WO2002072659A1 - Processes for producing norbornene open-ring polymers and hydrogenated norbornene open-ring polymers - Google Patents

Processes for producing norbornene open-ring polymers and hydrogenated norbornene open-ring polymers Download PDF

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WO2002072659A1
WO2002072659A1 PCT/JP2002/001649 JP0201649W WO02072659A1 WO 2002072659 A1 WO2002072659 A1 WO 2002072659A1 JP 0201649 W JP0201649 W JP 0201649W WO 02072659 A1 WO02072659 A1 WO 02072659A1
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ring
compound
group
product
norbornene
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PCT/JP2002/001649
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French (fr)
Japanese (ja)
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Shigetaka Hayano
Hiroshi Kurakata
Yasuo Tsunogae
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Zeon Corporation
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Abstract

A crystalline open-ring polymer is produced by ring-opening polymerization of a norbornene monomer through metathesis with a polymerization catalyst comprising both a product of reaction of a specific transition metal halide or oxyhalide with a substituted phenol or phenoxide and an organometallic reducing agent. Further, hydrogenation of the obtained polymer gives a crystalline hydrogenated open-ring polymer. When a novel polymerization catalyst comprising an aromatic dioxy ligand is used as the polymerization catalyst, highly crystalline norbornene open-ring polymers can be produced. Additionally, products of hydrogenation of them also exhibit high crystallinity.

Description

Field of the production method invention a light fine manual norbornene ring-opening polymer and a norbornene-based ring-opening polymer hydride

The present invention relates to a method for producing a norbornene-based ring-opening polymer and a norbornene-based ring-opening polymer hydrogenation product having crystallinity. BACKGROUND

Periodic Table: the 1-9 transition metal compound ring-opening metathesis polymerization of a norbornene-based monomer using the well known from the prior art, other periodic table group 6 of W or Mo, N b, T a , R e, Z r, T it, R u, O s, transition metal compounds, such as I r is used as the ring-opening polymerization catalyst.

The phenoxy groups have use a polymerization catalyst consisting of Ha port plasminogen product or Okishiha port Gen of compound and hydrogenated triorganotin and halogenated boron W having as a ligand, a method for ring-opening polymerization of dicyclopentadiene (U . S. PAT. NO. 5 2 1 8 0 6 5) and the periodic table 5 using the reaction product and a cocatalyst and group 8 I Mi de transition metal compound and Bifueno one Le ethers, Jishiku port Pentajen how to metathesis polymerization of a cyclic O Refuin such (U. S. PAT. NO. 5 4 0 5 9 2 4) have been reported.

Ziegler-type polymerization catalyst using a halide or Okishiharogen compound and an organometallic reducing agent W and M o are widely known. For example, WC] 6 Mo C l halide and Te Torafuenirusuzu Ya Te tiger like 5 (n-heptyl) polymerization catalyst comprising an organic tin such as tin, Okishiharoge emission products and preparative Rye such WOC 1 4 and Mo OC 1 4 Chiruaruminiumu, GETS chill Arumini © Solid b Li de, a polymerization catalyst consisting of an organoaluminum such Echiru aluminum Axis port Li de is rather good Shitsuguchi ( 'O lefin Me tathesisand M etathesis P ol ym erization K. J. I van, J. C. Mo l ed., 1 9 9 7 years, ACAD EM ICP RE SS, TOKYO, etc.). However, ring-opening polymer or a hydrogenated norbornene monomers polymerized with these Ziegler type polymerization catalyst, have no melting point amorphous. The polymer or when using the hydrides in various applications, mechanical strength, heat resistance, there is a time solvent resistance is insufficient.

Therefore, having a melting point in order to solve these problems, namely the development of a method for producing a norbornene ring-opening polymer or hydrogenated product thereof having a crystallinity and polymerization catalyst used therefor has been desired. Disclosure of the Invention

An object of the present invention is to provide a manufacturing method and a catalyst and a manufacturing method thereof for use in their preparation of the crystalline norbornene ring-opening polymer and crystalline norbornene ring-opening polymer hydride.

The present inventors have found that a reaction product of intensive research result of the halide of the particular transition metal, phenols or phenoxide compound having a Okishiharogen product or Jiokishiharogen compound with a substituent in order to solve the above problems, an organic using a polymerization catalyst comprising a metal reducing agent, the polymer having a crystallinity between ring-opening metathesis scan polymerizing a norbornene monomer can be obtained, and a polymer radical having a crystallinity hydrogenating polymer It found that product can be obtained, and have completed the present invention based on the observed such knowledge.

And thus, according to the present invention,

(1) the periodic table 4-6 transition metal halides, phenols or Fuwenokishi earth reaction product of (b) with a Okishiharogen product or Jiokishiharogen product (a) and substituents as (I), the organometallic reducing agent (II) from the composed polymerization catalyst producing method of a crystalline Norubo Runen ring-opening polymer of a ring-opening metathesis polymerization of a norbornene monomer in the presence of a medium it is provided.

The transition metal is molybdenum or tungsten are preferred.

Organometallic reducing agent (II), organolithium, organomagnesium, organozinc, it is preferably at least one selected from the group consisting of organoaluminum and organotin.

Phenols or Fuwenokishido compound having a substituent (b) is preferably a divalent Fueno Le acids or divalent phenoxide compound.

(2) Further, according to the present invention,

Periodic table 4-6 transition metal halides, Okishiharogen product or Jioki Shiharogen compound (a) and Funinoru acids or phenoxide compound having a substituent reaction product of (b) and (I), the organometallic reducing agent (II ) and after polymerizing ring-opening metathesis of norbornene-based monomer in the presence of a composed polymerization catalyst because, 5 carbon one-carbon double bonds present in the main chain of the resulting polymer 0. /. Method for producing a crystalline norbornene ring-opening polymer hydride is provided a hydrogenation in the presence of a hydrogenation catalyst over. The transition metal is molybdenum or tungsten are preferred.

Organometallic reducing agent (II), organolithium, organomagnesium, organozinc, it is preferably at least one selected from the group consisting of organic Aruminiumu and organotin.

Fuwenoru acids or Fuyunokishido compound having a substituent (b) is preferably a divalent Fuweno Le acids or divalent phenoxide compound.

(3) Further according to the present invention, the polymerization catalysts containing Group 4 of the periodic table to sixth transition metal Okishi compound or halide having an aromatic Jiokishi group as a ligand (III) ヽ

(4) the periodic table 4-6 transition metal halide, by reacting with Okishiharogen product or Jiokishiharogen product (a) and divalent phenols or divalent phenoxide compound, to produce a (3), wherein the polymerization catalyst a method is provided.

The transition metal is molybdenum or tungsten are preferred.

Organometallic reducing agent (II), organolithium, organomagnesium, organozinc, it is preferably at least one selected from the group consisting of organic Aruminiumu and organotin. BEST MODE FOR CARRYING OUT THE INVENTION

The method for producing a crystalline norbornene ring-opening polymer of the present invention, phenol having a periodic table Ha port Gen product of the 4-6 transition metals, Okishiha port Gen product or Jiokishiha port Gen of compound (a) and substituents reaction products of class or phenoxide compound (b) and (I), ring-opening metathesis polymerization of Norubo Runen based monomer in the presence of a polymerization catalyst consisting of an organometallic reducing agent (II).

