formula [3] include lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group, lower alkenyl groups such as vinyl group, allyl group and butenyl group, phenyl group, and tolyl group. Examples thereof include a group, an aryl group such as a naphthyl group, and a group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as fluorine, bromine, or chlorine. A plurality of these groups R may be all the same or different from each other.

More specific examples of the compound of the formula [3] include 1,1,3,3-tetramethyl-1,3-bis [4- (1,2,3,6-tetrahydroanhydrophthalic anhydride). Acid)] disiloxane, 1,3-dimethyl-1,3-divinyl-1,3-bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] disiloxane and 1,1,3, 3
-Tetravinyl-1,3-bis [4- (1,2,3,6
-Tetrahydrophthalic anhydride)] disiloxane.

Production Method The siloxane compound of the present invention described above corresponds to the siloxane compound.
Butadienyl group-containing siloxane with siloxane chain
By Diels-Alder reaction between the compound and maleic anhydride .
Can be easily synthesized. In this manufacturing method
The butadienyl group-containing siloxane compound used is
General formula [2], that is,

Embedded image (Wherein, R and n have the same meanings as described above).
You. For example, 1,1,3,3-tetramethyl-1,3-
Bis [2- (1,3-butadienyl)] disiloxane
Corresponds to this.

The reaction is carried out in tetrahydrofuran, dioxa
Ether compounds, such as
Aryl compounds such as toluene, xylene and methyl chloride
Halogenated alkyl such as len, chloroform, carbon tetrachloride
In a solvent that does not inhibit the reaction of
The reaction is carried out at the boiling point of the medium, preferably at a temperature of 0 ° C to 30 ° C.
You. If this temperature is too low, the reaction does not proceed effectively, and
If this temperature is too high, a side reaction occurs and the yield decreases.
Inconvenience may occur. The amount of solvent used (dilution
Rate) is determined in consideration of heat of reaction, volumetric efficiency and the like. When reacting
The time is generally between 30 minutes and 24 hours, preferably between 6 and 12 hours.
Time.

Further, maleic anhydride and pig used in the reaction are used.
The amount of the dienyl group-containing siloxane compound is on a molar basis.
1: 0.1 to 1: 2.5, especially 1: 0.2 to 1: 1.5
Is preferable.

The general method used in the above-mentioned manufacturing method
Butadienyl group-containing siloxane compound represented by the formula [2]
Products are easily manufactured using the so-called Grignard reaction
be able to.

The butadienyl group-containing siloxane compound
The Grignard reagent used in the production of
[4]:

Embedded image (Wherein X ¹ represents a halogen atom)
A magnesium halide-1,3-butadiene;
This halogen atom is chlorine, bromine or iodine.
Any of the elementary atoms may be used. This Grignard reagent
Are known per se, for example, Org. Che
m. , 44, 4788 (1979)
According to the method, for example, tetrahydrofuran, dioxa
2-ether in an ether solvent such as
Ride-1,3-butadiene mixed with magnesium metal
By doing so, it can be easily manufactured.

That is, the total amount of the maleic anhydride adduct of the present invention is
Butadienyl represented by the general formula [2] used for synthesis
The group-containing siloxane compound, the above Grignard reagent,
General formula [5]:

Embedded image (In the formula, X ² is a halogen atom or an alkoxy group.
And R and n have the same meaning as described above. )
A halogen-substituted or alkoxy-substituted siloxane compound
It is synthesized by reacting.

In the general formula [5], the group X ² represents
Halogen atoms include chlorine, bromine and iodine
May be any atom, and as the alkoxy group,
Xy , ethoxy, methoxy-substituted ethoxy, ethoxy
Si-substituted ethoxy, propoxy, butoxy and the like
Some or all of the hydrogen atoms bonded to the carbon atoms of these groups
Examples thereof include a group substituted with a halogen atom. Furthermore, this
Two radicals X ² may differ from each other in the same.

The reaction between a Grignard reagent and a siloxane compound
The reaction is carried out in a solvent that does not hinder the reaction, such as tetrahydrofuran.
Cooling the Grignard reagent prepared in
In the presence of an inert gas, the siloxane compound is added dropwise
It is done by responding. Also, contrary to the above,
Dilute the siloxane compound in a solvent, cool, and
The Grignard reagent prepared in
It is also possible to carry out the reaction.

