JP2003313295A - Novel silicon polymer and production process therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a novel silicon polymer showing excellent optical characteristics, and to provide a preparation process therefor. <P>SOLUTION: The novel silicon polymer is represented by formula (1) (wherein R<SB>1</SB>and R<SB>2</SB>are each independently hydrogen atom, a 1-15C alkyl group or an alkoxy group; and R<SB>3</SB>is a specific group). The production process for producing the polymer is also disclosed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicon polymer useful as an optical resin material and a method for producing the same. Its applications include optical lenses, prisms, optical disk substrates,
Examples thereof include optical fibers and optical films.

[0002]

2. Description of the Related Art In recent years, research on optoelectronics for realizing an advanced information society has been vigorously carried out.
At the same time, expectations are increasing for organic optical materials, particularly resin materials, as basic materials that support various developments of optoelectronics such as optical communication, optical recording, optical processing, optical measurement, and optical calculation. Optical resin materials have many features such as light weight and excellent flexibility, no electrical induction, and easy molding process. Optical fiber, optical waveguide, optical disk substrate, optical filter, lens, optical It is being developed for applications such as adhesives for automobiles.

The following characteristics are required for optical resin materials. That is, high transparency, low dispersibility (that is, high Abbe number), low birefringence, low water absorption, heat resistance, cleanability, easy moldability, chemical resistance / solvent resistance, light weight and the like.
As a typical non-thermoplastic resin material, for example, a resin obtained from the following diarylate (Chemical formula 7) and trade name "CR-39" can be mentioned.

[0004]

[Chemical 7]

"CR-39" is used as a monomer for spectacle lenses, and the resin obtained is lighter than inorganic glass,
It has the advantage of being easy to dye, but it does not
It has a big drawback that it takes a long time and a long time.

On the other hand, typical melt-moldable thermoplastic resin materials include PC (polycarbonate resin, for example, bisphenol A type aromatic polycarbonate resin such as trade name "Panlite"), PMMA (polymethylmethacrylate resin, acrylic resin). Resin, which has excellent transparency, is lighter than glass, and can be mass-molded because it can be melt-molded. Therefore, it can be used as an optical component in many fields. There is.

Among them, PCs are widely used for lenses and disk substrates because of their transparency and impact resistance. P
Since C has a benzene ring in its structure, it has a high refractive index but also a high birefringence, and it is difficult to apply it to a substrate of a disk having a higher information density or an optical fiber. On the other hand, since PMMA does not contain a benzene ring, it has excellent transparency and a low birefringence. However, it was difficult to develop into a lens that requires a low refractive index and a short focal length.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer having high transparency, having both a high refractive index and a low birefringence, and being thermoplastic, and a method for producing the same.

[0009]

The present inventors have found that a silicon polymer obtained by reacting a silane compound having two benzene rings with a dihydroxy compound has a high transparency and has both a high refractive index and a low birefringence. Moreover, they have found that they can be melt-molded and have completed the present invention.

The present invention relates to a silicon polymer having a repeating unit represented by the chemical formula (1) (formula 8).

[0011]

[Chemical 8]

(In the chemical formula (1), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms,
An alkoxy group, R ₃ represents a divalent bonding group represented by the chemical formula (2) (Chemical Formula 9), and is composed of one or more kinds of bonding groups selected from these.

[0013]

[Chemical 9]

In the chemical formula (2), X ₁ is represented by the chemical formula (3) (formula 10), and X ₂ and X ₃ are each independently a divalent bond represented by the chemical formula (4) (formula 11). Represents a group, which may be different, partly or wholly the same. In the chemical formula (2), R ₄ , R ₅ ,
At least one of R ₆ and R ₇ is an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and the others are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group. R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group. )

[0015]

[Chemical 10]

[0016]

[Chemical 11]

The present invention also relates to a method for producing a silicon polymer obtained by reacting a silane compound represented by the chemical formula (5) (Chemical formula 12) with a diol compound represented by the chemical formula (6) (Chemical formula 13). is there.

