JP2007119509A - Method for preparing cyclic olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably preparing cyclic olefin polymers showing same physical properties at a high polymerization rate, wherein properties such as molecular weight do not vary between different lots. <P>SOLUTION: Indenes with a purity of 90 wt.% or higher are fused with cyclopentadienes with a purity of 90% or higher to obtain 1,4-methanol-1,4,4a, 9a-tetrahydrofluorenes, having the Hasen unit color number of at most 50, which are subsequently polymerized and, if required, hydrogenated to obtain the cyclic olefin polymers. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a cyclic olefin polymer. Specifically, a cyclic olefin polymer for obtaining a molded product having no coloration, improved thermal stability and hue, is stable at a high polymerization conversion rate, without physical properties such as molecular weight being varied from production unit to production unit. The present invention relates to a method for producing a cyclic olefin polymer that can be produced.

1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as “MTF”) and substituted products thereof (in this specification, MTF and substituted products thereof are collectively referred to as 1,4 -Methano-1,4,4a, 9a-tetrahydrofluorenes)) is a polymer obtained by polymerizing a monomer composition that is excellent in heat resistance, mechanical strength, and transparency. It is used.
Incidentally, it has been proposed to modify the monomer in order to increase the polymerization conversion rate when producing the polymer. For example, Patent Document 1 proposes a monomer composition for metathesis ring-opening polymerization in which a norbornene derivative is blended with 10 to 10,000 ppm of a phenol compound. Patent Document 2 proposes a composition obtained by bringing a cyclic olefin into contact with an alkali, purifying the cyclic olefin, and blending the purified cyclic olefin with an antioxidant.

JP 7-179730 A JP 2005-145855 A

  The present inventor conducted studies on purifying 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes and further adding an antioxidant according to Patent Document 1 and Patent Document 2. However, it has been found that the polymerization activity of MTF is not necessarily high and varies from production unit to production unit. If the polymerization activity is not high, the polymerization conversion rate becomes low, unreacted MTFs remain, and it may be difficult to apply to medical equipment, electronic component processing equipment, and the like. In addition, if there are fluctuations in physical properties such as molecular weight, it becomes difficult to control molding conditions, and the manufacturing efficiency of optical parts and the like that require precise dimensional accuracy is reduced.

  An object of the present invention is to provide a method for producing a cyclic olefin polymer which can be stably produced at a high polymerization conversion rate, with physical properties such as molecular weight not varying from production unit to production unit.

  As a result of studying to achieve the above-mentioned object, the present inventor has refined indene and cyclopentadiene, which are raw materials for synthesizing MTFs, synthesized MTFs, and polymerized the obtained MTFs. Further, it has been found that polymerization of MTFs having a Hazen unit color number of 50 or less increases the polymerization activity and eliminates fluctuations in molecular weight and the like for each production unit. The present invention has been completed based on these findings.

Thus, according to the present invention,
(1) A process for producing a cyclic olefin polymer comprising polymerizing 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes having a Hazen unit color number of 50 or less is provided,
(2) 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes are obtained by condensation of indene having a purity of 90% by weight or more and cyclopentadiene having a purity of 90% by weight or more. A process for producing the cyclic olefin polymer,
(3) The method for producing the above cyclic olefin polymer in which at least one of indene and cyclopentadiene is in contact with an alkali compound, and / or (4) further comprising hydrogenation after polymerization A method for producing the cyclic olefin polymer is provided.

Furthermore, according to the present invention,
(5) a cyclic olefin polymer obtained by the production method,
(6) a polymer composition containing the cyclic olefin polymer,
(7) A molded product obtained by molding the polymer composition, and (8) the purity of indene and cyclopentadiene is 90% by weight or more, and at least one of indene and cyclopentadiene is an alkali. 1,4-Methano-1,4,4a, 9a-tetrahydrofluorenes obtained by condensation of the indene and the cyclopentadiene, which are brought into contact with a compound, are provided.

According to the production method of the present invention, physical properties such as molecular weight do not vary from production unit to production unit, and a cyclic olefin polymer can be produced stably at a high polymerization conversion rate.
By using the cyclic olefin polymer obtained by the production method of the present invention, it is possible to obtain a molded product having no coloring and having improved thermal stability and hue.
Further, the 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes of the present invention are excellent in stability and the Hazen unit color number hardly changes over time.

The method for producing the cyclic olefin polymer of the present invention includes polymerizing 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes having a Hazen unit color number of 50 or less.
1,4-Methano-1,4,4a, 9a-tetrahydrofluorene is a cyclic olefin represented by the formula [I] and a substituted product thereof.

