JP5239180B2 - Spirro ring-containing norbornene derivative, norbornene-based polymer, norbornene-based ring-opening polymer hydride, optical resin material and optical molded body - Google Patents

Description

  The present invention hydrogenates a novel spiro-ring-containing norbornene derivative, a norbornene-based polymer obtained by (co) polymerizing this derivative, and a norbornene-based ring-opened polymer obtained by ring-opening (co) polymerizing the derivative. In addition, the present invention relates to a hydrogenated norbornene-based ring-opening polymer, an optical resin material containing the hydride, and an optical molded body formed by molding the optical resin material.

  In recent years, with the advancement of functions of optical devices and the spread of applications, precise control is required for the optical properties of optical resin materials used in optical devices. In order to highly control the optical properties of the optical resin material, not only the resin processing technology and the higher order structure of the resin, but also the molecular structure of the resin raw material is important.

  Norbornene-based resins have excellent properties such as transparency, heat resistance, mechanical toughness, low water absorption and low birefringence, and are widely used in various optical applications such as optical lenses and optical films. . Among these, norbornene derivatives having a spiro skeleton are capable of fixing the orientation of substituents that affect optical properties, and are attracting attention as useful resin materials (monomers) that can satisfy the above requirements. Has been.

  Conventionally, as a norbornene derivative having a spiro skeleton, various compounds such as those described in Patent Documents 1 to 5 have been proposed.

However, in recent years, the functions of optical devices have become more sophisticated and their applications have become widespread, and precise control is required due to the optical characteristics of optical resin materials used in optical devices. There is a demand for the development of new optical resin materials that meet the requirements.
JP 2004-323489 A JP 2005-036201 A JP 2006-188671 A JP 2006-225316 A JP 2006-265176 A

  The present invention has been made in view of such a state of the art, and when used as an optical resin material, characteristic values such as positive / negative of wavelength dependency of phase difference, photoelastic coefficient, refractive index and the like are arbitrarily adjusted. Novel spiro-ring-containing norbornene derivative suitable as a monomer component that can be produced, norbornene-based polymer obtained by (co) polymerizing this derivative, norbornene-based ring-opening weight obtained by ring-opening (co) polymerizing the derivative An object of the present invention is to provide a norbornene-based ring-opening polymer hydride obtained by hydrogenating a polymer, an optical resin material containing the hydride, and an optical molded body formed by molding the optical resin material.

As a result of diligent research to solve the above problems, the present inventors have obtained a novel spiro ring-containing norbornene derivative by Diels-Alder reaction of 1-methyleneindane and cyclopentadiene. The ring-opening polymer obtained by metathesis ring-opening polymerization of this norbornene derivative, and the norbornene-based ring-opening polymer hydride obtained by hydrogenating this ring-opening polymer are excellent in transparency and low water absorption. I found.
Further, in the case of ring-opening copolymerization of a mixture comprising the spiro ring structure-containing norbornene derivative and other norbornene derivatives, the obtained opening can be obtained by changing the mixing ratio of the spiro ring structure-containing norbornene derivative and other norbornene derivatives. The inventors have found that the optical properties such as the wavelength dependence of the retardation of the ring copolymer (and its hydride), the photoelastic coefficient, and the refractive index can be controlled to desired values, and the present invention has been completed.
Thus, according to the first aspect of the present invention, a spiro ring-containing norbornene derivative represented by the formula (I) is provided.

[Wherein, R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom, a polar group, or a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. Moreover, the said C1-C30 hydrocarbon group may have a coupling group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom.
p, q, r, and s each independently represent an integer of 0 to 3.
a represents an integer of 0 to 2, and b and c are 1.
A represents a single bond . ]

According to the second aspect of the present invention, the spiro ring-containing norbornene derivative represented by the formula (I), the spiro ring-containing norbornene derivative, and other monomers copolymerizable with the spiro ring-containing norbornene derivative. A norbornene-based polymer obtained by polymerizing is provided.
According to the third aspect of the present invention, the spiro ring-containing norbornene derivative represented by the formula (I), the spiro ring-containing norbornene derivative, and other monomers copolymerizable with the spiro ring-containing norbornene derivative. There is provided a hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating a norbornene-based ring-opening polymer obtained by ring-opening polymerization.
According to a fourth aspect of the present invention, there is provided an optical resin material containing the norbornene-based polymer or the norbornene-based polymer hydride of the present invention.
According to the fifth aspect of the present invention, there is provided an optical molded body obtained by molding the optical resin material of the present invention.

The spiro ring-containing norbornene derivative of the present invention is a novel compound, and by polymerizing this, a norbornene-based polymer excellent in transparency and low water absorption can be obtained.
Further, by hydrogenating a ring-opening polymer obtained by metathesis ring-opening polymerization of the spiro ring-containing norbornene derivative of the present invention, a hydride of norbornene-based ring-opening polymer having excellent transparency and low water absorption can be obtained. it can.
Further, in the case of ring-opening copolymerization of the mixture comprising the spiro ring-containing norbornene derivative of the present invention and other monomers, by changing the mixing ratio of the spiro ring structure-containing norbornene derivative and other monomers, The optical properties such as the wavelength dependence of the retardation, the photoelastic coefficient, and the refractive index of the obtained ring-opening copolymer (and its hydride) can be controlled to desired values.
The optical resin material of the present invention contains the norbornene polymer or the norbornene ring-opening polymer hydride of the present invention, which has excellent transparency and low water absorption, and has optical properties controlled to a desired value. Therefore, it is suitable as a molding material for various optical products.
Since the optical molded body of the present invention is obtained by molding the optical resin material of the present invention, it has excellent optical characteristics.

  Hereinafter, the present invention is divided into 1) a spiro ring-containing norbornene derivative, 2) a norbornene-based polymer, 3) a norbornene-based ring-opening polymer hydride, 4) an optical resin material, and 5) an optical molded body. This will be described in detail.

1) Spiro ring-containing norbornene derivative The spiro ring-containing norbornene derivative of the present invention is a compound represented by the formula (I).
In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a halogen atom, a polar group, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. .

