JP2006188559A - METHOD FOR PRODUCING POLYMER BY POLYMERIZING 1,4-METHANO-1,4,4a,9a-TETRAHYDROFLUORENE COMPOSITION - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer of an MTF from which the polymer having stable physical properties in a high conversion ratio of polymerization is prepared. <P>SOLUTION: The method is produced a polymer by polymerizing a 1,4-methano-1,4,4a,9a-tetrahydrofluorene composition containing ≤20 ppm organic sulfur content. The 1,4-methano-1,4,4a,9a-tetrahydrofluorene composition is suitably prepared by condensing a cyclopentadiene with an indene. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polymer by polymerizing a composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes, and more specifically, has a high polymerization conversion rate and stable physical properties. The present invention relates to a method for producing a polymer by polymerizing a composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes to obtain a polymer.

1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as “MTF”) and a compound having an MTF structure (in the present invention, MTF and a compound having an MTF structure are named generically). Polymers obtained by polymerizing 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes (hereinafter sometimes referred to as “MTFs”) have heat resistance, mechanical strength, It has excellent transparency and is used as an optical material.
Patent Document 1 discloses a method for producing a polymer obtained by addition copolymerization of MTFs and ethylene.
Patent Document 2 discloses a method for producing a polymer for ring-opening polymerization of MTFs.
JP-A-5-97719 WO99 / 09085

However, when a polymer of MTFs is produced by the production methods described in Patent Document 1 and Patent Document 2, the polymerization is stopped in the middle, the polymerization conversion rate does not increase, or a polymer having stable physical properties cannot be obtained. There was a thing. A molded product made of a polymer obtained by a production method having a low polymerization conversion rate contains unreacted MTFs, has a large amount of outgas, and cannot be used for medical equipment or electronic component processing equipment. There is. In addition, a molded article made of a polymer obtained by a production method in which a polymer having stable physical properties cannot be obtained cannot be used for an optical component that requires precision molding because of variations in glass transition temperature and fluidity. There is a problem.
Accordingly, an object of the present invention is to provide a method for producing a polymer of MTFs which can obtain a polymer having a high polymerization conversion rate and stable physical properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that industrially available MTFs are compositions containing a large amount of organic sulfur compounds, and these organic sulfur compounds are used for the polymerization reaction of MTFs. Was found to have an adverse effect. Furthermore, the present inventors stably obtain MTF polymers having a high polymerization conversion rate by setting the content of the organic sulfur compound in the MTF compositions used for the polymerization to a specific value or less. As a result, the present invention has been completed.
Thus, according to the present invention, there is provided a method for producing a polymer by polymerizing a composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene having an organic sulfur compound content of 20 ppm or less. Is done.
The above production method is suitable when the composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is obtained by condensing cyclopentadiene and indene.
Moreover, the polymer obtained by the said manufacturing method, the resin composition containing the polymer, and the molded object formed by shape | molding the resin composition are provided.

  The method for producing a polymer by polymerizing 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes of the present invention provides a polymer having a high polymerization conversion rate and stable physical properties.

  The method for producing a polymer of the present invention is characterized by using a composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes having an organic sulfur compound content of 20 ppm or less.

で表される１,４−メタノ−１,４,４ａ,９ａ−テトラヒドロフルオレン（以下「ＭＴＦ」と略す場合がある）及びＭＴＦ構造を有する化合物を総称したものである。
ＭＴＦ構造を有する化合物としては、ＭＴＦに置換基を有する置換体などが挙げられる。
置換基としては、アルキル基、アルキレン基、ビニル基、アルコキシカルボニル基などが挙げられ、前記置換体は、これらを２種以上有していてもよい。 In the present invention, 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes (hereinafter sometimes abbreviated as “MTFs”) means the following formula [I]

1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as “MTF”) and compounds having an MTF structure.
Examples of the compound having an MTF structure include a substituent having a substituent in MTF.
Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group, and the substituent may have two or more of these.

  In the present invention, the composition of MTFs is a composition containing MTFs, and in addition to MTFs, raw materials used in the production of MTFs and organic sulfur compounds contained in the raw materials, etc. And a by-product in the production of MTFs.