  Examples of the substituent include monovalent substituents such as an alkyl group, an alkenyl group, a vinyl group, an alkoxycarbonyl group, a halogen, and a cyano group. From the viewpoint of polymerization reactivity, the substituent is preferably bonded to the 6, 7, 8 or 9 position of the cyclic olefin represented by the formula [I].

  The 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes used in the present invention have a Hazen unit color number of 50 or less, preferably 45 or less, more preferably 40 or less. The Hazen unit color number is a characteristic value defined in JIS K 0071-1 (1998).

In order to reduce the Hazen unit color number of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes to 50 or less, synthesis of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes As indene and cyclopentadiene which are raw materials, those having the following high purity are used.
Indene is indene and its substitute. Cyclopentadiene is cyclopentadiene and its substitutes and their dimers. Examples of the substituent include monovalent substituents such as an alkyl group, an alkenyl group, a vinyl group, an alkoxycarbonyl group, a halogen, and a cyano group. Examples of substituted indene include alkylindene such as methylindene and ethylindene. Examples of the substituted cyclopentadiene include alkylcyclopentadiene such as methylcyclopentadiene. The dimer of cyclopentadiene is dicyclopentadiene. This dimer is easily decomposed into a monomer by heat and is subjected to a condensation reaction.

  Inden fractions are generally produced by distilling coal tar or petroleum distillation residues. However, this indene fraction, together with indene, is a compound having a boiling point similar to that of the indene, such as organic sulfur compounds (sulfides such as dimethyl sulfide, thiols such as methyl mercaptan, disulfides such as dimethyl disulfide, And thiophenes such as benzothiophene and dibenzothiophene), phenols, alkylpyridines, benzonitrile, undecane, alkylbenzenes and the like.

  In the present invention, this indene fraction is purified, and the indene having a purity of preferably 90% by weight or more, more preferably 92% by weight or more is used. Examples of methods for increasing the purity include alkali cleaning, acid cleaning, water cleaning, distillation, and the like, and methods described in JP-A-7-196539, JP-A-2001-233804, JP-A-8-134466, and the like. Yes, these may be combined. In particular, alkali cleaning in contact with an alkali compound is preferred. When contacted with an alkali compound, the indene after contact is preferably washed with water.

  The cyclopentadiene fraction includes those obtained by rectification of the C5 fraction and dicyclopentadienes obtained by dimerizing it. The C5 fraction contains a large amount of a compound having 5 carbon atoms, which is obtained as a by-product when pyrolyzing naphtha to produce ethylene. Therefore, the cyclopentadiene fraction contains a compound having a boiling point close to that of cyclopentadiene, for example, an organic sulfur compound, together with cyclopentadiene, a substituted product thereof, and a dimer thereof.

  In the present invention, the cyclopentadiene fraction is purified and the purity of the cyclopentadiene is preferably 90% by weight or more, more preferably 92% by weight or more. As a method for increasing the purity, there are a method of bringing into contact with acidic clay or silica alumina (JP-A-5-201885, JP-A-2001-181217) and distillation (JP-A-5-0778263). May be combined. Further, it is preferable to contact an alkali with cyclopentadiene having a purity of 90% by weight or more because an MTF having a Hazen dye number of 50 or less can be easily obtained.

The alkali compound to be contacted with indene or cyclopentadiene is used in the form of an aqueous alkali solution or solid alkali.
Examples of alkaline aqueous solutions include aqueous solutions of alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium citrate, sodium malate and sodium oxalate; alkaline earths such as calcium hydroxide and magnesium hydroxide An aqueous solution of a metal salt can be mentioned. The concentration of these alkaline aqueous solutions is usually 0.001 N or more, preferably 0.05 to 10.0 N.
Examples of the solid alkali include basic ion exchange resins, hydrotalcite, and ion-supporting silica.

The alkaline aqueous solution is used in a volume ratio of usually 0.001 to 100, preferably 0.1 to 10 with respect to the volume 1 of indene or cyclopentadiene. The contact time with the aqueous alkali solution is usually 1 to 100 minutes, preferably 5 to 30 minutes, and the contact temperature is not particularly limited, but is usually in the range of 0 to 100 ° C, preferably 20 to 80 ° C. When contacting with the aqueous alkali solution, stirring may be performed.
After contacting indene or cyclopentadiene with an aqueous alkali solution, indene or cyclopentadiene is separated from the aqueous phase. In the present invention, washing of indene or cyclopentadiene that has been brought into contact with an aqueous alkali solution and separation from the aqueous phase may be repeated a plurality of times.

