JP2005281219A - Norbornene derivative, and (co)polymer obtained by polymerizing the derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new alicyclic structure-containing monomer capable of obtaining a polymer having extremely low birefringence and high heat resistance as well as excellent transparency and non-water absorbency. <P>SOLUTION: A norbornene derivative containing an N-mesogen-substituted dicarboximide group is suitable as the alicyclic structure-containing monomer. The mesogen group is preferably a group having two or more aromatic rings (including hetero-aromatic rings) or alicyclic rings. The (co)polymer having the above various characteristics is obtained by (co)polymerizing 1-100 wt% of the derivative with 99-0 wt% of alicyclic structure-containing monomer having no mesogen group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel norbornene derivative and a polymer obtained by polymerizing the derivative, and more specifically, a novel norbornene derivative capable of giving a polymer having low birefringence and excellent transparency and non-water absorption, and The present invention relates to a (co) polymer using the same.

  Polymers containing alicyclic structures such as norbornene and tetracyclododecene are excellent in transparency, non-water absorption, electrical insulation, chemical resistance, etc., so lenses, prisms, optical disks (CD, LD, DVD, etc.) ), Preferably used for light guide plates, optical films, etc. However, conventionally known alicyclic structure-containing polymers have birefringence. In recent years, optical elements have been required to have higher precision performance, such as pick-up lenses used to read laser reflected light applied to sound and video data, and liquid crystal elements using polarized light. Therefore, a transparent resin that hardly generates birefringence has been demanded.

  Patent Document 1 discloses that a 4-biphenylcarbonyloxy group, a 2-naphthalenecarbonyloxy group, and 9-fluorene are added to the alicyclic structure for the purpose of preventing the orientation of the alicyclic structure in the polymer molecule caused by the melt flow during the molding process. It has been proposed to polymerize norbornene derivatives having aromatic substituents such as carbonyloxy groups. However, since the aromatic substituent of the derivative is bonded to the alicyclic structure via a flexible carbonyloxy group, it is a structure that is easily flowed into the melt flow, and the effect of preventing orientation is small when used in a small proportion. On the other hand, when this is used in a large proportion of 50% by weight or more, the resulting polymer is inferior in non-water absorption, and the glass transition point is lowered, resulting in difficulty in heat resistance.

JP 2003-238494 A

  An object of the present invention is to provide a novel alicyclic structure-containing monomer that can realize a polymer having excellent low birefringence and high heat resistance in addition to excellent transparency and non-water absorption. There is.

  The present inventors paid attention to the fact that the birefringence of the conventional alicyclic structure-containing polymer is a positive orientation birefringence generated during the molding process, and an atomic group having anisotropy, It was intended to counteract by copolymerizing negatively oriented birefringent norbornene derivatives supported by rigid linking groups that are not flowed into the melt flow. As a result of intensive studies, the present inventors have adopted mesophase atomic groups (mesogens) that cause liquid crystal molecules to exhibit liquid crystallinity as anisotropic atomic groups, and have dicarbonimide groups rigid. It has been found that the above-mentioned intention can be realized by adopting it as a linking group, and that a homopolymer having no birefringence can be obtained by selecting a mesogenic group. The present invention has been completed based on this finding.

Thus, according to the present invention, the following items 1 to 7 are provided.
1. The following general formula (1):

(Here, X is a mesogenic group, and m is 0, 1 or 2.)
A norbornene derivative represented by:
2. 2. The norbornene derivative according to 1 above, wherein the mesogenic group is a group having two or more aromatic rings (including heteroaromatic rings) or alicyclic rings.
3. The norbornene derivative according to 1 above, wherein the mesogenic group is a 2-fluorenyl group, a 4-biphenyl group, or a 2-biphenyl group.
4). The norbornene derivative according to 1 above, wherein the mesogenic group is a 4-diphenyl ether group or a 4-benzophenone group.
5). (Co) polymerizing 1 to 100% by weight of the norbornene derivative according to any one of 1 to 4 above and 99 to 0% by weight of an alicyclic structure-containing monomer having no mesogenic group or / and an α-olefin. A (co) polymer.
6). The following general formula (2):

(Here, X is a mesogenic group, and m is 0, 1 or 2.)
A (co) polymer comprising 1 to 100% by weight of repeating units represented by the formula (1) and 99 to 0% by weight of repeating units derived from an alicyclic structure-containing monomer having no mesogenic group.
7). A (co) polymer hydride obtained by hydrogenating the 5 or 6 (co) polymer.
8). An optical element formed by molding the 5 or 6 (co) polymer or the 7 (co) polymer hydride.