Examples of the halogen atom for R ^{1 to} R ⁵ include a fluorine atom, a chlorine atom, and a bromine atom.
The polar group of R ^{1 to} R ⁵ is generally an atom having an electronegativity different from that of a carbon atom or a group containing the atom. For example, oxygen atom; sulfur atom; group containing one or more selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom;

  Specific examples of the polar group include divalent polar groups such as an oxo group (═O), an imino group (═NH), and a thioxo group (═S); a hydroxyl group; 1 to 1 carbon atoms such as a methoxy group and an ethoxy group 10 alkoxy groups; alkylcarbonyloxy groups such as acetoxy group and propionyloxy group; arylcarbonyloxy groups such as benzoyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; phenoxycarbonyl groups and naphthyloxycarbonyl groups; Aryloxycarbonyl groups such as fluorenyloxycarbonyl groups and biphenylyloxycarbonyl groups; cyano groups; amide groups; imide groups; triorganosiloxy groups such as trimethylsiloxy groups and triethylsiloxy groups; trimethylsilyl groups and triethylsilyl groups Triorganosilyl group; amino An amino group which may be substituted, such as methylamino group, dimethylamino group and phenylamino group; acyl group such as acetyl group, propionyl group and benzoyl group; alkoxysilyl such as trimethoxysilyl group and triethoxysilyl group Group; alkylsulfonyl group such as methylsulfonyl group and ethylsulfonyl group; arylsulfonyl group such as phenylsulfonyl group and 4-methylphenylsulfonyl group; nitro group; cyano group; carboxyl group; sulfonic acid group; mercapto group; It is done.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, anthracenyl groups, and the like.

  The hydrocarbon group may be substituted. Examples of the substituent include halogen atoms such as fluorine, chlorine and bromine; alkoxy groups such as methoxy group and ethoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; amino group, methylamino group, dimethylamino group, An optionally substituted amino group such as a phenylamino group; an alkylsulfonyl group such as a methylsulfonyl group; an arylsulfonyl group such as a phenylsulfonyl group; a cyano group; a nitro group;

  Moreover, the C1-C30 hydrocarbon group which may have the said substituent may have a coupling group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. That is, the C1-C30 hydrocarbon group which may have the said substituent may be couple | bonded directly with the ring structure, or may be couple | bonded through the coupling group.

Examples of the linking group include a carbonyl group (—CO—), a carbonyloxy group (—C (═O) —O—), a sulfonyl group (—SO ₂ —), a sulfonyl ester group (—SO ₂ —O—), Ether bond (—O—), thioether bond (—S—), imino group (—NH—), amide bond (—NHCO—), siloxane bond (—Si (r) (r ′) O— (r, r) Each independently represents an alkyl group such as a methyl group or an ethyl group; a phenyl group optionally having a substituent such as a phenyl group or a 4-methylphenyl group; A group containing an atom, a sulfur atom or a silicon atom; a combination of two or more of these groups; and the like.

p, q, r, and s each independently represent an integer of 0 to 3, and p, q, r, and s are preferably each independently 0 or 1.
When p, q, r, and s are each 2 or more, the plurality of R ^{1 to} R ⁴ may be the same or different.

  a, b and c each independently represent an integer of 0 to 2, and a, b and c are preferably each independently 0 or 1. However, neither b nor c is 0.

A is a single bond, —O—, —S—, —SO—, —SO ₂ —, —C (═O) —, —NR ⁵ — (R ⁵ has a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group having 1 to 30 carbon atoms has a linking group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Or a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

The hydrocarbon group having 1 to 30 carbon atoms which may have a substituent of R ⁵ is a hydrocarbon having 1 to 30 carbon atoms which may have a substituent of R ^{1 to} R ^4. Specific examples of the groups are the same as those listed.

Further, the hydrocarbon group of the R ⁵ substituent 1 to 30 carbon atoms which may have a can, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a linking group containing a sulfur atom or a silicon atom And may be the same as the hydrocarbon group having 1 to 30 carbon atoms which may have the substituent of R ^{1 to} R ⁴ .

Examples of the divalent hydrocarbon group having 1 to 30 carbon atoms of the divalent hydrocarbon group having 1 to 30 carbon atoms which may have the substituent of A include a methylene group, an ethylene group, a propylene group, C1-C30 alkylene groups such as trimethylene group, tetramethylene group and pentamethylene group; C2-C30 alkenylene groups such as vinylene group, propenylene group, butenylene group and pentenylene group; o-phenylene group, m- And an arylene group having 6 to 30 carbon atoms such as a phenylene group, a p-phenylene group, and a 1,4-naphthalene group; a combination of an alkylene group and an arylene group; Among these, an alkylene group represented by — (CH ₂ ) _n — (n is 0 or an integer of 1 to 3) is preferable.

Specific examples of the spiro ring-containing norbornene derivative represented by the formula (I) of the present invention include the following. Of course, the compounds shown below are merely examples, and the present invention is not limited to the following.
In the compounds shown below, the following formula (a)

The partial structure represented by the following formula (b)

(In the formula, R ³ , R ⁴ , b, c, r and s represent the same meaning as described above.)
The partial structure shown by is represented.
(I) a compound wherein a = 0 in the formula (I)

(Ii) a compound in which a = 1 in the formula (I)

(Iii) a compound wherein a = 2 in the formula (I)

  Specific examples of the partial structure represented by the formula (a) include the following.

The norbornene derivative of the present invention can be produced as follows.
Among the norbornene derivatives represented by the above formula (I), the compound (I-1) in which a is 0 is, for example, a Dials of cyclopentadiene (2-1) and an olefin compound represented by the formula (3). -It can be obtained by alder addition reaction (the following reaction formula).

(Wherein R ^{2 to} R ⁴ , A, b, c, q, r and s represent the same meaning as described above.)
Preferable specific examples of the olefin compound represented by the formula (3) include the following compounds.

Many of the olefin compounds represented by the formula (3) are known compounds and can be produced by a conventionally known method. Moreover, what is marketed can also be used as a starting material as it is.
For example, as shown in the following reaction formula, the corresponding carbonyl compound (4) can be produced by reacting a Wittig reagent such as methyltriphenylphosphonium bromide and a base such as alkyllithium.

(Wherein R ³ , R ⁴ , A, b, c, r and s represent the same meaning as described above.)
In the formula (I), the compound (I-2) in which a is 1 is obtained by reacting the norbornene derivative (I-1) obtained by the Diels-Alder addition reaction with cyclopentadiene (2-2). It can be obtained by Diels-Alder addition reaction (the following reaction formula).

(In the formula, R ^{1 to} R ⁴ , A, b, c, p, q, r and s represent the same meaning as described above.)
In the formula (I), the compound in which a is 2 is a Diels-Alder addition reaction between the norbornene derivative (I-2) obtained by the Diels-Alder addition reaction and cyclopentadiene (2-2). Can be obtained.
In any reaction, the reaction temperature is usually 100 to 300 ° C., preferably 150 to 250 ° C., and the reaction time is several minutes to several hours.

  In any reaction, after the completion of the reaction, the usual post-treatment operation in synthetic organic chemistry is performed, and if desired, the reaction product can be separated and purified by known methods such as distillation, column chromatography, and recrystallization. The target norbornene derivative represented by the formula (I) can be efficiently isolated.

The structure of the target product can be identified and confirmed by using analytical means such as NMR spectrum, IR spectrum, and mass spectrum.
The obtained norbornene derivative is useful as a raw material for producing a norbornene-based polymer described later.