  As a specific method of bringing indene or cyclopentadiene into contact with solid alkali, a method of placing a mixture of indene or cyclopentadiene and water in a container filled with solid alkali and allowing to stand, filling with solid alkali And a method of circulating a mixture of indene or cyclopentadiene and water through the column.

  The indene or cyclopentadiene brought into contact with the alkali compound can be further washed with water such as ion-exchanged water. Water is usually used in a volume ratio of 0.001 to 100, preferably 0.1 to 10, with respect to the volume 1 of indene or cyclopentadiene. The washing time with water is usually 1 to 100 minutes, preferably 5 to 30 minutes, and the washing temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 20 to 80 ° C. When washing with water, stirring may be performed.

  After washing with water, the indene or cyclopentadiene is separated from the aqueous phase. This washing with water and subsequent separation from the aqueous phase may be repeated multiple times.

  MTFs having a Hazen unit color number of 50 or less can be obtained by condensation reaction of the indenes purified as described above and cyclopentadiene. Preferably, both indene and cyclopentadiene have a purity of 90% by weight or more, more preferably, at least one of indene and cyclopentadiene is brought into contact with an alkali compound. MTFs having a color number of 50 or less can be obtained.

The MTFs obtained by the above method may be further purified. By refining, the content of the organic sulfur compound is preferably 20 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. From the viewpoint of productivity of MTFs, the content of the organic sulfur compound is preferably 1 ppb or more, more preferably 10 ppb or more, particularly preferably 100 ppb or more, and most preferably 500 ppb or more.
In addition, content of an organic sulfur compound is the value measured as a carbon disulfide conversion value using the gas chromatography (GC) provided with the sulfur chemiluminescence detector (SCD). The purification method is not particularly limited, and examples include alkali cleaning, acid cleaning, water cleaning, and distillation.

  Examples of the method for polymerizing MTFs include a ring-opening polymerization method and an addition polymerization method. The polymerization reaction can be performed by any of a bulk polymerization method, a solution polymerization method, and a suspension polymerization method. The polymerization reactor is not particularly limited, and may be a batch reactor or a continuous reactor.

(Ring-opening polymerization)
The ring-opening polymerization of MTFs can be performed with 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 ring-opening polymerization 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 a molar ratio to the total monomer amount. 1/100.

In ring-opening polymerization, MTFs and a monomer capable of ring-opening copolymerization with MTFs can be copolymerized.
Examples of the monomer capable of ring-opening copolymerization with MTFs include norbornene monomers other than MTFs and monocyclic olefins.
In the present invention, the norbornene-based monomer is a compound having a norbornene structure, and specifically includes bicyclo [2.2.1] hept-2-ene (common name: norbornene) and a substituted product thereof, tricyclo [ 4.3.0.1 ^2,5 ] Deca-3,7-diene (common name: dicyclopentadiene) and its substitute, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene (common name: tetracyclododecene) and its substituted product. Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group. The norbornene-based monomer may have two or more of these substituents.
Examples of monocyclic olefins include cyclohexene, cycloheptene, cyclooctene and the like.
In the case of ring-opening copolymerization of MTFs and this ring-opening copolymerizable monomer, structural units derived from other monomers copolymerizable with the structural units of MTFs in the ring-opening copolymer Is appropriately selected so that the weight ratio is usually 98/2 to 5/95, preferably 95/5 to 10/90, more preferably 90/10 to 15/85.

The ring-opening polymerization reaction is usually in the temperature range of −50 ° C. to 200 ° C., preferably −30 ° C. to 180 ° C., more preferably −20 ° C. to 150 ° C., usually 0 to 50 kgf / cm ² , preferably 0 to It is performed in a pressure range of 20 kgf / cm ² . 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.

In the ring-opening polymerization reaction, it is preferable to use a chain transfer agent. The chain transfer agent is not particularly limited, but α-olefins such as 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-dodecene; 1,4-hexadiene, etc. Among them, α-olefins and the like are preferable, and 1-hexene is more preferable. When a chain transfer agent is used, the weight average molecular weight and number average molecular weight of the polymer can be adjusted. The addition amount of the α-olefin is appropriately adjusted depending on the conditions such as the type and amount of the polymerization catalyst, the type and amount of the monomer, the type of α-olefin, etc. Generally, when the addition amount is large, the weight average molecular weight, number average When the molecular weight is small and the addition amount is small, both the weight average molecular weight and the number average molecular weight are large.
As a method for adding the chain transfer agent, it is preferable to measure and add the addition amount with high accuracy in order to stably obtain a polymer having a desired molecular weight. For example, the chain transfer agent is preferably diluted with a reaction solvent or the like in advance, or weighed and added using an apparatus with high measurement accuracy. When the weighing accuracy is usually 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less of the required amount of the chain transfer agent, a polymer having an optimum molecular weight can be obtained.