  The novel alicyclic structure-containing monomer of the present invention can realize a polymer having excellent low birefringence and high heat resistance, as well as excellent transparency and non-water absorption.

  The norbornene derivative of the present invention is a compound represented by the general formula (1). In the formula, X is a mesogenic group, and m is 0, 1 or 2.

  In the norbornene derivative of the present invention, the mesogenic group means a rigid rod-like intermediate phase (liquid crystal phase) forming atomic group that exhibits liquid crystallinity in liquid crystal molecules. The mesogenic group preferably has two or more aromatic rings (including a heteroaromatic ring) or an alicyclic ring, and may have a linking group that connects them, and part of the hydrogen atoms of the aromatic ring or alicyclic ring Or all may be substituted by the substituent.

  In the norbornene derivative of the present invention, when the aromatic ring or alicyclic ring constituting the mesogenic group is composed of only carbon atoms and hydrogen atoms, it is preferably a 6-membered ring, and preferably a benzene ring or a cyclohexane ring. Particularly preferred. When the aromatic ring is a heteroaromatic ring, it is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. As the hetero atom of the heteroaromatic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. As the heteroaromatic ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, pyridazine ring, Examples include a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring.

  2-20 are preferable, as for the number of the aromatic ring or alicyclic ring which comprises a mesogenic group, 2-12 are more preferable, 2-8 are especially preferable, and 2-6 are the most preferable.

The bond relationship between any two rings in the mesogen group includes (a) a condensed ring group, (b) a group in which a plurality of rings are directly connected by a single bond, and (c) a plurality of rings. May be formed by a linking group, and any of (a) to (c) may be used.
Examples of the condensed ring that is an element of the group (a) include an indene ring, naphthalene ring, azulene ring, fluorene ring, phenanthrene ring, anthracene ring, acenaphthylene ring, naphthacene ring, pyrene ring, indole ring, isoindole ring, Benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, cinnoline ring Quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring, thianthrene ring and the like.

  The ring bond of the group (b) is preferably a bond between carbon atoms. Two rings may be connected by two or more single bonds to form an alicyclic ring or a non-aromatic heterocyclic ring between the two rings. Examples of this type of group include a biphenyl group, a biphenylene group, and a terphenyl group.

  The linking group of the group (c) is also preferably one that bonds between carbon atoms. The linking group is preferably a group having less flexibility, such as an alkylene group, an alkenylene group, an alkynylene group, an azo group, an azoxy group, —CO—, —O—, —NH—, —CH═N—, —S— or a group thereof. A combination is more preferable. Examples of this type of group include 2,2-bisphenylpropyl group, diphenyl ether group, benzophenone group, and stilbene group.

  The aromatic ring, alicyclic ring and linking group in the mesogenic group may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, cyano groups, amino groups, nitro groups, sulfo groups, carbamoyl groups, sulfamoyl groups, ureido groups, alkyl groups, alkenyls. Group, alkynyl group, aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group Typical examples include aliphatic substituted carbamoyl groups, aliphatic substituted sulfamoyl groups, aliphatic substituted ureido groups, and non-aromatic heterocyclic groups.

  In general, the greater the number of rings constituting the mesogenic group, the greater the negative orientation birefringence of the norbornene derivative homopolymer having the mesogenic group. When the number of rings is the same, the case where the condensed ring group (a) is formed has a larger negative orientation birefringence, and the group (b) may be formed by directly connecting a plurality of rings with a single bond. Subsequent to this, the negative birefringence is smaller in the case of forming a group in which a plurality of rings in the above (c) are bonded by a linking group.

  The degree of negative birefringence differs depending on which carbon constituting the ring of the mesogenic group is bonded to the nitrogen atom of the dicarbonimide group. When the mesogenic group forms a condensed ring group, the negative birefringence is maximized when the carbon, which is the site where the length from the bonding carbon of the mesogenic group is the maximum, is bonded to the nitrogen atom of the imide group. When the mesogen group consists of multiple rings directly connected by a single bond, the negative birefringence is maximized when the carbon adjacent to the single bond or the carbon farthest from the single bond is bonded to the nitrogen atom of the imide group. Become.

Examples of the mesogenic group of the norbornene derivative in which the homopolymer has a large negative birefringence include 2-fluorenyl group, 4-biphenyl group, 2-biphenyl group, 2-naphthalene group, and the like. Group, 4-biphenyl group and 2-biphenyl group are preferred. The polymer of norbornene derivatives having these mesogenic groups has a large non-water absorption property.
Examples of the mesogenic group of the norbornene derivative in which the homopolymer hardly exhibits birefringence include a 4-diphenyl ether group, a 4-benzophenone group, a 4-benzylphenyl group, a 4-phenoxycarbonylphenyl group, and the like. 4-diphenyl ether groups and 4-benzophenone groups are preferred.