2) Norbornene polymer The second aspect of the present invention is the polymerization of the spiro ring-containing norbornene derivative of the present invention, or the spiro ring-containing norbornene derivative, and other monomers copolymerizable with the spiro ring-containing norbornene derivative. It is a norbornene-based polymer obtained as described above.

Examples of the norbornene polymer of the present invention include the following.
(A) Norbornene-based ring-opening polymer (A-1) Ring-opening polymer obtained by ring-opening polymerization of only one of the spiro ring-containing norbornene derivatives of the present invention (A-2) Spiro ring-containing norbornene derivatives of the present invention Ring-Opening Copolymer Obtained by Ring-Opening Copolymerization of Two or More of (A-3) The Spiro Ring-Containing Norbornene Derivative of the Present Invention, Others That Can Be Ring-Opening Copolymerized with the Spiro Ring-Containing Norbornene Derivative Ring-opening copolymer obtained by ring-opening copolymerization with other monomers

(B) Norbornene-based addition polymer (B-1) An addition polymer obtained by addition polymerization of only one of the spiro ring-containing norbornene derivatives of the present invention (B-2) Two types of spiro ring-containing norbornene derivatives of the present invention Addition copolymer obtained by addition copolymerization of the above (B-3) At least one spiro ring-containing norbornene derivative of the present invention, and other monomers capable of copolymerization with the spiro ring-containing norbornene derivative Of these, addition copolymer obtained by addition copolymerization Among these, the norbornene-based polymer of the present invention is preferably a ring-opening polymer of (A), and a norbornene-based ring-opening copolymer of (A-1). Is more preferable.

(A) Norbornene-based ring-opening polymer The norbornene-based ring-opening polymer is a spiro-ring-containing norbornene derivative of the present invention, or the spiro-ring-containing norbornene derivative and other single monomers copolymerizable with the spiro-ring-containing norbornene derivative. It is obtained by ring-opening polymerization of a monomer.

The other monomer capable of ring-opening copolymerization with the spiro ring-containing norbornene derivative of the present invention is not particularly limited as long as it is a monomer copolymerizable with the spiro ring-containing norbornene derivative, but heat resistance, strength In view of characteristics and the like, a repeating unit derived from a norbornene monomer is preferable.
The norbornene-based monomer is a compound having a norbornene structure represented by the following formula (c).

  Examples of the norbornene-based monomer capable of ring-opening copolymerization with the spiro ring-containing norbornene derivative of the present invention include compounds represented by the following formula (5).

In Formula (5), R ^{6 to} R ⁹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom, and R ⁶ And R ⁸ may combine to form a ring. m is 0 or 1.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ^{6 to} R ⁹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. An alkyl group having 1 to 20 carbon atoms such as n-hexyl group; an alkenyl group having 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, 2-propenyl group and crotyl group; carbon such as ethynyl group and propargyl group Alkynyl group having 2 to 20 carbon atoms; aryl groups having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group, and 2-naphthyl group;

Specific examples of the group containing a halogen atom, silicon atom, oxygen atom or nitrogen atom of R ^{6 to} R ⁹ include a halogen atom such as an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom. Group: a group represented by the formula: Sir ¹ r ² r ³ (wherein, r ^{1 to} r ³ each independently represents a hydrogen atom, an alkyl group or an aryl group), and the formula: Sir ¹ r ² a group containing a silicon atom such as an alkyl group substituted with a group represented by r ³ ; a group containing an oxygen atom such as an alkyl group substituted with a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an alkoxy group; amino Group, mono-substituted amino group, di-substituted amino group, alkyl group substituted with amino group, alkyl group substituted with mono-substituted amino group, alkyl group substituted with di-substituted amino group, Bamoiru group, an acylamino group, a group containing a nitrogen atom and a cyano group; and the like.

The ring formed by combining R ⁶ and R ⁸ is usually a 3- to 8-membered ring, preferably a 5- to 8-membered ring. The ring contains an oxygen atom, a sulfur atom, or a nitrogen atom. You may go out.

Specific examples of the norbornene-based monomer represented by the above formula (5) include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-ethylidene-2-norbornene, 5- Phenyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclohexenyl-2-norbornene, dicyclopentadiene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, tetracyclo [6 2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] norbornene monomer having no substituent such as dodeca-4-ene or having a hydrocarbon group as a substituent; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl 2-norbornene, 2-norbornene-5,6-dicarboxylic acid anhydride, 2-norbornene-5,6-dicarboxylic acid imide, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] norbornene monomers having a functional group such as dodec-4-ene; and the like.

  Among these, a norbornene-based monomer having no substituent or having a hydrocarbon group as a substituent can easily obtain a copolymer having a desired composition ratio and molecular weight, and has a hygroscopic property. Since it is low, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is particularly preferable because a ring-opening polymer hydride having low birefringence can be obtained.

In addition to the norbornene-based monomer as another monomer capable of ring-opening copolymerization with a spiro ring-containing norbornene derivative, for example, monocyclic olefins such as cyclohexene, cycloheptene, cyclooctene, and derivatives thereof; cyclohexadiene; And cyclic dienes such as cycloheptadiene and derivatives thereof;

  The norbornene-based ring-opening polymer can be copolymerized with (α) one or more of the spiro ring-containing norbornene derivatives of the present invention, or (β) the spiro ring-containing norbornene derivatives of the present invention and the spiro ring-containing norbornene derivatives. A mixture with other monomers can be obtained by ring-opening polymerization in the presence of a metathesis catalyst.

  Examples of the metathesis catalyst used in the production of the norbornene-based ring-opening polymer include (i) a ring-opening metathesis polymerization catalyst using a combination of a transition metal halogen compound and an alkylating agent or a Lewis acid that functions as a co-catalyst, and (ii) a period. Table 4-8 transition metal-carbene complex catalyst, (iii) metallacyclobutane complex catalyst, etc. are mentioned. These metathesis reaction catalysts can be used alone or in admixture of two or more. Among these, since a cocatalyst is not required and the activity is high, it is preferable to use a transition metal-carbene complex catalyst belonging to groups 4 to 8 of the periodic table of (ii), and use of a ruthenium carbene complex catalyst. Is particularly preferred.

Specific examples of the transition metal halogen compound (i) include molybdenum halides such as MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , MoOF ₄ , etc .; WBr ₂ , WCl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , WCl ₄ (OC ₆ H ₄ Cl ₂ ) _2, etc .; VOCl ₃ , VOBr ₃ And vanadium halides such as TiCl ₄ and TiBr ₄ .