Periodic table: 1-6 transition metal halides, Okishiharogen product or di O carboxymethyl halide (a) (. Hereinafter "compound (a) J hereinafter) as a metal constituting the can, T i, Z r , mention may be made of V, N b, T a, Mo, W and the like. among them Mo, W, the polymerization activity is high preferable. as the halide of the transition metal, T i C l 4, Z r C l 4, VC 1 5, N b C l 5, T a C l 5, Mo C l 5, WC l have T i B r 4, Z r B r 4, VB r 5, N b B r 5, T a B r 5, Mo B r 5, WB r have T i F 4, Z r F 4, VF 5, N b F 5, T a F 5, Mo F 5, WF had T i I 4, Z r I 4, VI 5, N bl 5, T a I 5, Mo I 5, WI 5 , and the like.

The Okishiharogen product of the transition metal, VOC l 3, Mo OC l 4, W OC l 4, VOB r 3, Mo OB r 4, WO B r 4, VOF 3, Mo OF 4, WO F 4, VO I 3, Mo OI 4, such as WO I 4 can be mentioned.

The Jiokishiharogen product of the transition metal, M o O 2 C 1 2 , WO 2 C 1 2, M o O 2 B r 2, WO 2 B r 2, Mo_〇 2 F 2, W_〇 2 F 2, M o O 2 I 2, WO 2, such as I 2 can be mentioned.

Fuwenoru acids or phenoxide compound having a substituent to be used in the present invention (b) (hereinafter, "Compound (b) J that.) Substituent is not particularly limited. Specifically, a halogen atom, 1 to carbon atoms 1 2 alkyl group, Ariru group, an alkoxy group, Ariruokishi group, a haloalkyl group, a haloaryl group, etc. Shiano group.

Then, the substituent high is preferably bulk, for example, secondary alkyl group, tertiary alkyl group, Hue alkenyl group § Rui substituent phenyl group such as t _ butyl group such as isopropyl group, triflate Ruo b Methyl arbitrariness preferred haloalkyl group such as a group. Substituents are preferably attached to a carbon adjacent to the carbon to which Okishido group is attached. The structure of the compound (b), for example, the general formula [1] of

[1]

(Wherein [1], R 1 and R 5 are each independently a halogen atom, the number 1 to 1 2 alkyl group having a carbon Ariru group, an alkoxy group, Ariruokishi group, Haroaruki group, a haloaryl group, or Shiano group shown. R 2 to R 4 are each independently in water atom, a halogen atom, an alkyl group of indicated number 1-1 2 carbon atoms, Ariru group, alkoxy group, Ariruokishi group, a haloalkyl group, a haloaryl group, or Shiano group, it may be bonded together to form a ring structure. M 1 is a metal atom selected from a hydrogen atom or a alkali metal, alkaline earth metal and aluminum. m is the valence of element M 1 from 0 to 2 integer It depends. X 1 can be mentioned Monofuenoru acids or Monofuenokishido compound represented by halogen atoms.).

Is in these embodiments, 2, 6-Jimechirufueno Ichiru, 2, 6 - Jechi Rufuenonore, 2, 6-di (Isopuropizore) Fueno one Honoré, 2, 6-di (t-Puchinore) Fuenonore, 2, 6- di (t-Puchinore) one 4-methylcarbamoyl Bruno reflex Hainaut Honoré, 2, 6-Jifue two Rufuenoru, 2, 6-di (triflate Honoré Oro methylcarbamoyl Honoré) Fueno over phenols such as Le; 2, 6-di (isopropyl) Fuenokishinatori U beam, 2, 6-di (t-heptyl) phenoxyethanol lithium, 2, 6-di (t-Petit Le) Single 4 one methyl phenoxyethanol potassium © beam, 2, 6- Jifuenino Refuenokishirichi © beam, 2, 6-di (triflate Ruo ii methyl) phenoxide compounds containing Al force Li metal such as phenoxyethanol lithium; 2, 6-di (isopropyl) Fuenokishimagu Neshiumupuromi de, 2, 6-di (t Buchinore) off Enoki Shi magnesium chloride Li de, 2, 6-diphenyl phenoxyethanol magnesium Promise de, 2, 6-di (g Rifuruoromechiru) phenoxide compound containing an alkaline earth metals such as phenoxyethanol magnesium bromide Mi de; 2, 6- di (t-butyl) phenoxide compound containing aluminum such as single 4-Mechirufuenoki sheet aluminum Axis port Li de; it is possible elevation gel.

Mention may also be made also like phenols or naphthyl preparative Lumpur such further aromatic ring is fused to the phenoxide compound or naphthoquinone Tokishido such Ya anthracenol acids or anthracenyl eaves Sid acids.

Specific examples thereof include 1, 3 over di (isopropyl) one 2-naphthoquinone torr, 1, 3-di (t-heptyl) one 2 - naphthoxy lithium, 2 - (isopropyl) - 1-naphthyl Tonore, 2 - Fueninore 1 Nafutonore, 2-phenylene Honoré one 1-Na full Tokishirichiumu, 1, 3-di (t-butyl) - 2 - naphthoquinone Tokishiaruminiu Mujikurori de, 2- Fueninore 1, such as single naphthoquinone shea magnetic Information & Technology Mubu Romi de naphthoquinone tall acids or naphthoquinone Tokishido like; 9- anthracenol, 2-methyl-_ 1 - can be exemplified anthracenol acids or anthracenyl eaves Sid such as anthracenol.

Further, as the compound (b), more preferably polyhydric Fuwenoru acids or multivalent Fuyunokishido acids, dihydric phenols or dihydric phenoxide compounds are particularly preferred. Is a divalent phenols or divalent Fuwenokishido acids, preferably those further having a substituent. Lay what is particularly preferred to have a bulky substituent, as the bulky substituent group include the same as those shown above. Substituent, it is good preferable bound to a carbon adjacent to the carbon linked to Okishi group. It is a structure of the divalent phenols or divalent phenoxide compound of the general formula

[2] or are preferably those represented by [7].

Of 2

[2]

Of 3 14

C

15

R

[3]

Of 4

14

R

Si-

15

[Four]

Of 5

C

II

o

〔Five]

Of 6

■ N-

14

R

[6]

(In the formula [2], each of R 6 to R 13 independently represent a hydrogen atom, a halogen atom, an alkyl group of from 1 to 1 2 carbon atoms, Ariru group, an alkoxy group, Ariruokishi group, Ha port alkyl or haloaryl group, or a Shiano group, bonded to the ring structure may be formed. Z each other, the general formula [3], the general formula [4], general formula [5], the general formula [6], an oxygen atom, a sulfur atom selected from. wherein, R 14 and R 15 represents a hydrogen atom or a hydrocarbon of carbon number. 1 to 6. q is 0 or 1. MM 2 each independently hydrogen atom or aralkyl force Li metal, Al a metal atom selected from Chikarari earth metals and aluminum Niumu. X is determined by a halogen atom, m and n are valences of the elements MM 2 at 0-2 integer.) of 7

[7]

(Wherein [7], R 16 ~R 21 independently represents a hydrogen atom, a halogen atom, the number of carbon atoms

1 to 1 2 alkyl group, Ariru group, an alkoxy group, Ariruokishi group, Ha port alkyl group, a haloaryl group, or Shiano group may be bonded together to form a ring structure. MM 2 each independently represent a hydrogen atom or an alkali metal is a metal atom selected from Al force Li earth metals and aluminum. X is a halogen atom, m and n is determined by the valence of the elements of MM 2 at 0-2 integer. ) Furthermore, q in the general formula [2] in is 0, that Bifuenoru acids or Bifueno Kishido acids are most preferred.