[0018]

[Chemical 12]

(In the chemical formula (5), R ₁ and R ₂ have the same meanings as described above, and X is a halogen atom or an alkyl group having 1 to 15 carbon atoms.

[0020]

[Chemical 13]

In the chemical formula (6), R ₃ has the same meaning as described above.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The novel silicon polymer of the present invention is a silicon polymer having a repeating unit represented by the chemical formula (1). The relationship between the birefringence index Δn and the molecular structure of the polymer is represented by the formulas (1) and (1) (“Optoelectronics and Polymer Materials” P19, 20 by Fumio Ide, Kyoritsu Shuppan).

[0023]

[Formula 1]

That is, the magnitude of the birefringence is basically proportional to the difference in the main polarizability (σ ₁ −σ ₂ ) of the monomer units.
For example, in the case of benzene, the polarizability of the ring per molecule in the parallel and vertical directions is 123.1 × 10 ^-25 cm ³ , 6 respectively.
The difference in polarizability (anisotropy of polarizability) is as large as 3.5 × 10 ⁻²⁵ cm ^3, and therefore, a polymer having a benzene ring in the molecule generally has a large birefringence. Further, the polymer material exhibits birefringence based on the stress received during the molding process, and this orientation birefringence is proportional to the ease of orientation of the polymer. In the case of PC, the benzene rings connected by the isopropylidene group are not arranged side by side on the plane, but are arranged slightly twisted with respect to each other.
Since the anisotropy of the polarizability is not eliminated and the orientation is relatively easy, the birefringence is large as a result, and the high birefringence and the low birefringence cannot be achieved at the same time.

On the other hand, the novel silicon polymer of the present invention is PC
Although it has a benzene ring in the same molecule, since the two benzene rings that bond to silicon have a twisted arrangement with respect to each other, the anisotropy of polarizability can be largely eliminated, and the benzene ring that bonds to silicon is Since it is arranged so as to stick to the polymer chain, it is difficult to orient and is amorphous. Due to these two reasons, the novel silicon polymer of the present invention has a low birefringence despite containing a benzene ring, and therefore can achieve both a high birefringence and a low birefringence, and has high transparency due to its amorphous nature. You have achieved the rate.

Also, Liaw et al. Obtained a silicon polymer from 2,2'-dimethyldiphenyl-4,4'-diol and diphenyldichlorosilane by a polycondensation reaction (Liaw, DJ; Liaw, B.Y .; JP
olym Sci Part A: Polym Chem
1999, 37, 4591-4595), there is no description of optical characteristics, and no mention is made of whether melt molding is possible. Therefore, from this knowledge, it cannot be expected that the novel silicon polymer of the present invention has excellent optical properties.

The novel silicon polymer of the present invention is obtained by condensing a silane compound represented by the chemical formula (5) and a diol compound represented by the chemical formula (6) in the presence of a condensation reaction catalyst, if necessary. Can be manufactured. In the chemical formula (1), R ₁ and R ₂ are each independently a hydrogen atom,
An alkyl group and an alkoxy group having 1 to 15 carbon atoms.
Specific examples of the alkyl group include a methyl group, ethyl group, hexyl group, cyclohexyl group and the like, and specific examples of the alkoxy group include a methoxy group, an ethoxy group and the like.

In the chemical formula (1), R ₃ represents a divalent bonding group represented by the chemical formula (2), and is composed of one or more kinds of bonding groups selected from these. In the chemical formula (2), X ₁ is represented by the chemical formula (3),
X ₂ and X ₃ are each independently represented by the chemical formula (4) 2
It represents a valent linking group, which may be different, partly or wholly the same. Further, in the chemical formula (2), at least one of R ₄ , R ₅ , R ₆ , and R ₇ is an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and the others are independently a hydrogen atom or 1 to 6 carbon atoms. An alkyl group of 6,
It is an alkoxy group. In the chemical formula (2), R
₈ , R ₉ , R ₁₉ , and R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.

