JPH07324108A - Preparation of hydrogenation product of norbornene ring opening polymerization product - Google Patents

Abstract

PURPOSE:To obtain a high-mol.-wt. gel-free hydrogenation product of a norbornene ring opening polymn. product having a sharp mol.wt. distribution and a good processability, and suitable as the starting material of an optical material. CONSTITUTION:100-50wt.% norbornene monomer of the formula (wherein R1 and R2, which may be the same or different from each other, is a hydrogen atom or an alkyl group; and m is an integer of 0 to 2) and 0-50wt.%, other norbornene monomer capable of ring opening copolymn. therewith are subjected to ring opening polymn. to prepare a solvent-soluble norbornene ring opening polymn. product having a number-average mol.wt. Mn of 10,000 to 50,000 and a ratio (Mw/Mn) of wt.-average mol.wt. Mw number-average mol.wt. Mn of at most 3. Subsequently, this norbornene ring opening polymn. product is hydrogenated in an org. solvent in the presence of a hydrogenation catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of producing a hydrogenated product of a solvent-soluble norbornene ring-opening polymer having a high molecular weight, a sharp molecular weight distribution and no gel. The present invention also relates to a novel norbornene-based ring-opening polymer and hydrogenated norbornene-based ring-opening polymer. The norbornene-based ring-opening polymer and the hydrogenated product thereof of the present invention are particularly suitable as an optical material.

[0002]

2. Description of the Related Art Conventionally, polymethylmethacrylate, polycarbonate, etc. have been used as an optical polymer material. The former has a relatively high water absorption, and the latter has a basic structure having a benzene ring. It has a problem that birefringence easily occurs due to high melt viscosity,
It is becoming difficult to meet ever-increasing demands.

In recent years, a polymer using a polycyclic norbornene-based monomer has been developed as a polymer material which has improved these drawbacks. For example, JP-A-60-26024 describes that a hydride of a ring-opening copolymer of tetracyclododecenes and norbornenes is excellent in transparency, water resistance and heat resistance. There is. In addition, JP-A-60-
No. 168708 and Japanese Patent Laid-Open No. 61-292601 disclose that an addition copolymer of a tetracyclododecene or a polycyclic norbornene-based monomer or more and an α-olefin has transparency, heat resistance and chemical resistance. It is disclosed that it has excellent water resistance. As described above, the polymer of polycyclic norbornene-based monomer has excellent properties as an optical polymer material. By the way, a norbornene-based monomer having an alkylidene group and represented by the following general formula (1) is easily available by carrying out a Diels-Alder reaction between cyclopentadiene and a chain conjugated diene and then moving a double bond. is there.

[0004]

[Chemical 3] (In the formula, R ₁ and R ₂ are the same or different from each other and represent a hydrogen atom or an alkyl group, and m represents an integer of 0 to 2.) Of these, particularly, an ethylidene group is included as an alkylidene group. Norbornene-based monomers are much easier to obtain than other norbornene-based monomers, since ethylidene norbornene is produced in large quantities as a comonomer for ethylene-propylene-terpolymer. The ring-opening polymer of the norbornene-based monomer represented by the general formula (1) is
It is expected that the polymer will have excellent optical properties such as transparency, and that it will be a polymer more suitable for optical materials when hydrogenated. However, heretofore, there has been no known method for producing a ring-opening polymer having physical properties useful as a raw material for optical materials, using this monomer, without crosslinking or gelation.

It is conventionally known that the norbornene-based monomer represented by the general formula (1) is subjected to bulk / ring-opening polymerization in a mold in the presence of a metathesis catalyst. For example,
JP-A-63-97611 discloses 5-ethylidene-
A method of bulk polymerizing 2-norbornene by a reaction injection molding (RIM) method in a mold in the presence of a metathesis catalyst is disclosed. Further, in Japanese Patent Laid-Open No. 63-37108 (European Patent Publication No. 251033), 6-alkylidene-2-tetracyclododecene is similarly prepared by RIM.
A method of bulk polymerization by the method is disclosed. However, all of the block-shaped ring-opening polymers obtained by the RIM method are cross-linked polymers and are unsuitable as optical materials.