Is a specific example of q in the general formula [2] is 0, 2, 2 'Bifue Nonore, 3, 3' - Jimechinore 2, 2 '- Bifuenoru, 3, 3, One Jechi Lou 2, 2 '- Bifuenonore, 3, 3' over-di (i Sopuropinore) one 2, 2 '- Bifuenonore, 3, 3, over-di (t one Puchinore) one 2, 2, one Bifuenonore, 3,

3 '- di (t-butyl) one 5, 5', 6, 6, One-tetramethyl-2, 2 '- bi Fuenonore, 3, 3, One Jiadamanchinore one 5, 5 ,, 6, 6' Tetoramechinore

- 2, 2 '- Bifuenoru such as Bifuenoru; 2, 2' - Bifuenokishi lithium, 3, 3, One dimethyl one 2, 2 'over Biff enoki Sina tri um, 3,

3, One Jechiru 2, 2, over Biff enoki shea potassium, 3, 3, over-di (isopropoxy opening pill) one 2, 2, over Biff hackberry shea lithium, 3, 3 ,, 5, 5 '- tetra (t one heptyl) one 2, 2 'over Biff enoki Sina tri um, 3, 3, over-di (t Buchi Le) one 5, 5', 6, 6, one-tetramethyl-2, 2 '- Biff Enoki with lithium,

3, 3, One Jiadamanchiru 5, 5 ,, 6, 6 'over-tetramethyl-2, 2' - Biff Enoki shea potassium, 2, 2 '- Biff enoki sheet magnesium bromide mi de, 3, 3, Jechiru one 2, 2' - Biff enoki Shi magnesium chloride Li de, 3, 3 '- di (isopropyl) one 2, 2' - Biff enoki sheet aluminum dichloride de, 3, 3, over-di (t one heptyl) one 2, 2 'Bifuenokishi magnesium chloride Li de, 3, 3 'over-di (t-butyl) one 5, 5 ,, 6, 6, over Te Toramechiru 2, 2, one Biff enoki sheet aluminum di Promise de, 3, 3, over di § Damman Chiru 5, 5 ,, 6, 6, one tetramethyl one 2, 2 '- can be exemplified Bifuenokishido such as Biff enoki shea magnesium blanking opening Mi de.

Mention may also be made also like Bifuenoru acids or Bifuenokishido bi naphtho Ichiru such further aromatic ring is bonded to the compound or Binafu Tokishido acids.

Specific examples thereof include 1, 1 '- binaphthyl _ 2, 2' Jioru, 3, 3 'single-dimethyl 1, 1, over binaphthyl-2, 2, One Jiokishirichiumu, 3, 3, One Jechiru 1, 1, Binafuchinore one 2, 2 '- Jiokishikari um, 3, 3' over-di (isopropyl) - 1, 1, - binaphthyl one 2, 2 '- Jioki sheet magnesium Promise de, 3, 3' - di (t-heptyl) one 1, 1 'Binafu chill _ 2, 2' Jioru, 3, 3, Jifueninore 1, 1, Binafuchinore - 2, 2 'over-di O carboxymethyl lithium, 3, 3, one di § Dammann Chino laser 1, 1, velvetleaf naphthyl one 2, 2, and the like one di O carboxymethyl aluminum dichloride de.

Is a specific example q is what is 1 in the general formula [2], 2, 2 '- methylene Nbisu (4 _ Black port Fueno / Les), 2, 2, single-methylenebis (6- t-Puchinore - 4-methylcarbamoyl Bruno reflex Hainaut Honoré), 2, 2, single-methylenebis (6-t-Buchinore one 4-E Chino reflex Hainaut Honoré), 2, 2, one methylenebis (3, 4, 6-Application Benefits black port Hue Nord ), 3, 3 'over-di (t-butyl) one 2, 2' Jihi Dorokishi _ 1, 1 '- diphenyl ether Honoré, 3, 3' - di (t Buchinore) one 2, 2, one dihydric mud carboxymethyl _ 1, 1 '- Jifue two Ruchioetenore, 1, 8-dihydrazide Dorokishiantora quinone, or the like of these metal salts can be cited.

Specific examples of the naphthoquinone Tojioru acid of the general formula [7], 1, 8-na off Tojioru, 2, 7-Jifue two Honoré _ 1, 8-naphthyl Tojio one / Les, 2, 7-di methyl-1 , 8-naphthoquinone Tojioru, 2, 7-di (t-butyl) one 1, may be mentioned 8-na Futojioru.

Reactant used in the present invention (I) is compound (a), obtained by mixing the compound (b).

Compound (a) and compound (b) it is usually mixed after dissolving or dispersing in an organic solvent. The organic solvent used, compound (a) and the compound (b) dissolve the properly dispersed, as long as it does not affect the reaction, is not particularly limited.

Specific examples of the I 'UNA organic solvents include benzene, toluene, xylene that any aromatic hydrocarbon solvent; dichloromethane, black hole Holm, 1, halogen-containing aliphatic, such as 2-Axis port Roetan hydrocarbon solvents; click every mouth benzene, halogen-containing aromatics such dichlorobenzene hydrocarbon solvents; nitromethane, nitro port benzene, nitrogen-containing hydrocarbon solvents such Asetonitoriru; Jechirue Ichite Le, aliphatic ethers such as tetrahydrofuran solvent; Aesoru , aromatic ether solvents such Fuene Torr; pentane, hexane, aliphatic hydrocarbon solvents such as heptane; cyclohexane, methylcyclohexane, Dekahi de Ronafuta Ren, bicycloheptane, preparative Rishikurodekan, fat such as cyclooctane use and alicyclic hydrocarbon solvents Rukoto can. Among these solvents, the solubility of the aromatic hydrocarbon solvents, halogen-containing aromatic hydrocarbon solvents, aliphatic ether solvents or aromatic ether solvents are compounds (a) and compound (b) excellent, preferred because less impact on the subsequent polymerization reaction and hydrogenation reaction arbitrariness. The concentration of the compound (a) and compound (b) compound in the solution containing (a) and compound (b) can be arbitrarily selected.

Mixing is carried out under a noble gas or nitrogen gas atmosphere such as argon, may be was added containing compound compound to a solution containing (a) (b), may be a reverse order, also, both at the same time it may be mixed in addition to a separate vessel.

Ratio of Compound (b) (a) is from 1 to 1 0 times lay preferred in a molar ratio from 1 to 8 times, more preferably from 1 to 5 times being particularly preferred. If ratio of Compound (b) (a) is too small, unreacted compound (a) is rest, it may cause side reactions. If too much is sometimes unreacted compound (b) to inhibit the polymerization. The reaction temperature is not particularly limited, in general, it carried out in the range of one 1 0 0 ° C~ 1 0 o ° c. Temperature is too a too slow progress of the reaction low, or One to put too high and side reaction products may or decompose. One preferred range of reaction temperature

In 80 ° C~80 ° C, furthermore preferably _ 70 ° C~ 70 ° C. Mixing was carried out at low temperatures below 0 ° C, then slowly increasing the temperature to near room temperature, preferably to reaction. The reaction time be in the range of 1 minute to 1 week is not particularly limited.

The reaction (I) can be used and the reaction solution directly as a polymerization catalyst. Further, the reaction product (I) is insoluble organic solvent (e.g., saturated hydrocarbon Motokei solvent such as pentane) distilling or, or Solvent employed in the reaction to precipitate by adding the reaction solution (I) those isolated by, for example, can be used as a polymerization catalyst. The main component of the reaction product (I) is a fourth to group 6 transition metal compound of the Periodic Table having an aromatic Okishi group having a substituent as a ligand. Among these, bulky substituents on the carbon next to the carbon Okishi group is bonded, for example, secondary alkyl groups such as isopropyl group, a tertiary alkyl group such as t- butyl group, phenyl group or a substituted phenylene Honoré group , those having such Haroanorekinore group such as tri Furuoromechiru group is preferred because a highly crystalline norbornene ring-opening polymer and can obtain a hydride thereof.