Butadienyl synthesized by the above reaction
Using a group-containing siloxane compound,
Subjecting the acid to the Diels-Alder reaction described above.
As a result, the novel siloxane compound of the present invention is produced.
You.

Further, among the siloxane compounds having a tetrahydrophthalic anhydride group of the present invention, the above-mentioned general formula [3], that is, the formula:

Embedded image (Wherein R is as defined above) is a butadienyl group-containing siloxane compound represented by the general formula [2], which is represented by the general formula [6]:

Embedded image In the formula, R is as described above. ) Can be obtained by the same method as described above.

The siloxane compound containing a butadienyl group represented by the above general formula [6] is represented by the following general formula [7]:

Embedded image (In the formula, Y is a hydrolyzable atom or group, and R is as described above.) It can also be obtained by a method having a step of hydrolyzing and condensing a silane containing a butadienyl group represented by the formula:

In the general formula [7], R is as described above, and typical examples are lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group, vinyl group,
Allyl groups, lower alkenyl groups such as butenyl groups, phenyl groups, tolyl groups, aryl groups such as naphthyl groups, and some or all of the hydrogen atoms of these groups described above are replaced with halogen atoms such as fluorine, chlorine, and bromine. Groups and the like. Examples of the hydrolyzable atom or group include a halogen atom selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom; a methoxyl group, an ethoxyl group, a methoxyl-substituted ethoxyl group, an ethoxyl-containing ethoxyl group, and a propoxy group. And a group in which part or all of the hydrogen atoms bonded to the carbon atoms of these alkoxyl groups have been substituted with halogen atoms such as fluorine, chlorine, and bromine. A halogen atom and an alkoxy group.

The hydrolysis of the butadienyl group-containing silane represented by the general formula [7] is carried out by preparing an aqueous solution of an alkali compound such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate or the like at room temperature. Solvents that do not hinder, for example, alkyl compounds such as pentane, hexane, and heptane; aryl compounds such as benzene, toluene, and xylene; ether compounds such as tetrahydrofuran, dioxane, and diethyl ether; and halogenated compounds such as methylene chloride, chloroform, and carbon tetrachloride. The reaction is carried out by dropping and reacting a butadienyl group-containing vinylsilane diluted with an alkyl compound. Conversely, it is also possible to dilute the above-mentioned vinyl silane with the above-mentioned solvent and to react by dropping the aqueous solution of the above-mentioned alkali compound therein.

By such an operation, Y in the silane represented by the general formula [7] undergoes hydrolysis and is converted into a silanol group. The generated silanol group immediately condenses with the silanol group of another molecule, thereby producing the desired compound of the formula [6].

The reaction temperature of such hydrolysis and condensation is generally from 0 ° C to the boiling point of the solvent, preferably from 10 to 30 ° C.
If the reaction temperature is too low, the progress of the reaction is too slow to be practical, and if it is too high, a side reaction may occur. The reaction time is usually 30 minutes to 24 hours, typically 2 to 24 hours.
12 hours. The use ratio of the silane of the general formula [7] to the alkali compound in this method is 1: 0.
The range is from 5 to 1:10, preferably from 1: 1 to 1: 5. The amount of the solvent used (dilution ratio) may be determined in consideration of the heat of reaction, volumetric efficiency and the like. In the above-mentioned hydrolysis reaction, only one kind of butadienyl group-containing silane may be used, and two or more kinds of butadienyl group-containing silanes having different kinds of groups represented by R and Y or halogen atoms are used. May be. When two or more butadienyl group-containing silanes having different Rs are used, the above general formula [6]
Butadienyl group-containing siloxane in which different Rs are bonded to two silicon atoms.

The silane compound of the general formula [7] used as a starting material in the above method is, for example, a compound of the general formula [8]:

Embedded image (Wherein, R and Y are as defined above) and a Grignard reagent represented by the general formula [4].