By the way, in JP-A-63-37108, when a metathesis polymerization of 6-alkylidene-2-tetracyclododecene is carried out under mild conditions such as solution polymerization, a chain polymer can be obtained. Has been suggested.
However, the publication points out that even if such a chain polymer is obtained, it has poor moldability and is not practical. Specifically, in Example 11 of the publication,
An experimental example is shown in which solution polymerization of ethylidene tetracyclododecene is carried out using a diethylaluminum / tungsten hexachloride catalyst. However, according to this experimental example, it was described that the product was a gel-like substance (that is, the reaction system was not homogeneous) even under a dilute condition where the monomer concentration was 10% or less. There is. The publication shows the IR spectrum of the product, which is described as a ring-opening polymer. However, its IR spectrum shows a double bond in the main chain 9
Absorption at 50-1000 cm ^-1 (Makromol. Ch
em. , 78 , 231, 196), but on the other hand,
Strong absorption of unidentified emission appears at around 1700 cm ^-1, and it is not clear from such IR spectrum that the product is a ring-opening polymer. Further, the present inventors polymerized this monomer using a conventional ring-opening polymerization catalyst in which an organoaluminum compound and a transition metal compound such as tungsten or molybdenum are combined, and the resulting product is: Only a polymer unsuitable as an optical material could be obtained because it gelled or had a large molecular weight distribution.

Solution polymerization of 5-methylidene norbornene among the norbornene-type monomers represented by the general formula (1) is known (Makromol. Chem. Rap).
idCommun. , 1 , 467-472, 198.
0). However, this monomer does not become a ring-opening polymer unless it is a special metathesis catalyst. For example, when a triethylaluminum / titanium tetrachloride-based catalyst is used,
It is reported that solvent-soluble polymers do not form.

[0008]

The object of the present invention is to have a high molecular weight, a sharp molecular weight distribution, no gel,
It is an object of the present invention to provide a method for producing a hydrogenated norbornene-based ring-opening polymer, which has good processability and is suitable as a raw material for optical materials. Another object of the present invention relates to a novel norbornene ring-opening polymer and a hydrogenated norbornene ring-opening polymer obtained by hydrogenating the ring-opening polymer.

As a result of intensive studies to solve the above problems, the present inventors have found that the norbornene-based monomer represented by the general formula (1) alone or a monomer mixture containing the norbornene-based monomer as a main component is present in the presence of a chain olefin. In addition, by ring-opening polymerization using a specific ring-opening polymerization catalyst, a norbornene-based ring-opening polymer having a high molecular weight and a sharp molecular weight distribution can be obtained without causing gelation due to the addition reaction of an alkylidene group. I found that I can. The obtained norbornene-based ring-opening polymer is itself useful as an optical material, and by hydrogenating it,
It is possible to obtain a hydrogenated product having further excellent heat deterioration resistance, light deterioration resistance, and optical characteristics. The present invention has been completed based on these findings.

[0010]

Thus, according to the present invention, 100 to 50% by weight of the norbornene-based monomer represented by the general formula (1),

[0011]

[Chemical 4] (In the formula, R ₁ and R ₂ are the same or different from each other and each represent a hydrogen atom or an alkyl group, and m represents an integer of 0 to 2.) Other norbornene-based copolymerizable ring-opening copolymerizable monomers Ring-opening polymerization of 0 to 50% by weight of a norbornene-based monomer,
A solvent-soluble norbornene ring-opening polymer having a number average molecular weight Mn of 10,000 to 50,000 and a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 3 or less is produced, and then, There is provided a method for producing a hydrogenated norbornene ring-opening polymer, which comprises hydrogenating the norbornene ring-opening polymer in an organic solvent in the presence of a hydrogenation catalyst. Further, according to the present invention, having a repeating unit represented by the general formula (2),

[0012]

[Chemical 5] (In the formula, R ₁ and R ₂ are the same or different from each other and represent a hydrogen atom or an alkyl group, and m represents an integer of 0 to 2.) The number average molecular weight Mn is 10,000 to 50,000. And a solvent-soluble norbornene ring-opening polymer having a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 3 or less, and at least a part of carbon-carbon double bonds of the ring-opening polymer. Provided is a hydrogenated norbornene ring-opening polymer hydrogenated product.

The present invention will be described in detail below. (Norbornene-based monomer) The norbornene-based monomer having an alkylidene group used in the present invention is the norbornene-based monomer (A) represented by the general formula (1). In the general formula (1), specific examples of R ₁ and R ₂ are:
Examples thereof include hydrogen atom and alkyl groups such as methyl, ethyl, propyl and butyl. Specific examples of the norbornene-based monomer (A) include 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene and 5-
Butylidene-2-norbornene, 6-Ethylidene-2-
Examples thereof include tetracyclododecene and 7-ethylidene-hexacycloheptadecene.