As the main component of the reaction product (I), the 4-6 transition metal compound of the Periodic Table having an aromatic Jiokishi group as a ligand is more preferable. Aromatic Jiokishi group is highly bidentate ligand sterically restricted by a ligand, it is possible to obtain a higher binding-crystalline norbornene ring-opening polymer and its hydride. The reaction (I) can be isolated by the above separation methods. The case in which can be isolated and identified by 1 H_NMR spectral and elemental analyzes, the structures of the compounds obtained.

As a polymerization catalyst of the present invention, Group 4 to 6 transition metal Okishi compound or halide periodic table having an aromatic Jiokishi group as a ligand (III) (hereinafter, referred to as "reduction compound (II 1)." ) is the main component of compound (a) and 2 Ataifu Nord acids or a reaction product of 2 Ataifu Enokishido compound (I). As the compound (III), for example, - general formula [8] or [9]

Of 8

[8]

(Wherein [8], Micromax is periodic table 4-6 transition metal atom, X is a halogen atom, each of R 22 to R 29 independently represent a hydrogen atom, a halogen atom, alkyl Le group of from 1 to 1 2 carbon atoms , Ariru group, an alkoxy group, Ariruokishi group, a haloalkyl group if Ku is a haloaryl group, or Shiano group may be bonded together to form a ring structure. Z has the general formula [3], the general formula [4 ], general formula [5], the general formula [6] is selected from oxygen atom and sulfur atom. here, a hydrocarbon of R 14 and R 15 each independently represent a hydrogen atom or a carbon atoms. 1 to 6. m is 0 or 1, n is 0 to 4, p is 1 or 2, q is 0~ 2, n + p + q is circle determined by the valence of M element.)

Of 9

[9]

(Wherein [9], M is the periodic table 4-6 transition metal atom, X is a halogen atom, R 30 to R 35 each independently represent a hydrogen atom, a halogen atom, alkyl Le group of from 1 to 1 2 carbon atoms , Ariru group, an alkoxy group, Ariruokishi group, a haloalkyl group if Ku is a haloaryl group, or Shiano group may be bonded together to form a ring structure. n is 0 to 4, p is 1 or 2, q is 0~2, n + p + q is determined by the valence of M elements.)

In represented.

Among them, metal Okishi compound or a halide central metal is molybdenum or tungsten, most preferred in view of polymerization activity.

Specific examples thereof include bis {3, 3, - di (t-butyl) - 5, 5 ', 6, 6, over Te Toramechiru 2, 2' Bifuenokishi} O carboxymethyl molybdenum (VI), {3, 3 '- di (t-heptyl) one 5, 5 ', 6, 6, one-tetramethyl-2, 2, one Bifuenokishi} Okishimoripuden (VI) AXIS port Li, bis {3, 3, one Jifue two Lou 1, 1, one binaphthyl chromatography 2, 2 '- Jiokishi} Okishimoribude emissions (VI), {3, 3, one Jifueyuru one 1, 1' - Binafuchinore _ 2, 2, temporary Okishi} O carboxymethyl molybdenum (VI) Jikurori, bis {3, 3 '- di (t-butyl) one 5, 5 6, 6, over tetramethyl one 2, 2' Bifuenokishi} O carboxymethyl tungsten (VI), {3, 3, over-di (t one heptyl) one 5, 5, 6 , 6 'over-tetramethyl-2, 2, one Bifuenokishi} old carboxymethyl tungsten (VI) dichloride Li, bis {3, 3, one Jifue - Honoré one 1, 1, One binaphthyl one 2, 2 '- Jiokishi} O carboxymethyl tungsten (VI), {3, 3' - diphenyl one 1, 1 'over-binaphthyl-2, 2' single Jiokishi} old carboxymethyl tungsten (VI) Jikurori, bis {3, 3, over-di (t-heptyl) one 5, 5 ', 6, 6' over tetramethyl one 2, 2 '- Bifuenokishi} tungsten (VI) Jikurori de, {3, 3 one di (t Buchinore) one 5, 5 ,, 6, 6, - tetramethyl one 2, 2, Bifueno carboxymethyl} tungsten (VI) Tetorakurori, bis {3, 3, Jifueniru one 1, 1, - binaphthyl-2 , 2, one Jiokishi} tungsten (VI) AXIS port Li de, {3, 3, Jifueeru 1, 1 '- Binafuchinore one 2, 2, and the like one Jioki shea} tungsten (VI) Tetorakurori de.

In the present invention, the reaction product (I), by combine with an organometallic reducing agent (II), a highly active polymerization catalyst.

Organometallic reducing agent, mention may be made of first, 2, 1 2, 1 3 or 1 4 Group organometallic compound of the periodic table having a hydrocarbon group of from 1 to 2 0 carbon atoms. Of these, organolithium, organomagnesium, organozinc, organic Arumyeumu or organic scan's are preferred, organolithium, organoaluminum or organotin is not particularly preferred. The organolithium, n- heptyl lithium, methyl lithium, Hue - butyllithium, neopentyl lithium, and the like neophyl lithium. Is an organomagnesium, butyl E chill magnesium, butyl O Chi Honoré magnesium, carboxymethyl Honoré magnesite Information & Technology arm to di-, E Ji / Remaguneshiumuku port Li de, n- heptyl magnesium chloride Re de, § drill magnesium Promise de, ne Openchi / Les magnesium chloride Li de, and the like Neofi / Les magnesium chloride Li de. The organozinc include dimethyl zinc, Jechiru zinc, di phenyl zinc and the like. The organic aluminum include trimethyl aluminum, tri-E chill aluminum Eu arm, triisobutyl heptyl Arumini © beam, Jefferies Chino rare Honoré mini © skeleton Li de, Echinoreanoremi two Umusesukiku port Li de, etc. E chill aluminum Axis port Li de can. As the organic tin may be mentioned tetramethyl tin, tetra (n- heptyl) tin, etc. te Torafueerusuzu.

The amount of organometallic reducing agent with respect to the central metal of the reactant (I), in a molar ratio 0 1:... 1 0 0 times preferably, 0 2-5 0 times, more preferably, 0 5 ~ 2 0 times is particularly preferred. Amount is 0. 1 times or less is not improved polymerization activity, if it is 1 0 0 times, side reactions are likely to occur.

The monomer used in the production method of the present invention is a norbornene monomer, specifically, the general formula [1 0]

Of 1 0

[ Ten]

(Wherein [1 0], R 36 to R 39 is a hydrogen atom, the carbon number 1-2 0 hydrocarbon group or a halogen atom, Kei atom, represents a substituent containing an oxygen atom or a nitrogen atom, and R 36 R 39 may bond together to form a ring. r is an integer of 0-2.) shown in, norbornenes r is 0, at r is 0 by bonding R 36 and R 39 Roh Ruborunen norbornene derivative having a cyclic structure in addition to the ring, r Te preparative Rashiku port dodecene compound is 1, r can and Ageruko the Putadesen acids to Kisashiku port to 2. Among them, norbornene compounds, norbornene derivatives or Te Torashikuro dodecene acids to have a ring structure other than the norbornene ring is preferably so easily obtained crystalline polymer hydrides, norbornene having a ring structure other than the norbornene or norbornene ring derivatives are particularly preferred.