  Moreover, as the repeating number m of the alicyclic structure in the general formula (1), norbornene of m = 0 and tetracyclododecene of m = 1 are preferable, and norbornene is more preferable.

  Although the manufacturing method of the norbornene derivative of the present invention is not limited, for example, as shown in the following formula (3), maleic anhydride and a mesogenic group-containing primary amine are usually 70 to 250 ° C., preferably 80 to After obtaining N-mesogen group-substituted maleimide by reacting at 200 ° C. for usually 0.5 to 48 hours, preferably 1 to 20 hours, it can be produced by reacting cyclopentadiene with Diels Alder. . The Diels Alder reaction is not particularly limited, and is usually 120 to 250 ° C., more preferably 130 to 230 ° C., preferably 0.1 MPa or more, more preferably 0.2 in an inert gas atmosphere such as nitrogen. The reaction is preferably performed at a pressure of ˜15 MPa for 0.1 to 4 hours, more preferably 0.5 to 3 hours.

(Here, X is a mesogenic group, and m is 0, 1 or 2.)
As another method for producing the norbornene derivative of the present invention, as shown in the following formula (4), an alicyclic structure-containing monomer having an acid anhydride group by Diels-Alder reaction of maleic anhydride and cyclopentadiene: Then, it can be obtained by reacting this with a mesogenic group-containing primary amine to convert the acid anhydride group to N-mesogen group-substituted dicarbonimide. The conditions for the Diels-Alder reaction and the imidization reaction are the same as described above.

  (Here, X is a mesogenic group, and m is 0, 1 or 2.)

The reason why birefringence is seen in conventional molded products of alicyclic structure-containing polymers is that the main chain of the polymer is oriented along the direction of melt flow and stretching during melt molding such as injection molding and extrusion molding. It is supposed to be. Since the major axis of the polarizability ellipsoid in the monomer-derived repeating unit is parallel to the main chain direction of the polymer, it exhibits positive orientation birefringence. In the norbornene derivative of the present invention, a mesogenic group having a large anisotropy (direction perpendicular to the main chain direction) is fixed to an alicyclic structure via a dicarbonimide group having a rigid structure that is difficult to flow in the melt flow. Thus, it can be a negative orientation birefringent repeating unit. Therefore, a copolymer having almost no birefringence can be realized by copolymerizing the norbornene derivative of the present invention and a conventional alicyclic structure-containing monomer having no mesogenic group. In addition, since the negative degree of orientation birefringence of the homopolymer of norbornene derivative having the mesogenic group can be adjusted by selecting the mesogenic group, the present invention has a mesogenic group that hardly exhibits birefringence. By using the norbornene derivative, it is possible to achieve the object with a homopolymer.
When the terms copolymer and homopolymer are described simultaneously, they are abbreviated as “(co) polymer”. In addition, when the terms “polymerization” and “copolymerization” are used at the same time, they are abbreviated as “(co) polymerization”.

  The first form of the (co) polymer of the present invention is 1 to 100% by weight, preferably 1 to 50% by weight, more preferably 1 to 25% by weight of the norbornene derivative of the present invention, and has no mesogenic group. The alicyclic structure-containing monomer and / or α-olefin is 99 to 0% by weight, preferably 99 to 50% by weight, more preferably 99 to 75% by weight (co) polymerized.

  Examples of the polymerization mode for obtaining the (co) polymer of the first aspect of the present invention include ring-opening (co) polymerization and addition (co) polymerization. In addition, although the alicyclic structure containing monomer which does not have a mesogenic group is used for ring-opening copolymerization and addition copolymerization, alpha olefin can be used only for addition copolymerization.

  Examples of the alicyclic structure of the alicyclic structure-containing monomer that does not have a mesogenic group include a cycloalkane structure and a cycloalkene structure, such as a monocyclic ring and a polycyclic ring (a condensed polycyclic ring, a bridged ring, a combination ring thereof, etc. ) Either is acceptable. Although there is no restriction | limiting in particular in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.

  Examples of such alicyclic structure-containing monomers having no mesogenic group include norbornene monomers, monocyclic olefins, cyclic conjugated dienes, and vinyl alicyclic hydrocarbons. Of these, norbornene monomers are preferred.