These norbornene-based monomers (A)
Can be used alone or in combination of two or more. Among these norbornene-based monomers (A), especially the tetracyclic compound has a glass transition temperature (T
g) and processability are preferable, and ethylidene-substituted compounds are preferable in view of easy availability of monomers. In the present invention, the norbornene-based monomer (A) may be used together with another norbornene-based monomer (B) capable of ring-opening copolymerization, if desired. Examples of the other copolymerizable norbornene-based monomer (B) include norbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, cyclopentadiene trimer, and alkyl-substituted products thereof. From the economical point of view, the proportion of both monomers used is preferably 50% by weight or more, more preferably 70% by weight or more, of the norbornene-based monomer (A).

(Other Monomer Components) In the ring-opening polymer of the present invention, a chain monoolefin, a chain non-conjugated diolefin, a cycloolefin, etc. are added in the ring-opening polymerization of the ring-opening polymer, The molecular weight and physical properties can be adjusted. Specific examples include 1-butene, 1-pentene, 1-
Hexene, 1-octene, 1-butene, 2-pentene,
Examples include 1,4-hexadiene and cyclopentene. If a chain olefin is used among these monomers, the physical properties of the obtained polymer can be preferably adjusted. The other monomer component is usually 1 with respect to the total amount of the norbornene-based monomers (A) and (B).
Used in the range of up to 0% by weight.

(Ring-Opening Polymerization Catalyst) The ring-opening polymerization catalyst used in the present invention is (a) an organic compound of a metal belonging to Group I to III of the periodic table, (b) titanium tetrahalide, and (c). It is a Ziegler type ring-opening polymerization catalyst composed of an amine activator.

Specific examples of the components (a) to (c) are given below. (A) Organometallic compound Specific examples of the organometallic compound include organoaluminum compounds,
Organolithium compounds, organomagnesium compounds and the like, and of these, organoaluminum compounds are preferable. Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n
-Propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, triphenyl aluminum, tribenzyl aluminum, diethyl aluminum monochloride, di-n-pyropyr aluminum monochloride, di-isobutyl aluminum monochloride, Di-n-butyl aluminum monochloride, diethyl aluminum monobromide, diethyl aluminum monoiodide, diethyl aluminum monohydride, di-
n-Propyl aluminum monohydride, diisobutyl aluminum monohydride, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl Aluminum diiodide and the like can be mentioned. Examples of the organic lithium compound include n-butyl lithium and n-hexyl lithium. As the organic magnesium compound, for example, methyl magnesium iodide, ethyl magnesium bromide, methyl magnesium bromide,
Examples include n-propyl magnesium chloride, t-butyl magnesium chloride, allyl magnesium chloride and the like.

(B) Titanium tetrahalide Specific examples of titanium tetrahalide include titanium tetrachloride,
Examples thereof include titanium tetrabromide. (C) Amine-based Activator Examples of the amine-based activator include aliphatic, alicyclic and aromatic third groups.
Examples include primary amines and heterocyclic amines. As a specific example,
Examples include trimethylamine, triethylamine, tripropylamine, dimethylaniline, tri-n-butylamine, pyridine and α-picoline. These compounds (a), (b) and (c) are usually (b) /
(A) = 1/1 to 1/500 (molar ratio), (c) /
It is used in the range of (a) = 1/2 to 10/1 (molar ratio).

The catalyst system used in the present invention is Japanese Patent Publication No. 57-
As described in Japanese Patent No. 17883, it is known as a ring-opening polymerization catalyst of dicyclopentadiene,
In the present invention, this catalyst system was diverted to the norbornene-based monomer (A) having an alkylidene group to obtain a ring-opening polymer having a high molecular weight, a sharp molecular weight distribution, and no gel, As described above, other tungsten or molybdenum ring-opening polymerization catalysts cannot prevent gelation or only give polymers unsuitable for optics having a wide molecular weight distribution.

(Solvent) In the present invention, the ring-opening polymer can be polymerized without using a solvent, but it is usually carried out in an inert organic solvent. Specific examples of the organic solvent include
Aromatic hydrocarbons such as benzene, toluene, xylene;
Aliphatic hydrocarbons such as n-pentane, hexane and heptane; Alicyclic hydrocarbons such as cyclohexane; Halogenated carbonization such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene Hydrogen; and the like. These organic solvents can be used alone or in combination of two or more.

(Polymerization temperature) The temperature conditions for ring-opening polymerization are not particularly limited, but it is usual to select any temperature from -20 ° C to 100 ° C. (Polymerization pressure) The polymerization pressure is usually 0 to 50 Kg / c.
It is preferable to select from the range of m ² .

