JP3522009B2 - Cyclic olefin ring-opening metathesis polymer hydrogenated product and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cyclic olefin ring-opening metathesis polymer hydrogenated product and a method for producing the same.

[0002]

2. Description of the Related Art Ring-opening metathesis polymers of cyclic olefin-based monomers and hydrogenated products of ring-opening metathesis copolymers are attracting attention as optical materials and resins having high rigidity or heat resistance, and various ring-opening metathesis polymers. A combined hydrogenated product and a method for producing the same have been proposed.

As a method for hydrogenating the carbon-carbon double bond of the main chain of the cyclic olefin ring-opening metathesis polymer, for example, in the case of a heterogeneous catalyst, metals such as palladium, platinum, rhodium, ruthenium and nickel are carbon, A method of using a supported metal catalyst supported on a simple substance such as silica, alumina, titania, magnesia, diatomaceous earth, and synthetic zeolite is known, and is disclosed in JP-A-3-174406 and JP-A-4-36312. , A method for producing a hydrogenated product of a ring-opening metathesis polymer using them is illustrated.

In the case of homogeneous catalysts, nickel naphthenate / triethyl aluminum, nickel acetylacetonate / triisobutyl aluminum, cobalt octenoate / n-butyl lithium, titanocene dichloride / diethyl aluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine). ) A method using rhodium, dichlorobis (triphenylphosphine) palladium or the like is known, and is disclosed in JP-A-5-239124.
JP-A-7-41549 and the like exemplify a method for producing a hydrogenated product of a ring-opening metathesis polymer using them.

However, the method using a supported metal catalyst has a problem that it is necessary to use a large amount of catalyst in order to obtain a high hydrogenation rate because the hydrogenation reaction is non-uniform. . On the other hand, a homogeneous catalyst has a characteristic that the hydrogenation reaction proceeds with a small amount of catalyst, but nickel,
Ziegler-type catalysts consisting of organic acid salts such as cobalt and titanium and organometallic compounds such as aluminum, lithium, magnesium and tin are complicated to handle because they are deactivated by water, air, polar compounds, etc. There is a problem that cannot be used.

Further, there is a problem that the metal complex such as rhodium is expensive and the activity of hydrogenation reaction is not always sufficiently high. These hydrogenation catalysts are particularly suitable for the hydrogenation reaction of a cyclic olefin ring-opening metathesis polymer because a bulky tricyclododecene ring exists in the ring-opening metathesis polymer in the vicinity of the carbon-carbon double bond. It is difficult to hydrogenate with a large steric hindrance at a high hydrogenation rate, and especially when the ring-opening metathesis polymer has a polar substituent such as a hydroxy, carbonyl, carboxyl or nitrile group, the hydrogenation rate is high. It was considered difficult to turn it into a product.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cyclic olefin ring-opening metathesis polymer hydrogenated product having a high hydrogenation rate and a method for producing the same, which solves the above problems of the prior art. It is a thing.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have solved the above problems and have a high glass transition temperature, and a process for producing a cyclic olefin-based ring-opening metathesis polymer hydrogenated product which is stable in a practical environment. The present invention has been completed.

That is, the present invention provides a ring-opening metathesis polymer obtained by polymerizing at least one cyclic olefin-based monomer represented by the following general formula [1] (Chemical Formula 4) with a ring-opening metathesis catalyst. Is a ring-opening metathesis polymer hydrogenated product represented by the following general formula [2] (Chemical formula 5) obtained by hydrogenating the carbon-carbon double bond of the main chain present in A method for producing a hydrogenated product of a cyclic olefin-based ring-opening metathesis polymer, which has a transition temperature of 100 ° C. or higher .

[0010]

[Chemical 4]

(In the formula, R ^{1 to} R ⁴ may be the same or different and each is hydrogen, an alkyl group having 1 to 12 carbon atoms,
Aryl group, aralkyl group, alkoxy group, halogen,
A halogenated alkyl group having 1 to 12 carbon atoms, a nitrile group,
It is selected from a carboxyl group or an alkoxycarbonyl group, and x represents an integer of 1 to 3. )

[0012]

[Chemical 5]

(In the formula, R ^{1 to} R ⁴ may be the same or different and each is hydrogen, an alkyl group having 1 to 12 carbon atoms,
Aryl group, aralkyl group, alkoxy group, halogen,
A halogenated alkyl group having 1 to 12 carbon atoms, a nitrile group,
It is selected from a carboxyl group or an alkoxycarbonyl group, and x represents an integer of 1 to 3. )

The present invention also provides a main chain present in a ring-opening metathesis polymer obtained by polymerizing at least one cyclic olefinic monomer represented by the above general formula [1] with a ring-opening metathesis catalyst. The carbon-carbon double bond of is hydrogenated in the presence of hydrogen using a ruthenium metal complex represented by the following general formula [3] (Chemical formula 6). It is a method for producing a combined hydrogenated product.