In general, MTFs are obtained by condensing cyclopentadiene and indene.
In the present invention, cyclopentadiene is cyclopentadiene and a substituent having a substituent thereon, and indene is indene and a substituent having a substituent thereon.

In general, indenes are produced by distilling coal tar or petroleum distillation residue. Accordingly, indenes are obtained as a fraction containing a compound having a boiling point close to that of the indenes, such as organic sulfur compounds, phenols, alkylpyridines, benzonitrile, undecane, alkylbenzenes and the like.
Further, in general, cyclopentadiene is produced by fractionating cyclopentadiene in the C5 fraction as dicyclopentadiene obtained by dimerization, or by fractionating cyclopentadiene itself. The C5 fraction is obtained as a by-product when pyrolyzing naphtha to produce ethylene. Therefore, cyclopentadiene is obtained as a fraction containing a compound having a boiling point similar to that of cyclopentadiene or dicyclopentadiene, such as an organic sulfur compound.

Therefore, industrially available MTFs are compositions containing a large amount of impurities such as organic sulfur compounds. In addition, the amount of impurities varies depending on the production area and production period of coal tar, petroleum, and naphtha, and the content of impurities in the composition of MTFs that are usually available as MTFs also varies.
For example, industrially available indene fractions contain about several hundred ppm of organic sulfur compounds as impurities, and dicyclopentadiene and cyclopentadiene fractions contain several organic sulfur compounds as impurities. Contains about 10 ppm.
Therefore, an industrially available composition of MTFs produced from an indene fraction and a cyclopentadiene or dicyclopentadiene fraction contains about several hundred ppm of an organic sulfur compound.

(Composition of MTFs)
The composition of MTFs used in the method for producing a polymer of the present invention has an organic sulfur compound content of 20 ppm or less. Among them, the content of the organic sulfur compound is preferably 10 ppm or less, and more preferably 1 ppm or less. Further, from the viewpoint of productivity of the composition 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. preferable.
In the present invention, the content of the organic sulfur compound in the composition of MTFs is a value measured as a carbon disulfide equivalent using a gas chromatography (GC) equipped with a sulfur chemiluminescence detector (SCD).

  In the present invention, the organic sulfur compound is an organic compound having a sulfur atom, and includes sulfides such as dimethyl sulfide, thiols such as methyl mercaptan, disulfides such as dimethyl disulfide, and thiophenes such as benzothiophene and dibenzothiophene. And the like.

A method for obtaining a composition of MTFs in which the content of the organic sulfur compound is in the above range is not particularly limited, but a method of bringing the composition of MTFs containing a large amount of the organic sulfur compound into contact with a component that adsorbs the organic sulfur compound And a method of precision distillation.
Among them, in order to obtain a composition of MTFs having a low content of organic sulfur compounds, (1) by removing the organic sulfur compounds other than those having a boiling point close to that of indenes by distilling the indene fraction, Obtain an indene fraction with a low content of sulfur compounds, and (2) organics other than those having a boiling point close to that of cyclopentadiene or dicyclopentadiene by distilling the fraction of cyclopentadiene or dicyclopentadiene The sulfur compound is removed to obtain a cyclopentadiene or dicyclopentadiene fraction having a low content of organic sulfur compound, and then (3) an indene fraction having a low content of organic sulfur compound, and cyclopentadiene. Obtaining a composition of MTFs from a fraction of pentadienes or dicyclopentadiene, and (4) distilling the composition of MTFs. It, indene, it is preferable to remove cyclopentadienes or dicyclopentadiene compound and a close organic sulfur compound boiling point.

(Method for producing a polymer for polymerizing a composition of MTFs)
In the method for producing a polymer by polymerizing a composition of MTFs of the present invention, a composition of MTFs having an organic sulfur compound content of 20 ppm or less is used.
The mode of polymerization is not particularly limited, and any of ring-opening polymerization and addition polymerization may be used, and any of bulk polymerization, solution polymerization, and suspension polymerization may be used. Moreover, a batch method or a continuous method may be used.

(Ring-opening polymerization)
When the polymerization reaction is ring-opening polymerization, the composition of the MTFs can be polymerized 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.

