JP2006282696A - Method for producing norbornene ring-opened polymer hydrogenate and norbornene ring-opened polymer hydrogenate obtained thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a norbornene ring-opened polymer hydrogenate by selectively hydrogenating the carbon-to-carbon double bonds in the main chain of a norbornene ring-opened polymer prepared by polymerizing an aromatic-ring-structure-containing norbornene monomer through ring opening, which method is excellent in productivity and gives a coloration-free hydrogenate. <P>SOLUTION: The method for producing the norbornene ring-opened polymer hydrogenate comprises the step (i) of polymerizing an aromatic-ring-structure-containing norbornene monomer through ring opening to obtain a norbornene ring-opened polymer and the step (ii) of hydrogenating the norbornene ring-opened polymer by contact with hydrogen in the presence of a hydrogenation catalyst being palladium-carrying silica of an average pore diameter of 3 to 50 nm under conditions including a reaction temperature of 150 to 250°C and a hydrogen pressure of 0.01 to 10 MPa. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a norbornene-based ring-opening polymer hydrogenated product and a norbornene-based ring-opened polymer hydrogenated product, and more particularly, a norbornene-based ring-opening polymer hydrogen having excellent transparency and high refractive index. The present invention relates to a method for producing an additive and a hydrogenated norbornene-based ring-opening polymer.

Phenylnorbornene and tetracyclo [7.4.0.0 ^2,7 . 1 ^{10, 13} ] triborna-2,4,6,11-tetraene and the like, a norbornene-based ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure is converted into The norbornene-based ring-opening polymer hydrogenated product obtained by selectively hydrogenating the hydrogenation rate of the heavy bond to 95% or more and the hydrogenation rate of the carbon-carbon double bond in the aromatic ring to 10% or less is transparent. It is known that it has excellent properties and refractive index.
In Patent Document 1, a norbornene-based ring-opening polymer obtained by ring-opening polymerization of phenylnorbornene is hydrogenated using cobalt (III) acetylacetonate as a hydrogenation catalyst, and a carbon-carbon double bond of a main chain is formed. A norbornene-based ring-opening polymer hydrogenated product having a hydrogenation rate of 99% or more and a hydrogenation rate of carbon-carbon double bonds in the aromatic ring of 1% or less is disclosed. Patent Document 1 describes that the selective hydrogenation reaction as described above is possible by using a catalyst combining a transition metal compound and an alkyl metal compound as a hydrogenation catalyst. It is described that when an alumina-supported nickel catalyst is used, the carbon-carbon double bond in the main chain of the ring-opening polymer and the carbon-carbon double bond in the aromatic ring are completely hydrogenated.
On the other hand, Patent Document 2 discloses tetracyclo [7.4.0.0 ^2,7 . 1 ^10,13] trideca -2,4,6,11- tetraene hydrogenation reaction of the norbornene-based polymer obtained Te ring-opening polymerization is disclosed.
In Example 1 of Patent Document 2, when the norbornene-based polymer is reacted for 5 hours under the conditions of a reaction temperature of 230 ° C. and a hydrogen pressure of 0.45 MPa, using an alumina-supported nickel catalyst, It is described that 99.9% or more of the carbon-carbon double bonds in the main chain and 99.7% of the carbon-carbon double bonds in the aromatic ring are hydrogenated.
Further, in Example 3 of Patent Document 2, when the norbornene-based polymer is reacted for 5 hours at a reaction temperature of 170 ° C. and a hydrogen pressure of 0.45 MPa using a silica-supported palladium catalyst, a ring-opened polymer is obtained. It is described that 99.9% or more of the carbon-carbon double bonds in the main chain and 99.7% of the carbon-carbon double bonds in the aromatic ring are hydrogenated.
JP H7-62068 A JP H9-263627A

  However, when the present inventors performed a hydrogenation reaction using the catalyst described in Patent Document 1 in which a transition metal compound and an alkyl metal compound are combined, the hydrogenation reaction is caused by a change in the reaction temperature of only a few degrees. It has been found that there is a problem that the selectivity of the product is lowered, and that the resulting hydrogenated product is colored. In addition, since the hydrogenation reaction has a large calorific value, it is difficult to control the temperature at several degrees on the plant scale. Therefore, the selective hydrogenation reaction described in Patent Document 1 has a problem in productivity.

  Therefore, the problem to be solved by the present invention is that a norbornene-based ring-opened polymer obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure is selectively hydrogenated at the carbon-carbon double bond of the main chain. A method for producing a norbornene-based ring-opening polymer hydrogenated product by adding the norbornene-based ring-opened polymer hydrogenated product, which is excellent in productivity and has no coloration in the resulting hydrogenated product. There is to do.