  Specific examples of alkylating agents or Lewis acids that function as cocatalysts include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride. Organic aluminum compounds such as di-n-butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, isobutylaluminoxane;

  Tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin Organotin compounds such as dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trichloride, butyltin trichloride, butyltin tribromide, dibutyltin triiodide;

  Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; Organic sodium compounds such as n-pentylsodium; methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propyl Organomagnesium compounds such as magnesium bromide, t-butylmagnesium chloride, arylmagnesium chloride; Organozinc compounds such as diethylzinc; Organocadmium compounds such as diethylcadmium; Trimethylboron, triethylboron, tri-n-butylboron, triphenylboron , Tris (perfluorophenyl) boron, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate, trityltetrakis (perf Orofeniru) organoboron compounds such borate and the like.

  Examples of the periodic table group 4-8 transition metal-carbene complex catalyst of (ii) include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.

Specific examples of the tungsten alkylidene complex ^{_{catalysts, W (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2 C 6 ^{_{H 3) (CHBu t) (}} OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2 ^{_{, 6-Pr i 2 C 6}} H 3) (CHCMe 2 Ph) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2 ^{_{, W (N-2,6-Pr}} i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and the like.

Specific examples of molybdenum alkylidene complex _{^{catalyst, Mo (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H _{^{3) (CHBu t) (OCMe}} 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2, _{^{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, _{^{Mo (N-2,6-Pr i}} 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (BIPHEN), Mo ( N-2,6-Pr i 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (BINO) (THF) and the like.

Specific examples of rhenium alkylidene complex ^{catalyst, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2- _{^{Bu t C 6 H 4) 2}} , Re (CBu t) (CHBu t) (OCMe 2 CF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu ^t ) (O-2,6-Me ₂ C ₆ H ₃ ) _{2 and the} like.

In the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl-3, 3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. .

  Specific examples of the ruthenium carbene complex catalyst include compounds represented by the following formula (A) or formula (B).

In the above formulas (A) and (B), ═CR ^a R ^b and ═C═CR ^a R ^b are carbene compounds containing a carbene carbon at the reaction center, and these carbene compounds contain a heteroatom. You don't have to. R ^a and R ^b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom.

L ¹ represents a heteroatom-containing carbene compound, and L ² represents a heteroatom-containing carbene compound or any neutral electron-donating compound. Both L ¹ and L ² or L ¹ is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.

  Here, the hetero atom-containing carbene compound refers to a compound containing a carbene carbon and a hetero atom. Specific examples of the hetero atom include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.

When L ² is a neutral electron donating compound, L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable.

L ³ and L ⁴ each independently represent an arbitrary anionic ligand.
The L ³ and L ⁴ anionic (anionic) ligands are ligands having a negative charge when separated from the central metal. For example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydrocarbon groups containing oxygen such as diketonate group, alkoxy group, aryloxy group and carboxyl group; halogen atoms such as cyclopentadienyl chloride group Examples thereof include substituted alicyclic hydrocarbon groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

Also, 2, 3, 4, 5 or 6 of R ^a , R ^b , L ¹ , L ² , L ³ and L ⁴ are bonded to each other to form a multidentate chelating ligand. May be.

  Examples of the ruthenium carbene complex catalyst represented by the formula (A) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl). Imidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2 Ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) Ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride, etc. A ruthenium carbene complex in which a heteroatom-containing carbene compound and a neutral electron donating compound are bonded;

  Ruthenium in which two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride are bonded. Carbene complex; and the like.

  Examples of the ruthenium carbene complex catalyst represented by the formula (B) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene). ) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Specific examples of the metallacyclobutane complex catalyst (iii) include titanacyclobutanes.

  The amount of the metathesis reaction catalyst used is the spiro ring-containing norbornene derivative or a mixture of the spiro ring-containing norbornene derivative and another monomer copolymerizable therewith (hereinafter simply referred to as “monomer”). In general, catalyst: monomer = 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000. ~ 1: 500,000. If the amount of catalyst is more than the molar ratio, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  The ring-opening polymerization of a monomer using a metathesis reaction catalyst can be performed in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

The solvent used is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction.
Examples of the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, ethyl methyl ketone, cyclopentanone and cyclohexanone; methyl acetate; Ethyl, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

  The concentration of the monomer in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. When the monomer concentration is less than 1% by weight, the productivity of the polymer may be deteriorated, and when it exceeds 50% by weight, the viscosity after polymerization may be too high, and subsequent hydrogenation and the like may be difficult. .

  The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used in the polymerization reaction.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight can be obtained usually by using 0.1 to 100 mol% of a molecular weight modifier with respect to the monomer.

  The polymerization temperature is not particularly limited, but is usually −50 ° C. to + 150 ° C., preferably 0 ° C. to 100 ° C., more preferably 10 ° C. to 60 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

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

  In addition, as long as the object of the present invention is not impaired, the ring-opening (co) polymer is converted into an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrenic polymer by a known method in JP-A-3-95235 or the like. Modifications can be made using hydrocarbons, organosilicon compounds having olefinic unsaturated bonds and hydrolyzable groups, and unsaturated epoxy monomers.

A norbornene-based ring-opening polymer can be produced as described above.
The weight average molecular weight (Mw) calculated | required by the gel permeation chromatography of the norbornene-type ring-opening polymer obtained is 5,000-1,000,000 normally in polystyrene conversion, Preferably it is 10,000-100. 000, more preferably 20000 to 50,000.

  The norbornene-based ring-opening polymer may be referred to as a repeating unit derived from the spiro ring-containing norbornene derivative of the present invention (hereinafter referred to as repeating unit [I]). And a copolymer containing a repeating unit derived from the norbornene-based monomer represented by the formula (5) (hereinafter sometimes referred to as “repeating unit [II]”), The coalescence may be a random copolymer or a block copolymer, but a random copolymer is preferred.

When the norbornene-based ring-opening polymer is a copolymer containing the repeating unit [I] and the repeating unit [II], the ratio of the repeating unit [I] to the total repeating units depends on the production purpose of the polymer. Although it can select arbitrarily, when optical characteristics, heat resistance, etc. are considered, 1 to 90 weight% is preferable and 1 to 80 weight% is more preferable. The ratio of the repeating unit [I] contained in the norbornene-based ring-opening copolymer to all repeating units can be determined, for example, by measuring the ¹ H-NMR spectrum of the obtained ring-opening polymer.

(B) Norbornene-based addition polymer The norbornene-based addition polymer is a spiro-ring-containing norbornene derivative of the present invention, or the spiro-ring-containing norbornene derivative and other monomers copolymerizable with the spiro-ring-containing norbornene derivative. Is obtained by addition polymerization.

  Other monomers capable of addition copolymerization with the spiro ring-containing norbornene derivative of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, C2-C20 alpha olefins, such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; Cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, and derivatives thereof; Non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; norbornene-based monomer having no aromatic ring structure Body; and the like. Among these, an α-olefin, particularly ethylene is preferable.

  These other monomers capable of addition polymerization can be used alone or in combination of two or more.