(Addition polymerization)
The addition polymerization reaction of MTFs can be performed with a known addition polymerization catalyst.
Examples of addition polymerization catalysts include Ziegler catalysts and metallocene catalysts.
Examples of the Ziegler catalyst include a catalyst composed of a reducing agent such as a vanadium compound and an alkylaluminum compound. Specifically, it is produced using a catalyst formed from a soluble vanadium compound and an organoaluminum compound. Specific examples of the vanadium compound include VOCl _3, VO (OC ₂ H ₅ ) Cl _2, VO (OC ₂ H ₅ ) ₂ Cl _, VO (O-iso-C ₃ H ₇ ) Cl _2, VO (On-N— _{C 4 H 9) Cl 2,} VO (OC 2 H 5) 3, VOBr 2, VCl 4, VOCl 2, and _{VO (O-n-C 4} H 9) 3 and the like. These vanadium compounds can be used alone or in combination.

  As the metallocene catalyst, usually a metallocene (transition metal component), an organoaluminum compound or JP-A-1-501950, JP-A-1-503636, JP-A-3-179005, JP-A-3-179006. Trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron described in JP-A-3-207703, JP-A-3-207704, USP-5321106, JP-A-2004-155899, Tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5 -Lewis acid such as dimethylphenyl) boron, It is selected from ionic compounds such as rucarbonium tetrakis (pentafluorophenyl) borate, borane compounds such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and carborane compounds. Examples include a catalyst formed by adding a cocatalyst component.

Examples of the metallocene transition metal include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. Zirconium and hafnium are preferred, and zirconium is more preferred from the viewpoint of easy control of the activity of the catalyst.
As the promoter component, an organoaluminum compound, a Lewis acid, or an ionic compound is preferable, and an organoaluminum compound or an ionic compound is particularly preferable from the viewpoint of easily controlling the activity of the catalyst.

  Specific examples of metallocenes include rac-dimethylsilyl-bis (1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis (1-indenyl) zirconium dichloride. Rac-phenylvinylsilyl-bis (1-indenyl) zirconium dichloride, 1-silacyclobutyl-bis (1-indenyl) zirconium dichloride, rac-diphenylsilyl-bis (1-indenyl) hafnium dichloride, rac-phenylmethylsilyl -Bis (1-indenyl) hafnium dichloride, rac-diphenylsilyl-bis (1-indenyl) zirconium dichloride, diphenylmethylene (9-fluorenyl) cyclopentadienyl di Benzalkonium dichloride, isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride, and the like. Of these, rac-dimethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis (1-indenyl) zirconium are particularly preferred. Examples include dichloride, rac-diphenylsilyl-bis (1-indenyl) hafnium dichloride, diphenylmethylene (9-fluorenyl) cyclopentadienylzirconium dichloride, or isopropylene (9-fluorenyl) cyclopentadienylzirconium dichloride. These metallocenes can be used alone or in combination of two or more.

  Examples of organoaluminum compounds used in Ziegler and metallocene catalysts include trialkylaluminum, dialkylaluminum alkoxide, alkylaluminum sesquialkoxide, partially alkoxylated alkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide. And alkylaluminum partially hydrogenated and partially alkylated and halogenated alkylaluminum, aluminoxane and the like. Of these, alkyl aluminum halide, alkyl aluminum dihalide, alkyl aluminum, and aluminoxane are particularly preferably used. These organoaluminum compounds can be used alone or in combination of two or more.

In addition, at the time of addition polymerization, MTFs and a monomer capable of addition copolymerization can be copolymerized.
Examples of monomers that can be addition copolymerized with MTFs include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Α-olefins having 2 to 20 carbon atoms such as hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, and derivatives thereof; 1,4-hexadiene; Non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and the like. Among these, an α-olefin, particularly ethylene is preferable.

  These monomers capable of addition copolymerization with MTFs can be used alone or in combination of two or more. In the case of addition copolymerization of MTFs and a monomer capable of addition copolymerization, the ratio of the structural units of MTFs in the addition copolymer to the structural units derived from other monomers capable of copolymerization However, it is appropriately selected so that the weight ratio is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, and more preferably 70:30 to 95: 5.