Examples of the norbornene monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,8-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (having substituents in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, an alkoxycarbonyl group, and a carboxyl group. Moreover, these substituents may be the same or different and a plurality may be bonded to the ring. Specifically, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene and the like. These can be used alone or in combination of two or more.

  Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like. Examples thereof include C2-C20 hydrocarbon compounds having a heavy bond and substituted derivatives thereof. These monomers can be used alone or in combination of two or more. Among these, ethylene is more preferable.

The ring-opening (co) polymerization is performed in the presence of a ring-opening polymerization catalyst in the absence of a solvent or in a solvent, usually at a temperature of −50 ° C. to 100 ° C. and a pressure of 0.01 to 5 MPa. Can do.
As the ring-opening polymerization catalyst, for example, a catalyst comprising a metal halide such as ruthenium or osmium and a sulfate or acetylacetone compound and a reducing agent; or a metal halide such as titanium, zirconium, tungsten or molybdenum, or And a catalyst comprising an acetylacetone compound and an organoaluminum compound.

  As the solvent for the polymerization reaction, a solvent that dissolves the produced polymer and does not inhibit the polymerization reaction is used without limitation. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane; benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzonitrile; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, ethyl methyl ketone, and cyclohexanone; methyl acetate and ethyl propionate And esters such as methyl benzoate; halogenated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane, and trichlorobenzene; Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable. The concentration of the monomer in the solvent is usually 1 to 50% by weight, preferably 2 to 45% by weight, more preferably 5 to 40% by weight.

When the addition (co) polymerization is performed, the monomer can be performed in a solvent in the presence of an addition polymerization catalyst at a temperature of -50 ° C to 100 ° C under a pressure of 0.01 to 5 MPa.
As the addition polymerization catalyst, for example, a catalyst composed of a metal compound such as titanium, zirconium, vanadium and an organoaluminum compound can be used. As the solvent for addition polymerization reaction, the same solvent as in the above ring-opening polymerization is used.

  When the (co) polymer of the present invention is formed by ring-opening (co) polymerization, the repeating unit represented by the general formula (2) is 1 to 100% by weight, preferably 1 to 50% by weight, more preferably 1 -25% by weight and 99 to 0% by weight, preferably 99 to 50% by weight, more preferably 99 to 75% by weight of repeating units derived from an alicyclic structure-containing monomer having no mesogenic group. If it is this structure, the thing of the following form is also the (co) polymer of this invention.

  The second form of the (co) polymer of the present invention is an alicyclic structure-containing monomer having an acid anhydride group which is an intermediate in the formula (4) instead of the norbornene derivative of the present invention in the first form. The ring-opening or addition (co) polymerization with an alicyclic structure-containing polymer having no mesogenic group or / and an α-olefin in the same ratio as in the first embodiment, followed by, for example, ring-opening ( In the case of (co) polymerization, as shown in the following formula (5), the acid anhydride group of the repeating unit derived from the alicyclic structure-containing monomer having an acid anhydride group in the (co) polymer molecule, A mesogen group-containing primary amine is reacted to form an N-mesogen group-substituted dicarbonimide.

(Here, X is a mesogenic group, and m is 0, 1 or 2.)
In the imidization reaction in the production of the (co) polymer of the second form, a mesogenic group-containing primary amine is added to the (co) polymer solution, and usually 70 to 250 ° C., preferably 80 to The reaction is usually carried out at 200 ° C. for 0.5 to 48 hours, preferably 1 to 20 hours.

The molecular weight of the (co) polymer of the present invention is appropriately selected according to the purpose of use, but cyclohexane (toluene if the polymer resin does not dissolve) is used as a developing solvent in any of the above two forms. The weight average molecular weight (Mw) in terms of polyisoprene or polystyrene measured by gel permeation chromatography, usually 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000.
The glass transition temperature (Tg) of the (co) polymer of the present invention is usually 100 ° C. or higher, preferably 120 to 250 ° C., more preferably 140 to 200 ° C. Thus, since the (co) polymer of the present invention has a high Tg, it can give a molded article having excellent heat resistance.

The (co) polymer hydride of the present invention is obtained by hydrogenating the (co) polymer of the present invention.
In the hydrogenation reaction of the (co) polymer, a known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the organic solvent solution of the (co) polymer, and is usually −10 to + 250 ° C., preferably Hydrogen is usually introduced into the reaction system at 0 to 200 ° C. at a pressure of 0.01 to 10 MPa, preferably 0.05 to 8 MPa, and is usually reacted for 0.1 to 50 hours. The hydrogenation rate is preferably 90% or more and more preferably 99% or more for the carbon-carbon unsaturated bond of the main chain. When the mesogenic group has an aromatic ring, the aromatic ring is preferably 90% or less, more preferably 70% or less.
The thus obtained (co) polymer hydride of the present invention gives a molded article having excellent heat aging resistance and mechanical strength in addition to low birefringence and high heat resistance similar to the above (co) polymer. be able to.