  In the case of addition copolymerization of the spiro ring-containing norbornene derivative of the present invention and an addition-polymerizable monomer, other monomer capable of copolymerization with the structural unit of the spiro ring-containing norbornene derivative in the addition copolymer The ratio with the structural unit derived from the body is appropriately selected so that the weight ratio is usually 20:80 to 99: 1, preferably 40:70 to 95: 5, more preferably 50:50 to 90:10. Is done.

Examples of addition polymerization catalysts include Ziegler catalysts and metallocene catalysts.
Examples of the Ziegler catalyst include a catalyst composed of a reducing agent such as a vanadium compound and an alkylaluminum compound. Specifically, it is produced using a catalyst formed from a soluble vanadium compound and an organoaluminum compound. 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 , VO (On-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 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, etc. , Tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3 Lewis acid such as 5-dimethylphenyl) boron, It is selected from ionic compounds such as rucarbonium tetrakis (pentafluorophenyl) borate, borane compounds such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, carborane compounds, and the like Examples include a catalyst formed by adding a cocatalyst component.

  Examples of the metallocene transition metal include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. Among these, zirconium and hafnium are preferable, and zirconium is more preferable. As the promoter component, organoaluminum compounds, Lewis acids, and ionic compounds are preferred, and organoaluminum compounds and ionic compounds are more preferred.

  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 dichloride, rac- Diphenylsilyl-bis (1-indenyl) hafnium dichloride, diphenylmethylene (9-fluorenyl) cyclopentadienylzirconium dichloride, and isopropylene (9-fluorenyl) cyclopentadienylzirconium dichloride are preferred.
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 as described above, alkylaluminum partially alkoxylated and halogenated, aluminoxane and the like.
Of these, alkyl aluminum halide, alkyl aluminum dihalide, alkyl aluminum, and aluminoxane are preferable. These organoaluminum compounds can be used alone or in combination of two or more.

  When the addition polymerization is solution polymerization, the solvent to be used 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; etc. Is mentioned. Among these, aromatic hydrocarbons and aliphatic alicyclic hydrocarbons are preferable, toluene, cyclohexane, cyclooctane and the like are more preferable, and toluene and cyclohexane are particularly preferable. These hydrocarbon solvents can be used alone or in combination of two or more.

  Further, the norbornene-based addition (co) polymer can be hydrogenated by a hydrogenation method described later, if necessary.

As described above, the norbornene-based addition (co) polymer can be produced.
The weight average molecular weight (Mw) calculated | required by the gel permeation chromatography of the norbornene type addition (co) polymer obtained is 5,000-1,000,000 normally in polystyrene conversion, Preferably it is 10,000. ~ 100,000.

3) Norbornene-based ring-opening polymer hydride The norbornene-based ring-opening polymer hydride of the present invention is obtained by hydrogenating the above-described norbornene-based ring-opening polymer.

The norbornene-based ring-opening polymer hydride of the present invention is a product in which 80% or more of all carbon-carbon double bonds of the norbornene-based ring-opening polymer are usually hydrogenated (hereinafter referred to as “total hydride”). However, in general, 80% or more of the carbon-carbon double bonds in the main chain of the norbornene-based ring-opening polymer are hydrogenated, and the carbon-carbon double bonds in the aromatic ring are hydrogenated. The hydrogenation rate may be one selectively hydrogenated so as to be 10% or less (hereinafter sometimes referred to as “partially hydride”), and is appropriately selected according to the purpose of use. .
Especially, the hydrogenation rate of the carbon-carbon double bond of the total hydride and the hydrogenation rate of the carbon-carbon double bond of the main chain of the partial hydride are more preferably 98% or more, and 99% or more. Is particularly preferable, and is most preferably 99.9% or more. When the hydrogenation rate is within this range, the hydride is excellent in light resistance and oxidation resistance.

  The hydrogenation reaction of the norbornene ring-opening polymer is carried out by bringing the norbornene ring-opening polymer into contact with hydrogen in the presence of a hydrogenation catalyst.

  Examples of the hydrogenation catalyst used include JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550, and the like. Can be used, and either a homogeneous catalyst or a heterogeneous catalyst may be used.

  Examples of homogeneous catalysts include combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst systems comprising combinations of transition metal compounds and alkali metal compounds; noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, etc. .

  Examples of the heterogeneous catalyst include a catalyst in which a hydrogenation catalyst metal such as Ni or Pd is supported on a carrier. Examples of the carrier include silica, alumina, silica alumina, diatomaceous earth and the like. Among these, a Ni catalyst supported on silica is preferable.

  The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the catalyst. However, since the solubility of the hydrogenated product to be produced is excellent, a hydrocarbon solvent is usually used.

  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 carried out according to a conventional method, but total hydrides and partial hydrides can be obtained by appropriately adjusting the reaction conditions such as the type of hydrogenation catalyst and reaction temperature.
When obtaining a total hydride, the hydrogenation catalyst is preferably a homogeneous catalyst, more preferably a ruthenium homogeneous catalyst. The reaction temperature is preferably in the range of 100 to 200 ° C, more preferably in the range of 130 to 195 ° C.
When obtaining a partial hydride, the hydrogenation catalyst is preferably a heterogeneous catalyst, more preferably a nickel heterogeneous catalyst. The reaction temperature is preferably in the range of 150 to 250 ° C, more preferably in the range of 200 to 240 ° C.
The hydrogen pressure is an absolute pressure and is usually 0.01 to 10 MPa, preferably 0.05 to 6 MPa, and more preferably 0.1 to 5 MPa.

  After completion of the hydrogenation reaction, the hydrogenation catalyst is removed from the reaction solution by centrifugation or filtration. 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. Further, if necessary, a catalyst deactivator such as water or alcohol can be used, or an adsorbent such as activated clay or alumina can be added.

  As described above, the hydride of the norbornene-based ring-opening polymer of the present invention can be obtained. The weight average molecular weight (Mw) calculated | required by the gel permeation chromatography of the norbornene-type ring-opening polymer hydride obtained is 5,000-1,000,000 normally in polystyrene conversion, Preferably it is 10,000. ~ 100,000, more preferably 20,000-50,000. When the weight average molecular weight (Mw) is in this range, it is preferable in terms of moldability and mechanical strength of the resulting resin composition.

  Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the hydride of the norbornene-based ring-opening polymer is not particularly limited, but is usually 10 or less, preferably Is 5 or less, more preferably 3 or less. The molecular weight distribution (Mw / Mn) is preferably in this range from the viewpoint of moldability and mechanical strength of the obtained resin composition.

  In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the norbornene-based polymer and the norbornene-based ring-opening polymer hydride are gel permeation chromatography (GPC) at 40 ° C. using tetrahydrofuran as an eluent. It is a value measured by the above and converted with standard polyisoprene. However, when the polymer is insoluble in tetrahydrofuran, the value is calculated using standard polyisoprene using cyclohexane as a solvent.