Specific examples of R4 to R11 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group,
iso-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, Examples thereof include a pentyloxy group, a hexyloxy group and a cyclohexyloxy group.

A method for producing the silicon polymer represented by the chemical formula (1) from a silane compound and a dihydroxy compound will be described. The reactor comprises a part for supplying raw materials, a stirrer inside the reactor, a part for controlling the temperature of the reactor, and the like. This reaction can be carried out without solvent or in a solvent. A silane compound represented by the chemical formula (5), a dihydroxy compound represented by the chemical formula (6), a condensation reaction catalyst, and a solvent are charged in a container. The condensation reaction catalyst can be charged in a solution state, a suspension state, or as it is without being dissolved in a solvent. The reaction solution is reacted at a predetermined temperature for a predetermined time with stirring while controlling the temperature. When a reaction solvent is used after a predetermined reaction time, the silicon polymer can be obtained by removing the solvent or precipitating the polymer by distillation under reduced pressure or the like. As the silane compound represented by the chemical formula (5) used as a raw material, difluorodiphenylsilane, dichlorodiphenylsilane, dibromodiphenylsilane, dichlorodi (4-methylphenyl) silane, dichlorodi (3-methylphenyl) silane, dichlorodi (4
-Ethyldichlorophenyl) silane, dichlorodi (4-
R which is another raw material such as isopropylphenyl) silane, dichlorodi (4-butylphenyl) silane, dichlorodi (4-tertbutylphenyl) silane, and dichlorodi (4-cyclohexylphenyl) silane.
_The dihydroxy compound represented by ₂ (OH) ₂ is 1,
2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 3,3 ′
-Dicyclohexanediol, 3,4'-dicyclohexanediol, 4,4'-dicyclohexanediol,
2,2-bis (3-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxycyclohexyl) propane, bis (3-hydroxycyclohexyl) ether, bis (4-hydroxycyclohexyl) ether,
Bis (3-hydroxycyclohexyl) sulfide, bis (4-hydroxycyclohexyl) sulfide, bis (3-hydroxycyclohexyl) methane, bis (4-
Hydroxycyclohexyl) methane, 2,5-norbornanediol, 2,6-norbornanediol, 1,4
-Norbornanediol, 2,3-norbornanediol, 4,8-bis (hydroxymethyl) tricyclo [5,2,1,0 ^2,6 ] decane, 4-hydroxy-8-
Hydroxymethyltricyclo [5,2,1,0 ^2,6 ] decane, 8-hydroxy-4-hydroxymethyltricyclo [5,2,1 0 ^2,6 ] decane, 2,2-bis (4-
Hydroxy-3-methylphenyl) propane, 2,2-
Bis (4-hydroxy-3-isobutylphenyl) propane, 2,2-bis (4-hydroxy-3-tertbutylphenyl) propane, 2,2-bis (4-hydroxy-)
3,5-Dimethylphenyl) propane, 4,4'-
(1,3-phenylenediisopropylidene) bisphenol, 4,4 '-(1,4-phenylenediisopropylidene) bisphenol, 6,6'-dihydroxy-3,
3,3 ', 3'-tetramethyl-1,1'-spirobisindane and the like can be mentioned.

The catalyst for the decondensation reaction that can be used can be roughly classified into an acid catalyst and a basic catalyst. When the substituent X of the silane compound represented by the chemical formula (5) of the raw material is a halogen atom, a basic catalyst is used. Can be used. When the substituent X is an alkoxy group,
Acid and basic catalysts can be used.