[0015]

Embedded image RuH _k T _p Z _q [3]

(In the formula, H represents a hydrogen atom, and T is an olefin.
Amines, cyclic diene compounds, nitrile compounds, diamines
, Pyridines, monosulfides, butanedione, tetra
Showing a ligand selected from boron fluoride and perchloric acid , Z
Is PR ′ ¹ R ′ ² R ′ ³ (P is a phosphorus atom, R ′ ¹ , R
′ ² and R ′ ³ each represent the same or different linear, branched or cyclic alkyl group, alkenyl group, aryl group, alkoxy group or allyloxy group. ) Represents an organophosphorus compound represented by the formula, k is a positive integer of 1 or more, and p
Is 0, 1 or 2, and q is a positive integer of 1 or more. )

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin-based monomer represented by the above general formula [1] in the present invention is x
A bicycloheptoene derivative in which x is 0, a tetracyclododecene derivative in which x is 1, a derivative of hexacycloheptadecene in which x is 2, an octacyclodococene derivative in which x is 3, and the like, R ^{1 to} R ⁴ may be the same or different. R ^{1 to} R ⁴ are hydrogen, methyl having 1 to 12 carbon atoms, ethyl, propyl,
Alkyl groups such as isopropyl, butyl, t-butyl and cyclohexyl, aryl groups such as phenyl and naphthyl, aralkyl groups such as benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-naphthylethyl and 2-naphthylisopropyl, methoxy, Alkoxy group such as ethoxy, mentoxy, halogen such as chlorine, bromine, iodine or fluorine, halogenation of fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, etc. Alkyl group, nitrile group,
A carboxyl group or an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, menthoxycarbonyl, etc., in which at least one of R ^{1 to} R ⁴ is a nitrile group is preferably used.

As a specific example, 5-cyanobicyclo
[2.2.1] Hept-2-ene, 5-cyano-5-me
Cylbicyclo [2.2.1] hept-2-ene, 5-di
Cyanobicyclo [2.2.1] hept-2-ene, 5-
Cyano-6-methylbicyclo [2.2.1] hept-2
-Ene, 5-cyano-6-methoxybicyclo [2.2.
1] hept-2-ene, 5-cyano-6-carboxyme
Cylbicyclo [2.2.1] hept-2-ene, 5-ci
Ano-6-carboxybicyclo [2.2.1] hept-
2-ene, 5-cyano-6-cyanobicyclo [2.2.
1] hept-2-ene, 5-cyano-6-trifluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Cyano-6-fluorobicyclo [2.2.1] hept-
2-ene, 5-cyano-6-difluorobicyclo [2.
2.1] Hept-2-ene, 5-cyano-6-phenyl
Bicyclo [2.2.1] hept-2-ene, 5-cyano
-6-Benzylbicyclo [2.2.1] hept-2-e
5-cyano-6-cyclohexylbicyclo [2.
2.1] Cyanobicycloheptoe such as hept-2-ene
8-cyanotetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-cyano-8-methylteto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-dicyanotetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-cyano-9-methylteto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-cyano-9-methoxytetracyclo [4.4.
0.1^2,5． 1^7,10] -3-Dodecene, 8-cyano-9
-Carboxymethyltetracyclo [4.4.0.
1^2,5． 1^7,10] -3-Dodecene, 8-cyano-9-carb
Rubonixitetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-cyano-9-cyanoteto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-cyano-9-trifluoromethyltetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
Cyano-9-fluorotetracyclo [4.4.0.1
^2,5． 1 ^7,10] -3-Dodecene, 8-cyano-9-diff
Liolotetracyclo [4.4.0.1^2,5． 1^7,10]-
3-dodecene, 8-cyano-9-phenyltetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
Cyano-9-benzyltetracyclo [4.4.0.1
^2,5． 1^7,10] -3-Dodecene, 8-cyano-9-siku
Lohexyl tetracyclo [4.4.0.1^2,5．
1^7,10] -3-Cyanotetracyclododecene such as dodecene
And 11-cyanohexacyclo [6.6.1.
1^{3, 6}． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-cyano-11-methylhexacyclo [6.
6.1.1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-
Ptadecene, 11-dicyanohexacyclo [6.6.
1.1^3,6． 1^10,13． 0 ^2,7． 0^9,14] -4-Hepta
Decene, 11-cyano-12-methylhexacyclo
[6.6.1.1^3,6． 1^10,13． 0^2,7． 0^9,14]-
4-heptadecene, 11-cyano-12-methoxyhex
Sacyclo [6.6.1.1^3,6． 1^10,13． 0^{2, 7}． 0
^9,14] -4-Heptadecene, 11-Cyano-12-Cal
Boniximethylhexacyclo [6.6.1.1^3,6． 1
^10,13． 0^2,7． 0^9,14] -4-Heptadecene, 11-
Cyano-12-carboxyhexacyclo [6.6.1.
1^3,6． 1 ^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-cyano-12-cyanohexacyclo [6.
6.1.1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-
Ptadecene, 11-cyano-12-trifluoromethyl
Hexacyclo [6.6.1.1 ^3,6． 1^10,13．
0^2,7． 0^9,14] -4-Heptadecene, 11-Cyano-
12-Fluorohexacyclo [6.6.1.1^3,6． 1
^10,13． 0^2,7． 0^9,14] -4-Heptadecene, 11-
Cyano-12-difluorohexacyclo [6.6.1.
1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-cyano-12-phenylhexacyclo [6.
6.1.1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-
Ptadecene, 11-Cyano-12-benzylhexacycle
B [6.6.1.1^3,6． 1^10,13． 0^2,7． 0^9,14]
-4-heptadecene, 11-cyano-12-cyclohex
Silhexacyclo [6.6.1.1^3,6． 1^10,13． 0
^2,7． 0^{9, 14}] -4-Heptadecene, etc.
Cloheptadecenes, 14-cyanooctacyclo [8.
8.0.1.^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0 ^{12, 17,}] -5-dococene, 14-cyano-1
4-methyloctacyclo [8.8.0.1^2,9．
1^4,7． 1^{11, 18}． 1^13,16． 0^3,8． 0^{12, 17,}] -5
-Dococene, 14-dicyanooctacyclo [8.8.
0.1^2,9． 1^4,7． 1^{11, 18}． 1^{13 , 16}． 0^3,8． 0
^{12, 17,}] -5-dococene, 14-cyano-15-methyl
Octacyclo [8.8.0.1^2,9． 1^4,7．
1^{11, 18}． 1^13,16． 0^3,8． 0^{12, 17,}] -5-Docose
14-cyano-15-methoxyoctacyclo [8.
8.0.1.^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0^{12, 17,}] -5-dococene, 14-cyano-1
5-Carboxymethyl octacyclo [8.8.0.1
^2,9． 1^{Four, 7}． 1^{11, 18}． 1^13,16． 0^3,8．
0^{12, 17,}] -5-dococene, 14-cyano-15-cal
Boxyoctacyclo [8.8.0.1^2,9． 1^4,7． 1
^{11, 18}． 1^{13 , 16}． 0^3,8． 0^{12, 17,}] -5-Docose
, 14-cyano-15-cyanooctacyclo [8.
8.0.1.^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0^{12, 17,}] -5-dococene, 14-cyano-1
5-trifluoromethyloctacyclo [8.8.0.1
^2,9． 1^4,7． 1^{11, 18}． 1^13,16． 0^3,8．
0^{12, 17,}] -5-dococene, 14-cyano-15-fur
Orooctacyclo [8.8.0.1^2,9． 1 ^4,7． 1
^{11, 18}． 1^13,16． 0^3,8． 0^{12, 17,}] -5-Docose
14-cyano-15-difluorooctacyclo
[8.8.0.1^2,9． 1^4,7． 1^{11, 18}． 1 ^13,16．
0^3,8． 0^{12, 17,}] -5-dococene, 14-cyano-1
5-phenyl octacyclo [8.8.0.1^2,9． 1
^4,7． 1^{11, 18}． 1^13,16． 0^3,8． 0^{12 , 17}] -5
Docosene, 14-cyano-15-benzyloctacyclo
[8.8.0.1^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0^{12, 17,}] -5-dococene, 14-cyano-1
5-cyclohexyloctacyclo [8.8.0.
1^2,9． 1 ^4,7． 1^{11, 18}． 1^13,16． 0^3,8． 0
^{12, 17,}] -5-dococene and other cyanooctacyclodocose
It is possible to list such items.