The glass transition temperature (hereinafter sometimes referred to as “Tg”) of the norbornene-based ring-opening polymer hydride of the present invention is usually 100 to 300 ° C., preferably 100 to 250 ° C., more preferably 120 to 200 ° C. It is. When Tg is within this range, the heat resistance of the norbornene-based ring-opening polymer hydride and the processability of the resulting resin composition are preferred.
Tg is a value measured under the condition of 10 ° C./min using a differential scanning calorimeter.

The hydrogenated norbornene-based ring-opening polymer of the present invention has a low water absorption rate. When the water absorption is low, the change in optical properties due to water absorption is small, and the optical material is excellent.
The water absorption of the norbornene-based ring-opening polymer hydride of the present invention was measured in accordance with JIS K7209 by measuring the change in weight after being immersed in distilled water at 23 ° C. for 24 hours using a molded plate having a thickness of 3 mm. The ratio of the weight change is usually 0.1% or less, preferably 0.05% or less, more preferably 0.01% or less.

  The hydride of norbornene-based polymer and norbornene-based ring-opening polymer of the present invention is a ring-opening copolymer of a spiro ring-containing norbornene derivative of the present invention and a mixture of other monomers copolymerizable with the spiro ring-containing norbornene derivative. When it is obtained by polymerization, by changing the mixing ratio of the spiro ring-containing norbornene derivative and other monomers, the optical properties of the resulting ring-opening copolymer (and its hydride) ( The retardation wavelength dependency, photoelastic coefficient, refractive index, etc.) can be controlled to desired values.

4) Optical resin material The optical resin material of the present invention contains, as an essential component, the norbornene-based polymer or hydride of norbornene-based ring-opening polymer of the present invention.

  The optical resin material of the present invention may be one or more of the norbornene-based polymer or the norbornene-based ring-opening polymer hydride of the present invention (hereinafter, these may be collectively referred to as “norbornene-based polymer etc.”). .) May be used, but various compounding agents can be blended as necessary.

  Examples of the compounding agent used include a modifier, an antioxidant, a light stabilizer, a lubricant, a plasticizer, an antistatic agent, an antiblocking agent, and a leveling agent.

  These modifiers, antioxidants, light stabilizers, lubricants, plasticizers, antistatic agents, antiblocking agents, leveling agents and the like are not particularly limited, and known ones can be used. The use amount of these additives is usually 0.001 to 100 parts by weight with respect to 100 parts by weight of the norbornene-based ring-opening polymer or the like.

  As a method of mixing the norbornene polymer and the like of the present invention and a compounding agent blended as necessary, a pellet-shaped resin is obtained by kneading the norbornene polymer and the like and a compounding agent blended as necessary. A method for obtaining a composition; a method for obtaining a resin composition by mixing a norbornene-based polymer and the like, and a compounding agent to be added if necessary in an appropriate solvent, and removing the solvent; a norbornene-based polymer, etc. And a method in which a compounding agent is blended in advance in the reaction liquid to be produced.

  For the kneading, a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder can be used. The kneading temperature is usually 100 to 400 ° C, preferably 150 to 350 ° C. Further, when kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

  Since the optical resin material of the present invention contains the norbornene-based polymer or hydride of norbornene-based ring-opening polymer of the present invention as an essential component, as described later, the raw material for producing the optical molded body of the present invention Useful as.

5) Optical molded body The optical molded body of the present invention is obtained by molding the optical resin material of the present invention.
That is, the optical resin material of the present invention can be molded into a desired shape by a known molding method to obtain an optical molded body having a desired shape.

  Molding methods include injection molding, extrusion blow molding, injection blow molding, two-stage blow molding, multilayer blow molding, connection blow molding, stretch blow molding, rotational molding, vacuum molding, extrusion Examples thereof include a molding method, a calendar molding method, a solution casting method, a hot press molding method, and an inflation method.

  Examples of the optical molded body of the present invention include various optical components such as an optical disk, an optical lens, an optical film, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, and a light guide plate.

(1) The composition ratio of the polymer was determined by ¹ H-NMR spectrum measurement using deuterated chloroform as a solvent. As an NMR measuring apparatus, JMN-AL series AL400, manufactured by JEOL Co., Ltd. was used (the same applies below).
(2) The hydrogenation rate (%) of the polymer was determined by ¹ H-NMR spectrum measurement.
(3) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and obtained as standard polystyrene equivalent values.

(4) The water absorption of the polymer was measured in accordance with JIS K7209 by measuring the change in weight after being immersed in distilled water at 23 ° C. for 24 hours using a molded plate having a thickness of 3 mm.
(5) The wavelength dependency of retardation is measured for retardation values at 450 nm and 550 nm using a retardation measuring device (KOBRA-21ADH, manufactured by Oji Scientific Co., Ltd.) for the oriented film, and the retardation value at 550 nm. Evaluation was made by taking the difference from the retardation value at 450 nm.
If the difference between the retardation value at 550 nm and the retardation value at 450 nm is positive (+), the wavelength dependence of the phase difference indicates a positive correlation, and if it is negative (−), the wavelength dependence of the phase difference is negative. It shows that the correlation is shown.

(6) The photoelastic coefficient ( _CR value) was measured according to the method described in the literature (Polymer Journal, 1995, 27, 943) using a cast film.
Specifically, four types of constant loads (25.5 g, 46.7 g, 76.6 g, and 97.8 g) were applied to the cast film at a temperature 15 ° C. higher than the glass transition temperature of the polymer. When the elongation was 20%, the film was slowly cooled to room temperature, and then the retardation generated in the obtained cast film was measured and calculated from the applied stress.
(7) The refractive index is the refractive index at d line (measurement wavelength: 587.6 nm) at 25 ° C. with a Karnew refractometer (KPR-200, manufactured by Shimadzu Corporation) using a molded plate having a thickness of 3 mm. It was measured.

(Reference Example 1)
(Synthesis of monomer precursor)
100 parts by weight of methyltriphenylphosphonium bromide and 200 parts by weight of diethyl ether were added to a glass reactor, and the system was purged with nitrogen. After sealing the system, 166 parts by weight of 1.6N butyllithium hexane solution was added dropwise with stirring, and the mixture was further stirred at 25 ° C. for 5 hours. Thereafter, a solution in which 35 parts by weight of 1-indanone was dissolved in 40 parts by weight of diethyl ether was dropped into the system and stirred at 50 ° C. for 12 hours. After completion of the reaction, the precipitate was removed by suction filtration, and then the reaction mixture was heated under reduced pressure to remove the solvent and unreacted substances, thereby obtaining a colorless and transparent liquid with a yield of 33% (boiling point: 66 ° C., 6.7 × 10 ² Pa). The ¹ H-NMR spectrum of the obtained colorless and transparent liquid was measured.
This measurement result confirmed that this compound was 1-methyleneindane. The spectrum data is shown below.