  The inventors of the present invention focused on the average pore diameter of silica of the silica-supported palladium catalyst and conducted intensive studies. As a result, when a palladium catalyst supported on silica having a specific average pore diameter is used, hydrogenation can be selectively performed regardless of fluctuations in the temperature of the hydrogenation reaction by several tens of degrees. When the hydrogenation reaction was carried out in the temperature range, it was found that the resulting hydrogenated product was excellent in transparency, and the present invention was completed.

Thus, according to the present invention,
(I) ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure to obtain a norbornene-based ring-opening polymer; and (ii) the norbornene-based ring-opening polymer having an average pore diameter of 3 to 50 nm. Hydrogenation by contacting with hydrogen under the conditions of a reaction temperature of 150 ° C. or more and 250 ° C. or less and a hydrogen pressure of 0.01 MPa or more and 10 MPa or less in the presence of a hydrogenation catalyst supported on palladium on a certain silica;
A process for producing a hydrogenated norbornene-based ring-opening polymer is provided.
The norbornene-based ring-opening polymer hydrogenated product has a hydrogenation rate of carbon-carbon double bonds in the main chain of 95% or more and a hydrogenation rate of carbon-carbon double bonds in the aromatic ring of 10% or less. And preferred.
Moreover, the norbornene-type ring-opening polymer hydrogenated product obtained by the said manufacturing method is provided.
The hydrogenated norbornene-based ring-opening polymer is preferably a 10% by weight toluene solution, and the solution light transmittance measured at an optical path length of 10 mm and a wavelength of 450 nm is preferably 90% or more.
Furthermore, the resin composition containing the said norbornene-type ring-opening polymer hydrogenated product, and the molded object formed by shape | molding it are provided. The molded body is suitable as an optical component.

  According to the method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention, the selectivity of hydrogenation is excellent and the transparency is excellent regardless of the fluctuation of the reaction temperature by tens of degrees during the hydrogenation. Thus, a hydrogenated norbornene-based ring-opening polymer is obtained. The obtained norbornene-based ring-opening polymer hydrogenated product is a 10% by weight toluene solution, and has a solution light transmittance of 90% or more measured at an optical path length of 10 mm. Therefore, it is suitable as a molding material for optical components. .

The method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention includes (i) a step of ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure to obtain a norbornene-based ring-opened polymer, and (ii) In the presence of a hydrogenation catalyst in which the norbornene-based ring-opening polymer is palladium-supported on silica having an average pore diameter of 3 to 50 nm, the reaction temperature is 150 ° C. or more and 250 ° C. or less, and the hydrogen pressure is 0.01 MPa or more and 10 MPa or less. A step of hydrogenation in contact with hydrogen,
Have

(Norbornene ring-opening polymer)
The norbornene ring-opening polymer used in the method for producing a hydrogenated norbornene ring-opening polymer of the present invention is obtained by ring-opening polymerization of a norbornene monomer having an aromatic ring structure.

(Norbornene monomer having an aromatic ring structure)
The norbornene-based monomer having an aromatic ring structure used in the present invention is a norbornene-based monomer having an aromatic ring structure among the norbornene-based monomers.
In the present invention, the norbornene monomer is a compound having a norbornene structure represented by the formula (1).

  Examples of norbornene monomers having an aromatic ring structure include 5-phenyl-2-norbornene, 5- (4-methylphenyl) -2-norbornene, 5- (1-naphthyl) -2-norbornene, and 9- (2 -Norbornene-based monomer having an aromatic substituent such as norbornene-5-yl) -carbazole; 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 1 , 4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 9a-tetrahydrodibenzofuran, 1,4-methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene, 1,4-methano-1,4,4a, 9,10,10a-hexahydrophenane Ren, norbornene monomer having a norbornene ring structure and an aromatic ring structure in condensed polycyclic structures such as; and the like.

These norbornene monomers having an aromatic ring structure may have a substituent.
Examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; an alkylidene group; an alkenyl group; a halogen group such as a fluoro group, a chloro group, a bromo group, and an iodo group; a hydroxyl group; an ester group; Cyano group; amide group; imide group; silyl group; The norbornene-based monomer having an aromatic ring structure may have two or more of these substituents.
Among the substituents, substituents having no polarity such as an alkyl group, an alkylene group, and a vinyl group are preferable from the viewpoint of moisture resistance of the obtained molded article.