The acid catalyst is HF, HCl, HB as an inorganic acid.
r, HI, H ₂ SO ₄ , HNO ₃ , H ₂ CO ₃ , HClO ₂ ,
H ₂ S, such as _{H 2 SO 3, H 2 S} 2 O 3 , and examples of the organic acid _{HCOOH, CH 3 COOH, C 6} H 5 COOH,
Oxalate, such as trifluoroacetic acid can be mentioned, Al ₂ O ₃ as a metal _{oxide, SiO 2 -Al 2 O 3,} A -type zeolite,
X-type zeolite, Y-type zeolite, L-type zeolite, molecular sieves, montmorillonite, acid clay, activated clay, diatomaceous earth and the like can be mentioned. As the ion exchange resin, sulfone type cation exchange resin, acrylic acid type cation exchange resin, etc. Can be mentioned.

The basic catalyst includes amine compounds such as ammonia, methylamine, triethylamine, triethanolamine and pyridine, metal amide compounds include lithium amide, sodium methylamide and potassium ethylamide, and metal imide compounds. Examples include lithium imide, sodium methylimide, potassium ethylimide, examples of the alkoxy compound include lithium methoxide, sodium methoxide, potassium ethoxide, and the like, examples of the organometallic compound include methyllithium, ethyl sodium, phenyl potassium, and the like. And metal oxides such as MgO and SiO ₂
-MgO etc. are mentioned, and a quaternary ammonium type anion exchange resin etc. are mentioned as an ion exchange resin.

The ratio of the silane compound represented by the chemical formulas (5) and (6) to the dihydroxy compound is not particularly limited, but preferably 1 mmol of hydroxy group to 100 mmol of X group contained in the silane compound.
To 500 mmol, preferably 50 to 200 mmol
Is. The acid catalyst or the basic catalyst as a catalyst can be used alone or in combination of two or more kinds. The amount of catalyst used was 0.
0001 mmol to 400 mmol, preferably 0.
It is 01 to 100 mmol.

It is desirable to replace the inside of the container with an inert gas such as high-purity nitrogen or high-purity argon. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and mesitylene, diethyl ether, n-butyl ether, anisole, diphenyl ether, tetrahydrofuran, dioxane, bis (2-methoxyethyl) ether, 1, 2-bis (2
Ether solvent such as -methoxyethoxy) ethane, dichloromethane, chloroform, chlorobenzene,
Halogen-containing solvent such as o-dichlorobenzene, N-
Organic polar solvents such as methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixed solvents thereof can be used. Among these, halogen-containing solvents such as dichloromethane, chloroform, chlorobenzene and o-dichlorobenzene are particularly preferable. The amount of the solvent is 0.1 to 40 relative to 1 mmol of the raw material hydroxysilane compound.
ml is preferred. Further, since the water contained in the solvent may reduce the activity of the catalyst, it is preferable to use a solvent that has been dehydrated and dried in advance.

The reaction temperature is -50 to 300 ° C, more preferably -20 to 150 ° C. More preferably 0-8
It is 0 ° C. The reaction pressure may be reduced pressure, normal pressure, or increased pressure, but when the reaction temperature is higher than the boiling point of the solvent, it is desirable to carry out the pressure reaction using a pressure resistant reaction vessel. The reaction time varies depending on the reaction temperature and the like, but is 0.1-2.
00 hours is appropriate.

Isolation of the silicon polymer by removal of the solvent
The reaction may be carried out without any treatment, but it may be dispersed in a saturated aliphatic hydrocarbon or alcohol compound, filtered, or treated with an aqueous solution (JP-A-11-23638).
8) Alternatively, it is preferably carried out after the catalyst is separated by a method such as treatment with an anion exchange resin in the case of an acid catalyst and treatment with a cation exchange resin in the case of a basic catalyst.

Examples of the saturated aliphatic hydrocarbon that can be used for separating the catalyst include pentane, hexane, heptane, octane and the like, and examples of the alcohol compound include methanol, ethanol and isopropyl alcohol. The amount of the saturated aliphatic hydrocarbon and alcohol compound used is 0.01 to 200 ml, and more preferably 0.1 to 50 ml, per 1 g of the siloxane-containing polymer.