¹ H-NMR (δ ppm): 2.80 (m, 2H), 2.98 (m, 2H), 5.03 (t, 1H), 5.44 (t, 1H), 7.21 (m, 3H), 7.49 (m, 1H)

(Monomer synthesis)
To the SUS bottle, 100 parts by weight of the obtained 1-methyleneindane and 50 parts by weight of dicyclopentadiene were added, and the system was purged with nitrogen. After the system was sealed, it was heated with a mantle heater and stirred at 180 ° C. for 2 hours. After completion of the reaction, the reaction mixture was heated under reduced pressure to remove unreacted substances, thereby obtaining a colorless and transparent liquid with a yield of 38% (boiling point: 160 ° C., 6.7 × 10 ² Pa).
The ¹ H-NMR spectrum of the obtained colorless and transparent liquid was measured.
This measurement result confirms that this compound is spiro [indan-3,3′-bicyclo [2.2.1] hept-5-ene] (hereinafter abbreviated as “monomer (A)”). It was. The spectrum data is shown below.

¹ H-NMR (δ ppm): 1.33 (d, 1H), 1.52 (d, 2H), 1.68 (m, 2H), 1.83 (m, 2H), 1.95 (m, 2H), 2.08 (dd, 1H), 2.15 to 2.31 (m, 2H), 2.61 (s, 1H), 2.68 (s, 1H), 2.75 (m, 1H) ) 2.80-2.90 (m, 2H), 2.95 (m, 3H), 5.82 (s, 1H), 6.28 (s, 2H), 6.37 (s, 1H) 6.93 (d, 1H), 7.04 (t, 1H), 7.10 (t, 1H), 7.12 to 7.19 (m, 3H), 7.21 (m, 1H), 7.27 (m, 1H)

(Production of ring-opening polymer)
(1,3-Dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts by weight, toluene 120 parts by weight, monomer (A) 30 parts by weight and 0.2 part by weight of 1-hexene as a chain transfer agent were added, and the whole volume was stirred at 70 ° C. for 2 hours to obtain a solution containing a ring-opening polymer. The yield of the ring-opening polymer was 95%.

(Synthesis of ring-opening polymer hydride)
The polymer solution obtained above was placed in an autoclave equipped with a stirrer, and the inside of the autoclave was purged with nitrogen, and then (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride 0.2 wt. And a solution of 0.5 parts by weight of ethyl vinyl ether and 15 parts by weight of toluene were added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. After the autoclave was cooled to room temperature, a suspension in which 1 part by weight of activated carbon powder was dispersed in 10 parts by weight of toluene was added to the autoclave and stirred at a hydrogen pressure of 4.0 MPa and 150 ° C. for 3 hours.
Next, the solution was taken out, the activated carbon powder was filtered off with a fluororesin filter having a pore size of 0.2 μm, and the obtained filtrate was poured into a large amount of 2-propanol to completely precipitate the solid content. The solid content was collected by filtration, washed, and dried under reduced pressure at 100 ° C. for 24 hours to obtain a ring-opened polymer hydride (1).

The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring-opened polymer hydride (1) is Mw = 36,000, Mw / Mn = 2.14.
The hydrogenation rate of the carbon-carbon double bond of the main chain of the ring-opening polymer hydride (1) was 98%, and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring was 0%.
The glass transition temperature of the ring-opened polymer hydride (1) was 106 ° C.

(Creation of specimen)
100 parts by weight of ring-opened polymer hydride (1) and tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (trade name) as an antioxidant : Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd. (0.1 part by weight) was kneaded with a twin-screw kneading extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) to obtain a resin composition (1).

Using an injection molding machine (ROBOSHOT S-2000i 100B, manufactured by FANUC), the resin composition (1) was molded at a mold temperature of 100 ° C., a cylinder temperature of 290 ° C., a nozzle temperature of 285 ° C., a holding pressure of 700 kg / m ² , and an injection speed. Injection molding was performed under the conditions of 20 mm / sec to obtain a molded plate (1) having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm.
Further, a solution in which 20 parts by weight of the resin composition (1) was dissolved in 80 parts by weight of tetrahydrafuran was cast on a release coat film and left at 25 ° C. for 4 hours. Then, the cast film (1) with a thickness of 100 μm was obtained by heating and drying at 50 ° C. for 12 hours.
The obtained cast film (1) was uniaxially stretched at a temperature of 175 ° C. and a draw ratio of 1.3 times using a tensile tester with a thermostatic bath (AGIS-20 kN, manufactured by Shimadzu Corporation), and an oriented film (1 )

(Evaluation)
Using the obtained molded plate (1), cast film (1), and oriented film (1), the refractive index, water absorption, photoelastic coefficient, and wavelength dependence of retardation were measured. The results are shown in Table 1.

(Reference Example 2)
In Reference Example 1 , instead of 30 parts by weight of monomer (A), 15 parts by weight of monomer (A) and 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene (hereinafter referred to as “MTF”) (Omitted) A polymer solution was obtained in the same manner as in Reference Example 1 except that a mixture consisting of 15 parts by weight was used. The polymer yield was 97%. The composition ratio of the obtained polymer was monomer (A) / MTF = 50/50 by weight.
Next, a hydrogenation reaction was performed in the same manner as in Reference Example 1 to obtain a ring-opening copolymer hydride (2).

The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring-opening copolymer hydride (2) is Mw = 39,000, respectively. Mw / Mn = 2.20.
The hydrogenation rate of the carbon-carbon double bond of the main chain of the ring-opening polymer hydride (2) was 98%, and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring was 0%.
Moreover, the glass transition temperature of the ring-opening polymer hydride (2) was 122 ° C.

In Reference Example 1 , a molded plate (2) and a cast film (2) were obtained in the same manner as in Reference Example 1 , except that the ring-opened polymer hydride (2) was used instead of the ring-opened polymer hydride (1). An oriented film (2) was obtained.
Using the obtained molded plate (2), cast film (2), and oriented film (2), the refractive index, water absorption, photoelastic coefficient, and wavelength dependence of retardation were measured. The results are shown in Table 1.

(Reference Example 3)
In Reference Example 1 , instead of 0.2 parts by weight of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, a nickel-silica supported catalyst (E22U, manufactured by JGC Chemical Co., Ltd.) Except having used 0.6 part, it carried out similarly to the reference example 1, and obtained the ring-opening polymer hydride (3).
The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring-opening copolymer hydride (3) is Mw = 40,000, respectively. Mw / Mn = 2.08.
The hydrogenation rate of the carbon-carbon double bond of the main chain of the ring-opening polymer hydride (3) was 99%, and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring was 99.9%. .
Moreover, the glass transition temperature of the ring-opening polymer hydride (3) was 137 ° C.