  The solvent used in the solution polymerization method is not particularly limited, but a hydrocarbon solvent is preferable. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic chain hydrocarbons such as n-pentane, hexane, and heptane; aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclooctane; Etc. Among these, aromatic hydrocarbons and aliphatic cyclic hydrocarbons are preferable, toluene, cyclohexane and cyclooctane are more preferable, and toluene and cyclohexane are particularly preferable. These hydrocarbon solvents can be used alone or in combination of two or more.

  According to the production method of the present invention, the polymerization conversion of the ring-opening polymerization reaction or the addition polymerization reaction can be usually 95% by weight or more, preferably 97% by weight or more, particularly preferably 99% by weight or more. When the polymerization conversion rate increases, a molded product with a small amount of released organic matter can be obtained. The polymerization conversion rate is a value obtained by dividing the difference between the weight of the raw material monomer and the weight of the unreacted monomer by the weight of the raw material monomer.

(Hydrogenation reaction)
The production method of the present invention preferably further includes hydrogenation after polymerization.
By hydrogenation, a carbon-carbon unsaturated bond in a ring, a main chain, and a side chain can be changed to a saturated bond. In the present invention, hydrogenation can be carried out with a hydrogenation catalyst.

  Examples of the hydrogenation catalyst include JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550, and the like. What is described can be used and can be homogeneous or heterogeneous. The homogeneous catalyst is easy to disperse in the hydrogenation reaction solution, so that the addition amount may be small, and since it has high activity, it can be hydrogenated with a small amount of catalyst in a short time. The heterogeneous catalyst becomes highly active by increasing the temperature and pressure, and is excellent in production efficiency such that it can be hydrogenated in a short time and can be easily removed.

  The homogeneous catalyst includes a Wilkinson complex, that is, a catalyst comprising a combination of chlorotris (triphenylphosphine) rhodium (I); a transition metal compound and an alkyl metal compound, specifically, cobalt acetate / triethylaluminum, nickel acetylacetonate / Triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxy titanate / dimethylmagnesium, and the like.

  Examples of the heterogeneous catalyst include a catalyst in which a known metal for hydrogenation catalyst such as Ni and Pd is supported on a carrier. Of these, Ni is preferably used from the viewpoint of activity and hydrogenation efficiency. As the carrier, it is preferable to use an adsorbent such as alumina or diatomaceous earth when it is preferable that the amount of impurities or the like is less.

  The hydrogenation reaction 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 solvent is usually used because it is excellent in solubility of the hydride to be produced.

  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; Among these, cyclic aromatic hydrocarbons and alicyclic hydrocarbons are preferable. These organic solvents can be used alone or in combination of two or more.

The hydrogenation reaction can be performed according to a conventional method, but the hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature. The reaction temperature is preferably in the range of 100 to 200 ° C, more preferably in the range of 130 to 195 ° C. When the hydrogenation reaction is carried out at a temperature exceeding 200 ° C., an isomerization reaction is likely to occur in each repeating unit of the polymer, and the heat resistance of the norbornene polymer decreases as the isomerization reaction proceeds.
The hydrogen pressure is usually 0.1 to 100 kgf / cm ² , preferably 0.5 to 60 kgf / cm ² , more preferably 1 to 50 kgf / cm ² .

In order to selectively hydrogenate the unsaturated bond of the main chain while leaving the aromatic ring structure derived from MTFs without hydrogenation, the hydrogen pressure is usually 0.1 to 50 kg / cm ^2. , Preferably 0.5 to 40 kg / cm ² , more preferably 1 to 30 kg / cm ² . When using a homogeneous catalyst, the reaction temperature of the hydrogenation reaction is usually −10 to 150 ° C., preferably 0 to 130 ° C., more preferably 20 to 110 ° C. When a heterogeneous catalyst is used, the reaction is usually performed at 0 to 300 ° C, preferably 100 to 250 ° C, more preferably 150 to 230 ° C. If the hydrogen pressure is too high or the reaction temperature is too high, it becomes difficult to control the reaction, and even with a short reaction time, the aromatic ring is easily hydrogenated together with the double bond in the main chain structure. It becomes difficult to control the rate with good reproducibility. In addition, if the temperature is too high or the hydrogen pressure is too high, it is difficult to control the reaction, the aromatic ring is easily hydrogenated even in a short reaction, and the hydrogenation rate of the aromatic ring is controlled with good reproducibility. It is difficult to control the refractive index of the hydride obtained. When the temperature is too low or the hydrogen pressure is too low, the hydrogenation reaction of the main chain structure does not proceed easily. As the solvent used for the reaction, it is preferable to use aliphatic hydrocarbons such as aliphatic hydrocarbons and alicyclic hydrocarbons from the viewpoint of the efficiency of the hydrogenation reaction.