Furthermore, bicyclo [2.2.1] hept
-2-ene, 5-methylbisic [2.2.1] hept-
2-ene, 5-ethylbicyclo [2.2.1] hept-
2-ene, 5-carboxybicyclo [2.2.1] hep
To-2-ene, 5-carboxymethylbicyclo [2.
2.1] Hept-2-ene, 5-benzylbicyclo
[2.2.1] hept-2-ene, 5-chlorobicyclo
[2.2.1] Hept-2-ene, 5-bromobicyclo
[2.2.1] Hept-2-ene, 5-methoxybisic
B [2.2.1] hept-2-ene, 5-ethoxyvic
Chloro [2.2.1] hept-2-ene, 5-methyl-6
-Methylbicyclo [2.2.1] hept-2-ene and the like
Bicycloheptoene derivative, tetracyclo [4.4.
0.1^2,5． 1^{7, Ten}] -3-Dodecene, 8-methylteto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-ethyltetracyclo [4.4.0.1^2,5． 1
^7,10] -3-Dodecene, 8-carboxytetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
Carboxymethyl tetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-benzyltetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
Chlorotetracyclo [4.4.0.1^2,5． 1^7,10]-
3-dodecene, 8-bromotetracyclo [4.4.0.
1^2,5． 1^7,10] -3-Dodecene, 8-methoxytetra
Cyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-ethoxytetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-methyl-9-methylteto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-methyl-9-carboxymethyl tetracyclo
[4.4.0.1 ^2,5． 1^7,10] -3-Dodecene, 8-
Phenyltetracyclo [4.4.0.1^{2, Five}． 1^7,10]
Tetracyclododecene derivatives such as 3-dodecene, hex
Sacyclo [6.6.1.1^3,6． 0^2,7． 0^9,14] -4
-Heptadecene, 11-methylhexacyclo [6.6.
1.1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Hepta
Decene, 11-ethylhexacyclo [6.6.1.1]
^3,6． 1^10,13． 0^2,7． 0^{9, 14}] -4-Heptadese
, 11-carboxyhexacyclo [6.6.1.1
^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-benzylhexacyclo [6.6.1.
1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-carboxymethylhexacyclo [6.6.
1.1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Hepta
Decene, 11-methoxyhexacyclo [6.6.1.1]
^{3, 6}． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-ethoxyhexacyclo [6.6.1.
1^3,6． 1^10,13． 0^2,7． 0^9,14] -4-Heptadese
, 11-methyl-12-carboxymethylhexacyclic
B [6.6.1.1^3,6． 1 ^10,13． 0^2,7． 0^9,14]
Derivation of hexacycloheptadecene such as 4-heptadecene
Body, octacyclo [8.8.0.1^2,9． 1^4,7． 1
^{11, 18}． 1^13,16． 0^{3, 8}． 0^{12, 17,}] -5-Docose
14-methyloctacyclo [8.8.0.1^{2, 9}．
1^4,7． 1^{11, 18}． 1^13,16． 0^3,8． 0^{12, 17,}] -5
-Dococene, 14-ethyloctacyclo [8.8.0.
1^2,9． 1^4,7． 1^{11, 18}． 1^13,16． 0^{3, 8}． 0
^{12, 17,}] -5-dococene, 14-carboxy octashik
B [8.8.0.1^2,9． 1^4,7． 1^{11, 18}．
1^13,16． 0^3,8． 0^{12, 17,}] -5-docosene, 14-
Benzyloctacyclo [8.8.0.1^2,9． 1^4,7．
1^{11, 18}． 1^13,16． 0^3,8． 0^{12, 17,}] -5-Docose
, 14-carboxymethyloctacyclo [8.8.
0.1^2,9． 1^4,7． 1^{11, 18}． 1^13,16． 0^3,8． 0
^{12, 17,}] -5-dococene, 14-methoxyoctacyclo
[8.8.0.1^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0^{12, 17,}] -5-dococene, 14-ethoxy
Kutacyclo [8.8.0.1^2,9． 1^4,7． 1^{11, 18}．
1^13,16． 0^3,8． 0^{12, 17,}] -5-docosene, 14-
Methyl-15-carboxymethyloctacyclo [8.
8.0.1.^2,9． 1^4,7． 1^{11, 18}． 1^13,16．
0^3,8． 0^{12, 17,}] -5-dococene and other octacyclodes
As a cosene derivative and a monocyclic olefin,
Clobutene, cyclopentene, cycloheptene, cyclo
Cycloolefins such as octene, and further dicyclo
Mention may be made of pentadienes. Especially nitrile group
When the ring-opening metathesis polymer containing
Good and preferred.