The removal of the catalyst by the anion exchange resin or the cation exchange resin is carried out by treating the reaction solution with the anion exchange resin or the cation exchange resin by the contact filtration method or the fixed bed method. The contact filtration method is specifically a method in which the reaction solution and an anion exchange resin or a cation exchange resin are mixed and stirred for a certain period of time, and then the resin is removed by filtration. The fixed bed method is a method of removing the catalyst from the reaction solution by passing the reaction solution through a fixed bed such as a column or a packed column packed with an OH type anion exchange resin or an H type cation exchange resin. is there. The number of treatments is usually once, but it may be performed a plurality of times from 2 to 100 times. The reaction solution is usually treated as it is, but may be diluted 1.1 to 100 times with a solvent. Anion exchange resins that can be used include -N (CH
_{3) 3} OH _{groups, -N (C 2 H 4 OH} ) (CH 3) strongly acidic OH-type anion-exchange resin having ₂ OH groups, -N as an exchange group
Examples include weakly acidic OH type anion exchange resins having an H ₂ -group and a -NH-group. As the cation exchange resin which can be used, a strongly acidic H-type cation exchange resin having a sulfone group as an exchange group, a weakly acidic H type cation exchange resin having a carboxyl group, a phenol group or a phosphon group as an exchange group, and these An example is one in which the resin is supported on a carrier such as silica or alumina. These anion exchange resins or cation exchange resins can be used alone or in combination of two or more. The form of the anion exchange resin or the cation exchange resin may be granular or powder. The anion exchange resin or cation exchange resin having a water content of more than 10 wt% may be used as it is, but it is preferable to keep the water content of 10 wt% or less by air drying, heat drying, vacuum drying or the like. .

The amount of the anion exchange resin or cation exchange resin used varies depending on the type of resin, the exchange capacity, the type of catalyst, and the catalyst content of the reaction solution, but 0.0001 to 10 g, preferably 1 to 1 ml of the reaction solution. It is 0.01 to 10 g. The treatment time or residence time varies depending on the type of anion exchange resin or cation exchange resin, the amount used, and the catalyst concentration in the reaction solution, but is 0.001 to 400 hours, preferably 0.1 to 150 hours. Processing temperature is -50 to 3
The temperature is 00 ° C, more preferably 0 to 150 ° C.

After the above catalyst removal operation, the silicon polymer is separated from the reaction solution by methods such as solvent removal, column separation and precipitation. The molecular weight of the silicon polymer of the present invention is not particularly limited, and may be any molecular weight depending on the application and processing method. The silicon polymer of the present invention, the amount ratio of the silane compound and the dihydroxy compound used, the reaction time,
It can be controlled by the reaction temperature and the like. For example, after the silicon polymer is dissolved in chloroform at a concentration of 0.5 g / 100 ml, the logarithmic viscosity value measured at 35 ° C. is 0.1 to 3.0 deciliter / g. It can be any value.

The silicon polymer of the present invention is thermoplastic and can be molded by ordinary melt molding. In order to enable melt molding, it is important that the temperature at which the resin flows is sufficiently lower than the decomposition temperature of the resin. In the present invention, the melt-molding is possible, specifically, a temperature at which 5% by weight of the resin is reduced by heating in air, that is, a melting rate of about 1 to 1000 Pascal · sec as compared with a 5% weight reduction temperature. It means that the temperature showing the viscosity is lower than 30 ° C, preferably lower than 50 ° C. Any of the silicon polymers of the present invention can be melt-molded, and various molded articles such as disks and fibers can be obtained by extrusion molding, injection molding, vacuum molding, blow molding, compression molding, blow molding, calender molding, lamination molding and the like. Can be obtained.