  These norbornene monomers having an aromatic ring structure can be used alone or in combination of two or more.

  A norbornene-based ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure used in the present invention is a norbornene-based monomer having an aromatic ring structure described above and a monomer capable of copolymerization therewith. It may be a copolymer with the body.

Other monomers that can be copolymerized with norbornene monomers having an aromatic ring structure include norbornene monomers having no aromatic ring structure, monocyclic cyclic olefin compounds such as cyclohexene, cycloheptene, and cyclooctene. Etc. These norbornene monomers having an aromatic ring structure and monomers capable of ring-opening copolymerization are used alone or in combination of two or more.
Among other monomers copolymerizable with a norbornene monomer having an aromatic ring structure, a norbornene monomer having no aromatic ring structure is preferable from the viewpoint of low birefringence of the obtained molded article. .

  Examples of norbornene-based monomers having no aromatic ring structure include JP-A-2-227424, JP-A-2-276842, JP-A-4-14882, JP-A-3-122137, and JP-A-4. -63807 and the like. Specifically, specific examples include 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butylnorbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl Norbornene such as -5-methoxycarbonyl-2-norbornene and compounds having a substituent on norbornene; dicyclopentadi 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 1,4 : 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6 , 7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro A cyclopentadiene multimer such as -2,3-cyclopentadienoanthracene, and a compound having a substituent on the cyclopentadiene multimer; and the like.

  The ratio of the other monomers copolymerizable with these norbornene monomers having an aromatic ring structure is not particularly limited, but is preferably 100 parts by weight of the norbornene monomer having an aromatic ring structure. Less than 100 parts by weight, more preferably less than 50 parts by weight, particularly preferably less than 20 parts by weight, and most preferably less than 1 part by weight.

(Ring-opening polymerization)
The norbornene-based ring-opening polymer used in the present invention is a norbornene-based monomer having an aromatic ring structure and, if necessary, other monomers copolymerizable with the norbornene-based monomer having an aromatic ring structure, It can be obtained by polymerization in the presence of a known ring-opening polymerization catalyst.
As the ring-opening polymerization catalyst, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like, and a reducing agent; titanium, vanadium, zirconium, tungsten And a catalyst system comprising a metal halide or acetylacetone compound selected from molybdenum and a co-catalyst organoaluminum compound; or JP-A-7-179575; Am. Chem. Soc. , 1986, 108, 733; Am. Chem. Soc. 1993, 115, 9858, and J.A. Am. Chem. Soc. , 1996, 118, 100, etc., known Schrock-type and Grubbs-type living ring-opening metathesis catalysts.
These catalysts are used alone or in combination of two or more. The amount of the catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 1 / 1,000,000 to 1/10, preferably 1 / 100,000 to 1 in terms of molar ratio to the total amount of monomers. 1/100.

  The polymerization temperature is usually in the range of −50 ° C. to 200 ° C., preferably −30 ° C. to 180 ° C., more preferably −20 ° C. to 150 ° C., and the polymerization pressure is usually 0 to 5 MPa, preferably 0 to The range is 20 MPa. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually in the range of 30 minutes to 20 hours, preferably 1 to 10 hours.

  When the ring-opening polymerization is solution polymerization, the solvent is not particularly limited, but a hydrocarbon solvent is preferable. Examples of hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; aliphatic alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclooctane; Preferred are aromatic hydrocarbons and aliphatic alicyclic hydrocarbons, and among these, toluene, cyclohexane, cyclooctane and the like are more preferred, and toluene and cyclohexane are most preferred. These hydrocarbon solvents can be used alone or in combination of two or more.

The polymerization conversion rate of the polymer obtained by ring-opening polymerization is preferably 95% by weight or more, more preferably 97% by weight or more, and particularly preferably 99% by weight or more. A high polymerization conversion rate is preferable because a molded product with a small amount of released organic matter can be obtained.
In the present invention, the polymerization conversion rate is a value obtained by dividing the value obtained by subtracting the weight of the unreacted monomer from the weight of the used monomer by the weight of the used monomer.

In addition, as long as the object of the present invention is not impaired, the ring-opening polymer is converted into an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrenic hydrocarbon, Modification can be made using an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, or an unsaturated epoxy monomer.
Among the modified ring-opening polymers, a modified ring-opening polymer that does not contain a polar group is preferable in terms of moisture resistance and chemical resistance of the obtained molded body.

