JP3475761B2 - Organosilicon polymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent chemical properties of polysilane and excellent solubility in various solvents.
And it shows a solid shape at room temperature, easy to handle,
The present invention relates to a novel organosilicon polymer that can be effectively used as a precursor of silicon carbide ceramics, a photoresist material, a photopolymerization initiator, various conductive materials, etc., and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a method for producing polysilane, a method using a Wurtz reaction of diorganodichlorosilane with metallic sodium is generally used, but this method has a problem of using metallic sodium and poor pot yield at the time of synthesis.

On the other hand, the method for producing polysilane by using the dehydrogenative condensation method has a high yield of polysilane and a high pot yield, but has a drawback that the molecular weight of the produced polysilane does not become so large. Was.

In this case, the chemical properties such as optical properties of polysilane are the same as those of polysilane having a degree of polymerization of 20 or more, without being much dependent on the molecular weight. In the production method, materialization by cross-linking using a side chain hydrogen group has been studied for increasing the molecular weight of polysilane.

Conventionally, in the study of the dehydrogenative condensation method, attention has been paid to obtaining a polymer having a high degree of polymerization. For this purpose, a zirconocene catalyst is used to carry out a reaction at a low temperature of 100 ° C. or lower for a long time. Have been found to be necessary. It has been reported that a polysilane having a weight average molecular weight of about 10,000 can be synthesized by such a long-term reaction, but a polymer having a molecular weight of 10,000 or less at such a level has a starch syrup shape at room temperature. And there was a problem in handling.

The present invention has been made in view of the above circumstances, and has an excellent chemical property as a polysilane and is easy to handle at room temperature, and an organosilicon polymer and a high yield of this polymer with good reproducibility. It is an object of the present invention to provide a method for producing the above organosilicon polymer that can be produced by

[0007]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above object, the present inventors have found that trihydrosilane is used as a starting material and metallocene catalysts, particularly zirconocene dehydrogenative condensation catalysts, are used. 20 to 8 in the presence of a solvent or in the presence of a solvent in an inert gas atmosphere.
After starting the reaction under the low temperature condition of 0 ° C. and performing the reaction for 24 hours or more in this temperature range to obtain a certain degree of polymerization, the reaction temperature is gradually raised and finally under the temperature condition of 120 to 180 ° C. By carrying out the reaction, a novel organosilicon polymer represented by the following general formula (1) can be obtained with good reproducibility by the dehydrogenative condensation method, and the polymer has a degree of polymerization showing the chemical properties of polysilane. It is possible to be 20 or more, has excellent chemical properties equivalent to high molecular weight polysilane as polysilane, is excellent in solubility, and has room temperature (2
It has a glass transition point (Tg) of 0 ° C. or higher, exhibits a solid shape at room temperature, and is easy to handle, and the organosilicon-based polymer of the above formula (1) is a precursor of silicon carbide ceramics, Photoresist material, photopolymerization initiator,
The inventors have found that they can be effectively used as a conductive material, a photoconductive material, a non-linear optical material, etc., and completed the present invention.

That is, as described above, a relatively high molecular weight polysilane can be obtained by a reaction using a zirconocene catalyst at a low temperature for a long time, but it has a starch syrup-like form, but at 120 to 180 ° C. Although only a low molecular weight polymer is produced when reacted at a high temperature, the obtained polymer has a high glass transition point (Tg) and exhibits a solid state at room temperature.

Therefore, in the present invention, trihydrosilane is used as a starting material in the presence of a metallocene catalyst at 20 to 80 ° C.
After the reaction is performed at the temperature of, the reaction is further performed at the temperature of 120 to 180 ° C., which is represented by the following general formula (1),
Provided is an organosilicon polymer having a glass transition point of 20 ° C. or higher.

[0010]

[Chemical 2] (In the formula, R represents a group selected from a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. Further, n and m are integers that satisfy n + m ≧ 20.)

Further, in the present invention, trihydrosilane is used as a starting material, the reaction is carried out in the presence of a metallocene catalyst in an inert atmosphere at a temperature of 20 to 80 ° C., and then the reaction temperature is raised to 120 to 180. There is provided a method for producing the above organosilicon polymer, which is characterized in that the reaction is further carried out at a temperature of ° C.