[0043]

[Example] (Example 1) Synthesis of compound 1

[0044]

[Chemical 14]

A magnetic stir bar was installed in a 200 ml four-necked flask, and the inside of the flask was replaced with high-purity nitrogen gas. Then, the raw material 2,2-di (4-hydroxy-) was placed in a flask.
3,5-Dimethylphenyl) propane 14.22 g (5
(0 mmol) and 50 ml of previously dehydrated dichloromethane as a solvent were charged. After the reaction solvent was ice-bathed and the internal temperature was confirmed to be 0 ° C., 12.66 g (50 mmol) of the raw material dichlorodiphenylsilane and 8.31 g (105 mmol) of pyridine were separately and simultaneously taken under a nitrogen blanket for 1 hour. For 15 minutes.
After completion of dropping, the mixture was returned to room temperature and stirred for 4 hours. The reaction solution was diluted with 50 ml of dichloromethane and then added to 1000 ml of methanol, and the precipitate was separated by filtration to obtain a powder. This powder is dissolved in 50 ml of dichloromethane and this solution is added to 500 ml of methanol.
The resulting mixture was added to a solution in ml and the precipitate was separated by filtration to obtain a powder. This operation was repeated once more and the powder thus obtained was vacuum dried at room temperature to obtain 20.44 g of the desired product. The yield was 89%. GP
The polystyrene-converted weight average molecular weight by C (gel permeation chromatography) was Polymer 22800.
The measured values of elemental analysis are carbon 79.9% (theoretical value 80.1%), hydrogen
6.8% (theoretical value 6.9%), and the measured value is in good agreement with the theoretical value within the range of measurement error. ¹ H-NMR (ppm, CD ₂ Cl ₂ ) 1.2 (-C H ₃ ), 1.4 (-C H ₃ ), 6.8-6.9
(C (OC = C H- ), 6.9-7.0 (C (CH ₃ ) ₂ -C = C H- ), 7.2-7.5 (C H = C
H- C H =), 7.6-7.8 (Si-C = CC H =) IR (cm ^-1 ) 700 (m), 720 (m), 740 (m), 760 (m), 840
(m), 1120 (m), 1130 (m), 1180 (m), 1250 (s), 1430 (m),
1510 (m), 1605 (m), 2960 (w) Next, the physical properties and optical properties of this novel silicon polymer were measured. 0.5g / 1 of polymer in chloroform solvent
The logarithmic viscosity [η] measured at 35 ° C. after dissolution at a concentration of 00 ml was measured. Further, the glass transition temperature [Tg] was measured by DSC, and the 5% weight loss temperature [Td ₅ ] in an air atmosphere was measured by TGA. Also, the light transmittance is glass transition temperature + 30 ° C using an ordinary heat press machine.
A plate-shaped test piece with a thickness of about 1.2 mm was prepared in 3 minutes by
It was measured according to STM D1003. Refractive index [nd]
The birefringence index [Δnd] was measured by spin-coating a chloroform solution of the polymer on a silicon wafer and heating the sample at a glass transition temperature of + 30 ° C. for 15 minutes in a nitrogen atmosphere at a wavelength of 633 nm using a prism coupler.
The measurement results are summarized in Table 1.

(Example 2) Synthesis of compound 2

[0047]

[Chemical 15]