Norbornenes r is 0 in the general formula [1 0], it can be classified as a substituent Therefore the following R 36 to R 39, any of the monomers can also that you use.

Specific examples of norbornenes, norbornene, 5-Mechirunoruborune emissions, 5 E cirno Lupo Le nen, 5-butyl Noreno Rubo Honoré Nene, 5- to Kishirunonore Porunen, 5 _ decyl norbornene, hexyl norbornene to 5-cyclopropyl, 5 - Norubo Runen compound having an unsubstituted or alkyl group such as cyclopentyl norbornene;

5-E Chile den norbornene, 5-vinyl Noreno Roh repo Honoré nen, 5 _ propenyl Nonorebonorenen, norbornene compound having 5-cycloheteroalkyl hexenyl Noreno Bruno levo Honoré Nene, an alkenyl group such as 5-Sik port pent two Honoré norbornene ; norbornenes having an aromatic ring such as 5-phenylpropyl-norbornene;

5 main butoxycarbonyl-norbornene, 5-d Toki deer Lupo sulfonyl norbornane nen, 5-methyl-one 5- main butoxycarbonyl norbornene, 5-methyl-one 5 - ethoxycarbonyl Bruno Lupo / Renen, norbornene - Lou 2- Mechirupuropio Ney DOO, Noruboruneniru 2 Mechiruotatanei DOO, norbornene -5, 6 Jikarubon acid anhydride, 5-hydroxycarboxylic methyl norbornene, 5, 6-di (human Dorokishimechiru) norbornene, 5, 5-di (human Dorokishimechiru) norbornene nen, 5-arsenide Dorokishi _ i - norbornene compound having pro Pinot Renono repo Honoré nen, 5, 6 Jikanorebokishi norbornene, a polar group containing 5 main butoxycarbonyl _ 6-carboxy-norbornene, such any oxygen atom;

5 Shianono / Reponorenen, Nonorepo / Renen 5, norbornene compound having a polar group containing 6 Jikanorebon San'i mi de of any nitrogen atom; and the like. Among them, preferable indicate norbornenes high crystallinity with unsubstituted or relatively small substituent. Specifically, norbornene, 5-Mechirunorubo Runen, 5 E chill-norbornene, 5-E Chile den norbornene, 5-vinyl norbornene-, Nonorebo / Renen 5, 6 Jikanorebon acid anhydride, 5-hydroxycarboxylic methylnorbornene , 5, 6-di (human Dorokishimechiru) norbornene, 5, 5-di (human Dorokishimechinore) Nonorebonorenen, 5- Shiano Nonorebonorenen, norbornene _ 5, such as 6-dicarboxylic acid imide and the like.

In r is 0 in formula [1 0], is a norbornene derivative having a cyclic structure in addition to the norbornene ring bonded R 36 and R 39 are, Jishiku port Pentajen such ring structure is a 5-membered ring, ring structure and the like norbornene derivative is an aromatic ring. It is a specific example of dicyclopentadiene acids, dicyclopenta diene or 5-membered ring portion of Jishiku port Pentajen double bond a tricycloalkyl of saturated [4. 3. I 2 '5. 0] dec-one 3 _ E down, tricyclo [4. 4. I 2 '5. 0] , such as Unda _ 3-E emissions can be mentioned. The norbornene derivative ring structure is an aromatic ring, tetracyclo [6.5-1 2 '5.0 6.0 8' 1 3] Preparative Rideka 3, 8, 1 0, 1 2 Tetoraen (1, 4- methanol 1, 4, 4 a, 9 a- Te also referred Torahi mud fluorene), Te Torashikuro [6. 6. 1 2, 5. o 1 '6. 0 8' 1 3] tetradec one 3, 8, 1 0 , 1 2-te Toraen (1,

4 one methanol 1, 4, 4 a, 5, 1 0, also called Kisahi Doroan anthracene 1 0 to a-), and the like.

Jishiku port Pentajen acids shown in the above specific example, Roh Ruporunen derivative ring structure is an aromatic ring, because it is composed of only the ring structure, preferably to obtain a crystalline ring-opening polymer or hydrogenated product thereof.

Is by r in the general formula [1 0] Specific examples of tetracyclo dodecene compound is 1, Te Torashikuro dodecene, 8-Mechirute Torashikuro dodecene, 8-Echirute preparative Rashikuro dodecene, 8-cycloheteroalkyl Kishirute Torashikuro dodecene, 8- Te tiger cycloalkyl dodecene compound having an unsubstituted or alkyl group such as cyclopropyl Penchirute Torashikuro dodecene;

8 Mechiridente Torashikuro dodecene, 8 - Echiridente Torashikuro dodecene, 8-Bininorete Torashikuro dodecene, 8-propenyl Nirute Torashikuro dodecene, Kisenirute Torashikuro dodecene to 8-Sik ports, 8-cyclopent two Norre tape - Torashiku opening dodecene, etc. Te Torashiku port dodecene acids having a double bond exocyclic;

Tetracyclo de decene compound having an aromatic ring such as 8 one Hue El tetracyclododecene dodecene;

8- main butoxy force / Reponirute Torashiku port dodecene, 8-methyl-8-main Toki Shikarubonirute Torashiku port dodecene, 8-arsenide Dorokishimechirute Torashiku port de-decene, 8-force Norebokishite Torashikuro dodecene, Te Torashikuro dodecene one 8, 9 Jikarubon acid, te tetracyclo dodecene compound having a substituent containing a Torashiku b dodecene one 8, 9 Jikarubon anhydrides of any oxygen atom;

8 Shianote Torashiku port dodecene, Te Torashikuro dodecene compound having a substituent containing a nitrogen atom such as tetracyclo dodecene one 8, 9 one dicaprate carboxylic acid I Mi de;

Lutein Torashikuro dodecene such that having a substituent containing a halogen atom such as 8-Kurorote Torashikuro dodecene;

Te Torashikuro dodecene compound having a location 换基 containing Kei atom such as 8-trimethyl-butoxy silyl tetracyclododecene dodecene; and the like.

Among them, preferable indicate tetracyclo dodecene such high crystallinity with unsubstituted or relatively small substituent. Specifically, tetracyclo dodecene,

8-methyl tetracyclo dodecene, 8-Echirute Torashikuro dodecene, 8-methylidene-tetracyclo dodecene, 8-E dust Den tetracyclododecene dodecene, 8-vinyl-tetracyclo dodecene, 8-arsenide Dorokishimechirute Torashikuro dodecene, tetracyclo dodecene one 8 , 9 Jikarubon anhydride, 8 Shianote Torashikuro dodecene, Te Torashikuro dodecene one 8, 9 Jikarubon acid I Mi de, like 8 _ chloro tetracyclododecene dodecene.