The molecular weight of the norbornene-based ring-opening polymer hydrogenated product used in the present invention is not particularly limited, but the weight average molecular weight (Mw) is preferably in the range of 15,000 to 55,000, preferably 20,000 to 50, Is more preferably in the range of 5,000, and particularly preferably in the range of 25,000 to 45,000. The number average molecular weight (Mn) is preferably in the range of 8,000 to 37,000, more preferably in the range of 10,000 to 30,000, and particularly preferably in the range of 13,000 to 27,000. preferable.
It is preferable that Mw and Mn are in this range because the obtained molded article has high mechanical strength.
In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the norbornene-based ring-opening polymer are such that when the norbornene-based ring-opening polymer is soluble in tetrahydrofuran, gel permeation is performed at 40 ° C. using tetrahydrofuran as a solvent. It is a value measured by an association chromatography (GPC) and converted to standard polystyrene. When the norbornene-based ring-opening polymer is insoluble in tetrahydrofuran and soluble in cyclohexane, gel permeation is performed at 40 ° C. using cyclohexane as a solvent. It is a value measured by an association chromatography (GPC) and converted with standard polyisoprene.
The molecular weight distribution (Mw / Mn) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn)) is preferably in the range of 1 to 3, more preferably in the range of 1 to 2.5, A range of 1 to 2 is particularly preferable. When Mw / Mn is in this range, the mechanical strength and heat resistance of the obtained molded product are highly balanced.

(Selective hydrogenation reaction)
The method for producing a hydrogenated norbornene-based ring-opening polymer according to the present invention comprises a norbornene-based ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure having an average pore diameter of 3 to 3. In the presence of a hydrogenation catalyst supported by palladium on silica of 50 nm, hydrogenation is performed by contacting with hydrogen under conditions of a reaction temperature of 150 ° C. to 250 ° C. and a hydrogen pressure of 0.01 MPa to 10 MPa.
According to the method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention, the norbornene-based ring-opened polymer has a main chain carbon-carbon double bond hydrogenation rate of 95% or more, The hydrogenation rate of the carbon-carbon double bond can be selectively hydrogenated to 10% or less.

(Hydrogenation catalyst)
The hydrogenation catalyst used in the present invention is palladium supported on silica having an average pore diameter of 3 to 50 nm. The average pore diameter of silica is in the range of 3-50 nm. Especially, it exists in the range of 6-30 nm, and it exists in the range of 10-15 nm.
In the present invention, the average pore diameter of silica is a value calculated based on the pore diameter distribution measured by the mercury intrusion method (porosimeter).

  The amount of palladium supported on silica is not particularly limited, but is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of silica. Parts by weight. It is preferable from the viewpoint of the reaction rate of the hydrogenation reaction that the supported amount of palladium is within this range.

  The reaction temperature of the hydrogenation reaction is 150 ° C. or higher and 250 ° C. or lower. Especially, it is preferable in it being the range of 180-220 degreeC. When the reaction temperature is within this range, it is preferable in terms of transparency of the resulting hydrogenated product.

  The hydrogen pressure of the hydrogenation reaction is 0.01 MPa or more and 10 MPa or less. Among these, 0.2 to 5 MPa is preferable, and 1 to 5 MPa is more preferable. When the hydrogen pressure is within this range, it is preferable in terms of transparency of the resulting hydrogenated product.

  According to the method for producing a hydrogenated norbornene-based ring-opening polymer of the present invention, a norbornene-based ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure is converted into a norbornene-based ring-opening polymer. The hydrogenation rate of the carbon-carbon double bond in the main chain can be selectively hydrogenated to 95% or more and the hydrogenation rate of the carbon-carbon double bond in the aromatic ring to 10% or less.

In the method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention, the hydrogen-hydrogenation rate of the carbon-carbon double bond of the main chain of the norbornene-based ring-opening polymer is preferably 98% or more, and 99% or more. Is more preferable, and it is especially preferable that it is 99.9% or more. When the hydrogenation rate of the carbon-carbon double bond of the main chain of the norbornene-based ring-opening polymer is in this range, it is preferable in terms of oxidation resistance, light resistance, and chemical resistance of the resulting polymer hydrogenated product.
The hydrogen hydrogenation rate of the aromatic ring of the norbornene-based ring-opening polymer is preferably 10% or less, more preferably 5% or less, particularly preferably 2% or less, and 1% or less. Most preferred. When the hydrogen hydrogenation rate of the aromatic ring of the norbornene-based ring-opening polymer is in this range, it is preferable from the viewpoint of the high refractive index of the resulting polymer hydrogenated product.
The hydrogenation rate of the carbon-carbon double bond in the main chain of the norbornene-based ring-opening polymer and the hydrogenation rate of the carbon-carbon double bond in the aromatic ring are values measured by ¹ H-NMR.