These cyclic olefin-based monomers are not necessarily used alone, and ring-opening copolymerization can be performed by using two or more kinds in an arbitrary ratio.

The ring-opening metathesis used in the present invention
Any catalyst can be used as long as it is a catalyst for ring-opening metathesis polymerization.
, But examples of ring-opening metathesis catalysts
As W (N-2,6-C₆H₃Prⁱ ₂) (CHBu^t) (OBu^t)₂, W
(N-2,6-C₆H₃Prⁱ ₂) (CHBu^t) (OCMe₂CF₃)₂, W (N-2,6-C₆H
₃Prⁱ ₂) (CHBu^t) (OCMe₂(CF₃)₂)₂, W (N-2,6-C₆H₃Prⁱ ₂) (C
HCMe₂Ph) (OBu^t)₂, W (N-2,6-C₆H₃Prⁱ ₂) (CHCMe₂Ph) (OCMe
₂CF₃)₂, W (N-2,6-C₆H₃Prⁱ ₂) (CHCMe₂Ph) (OCMe₂(C
F₃)₂)₂, (Pr in the formulaⁱIs iso-propyl group, Bu^tIs tert
-Butyl group, Me represents a methyl group, and Ph represents a phenyl group. )
Tungsten-based alkylidene catalysts such as W (N-2,6-Me₂C₆H
₃) (CHCHCMePh) (O-Bu^t)₂(PMe₃), W (N-2,6-Me₂C₆H ₃) (CHC
HCMe₂) (O-Bu^t)₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCPh₂)
(O-Bu^t)₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCMePh) (OCMe
₂(CF₃))₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCMe₂) (OCMe₂(C
F₃))₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCPh₂) (OCMe₂(C
F₃))₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCMe₂) (OCMe (C
F₃)₂)₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCMe₂) (OCMe (CF₃)
₂)₂(PMe₃), W (N-2,6-Me₂C₆H₃) (CHCHCPh₂) (OCMe (CF₃)₂)₂
(PMe₃), W (N-2,6-Prⁱ ₂C₆H₃) (CHCHCMePh) (OCMe₂(CF₃))
₂(PMe₃), W (N-2,6-Prⁱ ₂C₆H₃) (CHCHCMePh) (OCMe (CF₃)₂)₂
(PMe₃), W (N-2,6-Prⁱ ₂C₆H₃) (CHCHCMePh) (OPh)₂(PMe₃),
(Pr in the formula ⁱIs iso-propyl group, Bu^tIs tert-butyl
Group, Me represents a methyl group, and Ph represents a phenyl group. ) Etc.
Gustene-based alkylidene catalyst, Mo (N-2,6-Prⁱ ₂C₆H₃) (C
HBu ^t) (OBu^t)₂, Mo (N-2,6-Prⁱ ₂C₆H₃) (CHBu^t) (OCMe
₂CF₃)₂, Mo (N-2,6-Prⁱ ₂C₆H ₃) (CHBu^t) (OCMe (CF₃)₂)₂,
Mo (N-2,6-Prⁱ ₂C₆H₃) (CHCMe₂Ph) (OBu^t)₂ , Mo (N-2,6-P
rⁱ ₂C₆H₃) (CHCMe₂Ph) (OCMe₂CF₃)₂, Mo (N-2,6-Prⁱ ₂C
₆H₃) (CHCMe₂Ph) (OCMe (CF ₃)₂)₂, (Pr in the formulaⁱIs iso−
Propyl group, Bu^tIs a tert-butyl group, Me is a methyl group, Ph
Represents a phenyl group. ) Etc. molybdenum-based alkylidene
Catalyst, Re (CBu^t) (CHBu^t) (O-2,6-Prⁱ ₂C₆H₃)₂, Re (CBu^t)
(CHBu^t) (O-2-Bu^tC₆H_Four)₂, Re (CBu^t) (CHBu^t) (OCMe₂C
F₃)₂, Re (CBu^t) (CHBu^t) (OCMe (CF₃)₂)₂, Re (CBu^t) (CHB
u^t) (O-2,6-MeC₆H₃) ₂, (Bu in the formula^tIs a tert-butyl group
Represent ) And other rhenium-based alkylidene catalysts, Ta [C (Me) C
(Me) CHMe₃] (O-2,6-Prⁱ ₂C₆H₃)₃Py, Ta [C (Ph) C (Ph) CHMe₃]
(O-2,6-Prⁱ ₂C₆H₃)₃Py, (Me in the formula is a methyl group, Ph is a group
A phenyl group and Py represent a pyridine group. ) Etc.
Rukylidene catalyst, Ru (CHCHCPh₂) (PPh₃)₂Cl₂, (Ph in the formula
Represents a phenyl group. ) Etc. ruthenium-based alkylidene
Examples include catalysts and titanacyclobutanes. The ring opening method
The tassesis catalyst may be used alone or in combination of two or more.
Yes.