  In order to produce a resin molded product using the (co) polymer or (co) polymer hydride of the present invention, usually, first, if necessary, an antioxidant, an ultraviolet absorber, a weathering stabilizer, an antistatic agent. , Light stabilizers, near-infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, antiblocking agents, optical brighteners, deodorants, fillers, crosslinking agents, vulcanizing agents, other synthetic resins and A compounding agent such as a rubber chamber polymer is appropriately selected and blended to prepare a molding resin composition. The amount of each compounding agent is appropriately selected within a range not impairing the object of the present invention.

  The resin composition for molding is usually prepared by mixing with a known mixer such as a kneader, Banbury mixer, Henschel mixer, extruder, roll, etc., and then usually melted and kneaded at 160 to 350 ° C. to produce pellets. The method of setting it as the granular resin composition for shaping | molding is taken.

  In order to produce a resin molded product from the molding resin composition, a melt molding method such as injection molding, extrusion molding, blow molding, vacuum molding, rotational molding, press molding, roll molding or the like is usually employed. The resin temperature at the time of melt molding is usually 220 to 330 ° C, preferably 230 to 320 ° C, more preferably 240 to 310 ° C.

  The molded product of the (co) polymer or (co) polymer hydride of the present invention is in addition to the excellent transparency, non-water absorption, electrical insulation and chemical resistance of conventional alicyclic structure-containing polymers. It also has a remarkable low birefringence and high heat resistance. Further, the transparency of the (co) polymer of the present invention has a characteristic that hardly deteriorates even when placed in a high temperature and high humidity state. Furthermore, since the birefringence of the alicyclic structure-containing polymer can be significantly reduced by using a small amount of the norbornene derivative of the present invention, an increase in cost can be minimized. Therefore, it can be suitably used for a wide range of optical elements such as general lenses, pickup lenses, prisms, optical disks, light guide plates, optical films, and liquid crystal elements.

The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the following, [part] and [%] are based on weight unless otherwise specified.
The test method was as follows.

(1) Identification of Synthetic Monomer The purified synthetic reaction product was analyzed by ¹ H-NMR spectrum analysis and infrared absorption spectrum analysis.
(2) Weight average molecular weight (Mw)
The Mw of the ring-opening (co) polymer was measured by gel permeation chromatography (GPC) using cyclohexane as a developing solvent, and determined in terms of polystyrene.

(3) Repeating unit composition ratio and hydrogenation rate The composition ratio of the ring-opening copolymer and the hydrogenation rate (%) of the ring-opening (co) polymer hydride were determined by ¹ H-NMR spectrum analysis.
(4) Polymerization conversion rate The polymerization conversion rate (%) was determined by gas chromatography.
(5) Glass transition temperature (Tg)
The Tg of the ring-opening (co) polymer and the ring-opening (co) polymer hydride was measured by increasing the temperature at a rate of 10 ° C. per minute using a differential scanning calorimeter.

(6) Retardation (birefringence evaluation)
Using resin pellets, with an injection molding machine (DISC-3, manufactured by Sumitomo Heavy Industries, Ltd.), the resin temperature is set to 300 ° C., the mold temperature is set to 130 ° C., and the pressure is 5 MPa, and the thickness is 1.2 mm. An optical disk substrate having a diameter of 85 mm was molded, and a birefringence value at a radius of 25 mm from the center of the substrate was measured using a polarizing microscope (546 nm Senarmont Compensator, manufactured by Nikon Corporation). The smaller the value, the lower the birefringence.

(7) Saturated water absorption rate Saturated water absorption rate was measured based on JIS K7209 using the test piece produced using the resin pellet.

(8) Transparency A test piece having a length of 130 mm, a width of 120 mm, and a thickness of 3 mm obtained by press-molding at a temperature of 200 ° C. using the resin composition before the production of resin pellets is a high temperature of 80 ° C. and a relative humidity of 90%. After being placed in a high humidity state for 48 hours, it was transferred to a constant temperature and humidity chamber at 23 ° C. and a relative humidity of 60%. The spectral light transmittance at a wavelength of 600 nm before being placed in a high-temperature and high-humidity state, and the difference (ΔT) in spectral light transmittance at the same wavelength immediately after being transferred from the transmittance to the constant temperature and humidity chamber were measured. The higher the former, the higher the transparency, and the smaller the latter, the higher the transparency at high temperature and high humidity.