Formula [1 0] r as a specific example of Putadesen acids to the Kisashiku port to a 2 to the Kisashiku port Putadesen, 1 2 Mechinore Previous Kisashikuro Putadesen, Kisashiku port heptadecene to 1 2 Echinore, 1 2 Putadesen to consequent opening hexyl to Kisashiku port, Putadesen acids to Kisashiku port to an unsubstituted or alkyl group such as Putadesen to Kisashikuro to 1 2-cyclopentyl Honoré;

1 2 methylidene Previous Kisashiku port Putadesen, 1 2 - to Echiriden to Kisashi black Putadesen, 1 2 - to Bininore to Kisashiku port Putadesen, 1 2-propenyl two Norre Previous Kisashiku port Putadesen, to Kiseninore to 1 2 Shiku port Kisashiku port heptene Tadesen, Putadesen acids to Kisashiku port 1 to 2 consequent opening pent two Le to Kisashiku port exocyclic such Putadesen to a double bond;

Putadesen acids to Kisashi click port to an aromatic ring such as 1 2-Hue to double Le to Kisashiku port Putadesen;

1 2 main Tokishikarubo two Honoré to Kisashiku port heptadecene, 1 2- Mechinore 1 2 main Tokishikarubo two Le to Kisashiku port heptadecene, 1 2-arsenide Dorokishimechi to Le to Kisashiku port Putadesen, Putadesen to 1 2 Kisashiku port into single carboxy, Putadesen 1 2 Previous Kisashikuro, 1 3 - Putadesen such dicarboxylic acids to, to Kisashiku port to that having a substituent containing an oxygen atom, such as descriptor decene 1 2, 1 3-dicarboxylic anhydride to Kisashiku port;

1 2 Putadesen class to Kisashiku port Shiano Previous Kisashiku port Putadesen, to the Kisashiku port to having a substituent containing a nitrogen atom such as Putadesen 1 2, 1 3-dicarboxylic acid imide;

Putadesen acids to Kisashiku port to have a substituent containing a halogen atom such as Putadesen to Kisashiku port to 1 2 Black port;

1 2 trimethylene Tokishishiriru such Putadesen acids and the like to Kisashiku port to having a substituent containing a Kei atom such Putadesen to Kisashiku port to.

The monomers described above include isomers of the endo isomer and Ekiso body. Monomer for use in the present invention include, but may be a mixture of these isomers, out to achieve the crystallinity, the isomer mixture, the composition ratio of any one isomer component the higher is preferred. Specifically, any of isomers usually 70% or more, preferably those of particular 80% or more.

In the present invention, it may be copolymerized with the norbornene based monomer and other copolymerizable monomers. The other copolymerizable monomers, mention may be made of norbornene Nene monomer other than the cyclic Orefin class. The cyclic Orefin such other norbornene monomer, C 4 ~C 2. Cyclic Orefu fin or Jiorefin and substituted versions thereof or derivatives of monocyclic and the like.

Specific examples of the monocyclic Orefin acids or Jiorefin compound is consequent opening blanking Ten, consequent opening pentene, methylcarbamoyl Honoré cyclopentene, hexene consequent opening, hexene Mechinoreshi click port, consequent opening heptene, 2001-199175, etc. consequent opening Otaten Akira 6 4 - 6 6 2 1 6 JP and cyclic Orefin monomer monocyclic listed in; Kisajen cyclohexane, Kisajen to Mechinoreshiku port, cycloalkyl O Kuta Zhen, Mechirushiku Rookutajen, phenylalanine cycloalkyl O Kuta Gen as possible out a cyclic Jiorefin based monomer is described, for example, in JP-a-7- 2 5 8 3 1 8 JP such.

• In the present invention, it is also possible to carry out the polymerization reaction in the absence of a solvent, after the polymerization, when performing the water hydrogenation reaction is preferably polymerized in an organic solvent.

The organic solvent used in the present invention, polymers and hydrogenated polymer is dissolve or dispersed in a predetermined condition, as long as it does not affect the polymerization and hydrogenation are not particularly limited.

Specific examples of such organic solvents include pentane, hexane, aliphatic hydrocarbon solvents such as heptane; cyclopentane, cyclohexane, methylcyclohexane, hexane Jimechinoreshikuro, hexane trimethylene / Reshikuro, to Echinoreshi click port hexane, hexane Jechinoreshikuro, Dekahi mud naphthalene, bicyclo heptane, alicyclic hydrocarbon solvents tricyclodecane, to the Kisahi mud indene cycloalkyl hexane, etc. consequent opening octane; benzene, toluene, xylene that any aromatic hydrocarbon solvent: dichloromethane, black hole Holm, 1, 2-dichloroethylene port halogen-containing aliphatic hydrocarbon solvents such Roetan; chlorobenzene, halogen-containing aromatic hydrocarbon solvents such as Axis every mouth benzene; nitromethane, nitro port benzene, Asetonitoriru I Which nitrogen-containing hydrocarbon solvents; Jechirue Ichite Le, aliphatic ether solvents such as tetrahydrofuran; Anisoru, etc. may be used aromatic ether solvents such as Fuene Torr. Among these solvents, aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aliphatic ether solvents or aromatic ether solvents is preferred.

(Polymerization process)

In the method of the present invention, the proportion of the polymerization catalyst to the monomer, (transition metal in the polymerization catalyst: monomer) in a molar ratio of 1: 1 00-1: 2, 00 0, 000, good Mashiku 1: 200 to 1, 000, 000, more preferably 1:50 0-1: 500, 000. When the catalyst amount is too much catalyst removal is difficult, it may not be obtained little to too a sufficient polymerization activity.

If the polymerization is carried out in a solvent, the concentration of the monomer, rather preferably is 1-50 wt%, more preferably from 2 to 45 wt%, 3 to 40 wt. / 0 are particularly preferred. If the concentration of the monomer is less than 1 wt% poor productivity, in the case of 5 0 wt% or more solution viscosity after Polymerization is too high, there may be a subsequent hydrogenation reaction becomes difficult. The polymerization reaction is initiated by mixing the monomers with the polymerization catalyst. The polymerization temperature is not particularly limited. In general, one 30 ° C~ 200 ° C, preferably 0 ° C~ 1 80 ° C. Polymerization time, the desired molecular weight can be appropriately selected such that the polymerization conversion rate is usually 1 minute to 1 00 hours.

Furthermore, by adding an appropriate amount of vinyl compounds or diene compounds, it is possible to adjust the molecular weight of the resulting ring-opening polymer. Vinyl compounds used for the molecular weight regulator is not particularly limited as long as it is an organic compound having a vinyl group, for example, 1 - butene, 1 one-pentene, 1 one hexene, alpha Orefin such as 1 one Otaten; styrene, Binino styrenes such as Retonoreen; halogen-containing vinyl compounds such as Ariruku port Lai de; Echinorebi two ether, isobutyl vinyl ether, such as § re glycidyl ether acetic acid Ariru, esters such as glycidyl methacrylate rates; § Lil alcohol hydroxyl group-containing vinyl compounds, such as Akuriruami nitrogenous Bulle compounds such as de; and the like.

The Gen compounds, for example, 1, 4-Pentajen, 1, 4 one to Kisaji E down, 1, 5 one to Kisajen, 1, butadiene to 6, 2 Mechinore 1, 4 one Pentajen, 2, 5 _ Jimechinore - a 1, 5 non-conjugated di-E down such Kisajen to; 1, 3-butadiene, 2-Mechinore 1, 3-butadiene, 2, 3-di Mechinore 1, 3-butadiene, 1, 3-Pentajen, 1, conjugate, such as Kisaje down to the 3-Jen; can be mentioned. The amount of added vinyl compound or a di-E emission compound by the desired molecular weight of the monomer, 0. 1 may be ~ selected arbitrarily between 1 0 mol%.

(Hydrogenation reaction)

The hydrogenation reaction is carried out in the presence of a hydrogenation catalyst, carried out by supplying. Hydrogen in the reaction system. The hydrogenation catalyst may be used as long as it is commonly used during the hydrogenation of Orefin compounds may be either a homogeneous catalyst and a heterogeneous catalyst.