In ring-opening polymerization, MTFs and a monomer capable of ring-opening copolymerization therewith can be polymerized.
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 derivatives thereof (substituted on the ring). Group), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group, and the norbornene-based monomer may have two or more of these.
Examples of monocyclic olefins include cyclohexene, cycloheptene, cyclooctene and the like.

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 50 kgf / cm ² , preferably Is in the range of 0-20 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 present invention, 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 and 1-dodecene; Examples include hexadiene, among which 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 α-olefin is appropriately adjusted according to the conditions of the polymerization catalyst species, polymerization catalyst amount, monomer species, monomer amount, α-olefin species, and the like, but generally, when the addition amount is large, the weight average molecular weight The number average molecular weight decreases, and conversely when the addition amount is small, both the weight average molecular weight and the number average molecular weight increase.
As a method for adding the chain transfer agent, it is preferable to add it to the reaction system with high accuracy in order to stably obtain a polymer having a desired molecular weight. For example, it is preferable to dilute the chain transfer agent in advance with a reaction solvent or the like, or to weigh and add it using a device with high measurement accuracy. When the weighing accuracy is usually 3% or less, preferably 2% or less, more preferably 1% or less of the required amount of chain transfer agent, a polymer having an optimum molecular weight can be obtained.

(Addition polymerization)
When the polymerization reaction is an addition polymer, the composition of the MTFs can be polymerized in the presence of a known addition polymerization catalyst.
Examples of the addition polymerization catalyst include a Ziegler catalyst and a metallocene catalyst.

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- _{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, in addition to a metallocene (transition metal component), an organoaluminum compound or JP-A-1-501950, JP-A-1-502036, 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, and the like , Tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3 Lewis acids such as 5-dimethylphenyl) boron, tri It is selected from ionic compounds such as phenylcarbonium tetrakis (pentafluorophenyl) borate, borane compounds such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and carborane compounds. Produced using a catalyst formed by adding a promoter component. Examples of the transition metal of metallocene include titanium, zirconium, hafnium, vanadium, niobium, and tantalum, preferably zirconium and hafnium, and more preferably, using zirconium facilitates control of the activity of the catalyst. It is. The cocatalyst component is preferably an organoaluminum compound, Lewis acid, or ionic compound, and more preferably an organoaluminum compound or ionic compound is preferred from the viewpoint of control of polymerization activity.

  Examples of the metallocene 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) cyclopentadienylzirconium Chloride, isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride, and the like. Among these, rac-dimethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis (1-indenyl) zirconium are particularly preferable. 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 alkylaluminum partially alkoxylated and halogenated, 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, during the addition polymerization, MTFs can be copolymerized with a monomer capable of addition polymerization.
Examples of monomers that can be added 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, etc. are used. Among these, an α-olefin, particularly ethylene is preferable.

  These monomers capable of being added to MTFs and addition polymers can be used alone or in combination of two or more. In the case of addition copolymerization of MTFs and monomers capable of addition polymers, the ratio of structural units of MTFs in the addition copolymer to 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.

  When the 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 MTF polymers (hereinafter sometimes abbreviated as “MTF polymers”) obtained by ring-opening polymerization or addition polymerization is preferably 95% by weight or more, and 97% by weight or more. More preferably, it is 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.

The method for producing a polymer by polymerizing the composition of MTFs of the present invention provides a polymer having a high polymerization conversion rate and stable physical properties.
Therefore, the polymer obtained by the production method of the present invention can be used for various applications.

(Hydrogenation reaction)
In addition, the MTF polymers obtained by the production method of the present invention can hydrogenate a ring, a main chain and a side chain carbon-carbon unsaturated bond after the polymerization reaction.
The hydride of the MTF polymer is preferably such that the ratio of the number of carbon-carbon double bonds to the total number of carbon-carbon bonds in the hydride of the polymer is 0.15% or less, and 0.07% or less. Is more preferable, and 0.02% or less is particularly preferable. When the ratio of the number of carbon-carbon double bonds is small, a molded product with a small amount of released organic matter is obtained, which is preferable.

  Since the MTF polymers obtained by the production method of the present invention contain a small amount of organic sulfur compounds as impurities, it is difficult to poison the hydrogenation catalyst used in the hydrogenation reaction. Therefore, the MTF polymer is suitable as a raw material for the hydride of the MTF polymer.