(Synthesis Example 1)
Synthesis of N-2-biphenyl- (5-norbornene-2,3-dicarbonimide) In a glass reactor equipped with a stirrer, 700 parts of toluene, 16 parts of 5-norbornene-2,3-dicarboxylic anhydride and 2-aminobiphenyl After 17 parts were charged and purged with nitrogen, the mixture was refluxed at 180 ° C. for 10 hours and cooled to room temperature. After removing the solvent under reduced pressure, the precipitate was recrystallized with a mixed solvent of cyclohexane / ethyl acetate to obtain 25 parts of white crystals, and a purity of 99% by weight or more was confirmed by high performance liquid chromatography. The ¹ H-NMR spectrum of the obtained crystal is shown in FIG. 1, and the infrared absorption (IR) spectrum is shown in FIG.
In the NMR spectrum of FIG. 1, protons bonded to carbons at the 5th and 6th positions of the norbornene structure at 5.3 ppm and 6.3 ppm are respectively converted to carbons at the 1st to 4th positions of the norbornene structure at 3.1 to 3.4 ppm. Proton bonded to the phenyl ring at 7.0 to 7.5 ppm was observed, and in the IR spectrum of FIG. 2, the CH stretching vibration absorption of the benzene ring was 1720 cm near 2990 cm ^{−1. In the} vicinity of ^-1, CO stretching vibration absorption based on a carbonyl group was observed. From these results, this crystal was identified as N-2-biphenyl- (5-norbornene-2,3-dicarbonimide) produced by the reaction represented by the following formula (6).

(Synthesis Example 2)
Synthesis of N-2-fluorenyl- (5-norbornene-2,3-dicarbonimide) In Synthesis Example 1, 17 parts of 2-aminobiphenyl was converted to 2-aminofluorene 18
The procedure was the same as in Synthesis Example 1 except that 28 parts were obtained, and 28 parts of pale yellow crystals were obtained, and a purity of 99% by weight or more was confirmed by high performance liquid chromatography. The ¹ H-NMR spectrum of the obtained crystal is shown in FIG. 3, and the IR spectrum is shown in FIG.
In the NMR spectrum of FIG. 3, protons bonded to carbons at the 5th and 6th positions of the norbornene structure at 6.3 ppm are protons bonded to carbons 1 to 4 of the norbornene structure at 3.46 ppm and 3.53 ppm. Furthermore, the observed protons bonded to the fluorene ring 3.9ppm and 7.1～7.8Ppm, also in the IR spectrum of Figure 4, the CH stretching vibration absorption of the benzene ring in the vicinity of 2980cm ^-1, 1710cm ^{- In the} vicinity of ^1, CO stretching vibration absorption based on a carbonyl group was observed. From these results, this crystal was identified as N-2-fluorenyl- (5-norbornene-2,3-dicarbonimide) produced by the reaction represented by the following formula (7).

(Synthesis Example 3)
Synthesis of synthesis of 5- (9-fluorenecarbonyloxy) bicyclo [2.2.1] hept-2-ene According to the method of Example 5 described in Patent Document 1, the reaction represented by the following formula (8) 5- (9-fluorenecarbonyloxy) bicyclo [2.2.1] hept-2-ene was synthesized. A 500 ml flask equipped with a dropping funnel was charged with 28 g (253.9 mmol) of norbornene alcohol, and the system was purged with nitrogen. To this, 41 ml (507.8 mmol) of pyridine was added dropwise and dissolved by stirring with a stirrer. Next, the temperature of the reaction system was kept at 4 ± 2 ° C. with an ice-cooled bath, and a solution prepared by previously dissolving 52.8 g of 9-fluorenoyl chloride in 200 ml of dehydrated tetrahydrofuran was gradually added dropwise with sufficient stirring. After completion of the dropwise addition, stirring was continued for 1 hour in an ice-cooled bath, and the mixture was stirred at room temperature for 1 hour, further heated to 125 ° C. and refluxed for 30 minutes. After cooling to room temperature, the solvent was removed by heating under reduced pressure, and the resulting crystals were recrystallized repeatedly with a mixed solvent of n-hexane / methylene chloride to obtain 63 g of a yellow solid. When confirmed by high performance liquid chromatography, the purity was 99% by weight or more.