In the reaction between the silane of the general formula [8] and the Grignard reagent of the general formula [4], the Grignard reagent prepared by diluting with a solvent that does not inhibit the reaction such as tetrahydrofuran is cooled to room temperature or lower, and inertized. The reaction is carried out by dropping the above silane and reacting in the presence of a gas.
Conversely, it is also possible to carry out the reaction by diluting the above silane with a solvent and dropping the Grignard reagent prepared above under cooling and stirring.

[0026]

EXAMPLE 1 In a 30 ml flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, 1,1,3,3-tetramethyl-1,3-bis [2
-(1,3-butadienyl)] disiloxane 3.87 g
(16.3 mmol), 3.19 g of maleic anhydride (3
2.5 mmol), 5 ml of dry THF and 25 ° C.
For 10 hours.

Next, the solvent and unreacted raw materials were distilled off under reduced pressure to obtain 6.4 g of a white solid.
The precipitate was dissolved in ml of THF and reprecipitated using hexane to obtain 5.1 g of a white powder (yield: 72).
%).

This compound was measured by NMR, mass spectrum, infrared absorption spectrum and elemental analysis. The results are shown below. From the measurement results, the obtained compound was identified as 1,1,3,3-tetramethyl-1,3-
It is recognized as bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] disiloxane.

[0029]

Embedded image

FIG. 1 shows an infrared absorption spectrum. Elemental analysis; as C ₂₀ H ₂₆ O ₇ Si ₂

Example 2 3.5 g of white powder (yield: 5) was prepared in exactly the same manner as in Example 1 except that the aging conditions of the reaction components were changed to -10 ° C. and 15 hours.
0%). From the result of the same analysis as in Example 1, this white powder was found to be 1,1,3,3-tetramethyl-1,3-
It was confirmed to be bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] disiloxane.

Example 3 In a 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, 1,3-dimethyl-1,3-divinyl-1,3-bis [2- (1,3-butadienyl)] disiloxane72.
5 g (0.277 mol), maleic anhydride 54.3 g
(0.554 mol) and 150 ml of dry THF (tetrahydrofuran) were charged and aged at 25 ° C. for 10 hours. Next, the solvent and unreacted raw materials were distilled off under reduced pressure to obtain 119.3 g of a white solid. Further, the white solid was dissolved in 150 ml of THF, and reprecipitated using hexane to obtain a white powder. 96.4 g were obtained (76% yield).

The obtained compound was measured by ¹ HNMR, mass spectrum, infrared absorption spectrum and elemental analysis. The results are shown below. From this measurement result, this compound was found to be 1,3-dimethyl-1,3-divinyl-1,3-bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] disiloxane. confirmed.

[0034]

Embedded image

FIG. 2 shows an infrared absorption spectrum. Elemental analysis; as C ₂₂ H ₂₈ O ₇ Si ₂

Example 4 Example 3 was repeated except that the reaction conditions were -10 ° C. and 15 hours.
57.1 g of a white powder was obtained in the same manner as described above (yield 4
5%). In the same flask as in Example 3, the obtained compound was analyzed in the same manner as in Example 3. As a result, this compound was found to be 1,3-dimethyl-1,3-divinyl-1,
It was confirmed to be 3-bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] disiloxane.

[0037]

The maleic anhydride adduct of the butadienyl group-containing siloxane according to the present invention is an intermediate for the synthesis of various organic resins such as polyimide resins as a result of two acid anhydride groups being introduced in one molecule. It is expected to be used for a wide range of uses as a body and a modifier.

[Brief description of the drawings]

FIG. 1 is a graph showing an infrared absorption spectrum of a siloxane compound synthesized in Example 1.

FIG. 2 is a graph showing an infrared absorption spectrum of the compound obtained in Example 3.

Claims (2)

(57) [Claims] [Claim 1] General formula [1]: (Wherein, R is a substituted or unsubstituted C 1 -C 1)
And each R may be the same group or different from each other. N is an integer of 0 to 100. A siloxane compound represented by the formula: (A ) General formula [2]: (Wherein, R and n indicates. The meaning given above) siloxane according to claim 1, wherein the butadienyl group-containing siloxane compound represented by reacting the (b) maleic anhydride, city Method for producing compound.