In addition to the above, Olefin Metathesis (K
enneth J Ivin, Academic Press, New York 1983), a ring-opening metathesis catalyst system with a combination of a transition metal compound and a Lewis acid as a cocatalyst, for example,
A ring-opening metathesis catalyst composed of a transition metal halide such as molybdenum, tungsten, vanadium or titanium and an organoaluminum compound, an organotin compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium or boron as a cocatalyst is used. You can also

Specific examples of transition metal halides include:
MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ ,
MoOF ₄ , etc., molybdenum halide, WBr ₂ , WBr ₄ , WCl
₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WO
F ₄ , WCl ₄ (OC ₆ H ₄ Cl ₂ ) ₂ , etc.Tungsten halide, VOCl ₃ , VOBr ₃ , etc.Vanadium halide TiC
Examples thereof include titanium halides such as l ₄ and TiBr ₄ .

Specific examples of the organometallic compound as the cocatalyst include trimethylaluminum, triethylaluminum, triishibutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride, Organic aluminum compounds such as di-n-butylaluminum, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, tetramethyltin, diethyldimethyltin, tetraethyltin,
Dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride,
Organotin compounds such as dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, butyltin triiodide,
Organic lithium compounds such as n-butyl lithium, organic sodium compounds such as n-pentyl sodium, methyl magnesium iodide, ethyl magnesium bromide, methyl magnesium bromide, n-propyl magnesium bromide, t-butyl magnesium chloride, allyl magnesium chloride, etc. Examples thereof include organic magnesium compounds, organic zinc compounds such as diethylzinc, organic cadmium compounds such as diethylcadmium, and organic boron compounds such as trimethylboron, triethylboron, and tri-n-butylboron.

The molar ratio of the cyclic olefin-based monomer to the ring-opening metathesis catalyst is such that tungsten, molybdenum, rhenium, tantalum, and
In the case of an alkylidene catalyst such as ruthenium or titanacyclobutane, the amount is 0.01 to 10 mol, preferably 0.1 to 5 mol. Further, in the ring-opening metathesis catalyst comprising a transition metal halide and an organometallic compound, the transition metal halide is 0.001 to 5 mol, preferably 0.01 to 3 mol, and the organometallic compound as a cocatalyst is 0. The range is 0.005 to 10 mol, preferably 0.02 to 5 mol.

As the solvent used in the ring-opening metathesis polymerization, tetrahydrofuran, diethyl ether,
Ethers such as dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane and heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane,
Aliphatic cyclic hydrocarbons such as decalin and halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, trichlorobenzene and the like can be mentioned, and two or more kinds thereof may be mixed and used.

Further, in order to control the molecular weight, ethylene, propylene, 1-butene, isobutene, styrene,
The ring-opening metathesis polymerization may be carried out in the presence of an olefin such as 1-hexene, 4-methylpentene or hexadiene. In the ring-opening metathesis polymerization, the concentration of the monomer / ring-opening metathesis catalyst and the solvent is preferably in the range of 0.1 to 100 mol / L, though it depends on the reactivity of the monomer and the solubility in the polymerization solvent. 1 at a reaction temperature of -30 to 150 ° C
It is possible to obtain a ring-opening metathesis polymer by reacting for 10 minutes to 10 minutes and stopping the reaction with a quenching agent such as aldehydes, ketones and alcohols.

[0028] In the present invention, specific examples of T in the above general formula [3] include ethylene, propylene, butene, butadiene, olefins such as pentadiene, cyclopentadiene, cyclooctadiene, cycloalkyl decadiene, cyclododecadiene, Cyclic diene compounds such as norbornadiene and dicyclopentadiene, acetonitrile,
Propionitrile, allyl cyanide, benzonitrile,
Nitrile compounds such as cyclohexylisonitrile, diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, pyridine, lutidine, 2,2 '
-Pyridines such as bipyridine, dimethyl sulfide, methyl ethyl sulfide, monosulfides such as ethyl isobutyl sulfide, butanedione, boron tetrafluoride,
Examples thereof include perchloric acid.

Z is an organic phosphorus compound, and specific examples thereof include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-propylphosphine, tri-t-butylphosphine, triisobutylphosphine, tri-n-butylphosphine and tri-n-butylphosphine. Cyclohexylphosphine, tricyclopentylphosphine, dicyclohexylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethyldiphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolyl Phosphine, dichloro (ethyl) phosphine, dichloro (phenyl) phosphine, chlorodiphenylphosphine, trimethylphosphite, triethylphos Phosphite, diethyl phosphite, triisopropyl phosphite, triphenyl phosphite and the like.

