WO2017199980A1

WO2017199980A1 - Hydrogenated polymer, molding material and resin molded body

Info

Publication number: WO2017199980A1
Application number: PCT/JP2017/018427
Authority: WO
Inventors: 卓士寳川; 健作藤井
Original assignee: 日本ゼオン株式会社
Priority date: 2016-05-16
Filing date: 2017-05-16
Publication date: 2017-11-23
Also published as: JPWO2017199980A1

Abstract

A hydrogenated polymer that is obtained by hydrogenating 90% or more of all the carbon-carbon unsaturated bonds in the main chain and the side chains and carbon-carbon unsaturated bonds in the aromatic rings of a polymer which contains a unit derived from a monomer represented by formula (1), and which may contain a unit derived from a monomer that is copolymerizable with the monomer represented by formula (1); a molding material which contains this hydrogenated polymer; and a resin molded body which is obtained by molding this molding material.

Description

Hydrogenated polymer, molding material and resin molding

The present invention relates to a hydrogenated polymer useful as a resin component of an optical molded body such as an optical element, a molding material containing the hydrogenated polymer, and a resin molded body obtained by molding the molding material.

The resin component of an optical molded body such as a lens is required to have excellent transparency. From this viewpoint, conventionally, as a resin component of an optical molded article, polymethyl methacrylate, polycarbonate, diethylene glycol bisallyl carbonate, polycyclohexyl methacrylate, poly-4-methylpentene, amorphous alicyclic polyolefin, polycyclic norbornene polymer, vinyl Alicyclic hydrocarbon polymers have been used. For example, Patent Document 1 describes an optical molded body obtained by using a molding material containing a polycyclic norbornene polymer having a specific repeating unit.

In recent years, lenses for mobile phone cameras and the like have been required to be thinner and have higher resolution. Therefore, there is a demand for a resin having not only excellent transparency but also high mechanical strength, excellent balance between refractive index and Abbe number, and low birefringence.

In connection with the present invention, Patent Document 1 describes a ring-opened polymer hydride represented by the following formula (A).

However, this document does not describe a ring-opened polymer hydride obtained by hydrogenating an aromatic ring.

International Publication No. 2015/176588

The present invention provides a hydrogenated polymer useful as a resin component of a resin molded product such as an optical element, a molding material containing the hydrogenated polymer, and a resin molded product obtained by molding the molding material. For the purpose.

In order to solve the above problems, the present inventors have intensively studied a ring-opening polymer of a cyclic olefin monomer. As a result, according to the polymer hydride obtained by using the monomer represented by the formula (1) described later as the cyclic olefin monomer, the mechanical strength and the balance between the refractive index and the Abbe number are improved. It has been found that an excellent and low birefringent resin can be obtained, and the present invention has been completed.

Thus, according to the present invention, the following [1] to [3] hydrogenated polymers, [4] molding materials, and [5] and [6] resin moldings are provided.
[1] The following formula (1)

And a main chain and a side chain of a polymer containing a unit derived from a monomer represented by formula (1) and a unit derived from a monomer copolymerizable with the monomer represented by formula (1). A hydrogenated polymer obtained by hydrogenating at least 90% of the carbon-carbon unsaturated bonds of the aromatic ring and carbon-carbon unsaturated bonds of the aromatic ring.
[2] The hydrogenated polymer as described in [1], which contains a ring-opening unit of the monomer represented by the formula (1).
[3] The monomer copolymerizable with the monomer represented by the formula (1) comprises a norbornene monomer, a cyclic monoolefin, a cyclic polyene, and an α-olefin having 2 to 20 carbon atoms. The hydrogenated polymer according to [1] or [2], which is at least one selected from the group.
[4] A molding material containing the hydrogenated polymer according to any one of [1] to [3].
[5] A resin molded product obtained by molding the molding material according to [4].
[6] The resin molded product according to [5], which is an optical element.

ADVANTAGE OF THE INVENTION According to this invention, the hydrogenated polymer useful as a resin component of resin moldings, such as an optical element, the molding material containing this hydrogenated polymer, and the resin molding obtained by shape | molding this molding material are provided. The
The hydrogenated polymer of the present invention is a polymer that is excellent in mechanical strength, balance of refractive index and Abbe number, and can provide a low birefringence resin.
The hydrogenated polymer of the present invention is useful as a resin component of a resin molded product such as an optical element.

Hereinafter, the present invention will be described in detail by dividing it into 1) hydrogenated polymer, 2) molding material, and 3) resin molded body.

1) Hydrogenated polymer The hydrogenated polymer of the present invention has the following formula (1):

And a unit derived from a monomer that is copolymerizable with the monomer (1), including a unit derived from the monomer represented by (hereinafter, sometimes referred to as “monomer (1)”) In which 90% or more of the carbon-carbon unsaturated bonds in the main and side chains and the carbon-carbon unsaturated bonds in the aromatic ring are hydrogenated. Such a polymer can polymerize monomer (1) or polymerize monomer (1) and a monomer mixture of monomers copolymerizable with monomer (1). Can be obtained by obtaining a polymer and hydrogenating the polymer.
In the present specification, the polymer includes “units derived from the monomer (1)” or “can be copolymerized with units derived from the monomer (1) and the monomer (1)”. Including a unit derived from a simple monomer preferably means 99.0% by mass or more, more preferably 100% by mass of “monomer (1 ) Or “units derived from monomer (1) and units derived from monomer copolymerizable with monomer (1)”.
By using the monomer represented by the above formula (1) as the monomer, a hydrogenated polymer having excellent mechanical strength and a balance between the refractive index and the Abbe number and having a low birefringence can be obtained. .