Instead of 2,2-di (4-hydroxy-3,5-dimethylphenyl) propane, 4,4 '-(1,
3-phenylenediisopropylidene) bisphenol 1
The reaction was carried out in the same manner as in Example 1 except that 7.32 g (50 mmol) was used and dichlorodiphenylsilane and pyridine were simultaneously added dropwise at room temperature without ice-cooling the dichloroethylene solution of the diol. 22.38 g of the desired product was obtained with a yield of 85%. The weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) was polymer 194800. The measured values of elemental analysis are as follows: carbon 81.8% (theoretical value 82.1%), hydrogen 6.
6% (theoretical value 6.5%), and the measured value agrees well with the theoretical value within the range of measurement error. ¹ H-NMR (ppm, CD ₂ Cl ₂ ) 1.5 (-CC H ₃ ), 6.8-6.9 (0-C = C H
-), 6.9-7.0 (C (CH ₃ ) ₂ -C = C H- ), 7.2-7.5 (-C H = C H- ), 7.7-
7.8 (Si-C = C H- ) IR (cm ^-1 ) 700 (m), 720 (m), 740 (m), 760 (m), 8
40 (m), 1120 (m), 1130 (m), 1180 (m), 1250 (s), 1430
(m), 1510 (m), 1605 (m), 2960 (w) Physical properties and optical characteristics were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 3) Synthesis of compound 3

[0050]

[Chemical 16]

Instead of 2,2-di (4-hydroxy-3,5-dimethylphenyl) propane, 4,4 '-(1,
4-phenylenediisopropylidene) bisphenol 1
The reaction was carried out in the same manner as in Example 1 except that 7.32 g (50 mmol) was used and dichlorodiphenylsilane and pyridine were simultaneously added dropwise at room temperature without ice-cooling the dichloroethylene solution of the diol. 20.80 g of the desired product was obtained with a yield of 79%. The polystyrene-converted weight average molecular weight by GPC (gel permeation chromatography) was 174,000. The measured values of elemental analysis were carbon 82.1% (theoretical value 82.1%), hydrogen 6.
6% (theoretical value 6.5%), and the measured value agrees well with the theoretical value within the range of measurement error. ¹ H-NMR (ppm, CD ₂ Cl ₂ ) 1.5 (-CC H ₃ ), 6.8-6.9 (0-C = C H
-), 6.9-7.0 (C (CH ₃ ) ₂ -C = C H- , C (CH ₃ ) ₂ -C = C H- , CC H = C H
-C H = C), 7.2-7.5 (C H = C H- ), 7.7-7.8 (Si-C = C H- ) IR (cm ^-1 ) 700 (m), 720 (m), 740 (m ), 760 (m), 840
(m), 1120 (m), 1130 (m), 1180 (m), 1250 (s), 1430 (m),
1510 (m), 1605 (m), 2960 (w) Physical properties and optical characteristics were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 4) Synthesis of compound 4

[0053]

[Chemical 17]

Instead of 2,2-di (4-hydroxy-3,5-dimethylphenyl) propane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'
-Using 15.42 g (50 mmol) of bisindane,
The reaction was carried out in the same manner as in Example 1 except that dichlorodiphenylsilane and pyridine were simultaneously added dropwise at room temperature without cooling the dichloroethylene solution of diol with ice. 21.50 g of the desired product was obtained with a yield of 88%. GP
The polystyrene-converted weight average molecular weight by C (gel permeation chromatography) was 60,000.
The measured value of the elemental analysis is carbon 81.2% (theoretical value 81.1
%) And hydrogen 6.3% (theoretical value 6.6%), and the measured values are in good agreement with the theoretical values within the range of measurement error. ¹ H-NMR (ppm, CD ₂ Cl ₂ ) 1.2 (C H ₃ ), 1.9-2.2 (-C H ₂ ), 6.
2 to 6.3 (-OC (-CH) = C H- ), 6.7 to 6.9 (0-C (CH) = C H -C H ), 7.
1-7.3 (C H = C H- ), 7.5-7.7 (Si-C = C H- ) IR (cm ^-1 ) 700 (m), 720 (m), 760 (s), 970 (m), 1120
(m), 1210 (m), 1280 (m), 1430 (m), 1505 (s), 1600 (m),
2900 (m) Physical properties and optical characteristics were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 5) Synthesis of compound 5

[0056]

[Chemical 18]