  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 in a short time with a small amount of catalyst. The heterogeneous catalyst becomes highly active by increasing the temperature and pressure, and is excellent in production efficiency such as being hydrogenated in a short time and being easy to remove.

  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 those in which a hydrogenation catalyst metal such as Ni or Pd is supported on a support. Ni is used as the supported hydrogenation catalyst metal from the viewpoint of activity and hydrogenation efficiency. preferable. 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 the 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; 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 usually 200 ° C. or lower, preferably 195 ° C. or lower, most preferably 190 ° C. or lower.
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 performed 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-based polymer obtained as the hydrogenation reaction proceeds decreases with time. To do.
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 .

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.
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. It is preferable to use an adsorbent such as alumina having a specific pore volume and specific surface area as disclosed in Japanese Patent No. 317411 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.

  The MTF polymer and the hydride thereof according to the present invention can be used after being molded into various molded products after blending various compounding agents as necessary to obtain a resin composition. Although there is no special limitation as a compounding agent, stabilizers, such as antioxidant, a heat stabilizer, a light stabilizer, a weather stabilizer, a ultraviolet absorber, a near-infrared absorber; Resin modifiers, 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.

  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 MTF polymer or its hydride, Preferably it is 0.00. 01 to 1 part by weight.

  The above-mentioned compounding agent is uniformly dispersed in the MTF polymer or its hydride. For example, the compounding agent is dissolved in a suitable solvent and added to the MTF polymer or its hydride solution, and then the solvent is removed. To obtain a resin composition of an MTF polymer containing a compounding agent or a hydride thereof, a mixer, a twin-screw kneader, a roll, a Brabender, an extruder, etc. And kneading the compounding agent.

  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 product of the present invention is useful in various fields as various molded products.
Optical parts 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.
Liquid, powder, or solid drug containers (liquid drug containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed drug bags, press-through packages, solid drug containers, eye drop containers, etc.), sampling containers (Sampling test tubes for blood tests, 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 components (plastic lenses for medical examinations, etc.), piping materials (medical infusion tubes, piping, fittings, valves, etc.), artificial organs And medical equipment such as its component parts (tooth base, artificial heart, artificial tooth root, etc.);
Processing or transfer containers (tanks, trays, carriers, cases, etc.), protective materials (carrier tapes, separation films, etc.), piping (pipes, tubes, valves, flow meters, filters, pumps, etc.), liquid containers Equipment for processing electronic parts such as sampling containers (both sampling containers, bottles, ampoule bags, etc.);
Covering materials (for electric wires, cables, etc.), consumer and industrial electronic equipment (copiers, computers, printers, televisions, video decks, video cameras, etc.), structural members (parabolic antenna structural members, flat antenna structural members) Electrical insulating materials such as radar dome structural members;
Circuit boards such as general circuit boards (rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc.), high frequency circuit boards (circuit boards for satellite communication devices, etc.);
Base materials for transparent conductive films (liquid crystal substrates, optical memories, surface heating elements, etc.); semiconductor sealing materials (transistor sealing materials, IC sealing materials, LSI sealing materials, LED sealing materials, etc.), electric / electronic Sealing materials for parts sealing materials (motor sealing materials, capacitor sealing materials, switch sealing materials, sensor sealing materials, etc.);
Automotive interior materials such as room mirrors and meter covers;
Examples include 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) Content of each component in the composition of MTFs Measured by gas chromatography (GC).
(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.
(4) Composition of polymer The composition ratio of the polymer was calculated from ¹ H-NMR.
(5) Content of organic sulfur compound The content of the organic sulfur compound was measured as a carbon disulfide equivalent value using a gas chromatography (GC) equipped with a sulfur chemiluminescence detector (SCD). For this GC analysis, a TC-1 column (length 60 m, inner diameter 0.25 mm, film thickness 1.0 μm) manufactured by GL Sciences Inc. was used. Helium was flowed as a carrier gas at a flow rate of 2.0 ml / min. The sample inlet temperature was 150 ° C. The oven temperature was maintained at 50 ° C. for 5 minutes, then heated at a rate of temperature increase of 10 ° C./minute, and maintained at 250 ° C. for 5 minutes. The combustion temperature of the SCD detector was set to 800 ° C.