[Monomer (1)]
The monomer (1) used in the preparation of the hydrogenated polymer of the present invention is a known compound, and can be produced and obtained by a known method. For example, as shown in the following reaction formula, monomer (1) can be produced by subjecting norbornadiene (2) and anthracene (3) to a Diels-Alder addition reaction under heating in an appropriate solvent. (See Journal of the American Chemical Society, 102 (2), 1980, 671-8, JP-A-2-185520, International Publication No. 2015/176588).

In addition, as shown below, the monomer (1) is obtained by dispersing a quadricycle (4) and anthracene (3) in a suitable solvent to obtain a dispersion. (Journal of the American Chemical Society, 99 (3), 1977, 871-7). In this case, in addition to the monomer (1), the compound represented by the formula (5) is also produced as a by-product, so these are mixed in the obtained reaction product, but the reaction product is separated and purified by column chromatography or the like. By using the means, the monomer (1) can be isolated.

In addition to the repeating unit derived from the monomer (1), the hydrogenated polymer of the present invention has a monomer copolymerizable with the monomer represented by the above formula (1) (hereinafter, “ It may be referred to as “another monomer.”) It may have a repeating unit derived from.
Other monomers are not particularly limited as long as they are copolymerizable with monomer (1). Examples of the other monomer include at least one selected from the group consisting of norbornene monomers, cyclic monoolefins, cyclic polyenes, and α-olefins having 2 to 20 carbon atoms. Among these, norbornene monomers are preferable. These can be used individually by 1 type or in combination of multiple types.

[Norbornene monomer]
The norbornene-based monomer as the “other monomer” that can be used in the preparation of the hydrogenated polymer of the present invention is a compound having a norbornene ring and a polymerizable carbon-carbon unsaturated bond (provided that the monomer is a single monomer) Body (1) is excluded.)
Specific examples include bicyclic monomers such as bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof; tricyclo [4.3.0.1 ^2,5 ] deca -Tricyclic monomers such as 3,7-diene (common name: dicyclopentadiene) and derivatives thereof; 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene tetrahydrofluorene, also referred to as a tetracyclo [7.4.0.0 ^2,7 .1 ^10,13] trideca -2,4,6,11- tetraene), tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene (common name: tetracyclododecene) and tetracyclic monomers such as derivatives thereof; 1,2,3,3a, 4,6a-hexahydro-1,2 , 4-methenopentalene (common name: deltacyclene, hereinafter sometimes referred to as “DCL”) and its derivatives, etc., monomers having 5 or more rings; Of these, tetracyclododecene is preferred.

When these monomers have a substituent, the position of the substituent is not limited. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; an alkylidene group such as an ethylidene group and a propane-2-ylidene group; an aryl group such as a phenyl group; a hydroxy group; an acid anhydride group Carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group; and the like. When the monomer has a plurality of substituents, the plurality of substituents may be the same or different.
These norbornene monomers can be used singly or in combination of two or more.

[Cyclic monoolefin]
The cyclic monoolefin as the “other monomer” that can be used in the preparation of the hydrogenated polymer of the present invention is a compound having a cyclic structure and one polymerizable carbon-carbon unsaturated bond (provided that Monomer (1) and norbornene monomers are excluded.
Specific examples include cyclic monoolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene, and derivatives thereof (meaning those having a substituent in the ring; the same shall apply hereinafter). Moreover, these cyclic monoolefins may have a substituent, and the position of the substituent is not particularly limited. Examples of the substituent include the same substituents as those described above for the norbornene monomer. Further, when the monomer has a plurality of substituents, the plurality of substituents may be the same or different.
These cyclic monoolefins can be used singly or in combination of two or more.

[Cyclic polyene]
The cyclic polyene as the “other monomer” that can be used in the preparation of the hydrogenated polymer of the present invention is a compound having a cyclic structure and having two or more polymerizable carbon-carbon unsaturated bonds (provided that And norbornene monomers are excluded). Specific examples thereof include cyclic diolefins such as cyclohexadiene and cyclooctadiene and derivatives thereof; dimethylcyclopentadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5- Examples include ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, cyclooctatriene and the like. Moreover, these cyclic polyenes may have a substituent, and the position of the substituent is not particularly limited. Examples of the substituent include the same substituents as those described above for the norbornene monomer. Further, when the monomer has a plurality of substituents, the plurality of substituents may be the same or different.
These cyclic polyenes can be used alone or in combination of two or more.