  A hydrogenation catalyst suitable for hydrogenating only unsaturated bonds in the main chain without hydrogenating the aromatic ring is a catalyst comprising a combination of a transition metal compound and an alkyl metal compound. Examples include combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like. It is preferable to select a catalyst known from JP-A-7-2929, JP-A-7-41550, JP-A-7-149823, JP-A-9-31169, JP-A-9-77853, and the like. . By using these hydrogenation catalysts and strictly controlling the hydrogenation reaction conditions, it is possible to saturate only the unsaturated bonds in the main chain structure while leaving the unsaturated bonds in the aromatic ring structure.

The removal of the catalyst after completion of the hydrogenation reaction may be performed according to conventional methods such as centrifugation and 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.
In applications where it is not preferable to elute the remaining transition metal, such as medical equipment, it is preferable that the transition metal does not substantially remain. However, in order to obtain such a polymer hydride, JP-A-5-317411 It is preferable to use an adsorbent such as alumina having a specific pore volume and specific surface area as disclosed in Japanese Laid-Open Patent Publications, etc., or to wash the resin solution with acidic water and pure water.
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.

  In the hydrogenated cyclic olefin polymer, the ratio of the number of aliphatic carbon-carbon double bonds to the total number of carbon-carbon bonds in the hydride of the polymer is preferably 0.15% or less, It is more preferably 0.07% or less, and particularly preferably 0.02% or less. When the ratio of the number of aliphatic carbon-carbon double bonds is small, a molded product with a small amount of released organic matter is obtained, which is preferable.

  The cyclic olefin polymer (including hydrogenated cyclic olefin polymer) obtained by the production method of the present invention is blended with various compounding agents as necessary to form a resin composition, which is molded into various molded products. Can also be used. 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 thereof, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.

  Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. Among them, phenol-based antioxidants, particularly alkyl-substituted phenol-based antioxidants are preferable. By blending these antioxidants, it is possible to prevent coloration and strength reduction of the molded product due to oxidative degradation during molding without lowering transparency, low water absorption and the like. These antioxidants may be used alone or in combination of two or more. Although the compounding quantity of antioxidant is suitably selected in the range which does not impair the objective of this invention, it is 0.001-5 weight part normally with respect to 100 weight part of cyclic olefin polymers, Preferably it is 0.01-1 weight. Part.

  The method for uniformly dispersing the compounding agent in the cyclic olefin polymer is, for example, by dissolving the compounding agent in a suitable solvent and adding it to the solution of the cyclic olefin polymer, and then removing the solvent and including the compounding agent. Examples thereof include a method for obtaining a polymer resin composition, a method for kneading a compounding agent by melting a cyclic olefin polymer with a mixer, a twin-screw kneader, a roll, a Brabender, an extruder, or the like.

  The resin composition obtained by the above method can be molded into various molded bodies and used for various applications. Although there is no special limitation as a molding method, it is preferable to use a melt molding method in order to obtain a molded product excellent in low birefringence, mechanical strength, dimensional accuracy, and the like. Examples of the melt molding method include an injection molding method, an injection compression molding method, an extrusion molding method, an extrusion stretch molding method, a multilayer extrusion molding method, a press molding method, a blow molding method, an injection blow molding method, and an inflation molding method. 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 product of the present invention is useful in various fields as various molded products.
Applications of molded products include optical components such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquids, powders, Or solid medicine containers (liquid medicine containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags, press-through packages, solid medicine containers, eye drops containers, etc.), sampling containers (sampling for blood tests) Test tubes, caps for chemical containers, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterile containers for medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), experimental / analytical instruments ( Beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical parts (plastic lenses for medical examinations, etc.), piping materials (medical use) Medical equipment such as liquid tubes, pipes, joints, valves, etc.), artificial organs and their components (tooth base, artificial heart, artificial roots, etc.); processing or transfer containers (tanks, trays, carriers, cases, etc.) , Protective materials (carrier tape, separation film, etc.), piping (pipes, tubes, valves, flow meters, filters, pumps, etc.), liquid containers (sampling containers, bottles, ampoules bags, etc.) Equipment: Coating materials (for electric wires, cables, etc.), consumer / industrial electronic equipment (copiers, computers, printers, TVs, VCRs, video cameras, etc.), structural members (parabolic antenna structural members, flat antennas) Electrical insulation materials such as structural members, radar dome structural members, etc .; General circuit boards (rigid printed boards, flexible printed boards) Circuit boards such as multilayer printed wiring boards), high-frequency circuit boards (satellite communication equipment circuit boards, etc.); substrates for transparent conductive films (liquid crystal substrates, optical memories, surface heating elements, etc.); semiconductor encapsulants (transistors) Sealing materials, IC sealing materials, LSI sealing materials, LED sealing materials, etc.), electrical and electronic component sealing materials (motor sealing materials, capacitor sealing materials, switch sealing materials, sensor sealing materials, etc.) ) Sealing materials; automotive interior materials such as room mirrors and meter covers; automotive exterior materials such as door mirrors, fender mirrors, beam lenses, and light covers.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples. Unless otherwise specified, parts and% are based on weight, and pressure is gauge pressure. The measuring method of the physical property in an Example and a comparative example is as follows.