In this case, the above-mentioned production method of the present invention utilizes the fact that the selectivity of the dehydrogenative condensation reaction of trihydrosilane differs depending on the reaction temperature. First, in the low temperature reaction of 20 to 80 ° C. at the initial stage of the reaction, , The chain extension reaction of hydrosilane selectively proceeds, and side reactions other than the chain extension reaction are suppressed.
In the reaction under the high temperature condition of 20 to 180 ° C., the proportion of the three-dimensional crosslinking reaction gradually increases with deterioration,
It is thought that the three-dimensional crosslinking reaction proceeds relatively slowly,
As a result, an organosilicon polymer having a polymerization degree of 20 or more, excellent chemical properties as a polysilane, excellent solubility, and exhibiting a solid shape at room temperature and easy to handle can be produced with good reproducibility.

The present invention will be described in more detail below. The organosilicon-based polymer of the present invention is prepared by using trihydrosilane as a starting material in the presence of a metallocene catalyst for 20 to 8 parts.
It is represented by the following general formula (1), which is obtained by carrying out a reaction at a temperature of 0 ° C. and then a further reaction at a temperature of 120 to 180 ° C.

[0014]

[Chemical 3] (In the formula, R represents a group selected from a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. Further, n and m are integers that satisfy n + m ≧ 20.)

Here, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group and a hexyl group. , An octyl group, a decyl group, and the like, and the unsubstituted aromatic hydrocarbon group includes a phenyl group, a naphthyl group, a tolyl group, a benzyl group, a phenylethyl group, and the like. Also,
As the substituted alkyl group and aromatic hydrocarbon group, a part or all of the hydrogen atoms of the above-mentioned unsubstituted alkyl group and aromatic hydrocarbon group are halogen atoms such as fluorine, tertiary amino group, carboxyl group, ) A group substituted with an acrylic group, a mercapto group, a polyether group, a higher fatty acid ester group or the like can be mentioned.

N and m are integers satisfying n + m ≧ 20, and the larger n + m is, the more preferable. The upper limit is not particularly limited, but if the ratio of m is large and m + n is too large, the solubility in general organic solvents deteriorates, which is not preferable.

The weight average molecular weight of the polymer of the formula (1) is usually 2,000 or more, particularly 2,500 to
It is preferably 4,000.

The organosilicon polymer of the above formula (1) has a Tg of room temperature (20 ° C.) or higher, preferably 40 to 7.
It is necessary to be 0 ° C., and if Tg is lower than room temperature, handling becomes difficult.

The organosilicon-based polymer of the above formula (1) of the present invention is obtained by reacting trihydrosilane as a starting material in the presence of a metallocene catalyst in an inert atmosphere at a temperature of 20 to 80 ° C. Increase the temperature to 120-180
The reaction is further carried out at a temperature of ° C.

Here, RS is trihydrosilane.
iH ₃ (R has the same meaning as above) is used.

A zirconocene catalyst is usually used as the metallocene catalyst. As the zirconocene dehydrogenative condensation catalyst, a commonly used one can be used. Specifically, a dihydrozirconocene and an alkyllithium are reacted in the system to prepare a dehydrogenative condensation catalyst, and the polymerization reaction is immediately performed. It is preferable to carry out. The amount of the above catalyst used may be the amount of catalyst, for example, 100 to
The range of 1,000 ppm is preferred.

Argon, nitrogen or the like is used as the inert gas.

The above-mentioned dehydrogenative condensation reaction is generally carried out without a solvent. When a solvent is used, it is desirable to use a solvent such as octane or decane in the same amount as that of trihydrosilane.

In the present invention, the above-mentioned trihydrosilane raw material and the dehydrogenative condensation catalyst are used first at room temperature (20
C.) to 80.degree. C., preferably 50 to 70.degree. C., the dehydrogenative condensation reaction is started under the low temperature condition, and the reaction is carried out for 24 hours or more, preferably 48 to 72 hours. In the reaction under the low temperature condition, the raw material hydrosilane gradually generates hydrogen and the weight average molecular weight thereof is 3,000 to 5,0.
A polysilane having a molecular weight distribution close to a normal distribution can be obtained with a value of 00, but the polysilane usually has a starch syrup-like appearance at room temperature.