[C2-C20 α-olefin]
Examples of the α-olefin having 2 to 20 carbon atoms used in the present invention include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene, vinylcyclohexane Vinylcyclohexene, vinylcyclohexene, trimethylvinylsilane and the like. These α-olefins may have a substituent, and the position of the substituent is not particularly limited. Examples of the substituent include the same substituents as those described above for the norbornene monomer. Further, when the monomer has a plurality of substituents, the plurality of substituents may be the same or different.
These α-olefins can be used alone or in combination of two or more.

(Hydrogenated polymer)
Specifically, the hydrogenated polymer of the present invention is as follows.
(Α) Ring-opening polymer of monomer (1) [hereinafter referred to as “ring-opening polymer (α)”. ], A polymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds in the main chain and the side chain and the carbon-carbon unsaturated bonds in the aromatic ring [hereinafter referred to as “hydrogenated polymer (α)”]. There is. ]
(Β) a ring-opening copolymer obtained by ring-opening copolymerization of a monomer mixture of monomer (1) and monomer (1) and a monomer capable of ring-opening copolymerization; A polymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds of the main chain and side chain and the carbon-carbon unsaturated bonds of the aromatic ring. [Hereinafter, it may be referred to as “hydrogenated polymer (β)”. ]
(Γ) Addition polymer of monomer (1) [hereinafter sometimes referred to as “addition polymer (γ)”. ], A polymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds of the main chain and the side chain and the carbon-carbon unsaturated bonds of the aromatic ring [hereinafter referred to as “hydrogenated polymer (γ)”] There is. ]
(Δ) a copolymer obtained by addition copolymerization of a monomer mixture of the monomer (1) and the monomer (1) and an addition copolymerizable monomer [hereinafter referred to as “addition polymer ( δ) ”. ], A polymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds in the main chain and the side chain and the carbon-carbon unsaturated bonds in the aromatic ring (hereinafter referred to as “hydrogenated polymer (δ)”). There is. ]

The hydrogenated polymers (α) and (β) are polymers having a repeating unit represented by the following (I) in the molecule.

The hydrogenated polymer (α) is a ring-opened polymer hydride consisting only of the repeating unit of the formula (I).
Hydrogenated polymer (β) is a ring-opening copolymer hydrogen having in its molecule a repeating unit of the above formula (I) and a repeating unit derived from a monomer copolymerizable with monomer (1). It is a monster. The hydrogenated polymer (β) may have two or more kinds of repeating units derived from a monomer capable of ring-opening copolymerization with the monomer (1). The hydrogenated polymer (β) may be any of a random copolymer, an alternating copolymer, and a block copolymer.
In the hydrogenated polymer (β), the ratio of the repeating unit represented by the formula (I) to the total repeating units of the hydrogenated polymer (β) is not particularly limited, but is preferably 10 to 80 mol%, More preferably, it is 20 to 60 mol%, particularly preferably 30 to 55 mol%. The moldability of a molding material can be improved because the presence rate of the repeating unit shown by said Formula (I) shall be 80 mol% or less.

The ring-opening polymers (α) and (β) can be synthesized by subjecting the corresponding monomers to ring-opening polymerization according to a known method using a metathesis polymerization catalyst.
There is no limitation in particular as a metathesis polymerization catalyst, A well-known thing is used. As a metathesis polymerization catalyst, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; from titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a selected metal halide or acetylacetone compound and a co-catalyst organoaluminum compound; a Schrock-type or Grubbs-type living ring-opening metathesis polymerization catalyst (JP-A-7-179575, J. Am. Chem. Soc., 1986, 108, p.733, J. Am.Chem.Soc., 1993, 115, p.9858, and J.Am.Chem.Soc., 1996, 118, p.100); Chrome, molybdenum, tongue steak Catalyst system comprising a complex having a metal and an imide group-containing ligand and the like; and the like.

These metathesis polymerization catalysts can be used singly or in combination of two or more. The amount of the metathesis polymerization catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol, relative to 1 mol of all monomers. It is.

When performing the ring-opening polymerization, a molecular weight regulator can be added. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator. It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing can be used. Examples of molecular weight regulators to be used include α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene and 1-octadecene; styrenes such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl Ethers such as ether; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2 , 3-Dimethyl-1,3-butadiene, 1,3-pen Diene, such as a conjugated diene such as 1,3-hexadiene, and the like.
The addition amount of the molecular weight regulator is usually 0.001 to 0.030 mol, preferably 0.003 to 0.020 mol, more preferably 0.005 to 0.015 mol with respect to 1 mol of all monomers. It is.

The ring-opening polymerization can be performed in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the polymerization reaction. Organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; fats such as cyclohexane, methylcyclohexane, decalin and bicyclononane And cyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene;

The polymerization reaction is started by mixing the monomer (1), the monomer mixture of the monomer (1) and the monomer (1) and a copolymerizable monomer, and a polymerization catalyst. Is done. The polymerization temperature is not particularly limited, but is usually −20 to + 100 ° C., preferably 10 to 80 ° C., and more preferably 30 to 60 ° C. The polymerization time is not particularly limited, but is usually 1 minute to 100 hours. Although the pressure condition is not particularly limited, the polymerization is usually carried out under a pressure of 0 to 1 MPa.