Ruthenium metal complex represented by the general formula [3]
As a specific example of the body, RuH₂(PPh₃)_Four, RuH₂(PEt₃)_Four, RuH₂
[PMePh₂] 4, RuH₂[PClPh₂]_Four, RuH₂[PPhCl₂]_Four, RuH₂[PEtC
l₂] _Four, RuH₂(PCyh₃)_Four, RuH₂(PHex₃)_Four, RuH₂(POPh₃)_Four, Ru
H₂(POMe₃)_Four, (Ph in the formula is a phenyl group, Et is an ethyl group,
Me is a methyl group, Cyh is a cyclohexyl group, Hex is hex
Represents a radical. ) RuH_Four(PPh₃)₃, RuH_Four(PEt₃)₃, RuH_Four[PMePh
₂]₃, RuH_Four[PClPh₂]₃, RuH_Four[PPhCl₂]₃, RuH_Four[PEtCl₂]₃,
RuH_Four(PCyh₃)₃, RuH_Four(PHex₃)₃, RuH_Four[P (OPh)₃]₃, RuH_Four[P
(OMe)₃]₃, (Ph in the formula is a phenyl group, Et is an ethyl group, Me
Is a methyl group, Cyh is a cyclohexyl group, Hex is hexyl
Represents a group. ) RuH (C₂H_Four) (PPh₃)₂, RuH (Cp) (PPh₃)₂, RuH
[NH₂(CH₂)₂NH₂] (PPh₃)₂, RuH [(CH₃)₂SO] (PPh₃)₂, RuHCl
(PPh₃)₂, RuH (CH3COCOCH3) (PPh₃)₂, RuH (BF4) (PPh₃)₂,
RuH (ClO_Four) (PPh₃)₂, (Ph in the formula is a phenyl group, Cp is
Represents a lopentadienyl group. ) RuH₂(CH₃CN) (PPh₃)₃, Ru
H₂(CH₃CH₂CN) (PPh₃)₃, RuH₂[CH₃(CH₂)₃CN] (PPh₃)₃, RuH
₂[(CH₃)₂CHCN] (PPh₃)₃, RuH₂(CH₂CHCH₂CN) (PPh₃)₃, RuH
₂(C₆H_FiveCN) (PPh₃)₃, (Ph in the formula represents a phenyl group.)
RuH₂(C_FiveH_FiveN) (PPh₃)₃, RuH₂(C_FiveH_FourN) (PPh₃)₃, (Ph in the formula
Represents a phenyl group. ) RuH₃(Cp) (PPh₃) (Ph in the formula is
A phenyl group, Cp represents a cyclopentadienyl group. ) Etc.
Can be exemplified, especially RuH₂(PPh₃)_Four Is a hydrogenation reaction
Has high activity and is preferable.

As the solvent used in the hydrogenation reaction of the ring-opening metathesis polymer, any solvent may be used so long as it dissolves the ring-opening metathesis polymer and the solvent itself is not hydrogenated, for example, tetrahydrofuran, diethyl ether, Ethers such as dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, pentane, hexane,
Aliphatic hydrocarbons such as heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, aliphatic cyclic hydrocarbons such as decalin, methylene dichloride, halogenated hydrocarbons such as dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, trichlorobenzene, etc. And two or more of them may be used in combination.

The hydrogenation product of the cyclic olefin ring-opening polymer of the present invention can be prepared by isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution and then dissolving it again in a solvent. It is also possible to employ a method in which the hydrogenation catalyst is added without separation to perform hydrogenation.

The hydrogenation reaction of the ring-opening metathesis polymer is
The hydrogen pressure is usually atmospheric pressure to 300 kg / cm ² , preferably 20.
~ 200 kg / cm ² and the reaction temperature is usually 0 to 200 ° C, preferably room temperature to 150 ° C.
Temperature range.

Generally, the weight ratio of ring-opening metathesis polymer to hydrogenation catalyst is from 100: 0.005 to 100: 100, preferably from 100: 0.01 to 100: 10. The cyclic olefin ring-opening polymer hydrogenated product obtained in the present invention has a glass transition temperature of 100 ° C. or higher, particularly preferably 130 ° C. or higher.

The hydrogenation rate of the ring-opening metathesis polymer in the hydrogenation reaction can be measured from ¹ H-NMR and IR spectra of olefins. When the method of the present invention is used, a hydrogenation rate of 90% or more can be easily achieved, and can be 95% or more, particularly 99% or more. The hydrogen of the cyclic olefin-based ring-opening metathesis polymer thus obtained can be obtained. The additive is not easily oxidized and becomes an excellent cyclic olefin-based ring-opening metathesis polymer hydrogenated product.

[0036]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these.
The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. Average molecular weight: GPC
The resulting cycloolefin-based ring-opening metathesis polymer hydrogenated product was dissolved in chloroform, and was used as a detector by JASCO 830-RI and UVIDEC-100-VI, and as a column.
The molecular weight was calibrated with polystyrene standards using a Shodex k-805,804,803,802.5 at room temperature with a flow rate of 1.0 ml / min. Glass transition temperature: Shimadzu Sakusho made DSC-
According to 50, the temperature was raised in nitrogen at a rate of 10 ° C./min using 3.5 mg of a powder of a cyclic olefin-based ring-opening metathesis polymer hydrogenated product.

Example 1 Under nitrogen, in a 50 ml flask equipped with a magnetic stirrer,
Cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
0.5 g (2.71 mmol) of 3-dodecene and 30 ml of tetrahydrofuran were added, and further 10 ml of tetrahydrofuran was added.
Dissolved in. As a ring-opening metathesis polymerization catalyst, Mo (N-2,6-
_{^{C 6 H 3 Pr i 2)}} (CHCMe 2 Ph) (OBu t) 2 the 15 mg (0.027 mm
ol) was added and reacted at room temperature for 1 hour. Then, 14 mg (0.135 mmol) of benzaldehyde was added and stirred for 30 minutes to stop the reaction.