When the weight average molecular weight becomes 3,000 or more, the reaction temperature is 120 ° C. or more, preferably 120 to
The temperature is raised to 180 ° C., more preferably 120 to 150 ° C., and the dehydrogenative condensation reaction is performed for 1 to 12 hours, preferably 2 to 8 hours. If the temperature of the final stage of the reaction is too high, the progress of the degradation is extremely fast and the reaction time needs to be precisely adjusted, which is troublesome. Not practical because it takes a long time. If the reaction time is less than 1 hour, sufficient reaction is not carried out, and if the reaction time is longer than 12 hours, it is not practical. Therefore, it is practical to carry out the reaction at a slightly elevated temperature in a short time.

[0026]

INDUSTRIAL APPLICABILITY The novel organosilicon polymer represented by the above formula (1) of the present invention, having a silicon chain length of 20 or more and a glass transition point of room temperature or more, is a polysilane having a high molecular weight polysilane. It is a polysilane that is equivalent, but has excellent solubility, and is easy to handle because it is in solid form at room temperature and is not susceptible to chemical deterioration such as oxidation, and is easy to use for applications such as a strong polysilane film due to a crosslinking reaction. , A precursor of silicon carbide ceramics, a photoresist material, a photopolymerization initiator, a conductive material, a photoconductive material, a non-linear optical material, and the like. Further, according to the method for producing an organosilicon polymer of the present invention, the organosilicon polymer of the above formula (1) can be produced with good reproducibility by the dehydrogenative condensation method.

[0027]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.

Example 1 A dehydrogenative condensation catalyst was prepared by charging 30 mg of dichlorozirconocene, 20 ml of anhydrous ether and 50 μl of a methyllithium 1.6N ether solution in an argon atmosphere and reacting at room temperature for 1 hour. Next, the solvent was distilled off under reduced pressure, the obtained catalyst was dried and solidified, 50 g of phenylsilane was charged, and the reaction was carried out at 80 ° C. for 24 hours. Gradually hydrogen was generated, and the weight average molecular weight ( Mw) at about 3,300, polysilane having a molecular weight distribution close to a normal distribution was obtained. At this time, Tg was 16.3 ° C., and a candy-like appearance was exhibited. After that, when the reaction temperature was raised to 130 ° C. and the dehydrogenation reaction was further carried out for 3 hours, although a slight reduction in molecular weight was observed (Mw = 2,600), a glassy polymer (Tg 32.3) was obtained at room temperature. C) was obtained almost quantitatively. The structure estimated from the ¹ H NMR analysis result of the obtained polymer was represented by the following formula. The analysis results are shown in Table 1.

[0029]

[Chemical 4]

After the reaction at 130 ° C. for 3 hours, the reaction temperature was further raised to 200 ° C. and the reaction was carried out for 5 hours. As a result, the reaction accompanied by the generation of hydrogen gas proceeded, and M
w was decreased to 910, while Tg was 78.2 ° C., which was the same result as when the dehydrogenation reaction was carried out at 200 ° C.

Therefore, it is optimal to carry out the reaction at a reaction temperature of 80 ° C. or lower for 24 hours or more, and then to carry out the reaction at 120 to 150 ° C. for several hours. Other side reactions are suppressed, and the degradation reaction is not so fast under the condition of 150 ° C. or less, so that a three-dimensional crosslinked polysilane having a desired degree of polymerization and Tg can be obtained with good reproducibility. .

[Examples 2 to 5] 80 ° C. according to Example 1
After the chain extension reaction was carried out at, the high temperature reaction was carried out at the temperature and time shown in Table 1. As a result, in each case, a polymer having a glass transition point at room temperature or higher was obtained.

[0033]

[Table 1]

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Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I) obtained by reacting trihydrosilane as a starting material in the presence of a metallocene catalyst at a temperature of 20 to 80 ° C. and then further reacting at a temperature of 120 to 180 ° C. 1) An organic silicon-based polymer having a glass transition point of 20 ° C. or higher. [Chemical 1] (In the formula, R represents a group selected from a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. Further, n and m are integers that satisfy n + m ≧ 20.) 2. A reaction starting from trihydrosilane as a starting material in the presence of a metallocene catalyst in an inert atmosphere at a temperature of 20 to 80 ° C. and then raising the reaction temperature to 120 to 1
The method for producing an organosilicon polymer according to claim 1, wherein the reaction is further performed at a temperature of 80 ° C.