After completion of the reaction, the desired ring-opening polymer can be isolated by ordinary post-treatment operation.
By subjecting the obtained ring-opening polymer (α) or (β) to a hydrogenation reaction, the corresponding hydrogenated polymers (α) and (β) can be obtained, respectively.

The method for hydrogenating the ring-opening polymers (α) and (β) includes the main chain and side chain carbon-carbon unsaturated bonds, and the aromatic ring carbon contained in the ring-opening polymers (α) and (β). -Any method that can hydrogenate 90% or more of the total carbon unsaturated bonds is not particularly limited.
The hydrogenation reaction is usually carried out by supplying hydrogen in the presence of a hydrogenation catalyst in a ring-opening polymer (α) or a solution of the ring-opening polymer (β).
As the hydrogenation catalyst, there are a homogeneous catalyst and a heterogeneous catalyst.
Examples of homogeneous catalysts include Wilkinson complex, that is, chlorotris (triphenylphosphine) rhodium (1), cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride. Examples thereof include a catalyst comprising a combination of a transition metal compound / alkyl metal compound such as / sec-butyl lithium and tetrabutoxy titanate / dimethyl magnesium.

Examples of the heterogeneous catalyst include a catalyst in which a metal known as a hydrogenation catalyst such as nickel or palladium is supported on a carrier. In the present invention, a heterogeneous catalyst is preferable, and a combination of nickel and palladium as a metal or a heterogeneous catalyst using palladium is most preferable. Examples of the carrier include alumina, silica, diatomaceous earth, and the like.

The hydrogenation reaction is usually performed in a solvent. Examples of the solvent include the same solvents that can be used during the polymerization. The hydrogenation reaction is usually in the temperature range of 100 to 200 ° C., preferably 130 to 195 ° C., usually 0.1 to 100 kgf / cm ² , preferably 0.5 to 60 kgf / cm ² , more preferably 1 to 50 kgf / It is carried out at a hydrogen pressure (gauge pressure) of cm ² .

By this hydrogenation reaction, the hydrogenation rate in the carbon-carbon unsaturated bonds of the main chain and the side chain and the carbon-carbon unsaturated bonds of the aromatic ring is 90% or more, preferably 95% or more. The hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and the side chain and the carbon-carbon unsaturated bonds in the aromatic ring structure is determined by the ¹ H-NMR spectrum according to the carbon of the main chain and the side chain before hydrogenation. -Carbon unsaturated bond and amount of carbon-carbon unsaturated bond of aromatic ring structure (X ₁ ), main chain and side chain carbon-carbon unsaturated bond after hydrogenation, and carbon-carbon of aromatic ring structure The amount of unsaturated bonds (X ₂ ) can be measured and determined according to the formula: 100−X ₂ / X ₁ × 100.

After polymerization and hydrogenation reaction, the catalyst and the like are removed. The removal method is not particularly limited, and examples thereof include methods such as centrifugation and filtration. Furthermore, the catalyst removal can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.

The hydrogenated polymers (γ) and (δ) are polymers having a repeating unit represented by the following formula (II) in the molecule.

The hydrogenated polymer (γ) is an addition polymer hydride consisting only of the repeating unit represented by the formula (II).
The hydrogenated polymer (δ) is an addition copolymer hydrogen having a repeating unit of the formula (II) in the molecule and a repeating unit derived from a monomer that can be addition copolymerized with the monomer (1). It is a monster. The hydrogenated polymer (δ) may have two or more types of repeating units derived from the monomer (1) and a monomer copolymerizable with the monomer (1). Further, the hydrogenated polymer (δ) may be any of a random copolymer, an alternating copolymer, and a block copolymer.
In the hydrogenated polymer (δ), the ratio of the repeating unit represented by the formula (II) to the total repeating units is not particularly limited, but is preferably 10 to 80 mol%, more preferably 20 to 60 mol. %, Particularly preferably 30 to 50 mol%. The moldability of a molding material can be improved by making the presence rate of the repeating unit shown by the said formula (II) into 80 mol% or less.

The addition polymers (γ) and (δ) are, for example, the monomer (1) and, if necessary, the monomer (1) that can be added copolymerized with the monomer (1) in the presence of a metallocene catalyst. Can be obtained by addition copolymerization.

The metallocene catalyst to be used is not particularly limited, and a known catalyst conventionally used for addition polymerization reaction can be used. For example, a catalyst comprising a transition metal metallocene compound (a) and an organoaluminum oxy compound (b) or a borate or borane compound (c) can be mentioned.

Examples of the metallocene compound (a) include a bridged metallocene compound and a half metallocene compound. In order to efficiently polymerize the monomer (1), a crosslinked metallocene compound is preferred.
Examples of the bridged metallocene compound include those represented by the general formula (6).

In formula (6), M ¹ is a metal atom selected from the group consisting of titanium, zirconium, and hafnium, and zirconium is preferred because of its excellent catalytic activity.
X ¹ and X ² are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom.
R ¹ is a lower alkylene group such as a methylene group, an ethylene group or a propylene group; an alkylidene group such as an isopropylidene group; a substituted alkylene group such as diphenylmethylene; a substituted silylene group such as a dimethylsilylene group or a diphenylsilylene group; or a silylene group It is.
R ² and R ³ are each independently a cyclopentadienyl group, an indenyl group, or a fluorenyl group, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group; a phenyl group or a benzyl group May be substituted.