The hydrogenation step of the method for producing the norbornene-based ring-opening polymer hydrogenated product of the present invention is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the catalyst, but a hydrocarbon-based solvent is usually used because of the excellent solubility of the resulting hydrogenated product.
Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; ethers such as tetrahydrofuran and ethylene glycol dimethyl ether; These may be used, and two or more of these may be used in combination.
When using a solvent, it is preferable to adjust the amount of the solvent to 0.8 to 20 parts by weight, particularly 1 to 10 parts by weight, based on 1 part by weight of the norbornene-based ring-opening polymer. Usually, it may be the same as the polymerization reaction solvent, and the reaction can be carried out by adding the hydrogenation catalyst to the polymerization reaction solution as it is.

  The removal of the catalyst after completion of the hydrogenation reaction may be performed according to a conventional method such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used, and it is preferable to use a filter aid such as diatomaceous earth or pearlite from the viewpoint of efficiency.

  The method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention is excellent in the productivity of the hydrogenated product because the decrease in selectivity due to a temperature change of tens of degrees during the hydrogenation reaction is small. The transparency of the hydrogenated product is high.

(Hydrogenated product)
According to the method for producing a norbornene-based ring-opening polymer hydrogenated product of the present invention, a norbornene-based ring-opened polymer hydrogenated product having high transparency can be obtained.
Among them, the transparency of the norbornene-based ring-opening polymer hydrogenated product is preferably 10% by weight in a toluene solution, preferably 90% or more, and 92% or more in solution light transmittance measured at an optical path length of 10 mm and a wavelength of 450 nm. And preferably 95% or more.

The molecular weight of the norbornene-based ring-opening polymer hydrogenated product of the present invention is not particularly limited, but the weight average molecular weight (Mw) is preferably in the range of 20,000 to 60,000, preferably 25,000 to 55,000. It is more preferable in the range, and particularly preferable in the range of 30,000 to 50,000. The number average molecular weight (Mn) is preferably in the range of 10,000 to 40,000, more preferably in the range of 13,000 to 33,000, and in the range of 16,000 to 30,000. Particularly preferred.
It is preferable that Mw and Mn are in this range because the obtained molded article has high mechanical strength.
In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the norbornene-based ring-opening polymer hydrogenated product are determined using tetrahydrofuran as a solvent when the norbornene-based ring-opened polymer hydrogenated product is soluble in tetrahydrofuran. It is a value measured by gel permeation chromatography (GPC) at 40 ° C. and converted to standard polystyrene. When the norbornene-based ring-opening polymer hydrogenated product is insoluble in tetrahydrofuran and soluble in cyclohexane, cyclohexane is the solvent. And measured by gel permeation chromatography (GPC) at 40 ° C. and converted with standard polyisoprene.
The molecular weight distribution (Mw / Mn) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn)) of the norbornene-based ring-opening polymer hydrogenated product is preferably in the range of 1 to 2, Is more preferably in the range of 0.5, and particularly preferably in the range of 1-2. When Mw / Mn is in this range, the mechanical strength and heat resistance of the molded body are highly balanced.

The glass transition temperature of the norbornene-based ring-opening polymer hydrogenated product (hereinafter sometimes referred to as Tg) is preferably in the range of 100 to 200 ° C, and more preferably in the range of 120 to 180 ° C. When Tg is within this range, the heat resistance of the hydrogenated product and the processability of the resin composition of the hydrogenated product are preferable.
Here, Tg is a value measured under the condition of 10 ° C./min using a differential scanning calorimeter.

  The hydrogenated norbornene-based ring-opening polymer is preferably a 10% by weight toluene solution, and the solution light transmittance measured at an optical path length of 10 mm and a wavelength of 450 nm is preferably 90% or more. When the solution light transmittance is in this range, it is preferable in terms of the transparency of the obtained molded article.

The hydrogenated norbornene-based ring-opening polymer preferably has a refractive index [ _nd25 ] at a wavelength of 587.6 nm at 25 ° C of 1.560 or more. When the refractive index is in this range, the thickness can be reduced when the obtained molded body is a lens.

(Resin composition)
The hydrogenated norbornene-based ring-opening polymer of the present invention can be made into a resin composition by blending various compounding agents as necessary. The compounding agent is not particularly limited, but is a stabilizer such as an antioxidant, a heat stabilizer, a light stabilizer, a weathering stabilizer, an ultraviolet absorber, a near infrared absorber, and the like; a resin modifier such as a lubricant and a plasticizer. Colorants such as dyes and pigments; antistatic agents and the like. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.