As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and alkali metal compound, e.g., cobalt acetate Noto Rye chill aluminum, nickel Ruasechiruase Tonato ζ Toryi Seo heptyl aluminum Yu arm, Chitanosenjikuro Li de Zeta .eta. heptyl lithium, Gino Reco Bruno Sen dichloride de / sec one butyllithium © beam, Te 1, and a combination of such Love butoxy titanate / dimethyl magnesium. Further, there may be mentioned dichlorobis (triphenyl phosphine) palladium, Kurorohi drill Dokanorepo two Noreto list (g Re Hue Nino les phosphine) Noreteniumu, the noble metal complex catalyst such as chloro bets list (g Li Fueniruhosufi down) rhodium.

Is a heterogeneous catalyst, nickel, palladium, platinum, rhodium, a metal such as Ruteyuu beam, or these metals carbon, silica, Keisou earth, alumina, solid catalyst supported on a carrier such as titanium oxide, for example, , nickel / silica force, nickel Z Keisou earth, nickel / alumina, palladium z carbon, palladium / silica, palladium / Keisou earth include catalyst systems such as palladium z alumina.

The hydrogenation reaction is usually carried out in an inert organic solvent. Examples of such inert organic solvent medium, benzene, aromatic hydrocarbon solvents such as toluene; n-penta emissions, aliphatic hydrocarbon solvents such as hexane n-; cyclohexane, Dekahi mud naphthalene, etc. alicyclic hydrocarbon solvents; as tetrahydrofuran, ether solvents such as ethylene glycol dimethyl ether; and the like.

Inert organic solvent is preferably the same as the polymerization reaction solvent. In this case, it is directly reacted with the addition of the hydrogenation catalyst to the polymerization reaction solution. The hydrogenation reaction is conditions also suitable by hydrogenation catalysts to be used is different, the water hydride temperature is usually one 2 0~ 2 5 0 ° C, preferably one 1 0~ 2 2 0 ° C, more preferred properly 0 a 20 0 ° C, hydrogen pressure is usually 0. 0 1~: L OMP a, favored properly is 0. 0. 5 to 8MP a, more preferably from 0. l ~ 5MP a. Slow the reaction rate hydrogenation temperature is too low, too a side reaction takes place high. Further, when the hydrogen pressure is too low it slows the hydrogenation rate, too high a high pressure reactor is required.

Hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 80% or more, particularly preferably at 90% or more, the hydrogenation reaction time above usually from 0.1 to 1 0 hours hydrogenation rate can be achieved.

(Crystalline norbornene ring-opening polymer and Motobakemono crystalline norbornene ring-opening polymer solution)

Crystalline norbornene ring-opening polymer and ring-opening polymer hydride by the process of the present invention is obtained. The crystalline norbornene ring-opening polymer and ring-opening polymer hydride, has a melting point. Melting point in the range of usually 1 00~4 00 ° C.

Hereinafter, Examples and Comparative Examples further illustrate the present invention. All parts and percentages in the examples and comparative examples, Ru weight der unless otherwise stated.

(1) molecular weight of the ring-opening polymer gel 'Pamie one Chillon to the black hole Holm and solvent - was boss measured in terms of polystyrene by chromatography (GPC).

(2) hydrogenation rate was measured by infrared absorption spectrum.

(3) the thermal melting point (T m) and glass transition temperature (T g) at a differential run 查熱 meter, was measured by heating at 1 0 ° CZ min.

(Example 1)

Equipped with a stirrer glass reactor was added Okishi four molybdenum chloride (M o OC l 4) 1 . 5 parts of Jefferies chill ether 3 0 parts, was cooled to _ 7 8 ° C. Further to 3, 3 'over-di (t-butyl) - 5, 5, 6, 6, over Te Toramechiru 2, 2'. Over Biff enoki with lithium 4 dissolved 1 9 parts of 3 0 parts GETS chill ether solution was added. The mixture was slowly returned to room temperature, it was subjected to 1 8 hours. After the reaction, the precipitate is filtered off with Celite preparative, the solution portion was dried under reduced pressure. To give a solid A by standing and cooled to 3 0 ° C - this. Yield of the obtained solid was 2. 5 6 parts.

The solid 1 H- NM R spectrum of deuterated benzene was measured as solvent A was as follows.

δ 7. 2 4 (s, 1), 7. 1 9 (s, 1), 2. 1 3 (s, 3), 2. 0 3 (s, 3), 1. 6 8 (s, 3) , 1. 6 7 (s, 3), 1. 5 2 (s, 9), 1. 4 5 (s, 9).

Elemental analysis of this solid A was as follows.

Molybdenum 1 0. 9% carbon 7 0. 6% hydrogen 8.6%, chlorine <0. 1 ° / 0, Others 9. 9%. The other 9 for. 9%, is considered to contribute the oxygen was not possible measurement. These elemental composition, bis elemental composition of {3, 3, over-di (t - - heptyl) one 5, 5 ', 6, 6' tetramethyl - 2, 2 'Bifuenokishi} O carboxymethyl molybdenum (VI) (Molybdenum 1 1 . 7% carbon 7 0.6%, hydrogen 7.9%, oxygen 9. good agreement 8%) and. Note that Re is not the reason theoretical and measured values ​​is considered to contribute the oxygenate chill ether remaining.

These results, the structure of solid A is bis {3 represented by the chemical formula [1 1], 3, temporary (t one heptyl) one 5, 5 ,, 6, 6, One-tetramethyl-2, 2, over bi phenoxy} prove O carboxymethyl molybdenum (VI).

[1 1]

(Example 2)

Equipped with a stirrer glass reactor, after addition of solid A O. 0 9 2 parts of toluene, 4 parts synthesized in Example 1, which was cooled with an 7 8 ° C. Was added and further dissolved in hexane 1 part f the n _ butyllithium 0.0 1 4 5 parts, which is allowed to warm to room temperature, was subjected to 1 hour of reaction.

To the resulting mixture, dicyclopentadiene (DC PD) 7. 5 parts, Torue emissions 2 7 parts, and to 1 one added hexene 0.1 parts Polymerization was conducted under 8 0 ° C. After starting the polymerization reaction, a white precipitate was precipitated quickly. After 2 hours the reaction, the polymerization reaction solution to coagulate the precipitate by pouring a large amount of methanol, after filtration, washing and dried under reduced pressure for 24 hours at 40 ° C.

The yield of the resulting ring-opening polymer is 7.4 parts, molecular weight (polystyrene equivalent) number average molecular weight (Mn) of 8, 0 0 0, a weight average molecular weight (Mw) in 1 5, 00 0 there were. The melting point (Tm) of 24 5 ° C.

(Example 3)

Equipped with a stirrer Otokurebu it was added hexane 4 7 parts to the obtained ring-opening polymer 3 parts and consequent opening in Example 2. Was then dissolved bis (carboxymethyl Honoré phosphine to Torishi click port) Benjiri Jinruteyuumu (IV) dichloro Li de 0. 0 1 8 7 parts 及 Pi E chill ether 0.5 '4 5 parts of hexane 1 0 parts to consequent opening stuff was added to the O one Tokurepu, for 8 hours hydrogen Kahan response at a hydrogen pressure of 0. 78MP a, 1 75 ° C. After the hydrogenation reaction, the reaction solution was completely precipitate the those produced by pouring into a large amount of isopropanol, followed by filtration, washing and dried under reduced pressure for 24 hours at 40 ° C.

Hydrogenation ratio of the resulting ring-opening polymer hydride was 99% or more. Incidentally, Tm was 275 ° C.