Examples of the bridged metallocene compound represented by the formula (6) include isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropyl Riden- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-t-butyl) cyclopentadienyl] zirconium dichloride, isopropyl Liden- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1-indenyl) zirconium dichloride, ethylene-bis (1-indenyl) zirconium dichloride, diphenyl Styrene - bis (1-indenyl) zirconium dichloride, isopropylidene - bis (1-indenyl) zirconium dichloride can be mentioned.

The half metallocene compounds include (t-butylamido) dimethyl-1-indenylsilane titanium dimethyl, (t-butylamido) dimethyl-1-indenylsilane titanium dichloride, (t-butylamido) dimethyl-9-fluorenyl. Silane titanium dimethyl, (t-butylamido) dimethyl-9-fluorenylsilane titanium dichloride, (t-butylamido) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dimethyl, (t-butylamido) dimethyl- 9- [3,6-Di (i-propyl) fluorenyl] silane titanium dimethyl, (t-butylamido) dimethyl-9- [3,6-di (t-butyl) fluorenyl] silane titanium dimethyl, (t-butylamide) Dimethyl-9- [2,7-di (t-butyl) fluore Le] silane titanium dimethyl, and as (t-butylamido) dimethyl-9- (2,3,6,7-tetramethyl-fluorenyl) as silane titanium dimethyl is preferred.

The organoaluminum oxy compound (b) or borate or borane compound (c) constituting the metallocene catalyst is an activator for activating the metallocene compound.

The organoaluminum oxy compound (b) may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-78687.

The borate or borane compound (c) is an activator capable of reacting with the metallocene compound to convert the metallocene compound into a cationic species.
Examples of the borate or borane compound (c) include triethylammonium tetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocete. Borate compounds such as nium tetra (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) borate; tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) Examples thereof include borane compounds such as boron and tris (pentafluorophenyl) boron.

The metallocene catalyst can contain an organoaluminum compound (d) as necessary. Examples of the organoaluminum compound (d) include organoaluminum compounds other than the above organoaluminum oxy compounds. Specific examples of the organoaluminum compound (d) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum; dimethylaluminum chloride, diisobutylaluminum chloride Dialkylaluminum halides such as diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide; dialkylaluminum aryloxides such as diethylaluminum phenoxide.

The concentration of the metallocene compound (a) during the polymerization reaction is preferably 0.00005 to 1 mmol / liter, more preferably 0.0001 to 0.3 mmol / liter. The organoaluminum oxy compound (b) or borate or borane compound (c) is preferably 1 to 10,000 equivalents relative to the metallocene compound (a).
The organoaluminum compound (d) is preferably 0.1 to 1,000 equivalents relative to the metallocene compound (a).

The addition polymerization reaction is not limited by the form of the polymerization reaction, and can be adopted from polymerization methods such as solution polymerization, bulk polymerization, and slurry polymerization. The reactor can be either a continuous reactor or a batch reactor. Good.

Solvents used in the addition polymerization reaction include chain aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; aromatic carbonization such as benzene, toluene and xylene. Hydrogen; and the like. These solvents can be used alone or in combination of two or more.

The addition polymerization reaction is usually carried out in the temperature range of −50 to + 230 ° C., preferably −30 to + 200 ° C., more preferably −20 to + 150 ° C., usually 2 minutes to 5 hours, preferably 5 minutes to 3 hours. . The pressure (gauge pressure) during the reaction is usually 10 MPa or less, preferably 5 MPa or less.

In the metallocene catalyst, the metallocene compound (a), the organoaluminum oxy compound (b) or the borate or borane compound (c), and the organoaluminum compound (d), which constitute the metallocene catalyst, are separately added to the polymerization reactor. Alternatively, these may be mixed outside the reactor and then added to the polymerization reactor.

In order to hydrogenate the addition polymers (γ) and (δ), addition polymers (γ), main chain and side chain carbon-carbon unsaturated bonds of (δ), and aromatic ring carbon-carbon The method is not particularly limited as long as 90% or more of the total unsaturated bonds can be hydrogenated. The hydrogenation reaction is usually carried out by supplying hydrogen to a solution of the addition polymer (γ) or (δ) in the presence of a hydrogenation catalyst.
Examples of the hydrogenation catalyst used include the same ones listed as the hydrogenation catalysts used for the hydrogenation reaction of the ring-opening polymers (α) and (β).

The hydrogenation reaction is usually performed in a solvent. Examples of the solvent include the same solvents that can be used during the addition polymerization. The hydrogenation reaction and the post-treatment after the hydrogenation reaction can be performed under the same conditions as in the case of the ring-opening polymers (α) and (β).

This hydrogenation reaction can achieve the same hydrogenation rate as that of the ring-opening polymers (α) and (β).