  As a method for producing a resin composition, a compounding agent is dissolved in an appropriate solvent and added to a solution of a norbornene-based ring-opening polymer hydrogenated product, and then the solvent is removed to include a norbornene-based ring-opening polymer containing the compounding agent. A method of obtaining a resin composition of a hydrogenated product, a method of kneading a compounding agent by melting a norbornene-based ring-opening polymer hydrogenated product in a mixer, a twin-screw kneader, a roll, a Brabender, an extruder, etc. Can be mentioned.

  The resin composition obtained by the above method can be molded into various molded bodies and used for various applications. The molding method is not particularly limited, but in order to obtain a molded product having excellent low birefringence, mechanical strength, dimensional accuracy, etc., it is preferable to use a melt molding method. Examples of the melt molding method include injection molding method, injection compression molding method, extrusion molding method, extrusion stretch molding method, multilayer extrusion molding method, press molding method, blow molding method, injection blow molding method, inflation molding method and the like. From the viewpoints of low birefringence, dimensional stability, etc., an injection molding method and an extrusion molding method are preferred.

  The molding conditions are appropriately selected depending on the purpose of use and the molding method. For example, in the case of the injection molding method, the resin temperature is appropriately selected in the range of usually 150 to 350 ° C, preferably 200 to 300 ° C, more preferably 230 to 280 ° C. If the resin temperature is too low, fluidity deteriorates, causing sink marks or distortion in the molded product. If the resin temperature is too high, silver streaks occur due to thermal decomposition of the resin, or the molded product turns yellow. Defects may occur.

  The shape of the molded body is not particularly limited, and may be various shapes such as a spherical shape, a rod shape, a plate shape, a columnar shape, a cylindrical shape, a lens shape, a film or a sheet shape.

(Use)
The molded body of the present invention is useful in various fields as various molded articles including optical materials. For example, optical parts; medical equipment; electrical insulation materials; electronic parts processing equipment; electronic parts such as windows for light receiving elements; structural materials and building materials such as windows, equipment parts, housings; bumpers, room mirrors, head lamp covers Automotive equipment such as tail lamp covers and instrument panels; Speaker cone material, vibrating elements for speakers, electrical equipment such as microwave oven containers, films, sheets, helmets, etc.

(Optical parts)
The norbornene-based ring-opening polymer hydrogenated product of the present invention is excellent in transparency and low birefringence, and is suitable as a material for optical components. In particular, when used for a lens, a prism, or the like that utilizes light refraction, the refractive index is 1.560 or more, preferably 1.570 or more, particularly preferably 1.580 or more, which is useful. For example, the spectral power of the prism is large, and a lens with a short focal length can be obtained even if the surface curvature is small. In addition, because it has excellent heat resistance, low moisture absorption, water absorption resistance and mechanical toughness, for example, optical disks, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, light diffusion plates, polarizing films, It is useful as an optical material such as a retardation film.

Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. The present invention is not limited by these.
Parts and% are based on weight unless otherwise specified. Further, the pressure is a gauge pressure unless otherwise specified.

Various physical properties were measured according to the following methods.
(1) Average pore diameter The pore diameter distribution is a value calculated by measuring the pore diameter distribution by a mercury intrusion method (porosimeter).
(2) Hydrogenation rate The hydrogenation rate of the carbon-carbon double bond in the main chain and the carbon-carbon double bond in the aromatic ring was measured by ¹ H-NMR.
(3) Glass transition temperature (Tg)
The Tg of the polymer was measured with a differential scanning calorimeter based on JIS K7121 at a temperature rising rate of 10 ° C./min.
(4) Molecular weight When the polymer is soluble in tetrahydrofuran, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are determined by gel permeation chromatography (GPC) at 40 ° C. using tetrahydrofuran as a solvent. When the polymer is insoluble in tetrahydrofuran and soluble in cyclohexane, it is measured by gel permeation chromatography (GPC) at 40 ° C. using cyclohexane as a solvent. It is a value converted with isoprene.
(5) Light transmittance of polymer A 10 wt% toluene solution was used, and the light transmittance at 450 nm was measured using an ultraviolet-visible spectrophotometer (JASCO V-570 type) with an optical path length of 10 mm.
(6) Total light transmittance of test piece Using UV-Vis spectrophotometer (JASCO V-570 type), light transmittance at a wavelength of 400 to 830 nm in the thickness direction for test piece B (thickness 3.0 mm). The rate was measured.
(7) Turbidity of test piece Based on JIS K7361, the thickness direction was measured about the test piece B (thickness 3.0mm) using the turbidimeter (Nippon Denshoku NDH2000 type | mold).
(8) Refractive index The refractive index of wavelength 587.6nm in 25 degreeC was calculated | required using the Karnew refractometer (Karunew optical industry refractometer KPR-200).