(1) Hazen unit color number of MTFs Measured according to JIS K0071-1 (1998).
(2) Molecular weight The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The molecular weight distribution (MWD) is a value (Mw / Mn) obtained by dividing the weight average molecular weight by the number average molecular weight.
(3) Polymerization conversion rate The polymerization conversion rate was calculated by gas chromatography.

[Production Example 1]
100 parts of indene fraction from heavy tar gas oil (91% indene, 0.9% o-cresol, 0.36% phenol, 0.05% 1,2-dihydroxyindane) and 0.1N sodium hydroxide 100 parts of the aqueous solution was mixed and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated three times. To the organic layer, 95 parts of ion exchange water was added and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated 3 times to obtain 90 parts of alkali contact indene.

[Production Example 2]
100 parts of dicyclopentadiene (purity 94%) and 100 parts of a 0.1N aqueous sodium hydroxide solution were mixed and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated three times. To the organic layer, 95 parts of ion exchange water was added and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated 3 times to obtain 90 parts of alkali-contacted dicyclopentadiene.

[Example 1]
In an autoclave equipped with a stirrer, 100 parts of the alkali contact indene obtained in Production Example 1 and 230 parts of the alkali contact dicyclopentadiene obtained in Production Example 2 were charged, purged with nitrogen, and then reacted at 180 ° C. for 6 hours with stirring. I let you. The reaction product was purified by distillation under conditions of 0.07 kPa and a reflux ratio of 10 to obtain 125 parts of MTF (A) as a fraction at 88 to 92 ° C. When measured by gas chromatography, the purity of MTF (A) was 99.4% and the Hazen unit color number was 19. Further, the MTF (A) obtained after leaving the obtained MTF (A) in a nitrogen atmosphere at 30 ° C. for 2 weeks was visually transparent and had a Hazen unit color number of 20.

[Example 2]
The same operation as in Example 1 was carried out except that dicyclopentadiene (purity 94%) was used in place of the alkali-contacted dicyclopentadiene obtained in Production Example 2, and 124 parts of MTF (B) was obtained. The purity of MTF (B) measured by gas chromatography was 99.4%, and the Hazen unit color number was 20. The obtained MTF (B) was allowed to stand at 30 ° C. for 2 weeks under a nitrogen atmosphere, and was visually transparent and had a Hazen unit color number of 45.

[Comparative Example 1]
Instead of the alkali contact indene obtained in Production Example 1, an indene fraction (91% indene, 0.9% o-cresol, 0.36% phenol, 0.05% 1,2-dihydroxyindane) was used. Performed the same operation as Example 2, and obtained 120 parts of MTF (C '). 120 parts of the MTF (C ′) and 40 parts of a 0.1N aqueous sodium hydroxide solution were mixed and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated three times. The organic layer was mixed with 40 parts of ion exchange water and stirred for 5 minutes. The operation of allowing to stand and separating the organic layer was repeated three times. Next, simple distillation was performed to obtain 110 parts of MTF (C). The purity of MTF (C) measured by gas chromatography was 99.1%, and the Hazen unit color number was 26. Further, the MTF (C) after the obtained MTF (C) was allowed to stand at 30 ° C. for 2 weeks in a nitrogen atmosphere was visually colorless and transparent, and its Hazen unit color number was 55.

  From Examples 1 and 2 and Comparative Example 1, it can be seen that MTF synthesized using indene or dicyclopentadiene purified by contact with an alkali compound has a small Hazen unit color number.