[Production Example 1]
100 parts of indene fraction from heavy tar oil (92% indene, content of organic sulfur compound 300 ppm) and 230 parts of dicyclopentadiene (purity 95%, content of organic sulfur compound) in autoclave with stirrer After purging with nitrogen, the reaction was carried out at 180 ° C. for 6 hours with stirring. The reaction product was purified by distillation under conditions of 0.07 kPa and a reflux ratio of 10, and the composition of 1,4-methanol 1,4,4a, 9a-tetrahydrofluorene (hereinafter referred to as MTF) as a fraction at 88 to 92 ° C. 125 parts of product (A) were obtained. The purity of MTF in this composition was 99.4%, and the content of the organic sulfur compound was 50.0 ppm.

[Production Example 2]
The same operation as in Production Example 1 was carried out except that the reflux ratio was 12, to obtain 115 parts of an MTF composition (B). The purity of MTF in this composition was 99.4%, and the content of the organic sulfur compound was 30.0 ppm.

[Production Example 3]
The same operation as in Production Example 1 was carried out except that the reflux ratio was 18, and 115 parts of an MTF composition (C) was obtained. The purity of MTF in this composition was 99.4%, and the content of the organic sulfur compound was 15.0 ppm.

[Production Example 4]
The indene fraction from the heavy heavy oil oil is distilled under reduced pressure at a reflux ratio of 15 using a distillation column packed with helipack, and a fraction with a boiling point of 59.5-63.1 ° C. is obtained under a reduced pressure of 1.33 kPa. It was. This fraction contained 98.2% indene and 15 ppm organic sulfur compounds.
Dicyclopentadiene (purity 95% and organic sulfur compound content 10 ppm) was distilled under reduced pressure at 2 kPa and a reflux ratio of 5 to obtain a fraction having a temperature of 88.5 to 89.5 ° C. The dicyclopentadiene purity of this fraction was 98%, and the content of the organic sulfur compound was 0.1 ppm or less.
Except for using this indene fraction, the same operation as in Production Example 1 was carried out to obtain 125 parts of MTF composition (D). The purity of MTF in this composition was 99.4%, and the content of organic sulfur compound was 0.5 ppm.

[Example 1]
10 parts of MTF composition (C), 300 parts of dehydrated cyclohexane, 0.80 part of 1-hexene as molecular weight regulator, 0.2 part of diisopropyl ether, isobutyl alcohol 0.18 parts, 0.48 parts of triisobutylaluminum and 6 parts of a tungsten hexachloride 0.7 wt% toluene solution were added and stirred at 50 ° C. for 10 minutes. Thereafter, 90 parts of the composition and 10 parts of a tungsten hexachloride 0.7 wt% toluene solution were continuously added dropwise to the polymerization reactor with stirring for 2 hours, and after stirring for 30 minutes after completion of the dropwise addition. The polymerization reaction was stopped by adding 0.5 part of isopropyl alcohol.
When the polymerization reaction solution was measured by gas chromatography, the conversion of MTF was 99.9%. Moreover, the molecular weight of the obtained ring-opening polymer was Mw = 30,500 and MWD = 1.78. The results are shown in Table 1.

[Example 2]
A ring-opening polymer was obtained in the same manner as in Example 1 except that the MTF composition (D) was used instead of the MTF composition (C). The conversion rate of MTF was 99.9%, and the molecular weight of the obtained ring-opening polymer was Mw = 30,000 and MWD = 1.78. The results are shown in Table 1.

[Example 3]
100 parts of the MTF composition (C) and 300 parts of toluene were placed in a nitrogen-substituted reaction vessel and stirred for 5 minutes. Further, 0.15 part of triisobutylaluminum was added. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere, and the internal temperature of the autoclave was maintained at 60 ° C., and the internal pressure was increased to 0.6 MPa in terms of gauge pressure with ethylene. After stirring for 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 system. Ethylene was continuously supplied, and the reaction was performed at a temperature of 60 ° C. for 1 hour while maintaining the ethylene pressure in the system at 0.6 MPa. After the reaction, the polymerization reaction was stopped by adding isopropyl alcohol.
When the reaction mixture obtained by the reaction was measured by gas chromatography, the conversion of MTF was 98.9%. The composition of the obtained addition polymer was MTF / ethylene = 32/68 (mol / mol), and the molecular weight was Mw = 235,000 and MWD = 1.99. The results are shown in Table 2.