The weight average molecular weight (Mw) of the hydrogenated polymer of the present invention is preferably 10,000 to 300,000, more preferably 15,000 to 200,000, and particularly preferably 17,000 to 150,000. If the weight average molecular weight (Mw) of the hydrogenated polymer is too small, the mechanical strength of the resin molding may be lowered. On the other hand, if the weight average molecular weight (Mw) of the hydrogenated polymer is too large, the moldability of the molding material may be reduced.
In addition, the weight average molecular weight (Mw) of the hydrogenated polymer of this invention can be controlled by changing the addition amount of the molecular weight modifier added at the time of superposition | polymerization of a polymer.

The molecular weight distribution (Mw / Mn) of the hydrogenated polymer of the present invention is not particularly limited, but is preferably 1 to 8, more preferably 1 to 6.
When the molecular weight distribution of the hydrogenated polymer is within the above range, a resin molded product having sufficient mechanical strength can be obtained.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated polymer of the present invention are standard polyisoprene conversion values by gel permeation chromatography (GPC) using cyclohexane as an eluent.

Since the hydrogenated polymer of the present invention has a repeating unit derived from the monomer (1), it has excellent mechanical strength and a balance between the refractive index and the Abbe number, and becomes a low birefringence polymer.
The refractive index (n _d ) at 25 ° C. of the hydrogenated polymer of the present invention is preferably 1.540 or more, more preferably 1.545 to 1.560.
The Abbe number at 25 ° C. of the hydrogenated polymer of the present invention is preferably 40 or more, more preferably 45 or more, and usually 70 or less.
Here, the values of the refractive index and the Abbe number can be measured and calculated by the methods described in the examples.
The birefringence amount (δn) per unit thickness of the hydrogenated polymer of the present invention is preferably −200 to +200, more preferably −150 to +150, and particularly preferably −120 to +120.

The glass transition temperature of the hydrogenated polymer of the present invention is preferably 120 to 180 ° C, more preferably 130 to 165 ° C.
When the glass transition temperature of the hydrogenated polymer is within the above range, the balance between the moldability of the molding material and the heat resistance of the resin molded body becomes good.

As described above, since the hydrogenated polymer of the present invention has repeating units derived from the monomer (1), it is excellent in mechanical strength, balance between refractive index and Abbe number, and low birefringence. is there. Due to these characteristics, the hydrogenated polymers (α) and (β) are preferred as the hydrogenated polymer of the present invention.
The hydrogenated polymer of the present invention is useful as a resin component of a resin molded product such as an optical element.

2) Molding material The molding material of the present invention contains the hydrogenated polymer of the present invention. The molding material of the present invention may contain other components such as a resin component other than the hydrogenated polymer of the present invention and additives as long as the effects of the present invention are not impaired.

Examples of resin components other than the hydrogenated polymer of the present invention (hereinafter sometimes referred to as “other resin components”) include styrene / butadiene block copolymers, styrene / butadiene / styrene block copolymers, styrene / Examples include isoprene block copolymers, styrene / isoprene / styrene block copolymers, and hydrides thereof, styrene polymers such as styrene / butadiene / random copolymers, and the like.
When the molding material used in the present invention contains other resin components, the content is usually 0.1 to 100 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the hydrogenated polymer of the present invention. 50 parts by mass.

Examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a near infrared absorber, a plasticizer, an antistatic agent, and an acid scavenger.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

Examples of phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4 ' -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, [pentaerythritol tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate]] and the like.

Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.

Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.

Examples of the UV absorber include benzotriazole UV absorbers, bezoate UV absorbers, benzophenone UV absorbers, acrylate UV absorbers, and metal complex UV absorbers.
Examples of the light stabilizer include hindered amine light stabilizers.

Near-infrared absorbers are cyanine-based near-infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; azulenium-based near-infrared absorbers; phthalocyanine-based near-infrared absorbers; Examples include near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers;
Examples of the plasticizer include a phosphoric acid triester plasticizer, a fatty acid monobasic acid ester plasticizer, a dihydric alcohol ester plasticizer, and an oxyacid ester plasticizer.
Examples of the antistatic agent include fatty acid esters of polyhydric alcohols.
Examples of the acid scavenger include magnesium oxide and zinc stearate.

The content of these additives can be appropriately determined according to the purpose. The content thereof is usually in the range of 0.001 to 5 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer of the present invention.

A molding material can be obtained by mixing each component according to a conventional method. Examples of the mixing method include a method of mixing each component in an appropriate solvent and a method of kneading in a molten state.
Kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder. The kneading temperature is preferably in the range of 200 to 400 ° C, more preferably 240 to 350 ° C. In kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.
After kneading, it can be pelletized by extruding into a rod shape and cutting into an appropriate length with a strand cutter according to a conventional method.

The molding material obtained by the kneading method in a molten state usually has no melting point observed when DSC measurement is performed, and is excellent in transparency.

Since the molding material of the present invention contains the hydrogenated polymer of the present invention, by using the molding material of the present invention, the mechanical strength and the balance between the refractive index and the Abbe number are excellent, and the low birefringence is achieved. A certain resin molding can be obtained efficiently. For this reason, the molding material of this invention is used suitably as a molding material of optical molded objects, such as a lens. Further, the molding material of the present invention is suitably used as a fuel because of its high density and high combustion heat.
Further, the molding material of the present invention has at least the values of weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), refractive index (n _d ), Abbe number, and birefringence amount as “hydrogenated polymer”. It is preferable to satisfy the above-described preferable range.