Then, this opening was opened in a 100 ml autoclave.
The ring metathesis polymer solution was transferred and used as a hydrogenation catalyst.
R. Young and G. Willkinson's method (Inorg. Synth.,1
7, 75 (1977)).
(Triphenylphosphine) ruthenium, 0.005g
(0.0043 mmol) was added, and hydrogen pressure was 70 kg / cm.²10,
Perform hydrogenation reaction at 0 ° C for 5 hours, bring the temperature back to room temperature,
Hydrogen gas was released.

This reaction solution was added to a large amount of a mixed solution of methanol / n-heptane to precipitate a hydrogenated product of a ring-opening metathesis polymer, which was separated by filtration and further washed with methanol.
After vacuum drying, a hydrogenated product of a ring-opening metathesis polymer in the form of white powder was obtained. The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer calculated from ¹ H-NMR did not show a peak attributable to protons of the olefin of the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 18200, and the number average molecular weight Mn is 1790.
It was 0 and Mw / Mn was 1.02. The glass transition temperature measured by DSC was 208 ° C.

Example 2 Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (O
Bu ^t) ₂ in place of _{Mo (N-2,6-C 6} H 3 Pr i 2) (CHCMe 2 Ph) (OCMe 2
Except that 14 mg (0.027 mmol) of CF ₃ ) ₂ was used.
Ring-opening metathesis polymerization was performed in the same manner as in Example 1 to obtain a ring-opening metathesis polymer solution. The ring-opening metathesis polymer solution was added to a large amount of methanol to precipitate the ring-opening metathesis polymer, which was separated by filtration and further washed with methanol,
After vacuum drying, 0.495 g of a ring-opening metathesis polymer powder was obtained as a white powder.

Then, 0.495 g of this ring-opening metathesis polymer powder was added to a 100 ml autoclave and the method of RA Head and JF Nixon (J. Chem. So.
c., Dalton Trans., 885 (1978), tetrahydrido tris (triphenylphosphine) ruthenium 0.005 g (0.0063 mmol) was dissolved in 40 ml of tetrahydrofuran, and hydrogen pressure was 70 kg / cm ² , 100 ° C.
A hydrogenation reaction was performed for an hour, the temperature was returned to room temperature, and hydrogen gas was released. The reaction solution was added to a large amount of a mixed solution of methanol / n-heptane to precipitate a hydrogenated product of a ring-opening metathesis polymer, which was separated by filtration and further washed with methanol,
After vacuum drying, a hydrogenated product of a ring-opening metathesis polymer in the form of white powder was obtained. The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer calculated from ¹ H-NMR did not show a peak attributable to protons of the olefin of the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 18160, and the number average molecular weight Mn is 1810.
And Mw / Mn was 1.00. The glass transition temperature measured by DSC was 217 ° C.

Example 3 Except that the amount of Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OCMe ₂ CF ₃ ) ₂ used was changed to 7 mg (0.0135 mmol). The ring-opening metathesis polymerization and hydrogenation reaction were carried out in the same manner as in Example 2 to isolate and recover the hydrogenated product of the ring-opening metathesis polymer. ¹ H-of the obtained ring-opened metathesis polymer hydrogenated product
In the hydrogenation rate calculated from NMR, no peak attributed to the proton of the main chain olefin was observed, the hydrogenation rate was 100%, and the weight average molecular weight M measured by GPC.
w is 9200, number average molecular weight Mn is 9090, and Mw
/ Mn was 1.01. The glass transition temperature measured by DSC was 218 ° C.

Example 4 As a ring-opening metathesis polymerization catalyst, Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (C
HCMe ₂ Ph) (OCMe ₂ CF ₃ ) ₂ instead of W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCM
^{ePh) (O-Bu t)} 2 and (PMe ₃₎ 16.8mg (0.0271mmo
l) dihydridotetrakis (triphenylphosphine) ruthenium instead of tetrahydridotris (triphenylphosphine) ruthenium as hydrogenation catalyst
The ring-opening metathesis polymerization and hydrogenation reaction were performed in the same manner as in Example 2 except that 0.005 g (0.0043 mmol) was used to isolate the ring-opening metathesis polymer hydrogenated product,
Recovered.

The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer calculated from ¹ H-NMR showed no peak attributed to the proton of the olefin of the main chain, and the hydrogenation rate was 100%. , The weight average molecular weight Mw measured by GPC is 18300, and the number average molecular weight Mn is 1797.
It was 0 and Mw / Mn was 1.02. The glass transition temperature measured by DSC was 206 ° C.

Example 5 In a 50 ml flask equipped with a magnetic stirrer under nitrogen 8-
Cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
0.3 g (1.63 mmol) of 3-dodecene and 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene 0.2g and (1.15 mmol) were placed in tetrahydrofuran 30 ml, it was further dissolved in tetrahydrofuran 10 ml. Mo (N-2,6-C ₆ H ₃ Pr as a ring-opening metathesis polymerization catalyst
ⁱ ₂₎ (was ^{_{CHCMe 2 Ph) (OBu t)}} 2 the 5 mg (0.028 mmol) was added and reacted at room temperature for 1 hour. Then benzaldehyde 1
5 mg (0.142 mmol) was added and stirred for 30 minutes to stop the reaction. Then, this ring-opening metathesis polymer solution was transferred to a 100 ml autoclave, and dihydridotetrakis (triphenylphosphine) ruthenium, 0.005 g (0.0043 mmol) was added as a hydrogenation catalyst,
Hydrogenation reaction was carried out at a hydrogen pressure of 70 kg / cm ² and 100 ° C. for 5 hours, the temperature was returned to room temperature, and hydrogen gas was released.