[Example 3]
In a dry and nitrogen-substituted polymerization reactor, 10 parts of MTF (A) having a Hazen unit color number of 20, 300 parts of dehydrated cyclohexane, 0.90 part of 1-hexene as a molecular weight regulator, 0.2 part of diisopropyl ether Then, 0.18 parts of isobutyl alcohol, 0.48 parts of triisobutylaluminum and 6 parts of a 0.7% tungsten hexachloride toluene solution were charged, and the mixture was stirred at 50 ° C. After 10 minutes, 90 parts of MTF (A) having a Hazen unit color number of 20 and 10 parts of tungsten hexachloride 0.7% toluene solution were continuously dropped into the polymerization reactor over 2 hours. After completion of the dropwise addition, the mixture was further stirred for 30 minutes. Thereafter, 0.5 part of isopropyl alcohol was added to stop the polymerization reaction to obtain a ring-opened polymer.
The same polymerization operation was performed 3 times, and the conversion rate of each polymerization reaction and the molecular weight of the obtained ring-opened polymer are shown in Table 1.

[Example 4]
A ring-opened polymer was obtained in the same manner as in Example 3 except that MTF (B) having a Hazen unit color number of 45 was used instead of MTF (A). Table 1 shows the conversion rate of each polymerization reaction repeated three times and the molecular weight of the resulting ring-opened polymer.

[Comparative Example 2]
A ring-opening polymer was obtained in the same manner as in Example 3 except that MTF (C) having a Hazen unit color number of 55 was used instead of MTF (A). Table 1 shows the conversion rate of each polymerization reaction repeated three times and the molecular weight of the resulting ring-opened polymer.

[Example 5]
In a nitrogen-substituted autoclave, 100 parts of MTF (A) having a Hazen unit color number of 20 and 300 parts of toluene were charged and stirred for 5 minutes. Further, 0.15 part of triisobutylaluminum was added. While stirring the inside of the autoclave, ethylene was passed at normal pressure to make the inside of the autoclave an ethylene atmosphere. The internal temperature of the autoclave was kept at 60 ° C., and ethylene was poured into the autoclave so that the internal pressure was 0.6 MPa. After 10 minutes, the polymerization reaction was initiated by adding 0.5 parts of a 5% toluene solution of ethylenebis (indenyl) zirconium dichloride and 5 parts of a 10% toluene solution of methylalumoxane to the autoclave. Ethylene was supplied so that the ethylene pressure in the autoclave was maintained at 0.6 MPa, and the reaction was performed at a temperature of 60 ° C. for 1 hour. Thereafter, isopropyl alcohol was added to stop the polymerization reaction to obtain an addition copolymer.
The same polymerization operation was performed three times, and Table 2 shows the MTF conversion rate, the composition and molecular weight of the addition copolymer in each polymerization reaction.

[Example 6]
An addition copolymer was obtained in the same manner as in Example 5 except that MTF (B) having a Hazen unit color number of 45 was used instead of MTF (A). Table 2 shows the conversion rate of MTF and the composition and molecular weight of the resulting addition copolymer in each polymerization reaction repeated three times.

[Comparative Example 3]
An addition copolymer was obtained in the same manner as in Example 5 except that MTF (C) having a Hazen unit color number of 55 was used instead of MTF (A). Table 2 shows the conversion rate of MTF and the composition and molecular weight of the resulting addition copolymer in each polymerization reaction repeated three times.

From the above results, when MTFs having a Hazen unit color number of 50 or less are used (Examples 3 to 6), a polymer that can be polymerized at a high polymerization conversion rate and has no variation in molecular weight and molecular weight distribution among production units. It can be seen that In particular, when MTFs having a Hazen unit color number of 40 or less are used (Examples 3 and 5), it is understood that polymers having exactly the same molecular weight and molecular weight distribution can be obtained. On the other hand, when MTFs having a Hazen unit color number exceeding 50 are used (Comparative Examples 2 and 3), the polymerization conversion may not be 90% or more, and the molecular weight and molecular weight distribution vary greatly from production unit to production unit. I understand that.

Claims (8)

  A process for producing a cyclic olefin polymer comprising polymerizing 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes having a Hazen unit color number of 50 or less. 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes
The process for producing a cyclic olefin polymer according to claim 1, wherein the cycloolefin polymer is obtained by condensation of indene having a purity of 90% by weight or more and cyclopentadiene having a purity of 90% by weight or more.   The method for producing a cyclic olefin polymer according to claim 2, wherein at least one of indene and cyclopentadiene is in contact with an alkali compound.   The method for producing a cyclic olefin polymer according to any one of claims 1 to 3, further comprising hydrogenation after the polymerization.   The cyclic olefin polymer obtained by the manufacturing method in any one of Claims 1-4.   A polymer composition comprising the cyclic olefin polymer according to claim 5.   The molded object formed by shape | molding the polymer composition of Claim 6. Condensation of the indene and the cyclopentadiene, wherein the indene and the cyclopentadiene have a purity of 90% by weight or more, and at least one of the indene and the cyclopentadiene is in contact with an alkali compound 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes obtained by