9.92 g (50 mmol) of 4,4'-dicyclohexanediol was used in place of 2,2-di (4-hydroxy-3,5-dimethylphenyl) propane, and the dichloroethylene solution of the diol was cooled with ice. The reaction was carried out under the same conditions as in Example 1 except that dichlorodiphenylsilane and pyridine were simultaneously added dropwise at room temperature. 14.57 g of the desired product was obtained with a yield of 77%.
The polystyrene-converted weight average molecular weight by GPC (gel permeation chromatography) was 83,000 polymer. The measured value of elemental analysis is carbon 76.2% (theoretical value 7
6.1%) and hydrogen 8.2% (theoretical value 8.0%), and the measured values are in good agreement with the theoretical values within the range of measurement error. ¹ H-NMR (ppm, CD ₂ Cl ₂ ) 0.8-2.0 (-C H _2- , -C H -C H- ),
3.6-3.8 (-OC H ), 7.2-7.5 (C H = C H- ), 7.7-7.8 (Si-C = C H- ) IR (cm ^-1 ) 700 (m), 720 (m), 740 (m), 760 (m), 1080
(S), 1120 (s), 1430 (m), 1450 (m), 1590 (w), 2850 (m),
2930 (m), 3190 (w) Physical properties and optical characteristics were measured in the same manner as in Example 1. The results are shown in Table 1.

[0058]

[Table 1]

(Reference Example) PM which is a typical optical resin
The physical properties and optical properties of MA, PC and Arton were measured.
The glass transition temperature [Tg] of PMMA is 93 ° C., the light transmittance is 93%, the refractive index [nd] is 1.49, and the birefringence [Δ].
nd] was 1.46 × 10 ³ . The glass transition temperature [Tg] of PC is 150 ° C., the light transmittance is 90%, the refractive index [nd] is 1.59, and the birefringence [Δnd] is 11.7 ×.
It was 10 ³ . The glass transition temperature [Tg] of Arton is 171 ° C., the light transmittance is 92%, and the refractive index [nd] is 1.
51, and the birefringence [Δnd] was 1.52 × 10 ³ .

[0060]

The present invention provides a novel silicon polymer having excellent optical properties by subjecting a silane compound having two aromatic rings and a dihydroxy compound to a condensation reaction. The polymers of the present invention are excellent in transparency, have both a high refractive index and a low birefringence, can be melt-molded, and are suitable for optical lenses, prisms, optical disk substrates, optical fibers, optical films and the like.

Continued front page    (72) Inventor Masashi Tamai             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 4J035 BA02 EA01 EB01 EB02 EB04                       EB10 LB20

Claims (2)

[Claims] 1. A silicon polymer having a repeating unit represented by the chemical formula (1) (chemical formula 1). [Chemical 1] (In the chemical formula (1), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group, and R ₃ is a divalent group represented by the chemical formula (2) (chemical formula 2). And is composed of one or more kinds of bonding groups selected from these. In the chemical formula (2), X ₁ is represented by the chemical formula (3) (Chemical formula 3), X ₂ and X ₃ each independently represent a divalent bonding group represented by the chemical formula (4) (Chemical formula 4), These may be different, or some or all may be the same. Further, in the chemical formula (2), at least one of R ₄ , R ₅ , R ₆ , and R ₇ is an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and the others are each independently a hydrogen atom or 1 to 6 carbon atoms. Is an alkyl group or an alkoxy group. In addition, R ₈ , R ₉ , R ₁₀ , R ₁₁
Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group. ). [Chemical 3] [Chemical 4] 2. The condensation reaction of the silane compound represented by the chemical formula (5) (Chemical formula 5) and the dihydroxy compound represented by the chemical formula (6) (Chemical formula 6). The method for producing a silicon polymer. [Chemical 5] (In the chemical formula (5), R ₁ and R ₂ have the same meanings as described above, and X is a halogen atom or an alkoxy group having 1 to 15 carbon atoms.) (In the chemical formula (6), R ₃ has the same meaning as described above.)