(Ring-Opening Polymer) The ring-opening polymer obtained in the present invention has a polystyrene-reduced number average molecular weight (Mn) of 1
50,000-50,000, preferably 10,000-
45,000, more preferably 15,000-35,
000 is a relatively high molecular weight polymer, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3 or less, preferably 2.5 or less, more preferably 2.3. It is a polymer with the following narrow molecular weight distribution. When the molecular weight and the molecular weight distribution are within the above ranges, the processability and birefringence of the polymer after hydrogenation are good.

The ring-opening polymer of the present invention is free of gel formation and is amorphous, and is benzene at room temperature.
It is soluble in organic solvents such as toluene, cyclohexane, carbon tetrachloride and carbon disulfide. Therefore, it is possible to efficiently carry out the hydrogenation reaction in a homogeneous system in an organic solvent. The ring-opening polymer obtained by the method of the present invention has a glass transition temperature (Tg) of usually 80 ° C. or higher, though it varies depending on the monomer composition, and when a tetracyclic compound is used as the monomer, it becomes 150 ° C. or higher. Tg is 100 ° C. or higher, preferably 120 to 200 ° C., more preferably 150 to 200, by using two or more norbornene-based monomers (A) together or with the norbornene-based monomer (B) together.
It is possible to control in the range of ° C.

Specific examples of preferable ring-opening polymers include homopolymers of alkylidene tetracyclododecene, copolymers of alkylidene tetracyclododecene and other alkyltetracyclododecene, DCPD, or norbornene. it can. The ring-opening polymer of the present invention has excellent optical properties by itself, but for use as an optical material, it is preferable to add hydrogen to further improve heat deterioration resistance and light deterioration resistance. Therefore, this ring-opening polymer is useful as an intermediate raw material for optical materials.

The norbornene-based ring-opening polymer of the present invention was analyzed by proton NMR in Example 1 to be described later, and as a result, the absorption due to the olefin double bond proton was observed between δ = 5.0 to 5.4 ppm. It was observed, the absorption intensity was almost the same as the theoretical value, and further, as a result of analysis by IR spectrum, strong absorption based on the trans double bond in the main chain was observed at about 975 cm ⁻¹ ,
It is clear that the polymer is a ring-opening polymer having a repeating unit represented by the following general formula (2).

[0026]

[Chemical 6] When the ring-opening polymer is a copolymer, it also has repeating units based on comonomers.

(Hydrogenation) The ring-opening polymer of the present invention can be made into a hydrogenated product by hydrogenating and saturating some or all of its double bonds, whereby the heat deterioration resistance of the polymer is improved. And resistance to light deterioration can be improved. The hydrogenation rate is theoretically in the range of 0 to 100% when 100% is assumed when all the double bonds of the ring-opening polymer are saturated by hydrogenation, and in practice, the hydrogenation rate is arbitrary. However, in order to improve the heat deterioration resistance and the light deterioration resistance, it is preferable that 50% or more of the double bonds be hydrogenated.

The hydrogenation reaction of this ring-opening polymer is carried out by a conventional method in the presence of a hydrogenation catalyst in an organic solvent using molecular hydrogen to hydrogenate at least a part of carbon-carbon double bonds. It is performed by adding. The hydrogenation catalyst can be used as long as it is generally used for hydrogenating an olefin compound, and is not particularly limited, but examples thereof include the following. As the heterogeneous catalyst, a solid catalyst in which nickel, palladium, platinum or a metal thereof is supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide, for example, nickel /
Examples thereof include silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina. As the homogeneous catalyst, a catalyst based on a metal of Group VIII of the periodic table,
For example, nickel naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum and the like, cobalt compounds and periodic table groups I to II.
Examples include organic metal compounds of Group I metals, rhodium compounds, and the like.

The hydrogenation reaction is a homogeneous system or a heterogeneous system, depending on the type of catalyst, under a hydrogen pressure of 1 to 150 atm and 0 to 2
It is carried out at 50 ° C, preferably 20 to 200 ° C. The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration and the like, but in order for the hydrogenated product to exhibit excellent heat deterioration resistance and light deterioration resistance, It is preferable that 50% or more of the double bonds in the coalescence are hydrogenated, more preferably 80% or more, and further preferably 90% or more.

(Molding) The ring-opening polymer and its hydrogenated product obtained by the method of the present invention can be molded by a well-known method. When molding
If desired, various additives such as inorganic or organic fillers, stabilizers, antistatic agents, lubricants and the like may be added.