In Reference Example 1 , a molded plate (3) and a cast film (3) were obtained in the same manner as in Reference Example 1, except that the ring-opened polymer hydride (3) was used instead of the ring-opened polymer hydride (1). An oriented film (3) was obtained.
Using the obtained molded plate (3), cast film (3), and oriented film (3), the refractive index, water absorption, photoelastic coefficient, and wavelength dependence of retardation were measured. The results are shown in Table 1.

Example 1
(Synthesis of monomer precursor)
In Reference Example 1, a reaction mixture was obtained in the same manner as Reference Example 1 except that 48 parts by weight of 9-fluorenone was used instead of 35 parts by weight of 1-indanone. After completion of the reaction, the precipitate was removed by suction filtration, and then the reaction mixture was heated under reduced pressure to remove the solvent and unreacted substances. The residue after heating under reduced pressure was recrystallized with ethanol to obtain a light yellow solid with a yield of 30% (melting point: 49 ° C.).
The obtained solid was dissolved in deuterated chloroform, and a ¹ H-NMR spectrum was measured with an NMR measuring apparatus. This measurement result confirmed that this compound was 9-methylenefluorene.

(Monomer synthesis)
In Reference Example 1 , a reaction mixture was obtained in the same manner as in Reference Example 1 except that 137 parts by weight of 9-methylenefluorene was used instead of 100 parts by weight of 1-methyleneindane. The reaction mixture was heated under reduced pressure to remove unreacted substances, whereby a colorless and transparent liquid was obtained in a yield of 31% (boiling point: 180 ° C., 6.7 × 10 2 Pa).
The obtained colorless and transparent liquid was dissolved in deuterated chloroform, and a ¹ H-NMR spectrum was measured with an NMR measuring apparatus. This measurement result confirms that this compound is spiro [fluorene-3,3′-bicyclo [2.2.1] hept-5-ene] (hereinafter abbreviated as “monomer (B)”). It was.

(Synthesis of ring-opening polymer)
In Reference Example 1 , a polymer solution was obtained in the same manner as Reference Example 1 except that 41 parts by weight of monomer (B) was used instead of 30 parts by weight of monomer (A). The yield of polymer was 95%.

(Synthesis of ring-opening polymer hydride)
Next, a ring-opened polymer hydride (4) was obtained in the same manner as in Example 1 except that the polymer solution was used.
The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring-opened polymer hydride (4) is Mw = 38,000, Mw / Mn = 2.02.
The hydrogenation rate of the carbon-carbon double bond of the main chain of the ring-opening polymer hydride (4) was 97%, and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring was 0%.
Moreover, the glass transition temperature of the ring-opening polymer hydride (4) was 185 ° C.

In Reference Example 1 , a molded plate (4) and a cast film (4) were obtained in the same manner as in Reference Example 1, except that the ring-opened polymer hydride (4) was used instead of the ring-opened polymer hydride (1). An oriented film (4) was obtained.
Using the obtained molded plate (4), cast film (4), and oriented film (4), the refractive index, the water absorption, the photoelastic coefficient, and the wavelength dependence of the retardation were measured. The results are shown in Table 1.

(Reference Example 4)
In Reference Example 3 , a polymerization solution was obtained in the same manner as Reference Example 3 except that 30 parts by weight of MTF was used instead of the mixture consisting of 15 parts by weight of monomer (A) and 15 parts by weight of MTF. The polymer yield was 97%.
Next, a ring-opened polymer hydride (5) was obtained in the same manner as in Reference Example 3 .
The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring-opening polymer hydride (5) is Mw = 37,000, Mw / Mn = 2.05.
The hydrogenation rate of the carbon-carbon double bond of the main chain of the ring-opening polymer hydride (5) was 100%, and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring was 100%.
Moreover, the glass transition temperature of the ring-opening polymer hydride (5) was 139 ° C.

In Reference Example 1 , a molded plate (5) and a cast film (5) were obtained in the same manner as in Reference Example 1 , except that the ring-opened polymer hydride (5) was used instead of the ring-opened polymer hydride (1). An oriented film (5) was obtained.
Using the obtained molded plate (5), cast film (5), and oriented film (5), the refractive index, water absorption, photoelastic coefficient, and wavelength dependence of retardation were measured. The results are shown in Table 1.

From Table 1 , the polymers of Reference Example 1 and Example 1 show the wavelength dependence of negative retardation, have a high refractive index of 1.58 or more and a low water absorption of 0.01%. Thus, it can be seen that an optical molded body having a wavelength dependency of a negative phase difference can be obtained with a low water absorption, and an optical molded body having a high refractive index can be obtained.
The polymers of Reference Examples 2 and 3 have low photoelastic coefficients of 400 × 10 ⁻⁶ Pa and −400 × 10 ⁻⁶ Pa, low water absorption of 0.01%, and low water absorption. It can be seen that an optical molded body having a small absolute value of the photoelastic coefficient can be obtained.
Therefore, when used as an optical resin material, the spiro ring-containing norbornene derivative of the present invention is suitable as a monomer component that can arbitrarily adjust the characteristic values of retardation, such as wavelength dependence, photoelastic coefficient, and refractive index. It turns out that it is.

Claims (5)

A spiro ring-containing norbornene derivative represented by the following formula (I).

[Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a halogen atom; oxo group (═O), imino group (═NH), thioxo group (═S), hydroxyl group, carbon atom Number 1-10 alkoxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, amide group, imide group, triorganosiloxy group, triorganosilyl group, substituted A group selected from amino group, acyl group, alkoxysilyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, carboxyl group, sulfonic acid group, mercapto group; or halogen atom, alkoxy group, alkoxycarbonyl group, substituted Optionally substituted amino group, alkylsulfonyl group, arylsulfonyl group, Or a hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent selected from a nitro group or a nitro group. Moreover, the said C1-C30 hydrocarbon group may have a coupling group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom.
p, q, r and s each independently represent an integer of 0 to 3.
a represents an integer of 0 to 2, and b and c are 1.
A represents a single bond . ]   A norbornene-based polymer obtained by polymerizing the spiro ring-containing norbornene derivative according to claim 1 or the spiro ring-containing norbornene derivative and another monomer copolymerizable with the spiro ring-containing norbornene derivative.   The norbornene-based ring-opening obtained by ring-opening polymerization of the spiro-ring-containing norbornene derivative according to claim 1, or the spiro-ring-containing norbornene derivative and another monomer copolymerizable with the spiro-ring-containing norbornene derivative. A hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating a polymer.   An optical resin material containing the norbornene-based polymer according to claim 2 or the hydrogenated norbornene-based ring-opening polymer according to claim 3.   An optical molded body obtained by molding the optical resin material according to claim 4.