(Reference Example 1)
In an autoclave equipped with a stirrer substituted with nitrogen, 33 parts by weight of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as MTF), 80 parts by weight of cyclohexane, 0.1 weight of 1-hexene I put a part. After the solution was heated to 45 ° C., 3.5 parts by weight of a 15% toluene solution of triisobutylaluminum as a polymerization catalyst, 0.03 parts by weight of isobutyl alcohol, 0.04 parts by weight of diisopropyl ether, and 20% of tungsten chloride 42 parts by weight of a cyclohexane solution was added to initiate ring-opening polymerization. When the reaction was carried out for 1 hour while maintaining the temperature of the solution at 45 ° C., 0.1 part by weight of isopropyl alcohol was added to stop the reaction, and an MTF ring-opening polymer was obtained. The number average molecular weight (Mn) of the MTF ring-opening polymer was 18,300, the weight average molecular weight (Mw) was 44,000, and the molecular weight distribution (Mw / Mn) was 2.4.

Example 1
An autoclave equipped with a stirrer was prepared by dissolving 20 parts by weight of the MTF ring-opened polymer obtained in Reference Example 1 in 80 parts by weight of toluene and 0.1 part by weight of Pd catalyst supported on silica having an average pore diameter of 10.0 nm. Put in. After replacing the gas part in the autoclave with hydrogen, hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. for 5 hours. After completion of the reaction, the solution was filtered through a filter paper having a pore size of 2 μm to remove the hydrogenation catalyst. The filtrate was poured into 500 parts by weight of isopropyl alcohol that was vigorously stirred to precipitate the hydrogenated product of the MTF ring-opening polymer and filtered to obtain a hydrogenated product of the MTF ring-opened polymer. The obtained hydrogenated product of MTF ring-opening polymer was dried at 100 ° C. for 24 hours in a vacuum drier reduced to 1 mmHg or less, and 18 parts by weight of hydrogenated product of MTF ring-opening polymer (polymer (A1 )).

  The Tg of the polymer (A1) was 136 ° C. Further, the hydrogenation rate and solution light transmittance of the polymer (A1) were measured. The results are shown in Table 1. Further, the polymer (A1) was wet-decomposed and the sample was analyzed by inductively coupled plasma emission spectrometry. As a result, the amount of Pd atoms in the resin was 1 ppm (detection limit) or less.

  To 17 parts by weight of this polymer (A1), 0.008 part by weight of an antioxidant (Ciba Geigy, Irganox 1010) was added, and a twin screw extruder (TEM-35B, Toshiba Machine Co., Ltd., screw diameter 37 mm, L / D = 32, screw rotation speed 250 rpm, resin temperature 270 ° C., feed rate 10 kg / hour) to give pellets.

  Using this pellet, injection molding (clamping pressure: 350 tons, resin temperature: 280 ° C., mold temperature: 70 ° C.) was performed to produce a 40 mm × 40 mm × 3.0 mm test piece (B1). Using the obtained test piece (B1), total light transmittance, turbidity, and refractive index were measured. The results are shown in Table 1.

(Example 2)
A polymer (A2) and a test piece (B2) were obtained in the same manner as in Example 1 except that the temperature of the hydrogenation reaction was 200 ° C. The Tg of the polymer (A2) was 136 ° C. Further, the hydrogenation rate and solution light transmittance of the polymer A2 were measured. Furthermore, the total light transmittance, turbidity, and refractive index were measured using the test piece (B2). The results are shown in Table 1.

(Example 3)
A polymer (A3) and a test piece (B3) were obtained in the same manner as in Example 1 except that the temperature of the hydrogenation reaction was 220 ° C. The Tg of the polymer (A3) was 136 ° C. Further, the hydrogenation rate and solution light transmittance of the polymer (A3) were measured. Furthermore, the total light transmittance, turbidity, and refractive index were measured using the test piece (B3). The results are shown in Table 1.

(Comparative Example 1)
A polymer (A4) and a test piece (B4) were obtained in the same manner as in Example 1 except that the temperature of the hydrogenation reaction was 140 ° C. The Tg of the polymer (A4) was 136 ° C. Further, the hydrogenation rate and solution light transmittance of the polymer (A4) were measured. Furthermore, total light transmittance, turbidity, and refractive index were measured using test piece B4. The results are shown in Table 1.