(Usage) The ring-opening polymer obtained by the method of the present invention has a high glass transition temperature, and its hydrogenated product is clear from the fact that the carbon-carbon double bond is hydrogenated. As described above, since it is a polymer excellent in heat deterioration resistance and light deterioration resistance and excellent in optical properties such as transparency, water resistance, and birefringence, it is useful in various fields as various molded products. is there. For example, optical fields such as optical lenses, optical disks, optical fibers, pellicles, glass window applications, electric iron water tanks, microwave oven products, liquid crystal display substrates, printed circuit boards, high frequency circuit boards, transparent conductive sheets and films, etc. Electrical field, medical field such as syringe, pipette, animal gauge, chemical field,
It can be used in various fields such as camera bodies, various instrument housings, films, sheets and helmets.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Preparation of Ring-Opening Polymer In a 500 ml separable flask that was sufficiently dried and purged with nitrogen, 13.5 g of 6-ethylidene-2-tetracyclododecene (hereinafter abbreviated as ETD), 1- Hexen 1.0m
mol and 60 ml of toluene were added. Furthermore, triethylaluminum 1.5 mmol, titanium tetrachloride 0.30
mmol and triethylamine 1.5 mmol were added, and the mixture was reacted at 25 ° C. for 4 hours with stirring. After the reaction, the desired product was precipitated with a mixed solvent of acetone / isopropyl alcohol (1/1), filtered, and then dissolved again in toluene. Furthermore, the target product was obtained by precipitating with a mixed solvent of acetone / isopropyl alcohol (1/1), filtering and drying. No gel was found in the reaction product.

As a result of analysis of the obtained polymer by proton NMR, absorption due to the olefin double bond proton was observed in the range of δ = 5.0 to 5.4 ppm, and the absorption intensity was theoretical value (16. 7%), which is almost the same,
It was confirmed that the above polymer was ring-opening polymerized. The physical properties of this ring-opening polymer were measured under the following conditions, and the results are collectively shown in Table 1. This ring-opening polymer was soluble in benzene, toluene, cyclohexane, carbon tetrachloride, and carbon disulfide at room temperature. For reference, the IR spectrum of the above polymer is shown in FIG. 1, and also from this spectrum, strong absorption due to the trans double bond in the main chain was observed at about 975 cm ⁻¹ , and the above polymer was opened. It was confirmed to be a polymer. This IR spectrum is shown in the above-mentioned JP-A-63-3710.
It is significantly different from the IR spectrum described in JP-A-8.

Manufacture of hydrogenated product A solution prepared by dissolving 3 g of the above ring-opening polymer in 30 ml of cyclohexane was placed in a stainless steel ampoule having a capacity of 100 cc together with 0.3 g of palladium carbon, and after mixing,
Replace the air in the ampoule with hydrogen to increase the hydrogen pressure to 50 kg /
cm ² G, and the mixture was held at 10 ° C. for 30 minutes while stirring.
Then, the temperature was raised to 120 ° C. and the mixture was stirred for 18 hours, then, the solution was filtered through a 1 μm filter, the product was reprecipitated in methanol, dried and purified. ^{By 1} H-NMR analysis, it was confirmed that the absorption at δ = 5.0 to 5.4 ppm due to the double bond disappeared, and that hydrogenation was almost complete. The physical properties of this hydrogenated product are shown in Table 1.

<Methods for measuring physical properties> Molecular weight and molecular weight distribution : HLC802A type manufactured by Toyo Soda Co., Ltd. was used by GPC method, and polystyrene-equivalent number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were used in cyclohexane. Was measured. Melt viscosity : Shimadzu Flow Tester CFT-50
It was measured with a 0 type. Extrusion die diameter 1mmφ, length 10m
m, load 50 kgf, calculated from the outflow rate at 300 ° C. Light transmittance : With a total light transmittance measuring device manufactured by Shimadzu Corporation,
The transmittance at a wavelength of 830 nm was measured. Glass transition temperature (Tg) : DSC manufactured by Seiko Instruments Inc.
It was measured at a temperature rising rate of 10 ° C./min using a 20 type. Birefringence : Measured with a single pass at a wavelength of 633 nm using a fully automatic birefringence measuring device manufactured by JEOL Ltd. Moisture resistance : The water absorption rate (% by weight) was measured according to the moisture resistance test method of JIS K6911. Molding method : A hydrogenated product is injection-molded with a M-70A-DM type injection molding machine manufactured by Meiki Co., Ltd. under conditions of a resin temperature of 330 ° C. and a mold temperature of 90 ° C., and a circle having a diameter of 130 mm and a thickness of 1.2 mm. The plate was molded. Using the obtained disc, light transmittance, birefringence, and water absorption were measured.