(Example 4)

Equipped with a stirrer glass reactor, 3, 3 '- di (t one-heptyl) - 5, 5 ,, 6, 6' - Te Toramechiru one 2, 2, Bifuenoru (BMB P) 0. 4 25 parts of toluene 5 parts and added te Torahi Dorofuran (THF) 5 parts of which was cooled with an 7 8 ° C. Further, adding a solution obtained by dissolving in hexane 1.5 parts n- Butyl lithium 0.2 3 1 part to n-, gradually obtain a reaction solution B to return to room temperature. To another with a stirrer glass reactor from the above, Okishi four molybdenum chloride (Mo OC 1 4) to 0.1 5 2 parts was added Toruen 1 0 parts of as tetrahydrofuran 1 0 parts of which one 78 ° C and cooled to. To this solution was added the reaction solution B whole amount was returned to the mixture slowly to room temperature. After returning to room temperature and stirred for a further 3 0 min 5 0 ° C. The solution was cooled to an 78 ° C and the solution was added a solution obtained by dissolving n _ butyllithium © beam 0.1 5 1 part to n- in hexane 0.75 parts of the catalyst solution C returned to room temperature gradually It was obtained.

Dicyclopentadiene 24 parts, 9 6 parts of toluene, the catalyst solution C was added to a stirred glass reactor was added cyclohexene 0.3 parts to 1, it was carried out for 2 hours Polymerization reaction at 8 0 ° C. After starting the polymerization reaction, a white precipitate was precipitated quickly. To the resulting et a polymerization reaction was allowed to agglomerate the precipitate by pouring a large amount of methanol. After filtration, washing the precipitate was dried under reduced pressure for 24 hours at 40 ° C. Yield of the resulting ring-opening polymer is 2 3.5 parts, Tm was 245 ° C.

(Example 5)

Except for using Okishi forty-six tungsten chloride instead of molybdenum chloride 0.1 5 9 parts was catalyst preparation and polymerization reaction in the same manner as in Example 4. The yield of the resulting ring-opening polymer is 2 3.5 parts, Tm was 24 5 ° C.

(Example 6)

Okishi four except for using di-O alkoxy-dichloro molybdenum 0.2 3 9 parts instead of molybdenum chloride was subjected to catalyst preparation and polymerization reaction in the same manner as in Example 4. The yield of the resulting ring-opening polymer is 1 5.6 parts, Tm was 24 5 ° C.

(Example 7)

Except for using the norbornene (NB E) in place of dicyclopentadiene was performed catalyst preparation and polymerization reaction as the actual 施例 4. The yield of the resulting ring-opening polymer is 2 3.5 parts, Tm was 1 0 5 ° C.

(Example 8)

In an autoclave equipped with a stirrer, was added hexane 4 7 parts to the obtained ring-opening polymer 3 parts and consequent opening in Example 4. Then added hydrogenation catalyst solution in hexane 1 0 parts 04 parts of nickel acetate 0.5 and Toriisobu Chiruaruminiumu 0.1 1 8 parts to consequent opening, a hydrogen pressure of 0. 9 8MP a, 1 6 0 ° C in 8 hours having conducted the hydrogenation reaction. To completely precipitate the polymer by pouring the hydrogenation reaction solution into a large amount of I isopropanol, after filtration, washing and dried under reduced pressure for 24 hours at 40 ° C.

Hydrogenation ratio of the resulting ring-opening polymer hydride was 99% or more. Also, Tm was 2 7 5 ° C.

(Example 9~: L 1)

Using the polymer obtained in Example 5-8 was subjected to hydrogenation reaction in the same manner as in Example 8. The results are shown in Table 1.

(Example 1 2)

3 '- di (t-butyl) one 5, 5 ,, 6, 6' - use tetramethyl-2, 2 'in place of the one biphenol 2, 6- di (t-butyl) one 4-methyl phenol (B HT) except that had performs catalyst preparation and polymerization reaction in the same manner as in example 4, was subjected to hydrogenation reaction in the same manner as in example 10 and. The results are shown in Table 1.

(Comparative Example 1)

3, 3 '- di (t one heptyl) one 5, 5 ,, 6, 6, over Te Toramechiru 2, 2' except for using phenol in place of one Bifuwenoru, catalyst preparation and polymerization in the same manner as in Example 1 reaction was carried out. After completion of the polymerization reaction, the reaction solution was filed remain uniform. Further, 1 2 5 ° C around the glass transition temperature (T g) but was observed, Tm was observed.

(Comparative Example 2)

Hydrogenation was carried out the same reaction as in Example 8 using a polymer obtained in Comparative Example 1. After completion of the hydrogenation reaction, the reaction solution remained uniform. Further, 9 5 but ° C near the T g was observed, T m was observed.

Above, embodiments according to the comparative example, the reaction product (I) or compound using a polymerization catalyst consisting of (III) and organic metal reducing agent (II) to ring-opening polymerization of a norbornene monomer, required by hydrogenating, it can be seen that the polymer or hydride having i.e. crystalline with a melting point can be obtained in a high yield in accordance with the. Industrial Applicability

According to the present invention, the polymerization catalyst, the polymerization catalyst crystalline Roh Ruporunen ring-opening polymer and ring-opening using give crystalline norbornene ring-opening polymer and crystalline Noruporune down ring-opening polymer hydride c the method for manufacturing a hydrogenated polymer is provided

Claims

The scope of the claims
1. periodic table 4-6 transition metal halide, the reaction products of phenols or phenoxy earth (b) having a Okishiharogen product or Jiokishiharogen product (a) and substituents as (I), the organometallic reducing agent (II) from the composed polymerization catalyst producing method of a crystalline Norubo Runen ring-opening polymer of a ring-opening metathesis polymerization of a norbornene monomer in the presence of a medium.
2. preparation method of the transition metal is according claim 1, wherein a molybdenum or tungsten.
3. organometallic reducing agent (II) force S, organolithium, organomagnesium, organozinc, method of manufacturing also one in which according claim 1, wherein the least is selected from the group consisting of organoaluminum and organotin .
4. phenols or phenoxide compound having a substituent (b), the divalent Hue Nord acids or divalent phenoxide such a method according claim 1, wherein a.
5. periodic table 4-6 transition metal halide, since the reaction product of Okishiharogen product or Jiokishiharogen product (a) and phenols or phenoxide compound (b) and (I), the organometallic reducing agent (II) composed after the presence in Bruno Ruborunen monomer of the polymerization catalyst was ring-opening metathesis polymerization, the resulting carbon one-carbon double bonds 50% or more hydrogenation catalysts the presence of which in the main 鎮中 polymer method for producing in you hydrogenated crystalline norbornene ring-opening polymer hydrogenation product.
6. the method for producing a transition metal, wherein the range 5 preceding claims is Moripuden or tungsten.
7. organometallic reducing agent (II) mosquitoes, organolithium, organomagnesium, organozinc, organic Aruminiumu and manufacturing methods also one in which the stated range fifth of claims and less selected from the group consisting of organotin.
Phenols or phenoxide compound (b) force S, divalent Hue Nord acids or divalent phenoxide such a method for producing a range fifth claim of claim is having 8. substituent.
9. polymerization catalyst containing a Group 4 to 6 transition metal Okishi compound or halide Periodic Table having to aromatic Jiokishi group as a ligand (III).
1 0. The transition metal polymerization catalyst according range ninth of claims molybdenum or tungsten.
1 1. periodic table 4-6 transition metal halides, Okishiharogen product or Jiokishiharogen product (a) and divalent phenols or divalent phenoxide such claims by reacting a ninth claim of the polymerization catalyst method for producing a.
PCT/JP2002/001649 2001-02-26 2002-02-25 Processes for producing norbornene open-ring polymers and hydrogenated norbornene open-ring polymers WO2002072659A1 (en)

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