(Example 1)
In a glass reactor substituted with nitrogen, 300 parts of tetrahydrofuran, 11 parts of N- (2-biphenyl)-(5-norbornene-2,3-dicarbonimide) obtained in Synthesis Example 1, 8-ethyltetracyclo [4.4 .0.1 ^2,5 . After adding 19 parts of 17, ¹⁰ ] -dodec-3-ene (hereinafter abbreviated as ETD) and 0.7 part of 1-hexene as a chain transfer agent, the mixture was heated to 80 ° C. To this was added 4.5 parts of a tetrahydrofuran solution (0.162% solution) of benzylidene (1,3-dimesitymimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, which is a polymerization catalyst, under stirring. Polymerization was performed at 80 ° C. for 3 hours. When a part of the polymer solution was collected and analyzed, the polymerization conversion rate was 99% or more and Mw was 47,000. Moreover, it confirmed that this polymer was a ring-opening polymer which has a structure of Formula (2) by < ¹ > H-NMR measurement.

Subsequently, the whole amount of the obtained polymer solution was added to an autoclave equipped with a stirrer, and the inside of the autoclave was purged with nitrogen, to which 1.38 parts of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and ethyl vinyl ether 1.3 A hydrogenation catalyst solution having parts dissolved in 13 parts of toluene was added, and hydrogenation was performed at 160 ° C. and a hydrogen pressure of 4.5 MPa for 4 hours. Next, the hydrogenation reaction solution was poured into a large amount of methanol to completely precipitate the solid content. The solid content was collected by filtration, washed, and then dried under reduced pressure at 70 ° C. for 12 hours to obtain a ring-opened polymer hydride. The Mw of this product is 48,000. From ¹ H-NMR, the side chain aromatic ring is not substantially hydrogenated, the main chain hydrogenation rate is 99% or more, and the copolymer has It was confirmed that the repeating unit derived from ETD was 69%. Moreover, Tg of this ring-opening polymer hydride was 148 degreeC.
A resin composition was prepared by mixing 0.05 part of an anti-aging agent (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.) with 100 parts of the obtained hydrogenated ring-opening copolymer. Extrusion was carried out with a shaft extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd., screw diameter 37 mm, L / D32, screw rotation speed 250 rpm, resin temperature 240 ° C., feed rate 10 kg / h) to produce resin pellets. Table 1 shows the results of the tests of Tg, retardation (birefringence), saturated water absorption, and transparency at high temperature and high humidity of the ring-opened polymer hydride by the above test method.

(Example 2)
In Example 1, N-2-fluorenyl- (5-norbornene-2,3-dicarboxylic acid) obtained by synthesizing Example 2 with 11 parts of N- (2-biphenyl)-(5-norbornene-2,3-dicarbonimide) was synthesized. Imide) A ring-opening polymer hydride was obtained by performing ring-opening polymerization and hydrogenation reaction in the same manner as in Example 1 except that 7 parts were changed to 19 parts of ETD, respectively. The polymerization conversion rate was 99% or more. Mw of the ring-opened polymer hydride was 22,000, and Tg was 150 ° C. Further, according to ¹ H-NMR measurement, the repeating unit derived from ETD of the copolymer was 78% by weight, the hydrogenation ratio of the main chain to the carbon-carbon double bond was 99% or more, and the side chain It was confirmed that the aromatic ring was not substantially hydrogenated. The results of tests similar to those in Example 1 are shown in Table 1.

(Comparative Example 1)
In Example 1, the procedure was the same as in Example 1 except that 6 parts of N- (2-biphenyl)-(5-norbornene-2,3-dicarbonimide) was not used and 24 parts of ETD were changed to 30 parts. Ring polymerization and hydrogenation reaction were performed to obtain a ring-opened polymer hydride. The polymerization conversion rate was 99% or more. Mw of the ring-opened polymer hydride was 33,000, and Tg was 138 ° C. Further, it was confirmed by ¹ H-NMR measurement that the hydrogenation rate was 99% or more. The results of tests similar to those in Example 1 are shown in Table 1.

(Comparative Example 2)
In Example 1, instead of 6 parts of N- (2-biphenyl)-(5-norbornene-2,3-dicarbonimide), 5- (9-fluorenecarbonyloxy) bicyclo [2. 2.1] A ring-opening polymer hydride was obtained by performing ring-opening polymerization and hydrogenation reaction in the same manner as in Example 1 except that 6 parts of hept-2-ene was used. The polymerization conversion rate was 99% or more. Mw of the ring-opened polymer hydride was 43,000, and Tg was 127 ° C. Further, by ¹ H-NMR measurement, the repeating unit derived from ETD of the copolymer is 79% by weight, the hydrogenation rate is 99% or more, and the side chain aromatic ring is substantially hydrogenated. Not confirmed. The results of tests similar to those in Example 1 are shown in Table 1.