This reaction solution was added to a large amount of a mixed solution of methanol / n-heptane to precipitate the hydrogenated product of the ring-opening metathesis polymer, which was separated by filtration and washed with methanol.
After vacuum drying, a hydrogenated product of a ring-opening metathesis polymer in the form of white powder was obtained. The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer calculated from ¹ H-NMR showed no peak attributed to the olefin proton, the hydrogenation rate was 100%, and the weight was measured by GPC. The average molecular weight Mw was 17,700, the number average molecular weight Mn was 17430, and Mw / Mn was 1.02. The glass transition temperature measured by DSC was 180 ° C.

Comparative Example 1 Tetrahydridotris (triphenylphosphine) ruthenium was used as a hydrogenation catalyst in place of 5% palladium /
A ring-opened metathesis polymer hydrogenated product was obtained in the same manner as in Example 4 except that 0.05 g of the carbon-supported catalyst was used, the hydrogenation reaction temperature was 140 ° C., and the hydrogenation reaction time was 4 hours. The hydrogenation rate of the obtained hydrogenated ring-opening metathesis polymer calculated from ¹ H-NMR was 21%.

Comparative Example 2 Tetrahydridotris (triphenylphosphine) ruthenium was used as a hydrogenation catalyst in place of 5% palladium /
A ring-opened metathesis polymer hydrogenated product was obtained in the same manner as in Example 4 except that 0.05 g of the alumina carrier catalyst was used, the hydrogenation reaction temperature was 140 ° C., and the hydrogenation reaction time was 8 hours. Obtained ring-opening metathesis polymer hydrogenated product
^The hydrogenation rate calculated from ¹ H-NMR was 35%.

Comparative Example 3 Tetrahydridotris (triphenylphosphine) ruthenium was used as a hydrogenation catalyst in place of 5% ruthenium /
A ring-opened metathesis polymer hydrogenated product was obtained in the same manner as in Example 4 except that 0.05 g of the carbon-supported catalyst was used, the hydrogenation reaction temperature was 190 ° C., and the hydrogenation reaction time was 4 hours. Obtained ring-opening metathesis polymer hydrogenated product
^The hydrogenation rate calculated from ¹ H-NMR was 8.1%.

Comparative Example 4 Example except that 0.05 g of chlorotris (triphenylphosphine) rhodium was used as the hydrogenation catalyst in place of tetrahydridotris (triphenylphosphine) ruthenium, and the hydrogenation reaction time was 20 hours. A hydrogenated product of a ring-opening metathesis polymer was obtained in the same manner as in 4. ¹ H-NMR of the obtained hydrogenated product of the ring-opening metathesis polymer.
The hydrogenation rate calculated from was 81%.

[0051]

EFFECT OF THE INVENTION The hydrogenated product of the cyclic olefin ring-opening polymer of the present invention has a high glass transition temperature and can be expected as a stable heat-resistant polymer in a practical environment. Further, the method for producing a hydrogenated product of the cyclic olefin ring-opening polymer of the present invention can provide a heat resistant polymer efficiently, and is industrially extremely valuable.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-1-132626 (JP, A) JP-A-1-240517 (JP, A) JP-A-4-202404 (JP, A) JP-A-7- 2929 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 61/00-61/12

Claims (4)

(57) [Claims] 1. A ring-opening metathesis polymer obtained by polymerizing at least one cyclic olefin-based monomer represented by the following general formula [1] (Chemical formula 1) with a ring-opening metathesis catalyst. In the presence of hydrogen , the carbon-carbon double bond of the main chain
Ruthenium metal represented by the following general formula [3]
Hydrogenation using a complex, and the glass transition temperature of the resulting hydrogenated ring-opening metathesis polymer represented by the following general formula [2] (Chemical Formula 2) is 100 ° C. or higher. A method for producing a hydrogenated product of a cyclic olefin-based ring-opening metathesis polymer, which comprises : [Chemical 1] (In the formula, R ^{1 to} R ⁴ may be the same or different and each is hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen, or a carbon number 1
To 12 halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups, and x represents an integer of 1 to 3. ) [Chemical 2] (In the formula, R ^{1 to} R ⁴ may be the same or different and each is hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen, or a carbon number 1
To 12 halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups, and x represents an integer of 1 to 3. ## STR00003 ## RuH _k T _p Z _q [3] (In the formula, H represents a hydrogen atom, T represents an olefin, and a cyclic group.
Diene compounds, nitrile compounds, diamines, pyridine
, Monosulfides, butanedione, tetrafluoroborate
Represents a ligand selected from hydrogen and perchloric acid , and Z is PR ' ¹ R
′ ² R ′ ³ (P represents a phosphorus atom, R ′ ¹ , R ′ ² , R ′ ³
Are the same or different linear, branched or cyclic alkyl, alkenyl, aryl, alkoxy or allyloxy groups. ), An organic phosphorus compound represented by), k is a positive integer of 1 or more, p is 0, 1 or 2, and q is a positive integer of 1 or more. ) 2. X in the general formula [2] is 1 and R
¹ is a nitrile group and R ^{2 to} R ⁴ are hydrogen.
A method for producing a hydrogenated product of the cyclic olefin-based ring-opening metathesis polymer as described . R'wherein the general formula [3] ^1, R'is ² and ^R'3 is phenyl group, k is 2, p is 0, q is 4
The method for producing a hydrogenated product of a cyclic olefin-based ring-opening metathesis polymer using the ruthenium metal complex according to claim 1 . R'wherein the general formula [3] ^1, R'is ² and ^R'3 is a phenyl group, k is 4, p is 0, q is 3
The method for producing a hydrogenated product of a cyclic olefin-based ring-opening metathesis polymer using the ruthenium metal complex according to claim 1 .