[Examples 2 to 3] An experiment was conducted in the same manner as in Example 1 except that the amount of 1-hexene used was changed to 0.4 mmol (Example 2) or 0.1 mmol (Example 3). , A ring-opening polymer of EDT was obtained. The obtained ring-opening polymers were all soluble in all the above organic solvents. These ring-opened polymers were hydrogenated in the same manner as in Example 1 to prepare hydrogenated products. The physical properties of the ring-opening polymer and the hydrogenated product were measured by the same methods as in Example 1, and the measurement results are collectively shown in Table 1.

[0038]

[Table 1]

[Embodiment 4] EDT75 in place of EDT
An experiment was conducted in the same manner as in Example 1 except that a mixed monomer of wt% and ethylidene norbornene of 25 wt% was used to obtain a ring-opened polymer. The obtained ring-opening polymer was soluble in all the above organic solvents and had a number average molecular weight (Mn).
Was 21,000, the molecular weight distribution (Mw / Mn) was 2.2, and the glass transition temperature (Tg) was 130 ° C. This ring-opened polymer was hydrogenated in the same manner as in Example 1 (hydrogenation rate 100%) to prepare a hydrogenated product. The birefringence of the obtained hydrogenated product was 5.

[Embodiment 5] Instead of EDT, EDT70
An experiment was conducted in the same manner as in Example 1 except that a mixed monomer of 30% by weight of methyltetracyclododecene was used, and a ring-opened polymer was obtained. The obtained ring-opening polymer was soluble in all the above organic solvents and had a number average molecular weight (M
n) was 20,000, the molecular weight distribution (Mw / Mn) was 2.1, and the glass transition temperature (Tg) was 183 ° C.
This ring-opened polymer was hydrogenated (hydrogenation ratio 1
00%) to prepare a hydrogenated product. The birefringence of the obtained hydrogenated product was 5.

[0041]

According to the production method of the present invention, it is possible to efficiently obtain a hydrogenated norbornene ring-opening polymer having a high molecular weight, a sharp molecular weight distribution, and good gelability and good processability. it can. The ring-opening polymer and hydrogenated product thereof of the present invention can be suitably used in a wide range of fields as an optical material industrially.

[Brief description of drawings]

1 is an infrared absorption spectrum (IR spectrum) of the ring-opened polymer obtained in Example 1. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ima Natsume 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center

Claims (4)

[Claims] 1. 100 to 50% by weight of a norbornene-based monomer represented by the general formula (1): (In the formula, R ₁ and R ₂ are the same or different from each other and each represent a hydrogen atom or an alkyl group, and m represents an integer of 0 to 2.) Other norbornene-based copolymerizable ring-opening copolymerizable monomers Ring-opening polymerization of 0 to 50% by weight of a norbornene-based monomer,
A solvent-soluble norbornene ring-opening polymer having a number average molecular weight Mn of 10,000 to 50,000 and a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 3 or less is produced, and then, A method for producing a hydrogenated norbornene ring-opening polymer, which comprises hydrogenating the norbornene ring-opening polymer in an organic solvent in the presence of a hydrogenation catalyst. 2. The solvent-soluble norbornene-based ring-opening polymer comprises 100 to 50% by weight of the norbornene-based monomer represented by the general formula (1), and another norbornene-based monomer capable of ring-opening copolymerization with the norbornene-based monomer. To 50% by weight in the presence of a chain olefin, (a) an organic compound of a metal belonging to Group I to III of the periodic table, (b) titanium tetrahalide, and (c) an amine activator. The method for producing hydrogenated norbornene ring-opening polymer according to claim 1, which is produced by ring-opening polymerization using a Ziegler type ring-opening polymerization catalyst consisting of 3. Having a repeating unit represented by the general formula (2): (In the formula, R ₁ and R ₂ are the same or different from each other and represent a hydrogen atom or an alkyl group, and m represents an integer of 0 to 2.) The number average molecular weight Mn is 10,000 to 50,000. A solvent-soluble norbornene ring-opening polymer having a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 3 or less. 4. A hydrogenated norbornene ring-opening polymer in which at least a part of carbon-carbon double bonds of the solvent-soluble norbornene ring-opening polymer according to claim 3 is hydrogenated.