(Comparative Example 3)
In Comparative Example 2, ring-opening polymerization was performed in the same manner as in Comparative Example 2 except that 5- (9-fluorenecarbonyloxy) bicyclo [2.2.1] hept-2-ene was changed to 18 parts and ETD was changed to 12 parts. And hydrogenation reaction was performed and the ring-opening polymer hydride was obtained. The polymerization conversion rate was 99% or more. Mw of the ring-opened polymer hydride was 35,000, and Tg was 108 ° C. Further, according to ¹ H-NMR measurement, the repeating unit derived from ETD of the copolymer is 38% by weight, the hydrogenation rate is 99% or more, and the aromatic ring in the side chain is substantially hydrogenated. Not confirmed. The results of tests similar to those in Example 1 are shown in Table 1.

As shown in Table 1, compared with ETD-only ring-opening polymer hydride (Comparative Example 1), N-mesogen group-substituted dicarbonimide group-containing norbornene of the present invention in ETD in Example 1 and Example 2 The hydride of a ring-opening copolymer obtained by copolymerizing about 20% by weight of a derivative (mesogen group is 2-biphenyl group or 2-fluorene group) has excellent non-water absorption and transparency. The remarkably low retardation (birefringence) was shown on the top. Both of these are monomers having mesogenic groups that give large negative birefringent homopolymers, so that a copolymer with almost no birefringence can be produced by copolymerization in a small proportion with respect to ETD. Means that These copolymers showed almost no decrease in transparency even at high temperature and high humidity. Also, the Tg of the ring-opening copolymer hydride of the present invention was high and high in heat resistance.
On the other hand, in the case of a hydride of a copolymer obtained by copolymerizing a norbornene derivative having a mesogen group (9-fluorene group) via a carbonyloxy group with 21 wt% with respect to ETD 79 wt%, the retardation is large. Birefringence hardly decreased, and Tg decreased and heat resistance decreased (Comparative Example 2). Therefore, 62 wt% of the same derivative with respect to 38 wt% of ETD, and when the proportion of the same derivative was increased, the hydride of the obtained copolymer had a sufficiently reduced retardation, but the water absorption increased greatly. Moreover, the transparency under high temperature and high humidity was remarkably lowered, and the heat resistance as seen by Tg was also greatly lowered (Comparative Example 3).

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of N-2-biphenyl- (5-norbornene-2,3-dicarbonimide) obtained in Synthesis Example 1. FIG. 2 is a diagram showing an IR spectrum of N-2-biphenyl- (5-norbornene-2,3-dicarbonimide) obtained in Synthesis Example 1. 3 is a diagram showing a ¹ H-NMR spectrum of N-2-fluorenyl- (5-norbornene-2,3-dicarbonimide) obtained in Synthesis Example 2. FIG. FIG. 4 is a diagram showing an IR spectrum of N-2-fluorenyl- (5-norbornene-2,3-dicarbonimide) obtained in Synthesis Example 2.

Claims (8)

The following general formula (1):
(Here, X is a mesogenic group, and m is 0, 1 or 2.)
A norbornene derivative represented by: The norbornene derivative according to claim 1, wherein the mesogenic group is a group having two or more aromatic rings (including heteroaromatic rings) or alicyclic rings. The norbornene derivative according to claim 1, wherein the mesogenic group is a 2-fluorenyl group, a 4-biphenyl group or a 2-biphenyl group. The norbornene derivative according to claim 1, wherein the mesogenic group is a 4-diphenyl ether group or a 4-benzophenone group. The norbornene derivative according to any one of claims 1 to 4 is (co) polymerized with 1 to 100% by weight of the norbornene derivative and 99 to 0% by weight of an alicyclic structure-containing monomer having no mesogenic group and / or an α-olefin. A (co) polymer. The following general formula (2):
(Here, X is a mesogenic group, and m is 0, 1 or 2.)
A (co) polymer comprising 1 to 100% by weight of repeating units represented by the formula (1) and 99 to 0% by weight of repeating units derived from an alicyclic structure-containing monomer having no mesogenic group. A (co) polymer hydride obtained by hydrogenating the (co) polymer according to claim 5 or 6. The optical element formed by shape | molding the (co) polymer of Claim 5 or 6, or the (co) polymer hydride of Claim 7.