(Comparative Example 2)
A polymer (A5) was obtained in the same manner as in Example 1 except that the hydrogenation catalyst was a Pd catalyst supported on silica having an average pore diameter of 100.0 nm and the temperature of the hydrogenation reaction was 200 ° C.
When the hydrogenation rate of the polymer (A5) was measured, the hydrogenation rate of the carbon-carbon double bond in the main chain structure was insufficient at 50.0%.

(Comparative Example 3)
A polymer (A6) was obtained in the same manner as in Example 1 except that the hydrogenation catalyst was a Pd catalyst supported on silica having an average pore diameter of 1.0 nm and the temperature of the hydrogenation reaction was 200 ° C.
When the hydrogenation rate of the polymer (A6) was measured, the hydrogenation rate of the carbon-carbon double bond in the main chain structure was insufficient at 50.0%.

(Comparative Example 4)
A polymer (A7) was obtained in the same manner as in Example 1 except that the hydrogenation catalyst was a Ni catalyst supported on silica having an average pore diameter of 10.0 nm and the temperature of the hydrogenation reaction was 200 ° C. The Tg of the polymer (A7) was 136 ° C. The hydrogenation rate, solution light transmittance, and refractive index of the polymer (A7) were measured. The results are shown in Table 1.

Table 1 shows the following.
(I) ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure to obtain a norbornene-based ring-opening polymer; and (ii) the norbornene-based ring-opening polymer having an average pore diameter of 3 to 50 nm. A norbornene-based ring-opening weight having a step of hydrogenation by contacting with hydrogen under the conditions of a reaction temperature of 150 ° C. or more and 250 ° C. or less and a hydrogen pressure of 0.01 MPa or more and 10 MPa or less in the presence of a hydrogenation catalyst supported on palladium on a certain silica. The method for producing the combined hydrogenated product has a high hydrogenation selectivity even when the hydrogenation reaction temperature changes by a dozen degrees, and the resulting norbornene-based ring-opening polymer hydrogenated product is excellent in transparency ( Examples 1 to 3).
On the other hand, the norbornene-based ring-opening polymer hydrogenated product obtained when the temperature of the hydrogenation reaction is lower than 150 ° C. is inferior in transparency (Comparative Example 1).
In addition, when a catalyst on which palladium is supported on silica having an average pore diameter larger than 50 nm is used as the hydrogenation catalyst, the hydrogenation rate of the main chain is low (Comparative Example 2). Furthermore, when a catalyst on which palladium is supported on silica having an average pore diameter of less than 3 nm is used as the hydrogenation catalyst, the hydrogenation rate of the main chain is low (Comparative Example 3). If a catalyst having nickel supported on silica having an average pore diameter of 3 to 50 nm is used as the hydrogenation catalyst, the selectivity of the hydrogenation reaction is poor, and the refractive index of the resulting hydrogenated product is poor (Comparative Example 4).

Claims (7)

(I) ring-opening polymerization of a norbornene-based monomer having an aromatic ring structure to obtain a norbornene-based ring-opening polymer; and (ii) the norbornene-based ring-opening polymer having an average pore diameter of 3 to 50 nm. Hydrogenation by contacting with hydrogen under the conditions of a reaction temperature of 150 ° C. or more and 250 ° C. or less and a hydrogen pressure of 0.01 MPa or more and 10 MPa or less in the presence of a hydrogenation catalyst supported on palladium on a certain silica;
A process for producing a hydrogenated norbornene-based ring-opening polymer.   The hydrogenated norbornene-based ring-opening polymer has a hydrogenation rate of carbon-carbon double bonds in the main chain of 95% or more and a hydrogenation rate of carbon-carbon double bonds in the aromatic ring of 10% or less. Item 4. A process for producing a hydrogenated norbornene-based ring-opening polymer according to Item 1.   A norbornene-based ring-opening polymer hydrogenated product obtained by the production method according to claim 1 or 2.   The norbornene-based ring-opening polymer hydrogenated product according to claim 3, wherein the solution light transmittance measured with a 10 wt% toluene solution at an optical path length of 10 mm and a wavelength of 450 nm is 90% or more.   A resin composition comprising the norbornene-based ring-opening polymer hydrogenated product according to claim 4 or 5.   The molded object formed by shape | molding the resin composition of Claim 5.   The molded article according to claim 6, which is an optical component.