3) Resin molding The resin molding of the present invention is obtained by molding the molding material of the present invention.
The molding method is not particularly limited, and examples thereof include injection molding, press molding, and extrusion molding. Among these, when a molded object is an optical member etc., since the target molded object can be obtained with sufficient precision, injection molding is preferable.

The melting temperature at the time of molding varies depending on the molding material used, but is usually 200 to 400 ° C., preferably 210 to 350 ° C. The mold temperature in the case of using a mold is usually 20 ° C. to (Tg + 15) ° C., preferably (Tg−30) ° C. to (Tg + 10) ° C., more preferably Tg as the glass transition temperature of the molding material. The temperature is from (Tg−20) ° C. to (Tg + 5) ° C.

Since the resin molding of the present invention is obtained by molding the molding material of the present invention, it is excellent in mechanical strength, balance between refractive index and Abbe number, and has low birefringence.
The resin molding of this invention can be used as optical elements, such as an optical lens, an optical disk, a light-guide plate, an optical film, and a light reflection board.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
In addition, in a polymer produced by copolymerizing a plurality of types of monomers, the proportion of monomer units formed by polymerizing a certain monomer in the polymer is usually unless otherwise specified. This coincides with the ratio (preparation ratio) of the certain monomer in the total monomers used for polymerization of the polymer.
In the examples, various physical properties were measured according to the following methods.

(1) Analysis of monomer (1) (NMR)
The monomer (1) obtained in the example was dissolved in deuterated chloroform (with TMS) to prepare a measurement solution having a concentration of 5%. Using this solution, ¹ H-NMR was measured at 40 ° C.

(Gas chromatography)
The monomer was analyzed by gas chromatography (GC) under the following conditions.
Sample solution: Cyclohexane solution with a concentration of 5% Gas chromatography analyzer: manufactured by Agilent Technologies, product name: 6850 series Column: manufactured by Agilent Technologies, product name: HP-1, 30 m, inner diameter 0.32 mm, membrane 25 μm thick
Split ratio: 70: 1
Split flow rate: 140 mL / min Injection temperature: 160 ° C.
Injection volume: 1.0 μL
Detection temperature: 250 ° C
N ₂ flow rate: 2.0 mL / min Temperature condition: held at 40 ° C. for 6 minutes, then raised to 240 ° C. at 10 ° C./min

(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated polymer
The weight average molecular weight (Mw) of the hydrogenated polymer was measured by gel permeation chromatography (GPC) using cyclohexane as an eluent and obtained as a standard polyisoprene conversion value.
Standard polyisoprene (manufactured by Tosoh Corporation, Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) was used as the standard polyisoprene.
The measurement was performed under the conditions of using three columns (manufactured by Tosoh Corporation, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL) connected in series, a flow rate of 1.0 mL / min, a sample injection amount of 100 μL, and a column temperature of 40 ° C.

(3) Refractive Index The hydrogenated polymer pellets obtained in the examples were formed into a sheet having a thickness of 5 mm and left for 20 hours in an atmosphere of [polymer glass transition temperature (Tg) -15] ° C. This was used as a measurement sample.
The obtained measurement sample was measured for refractive index (nd) at 25 ° C. using a precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-200, light source = He lamp (587.6 nm)).

(4) Abbe number (ν _d )
Using the refractive index (n _d , n _C , n _F ) at 25 ° C. obtained by refractive index measurement for the same measurement sample as that obtained in (3) above, Abbe according to the following formula (1) The number (ν _d ) was calculated.
ν _d = (n _d −1) / (n _F −n _C )

In the formula (1), nd, nC, and nF represent refractive indexes at wavelengths of 587.6 nm, 656.3 nm, and 486.1 nm, respectively.

(5) Birefringence amount per unit thickness (δn)
The hydrogenated polymer pellets obtained in the examples were molded into a shape of 35 mm × 10 mm × 1 mm. After fixing both ends of this sheet with clips, a 160 g weight was fixed to one clip. Next, in a [glass transition temperature of polymer (Tg) −15] ° C., starting from the clip on which the weight is not fixed, the sheet is hung for 10 minutes and stretched, and this is measured. It was.
With respect to the obtained measurement sample, the retardation value at the center of the measurement sample was measured with a birefringence meter (manufactured by Oji Scientific Instruments, product name: KOBRA-CCD / X) at a wavelength of 650 nm. a).
Further, the thickness of the central portion of the measurement sample was measured (this measured value is defined as b (mm)), and the δn value was determined by the formula: δn = a × (1 / b).
The closer the δn value is to 0, the smaller the birefringence. Moreover, the thing with which birefringence generate | occur | produced in the extending | stretching direction shows a positive value, and the thing which birefringence generate | occur | produced in the direction orthogonal to an extending | stretching direction shows a negative value.

(6) Glass transition temperature The glass transition temperature (Tg) of the molding material is a differential scanning calorimeter (product name: DSC6220SII, manufactured by Nanotechnology) using the hydrogenated polymer pellets obtained in the examples as measurement samples. Was measured based on JIS K 6911 under a temperature rising rate of 10 ° C./min.