[Example 4]
An addition copolymer was obtained in the same manner as in Example 3 except that the MTF composition (D) was used instead of the MTF composition (C). The conversion rate of MTF was 99.1%, the composition of the obtained addition polymer was MTF / ethylene = 32/68 (mol / mol), the molecular weight was Mw = 232,000, and MWD = 2.01. It was. The results are shown in Table 2.

[Comparative Example 1]
A ring-opening polymer was obtained in the same manner as in Example 1 except that the MTF composition (A) was used instead of the MTF composition (C). The conversion of MTF was 65.0%, and the molecular weight of the obtained ring-opening polymer was Mw = 54,000 and MWD = 3.05. The results are shown in Table 1.

[Comparative Example 2]
A ring-opening polymer was obtained in the same manner as in Example 1 except that the MTF composition (B) was used instead of the MTF composition (C). The conversion rate of MTF was 80.0%, and the molecular weight of the obtained ring-opening polymer was Mw = 26,000 and MWD = 1.73. The results are shown in Table 1.

[Comparative Example 3]
An addition copolymer was obtained in the same manner as in Example 3 except that the MTF composition (A) was used instead of the MTF composition (C). The conversion ratio of MTF was 70.0%, the composition of the obtained addition polymer was MTF / ethylene = 30/70 (mol / mol), the molecular weight was Mw = 163,000, and MWD = 2.20. It was. The results are shown in Table 2.

[Comparative Example 4]
An addition copolymer was obtained in the same manner as in Example 1 except that the MTF composition (B) was used instead of the MTF composition (C). The conversion of MTF was 80.0%, the composition of the resulting addition polymer was MTF / ethylene = 30/70 (mol / mol), the molecular weight was Mw = 189,000, and MWD = 2.10. It was. The results are shown in Table 2.

表２から以下の事がわかる。
有機硫黄化合物の含有量が２０ｐｐｍ以下であるＭＴＦ類の組成物を重合して重合体を製造する方法によって得られる重合体は、転化率が高く、Ｍｗ及びＭＷＤがほぼ一定であり、生産安定性に優れる（実施例３及び４）。
それに対して、有機硫黄化合物の含有量が２０ｐｐｍより多いＭＴＦ類の組成物を重合して重合体を製造する方法によって得られる重合体は、転化率が低く、同様の触媒量を用いてもＭｗ及びＭＷＤが大きく異なり、物性の安定性に劣る。（比較例３及び４）。 Table 1 shows the following.
A polymer obtained by a method of producing a polymer by polymerizing a composition of MTFs having an organic sulfur compound content of 20 ppm or less has a high conversion rate, Mw and MWD are almost constant, and production stability. (Examples 1 and 2).
On the other hand, the polymer obtained by the method for producing a polymer using a composition of MTFs having an organic sulfur compound content of more than 20 ppm has a low conversion rate, and even when the same catalyst amount is used, Mw and MWD are low. It is very different and inferior in stability of physical properties. (Comparative Examples 1 and 2).

Table 2 shows the following.
A polymer obtained by a method of producing a polymer by polymerizing a composition of MTFs having an organic sulfur compound content of 20 ppm or less has a high conversion rate, Mw and MWD are almost constant, and production stability. (Examples 3 and 4).
On the other hand, the polymer obtained by the method of producing a polymer by polymerizing a composition of MTFs having an organic sulfur compound content of more than 20 ppm has a low conversion rate, and even when a similar catalyst amount is used, the Mw And MWD is greatly different, and stability of physical properties is inferior. (Comparative Examples 3 and 4).

Claims (5)

  A method for producing a polymer by polymerizing a composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorenes having an organic sulfur compound content of 20 ppm or less.   The production method according to claim 1, wherein the composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is obtained by condensing cyclopentadiene and indene.   A polymer obtained by the production method according to claim 1.   A resin composition comprising the polymer according to claim 3.   The molded object formed by shape | molding the resin composition of Claim 4.