[Production Example 1]
Synthesis of [Monomer (1)] To a reaction vessel purged with nitrogen inside, 30 parts of toluene, 30 parts of norbornadiene and 10 parts of anthracene were added, and the whole volume was heated to 200 ° C. with stirring, and the reaction was continued for 12 hours. went.
After cooling the reaction solution, 50 parts of toluene was added, the whole volume was stirred, solids were filtered off, and toluene was distilled off under reduced pressure to obtain 21 parts of a crude product. The obtained crude product was recrystallized with a mixed solvent of toluene / hexane = 1/2 to obtain 17 parts of a pure product. The obtained pure product was subjected to NMR analysis according to the above conditions, and the pure product identified the monomer (1). Moreover, when gas chromatography was performed according to the said conditions, purity was 98%.

[Example 1]
15 parts of monomer (1), 15 parts of tetracyclododecene as another monomer copolymerizable with monomer (1), and 0.09 part of molecular weight regulator (1-hexene) A mixed monomer mixture was prepared. Next, 0.02 part of a polymerization catalyst [(1,3-dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride] in a glass reaction vessel purged with nitrogen inside, toluene as an organic solvent After adding 100 parts, the monomer mixture was added dropwise over 1 hour while stirring at 60 ° C. to conduct a ring-opening polymerization reaction. The conversion ratio of the monomer to the polymer was 100%, and the weight average molecular weight (Mw) of the polymer measured according to the above was 18,000 and the molecular weight distribution (Mw / Mn) was 1.5.

Next, 130 parts of the resulting polymerization reaction solution was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Co., Ltd., product name “T8400RL”, nickel support rate 58%) were added. It was. After the inside of the autoclave was replaced with hydrogen, hydrogenation reaction was performed for 12 hours at 200 ° C. and 4.5 MPa hydrogen pressure.
After completion of the hydrogenation reaction, a pressure filter (made by Ishikawajima-Harima Heavy Industries Co., Ltd., product name “Fundafilter”) is made using diatomaceous earth (made by Showa Chemical Industry, product name “Radiolite (registered trademark) # 500”) as a filter bed. ) And pressure filtered at a pressure of 0.25 MPa to obtain a colorless and transparent solution. The hydrogenation rate of the main chain and side chain carbon-carbon unsaturated bonds of the hydrogenated polymer obtained by the hydrogenation reaction and the total carbon-carbon unsaturated bonds of the aromatic ring were analyzed by ¹ H-NMR. ^{In 1} H-NMR analysis, the amount of carbon-carbon unsaturated bonds contained in the polymer before and after hydrogenation was measured. The hydrogenation rate calculated based on the measurement results was 95%. The conditions for ¹ H-NMR analysis were the same as those for monomer (1).
Subsequently, an antioxidant [pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, product name “Irganox (registered)” was added to the resulting solution. Trademark) 1010 ")] was added per 100 parts of polymer hydride.

This solution was filtered with a filter (product name “Zeta Plus (registered trademark) 30H”, pore size 0.5 to 1 μm, manufactured by Cunnow Filter Co., Ltd.), and then the filtrate was made of a metal fiber filter (manufactured by Nichidai, pore size 0.4 μm). ) To remove foreign matters.

Next, after removing the cyclohexane and other volatile components from the solution at a temperature of 260 ° C. and a pressure of 1 kPa or less, the polymer hydride was obtained from the filtrate obtained above using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.). Is extruded into a strand form in a molten state from a die directly connected to a concentrator, cooled with water, and then cut with a pelletizer (product name “OSP-2”, manufactured by Nagata Seisakusho) to contain pellets containing a hydrogenated polymer as a molding material Got. The obtained molding material had a weight average molecular weight (Mw) of 17,300, a molecular weight distribution (Mw / Mn) of 1.5, a glass transition temperature (Tg) of 162 ° C., a refractive index of 1.548, and an Abbe number of 48. Met. The birefringence amount per unit thickness was 110.
Thus, it turns out that the molding material containing the hydrogenated polymer of this invention produced according to the Example was excellent in mechanical strength, the balance of refractive index and Abbe number, and low birefringence.

Claims

Following formula (1)

And a main chain and a side chain of a polymer containing a unit derived from a monomer represented by formula (1) and a unit derived from a monomer copolymerizable with the monomer represented by formula (1). A hydrogenated polymer obtained by hydrogenating at least 90% of the carbon-carbon unsaturated bonds of the aromatic ring and carbon-carbon unsaturated bonds of the aromatic ring.
The hydrogenated polymer according to claim 1, comprising a ring-opening unit of the monomer represented by the formula (1).
The monomer copolymerizable with the monomer represented by the formula (1) is selected from the group consisting of norbornene monomers, cyclic monoolefins, cyclic polyenes, and α-olefins having 2 to 20 carbon atoms. The hydrogenated polymer according to claim 1, wherein the hydrogenated polymer is at least one kind.
A molding material containing the hydrogenated polymer according to any one of claims 1 to 3.
A resin molded body obtained by molding the molding material according to claim 4.
The resin molded body according to claim 5, which is an optical element.