JPH10176037A - Production of hydrogenation product of cyclic olefinic ring-opening metathesis polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject hydrogenation product in a mild condition by ring-opening polymerizing a specific cyclic olefin in the presence of a ring-opening metathesis catalyst and subsequently bringing the obtained ring-opening polymerization product into contact with hydrogen in the presence of a rare earth metal complex. SOLUTION: This method for producing the hydrogenation product of a cyclic olefinic ring-opening metathesis polymer comprises ring-opening polymerizing (A) a monocyclic olefin or a cyclic olefin monomer of formula I [R<1> -R<4> are each H, a 1-12C alkyl, an aryl, an aralkyl, a halogen, etc.; (x) is an integer of 0-3] in the presence of (B) a ring-opening metathesis catalyst [e.g. W(N-2,6-C6 H3 Pr<i> 2 )(CHBu<t> )(OBu<t> )2 , etc.,] and subsequently bringing the obtained ring-opening metathesis polymer into contact with hydrogen in the presence of (C) a rare earth metal complex of formula II (M is a rare earth metal element; L<1> , L<2> are each cyclopentadienyl, etc.; Q is H, a 1-20C linear or branched alkyl, a halogen, etc.) to hydrogenate the carbon-carbon double bonds in the main chain of the ring-opening metathesis polymer. The method is also effective for a ring-opening polymer having polar substituents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a novel hydrogenated cyclic olefin-based ring-opening metathesis polymer.

[0002]

2. Description of the Related Art Ring-opening metathesis polymers of cyclic olefin monomers and hydrogenated products of ring-opening metathesis copolymers have attracted attention as optical materials and resins having high rigidity or heat resistance, and have been used in 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, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, cobalt octenoate / n-
Methods using butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and the like are known.
JP-A-41549 and the like exemplify a method for producing a hydrogenated ring-opening metathesis polymer using them.

[0003] However, Ziegler-type catalysts composed of organic acid salts such as nickel, cobalt and titanium and organic metal compounds such as aluminum, lithium, magnesium and tin are inactivated by water, air, polar compounds and the like. There is a problem that a complicated and highly polar solvent cannot be used.

In addition, when a hydrogenation reaction of a cyclic olefin-based ring-opening metathesis polymer is carried out using these hydrogenation catalysts, a bulky tricyclododecene ring is contained in the ring-opening metathesis polymer. The steric hindrance is large because it exists near the inter-double bond, hydrogenation is considered difficult,
Hydrogenation is considered to be difficult particularly when the ring-opening metathesis polymer has a polar substitution value such as a hydroxy, carbonyl, carboxyl or nitrile group.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing a hydrogenated cyclic olefin-based ring-opening metathesis polymer which has solved the above-mentioned problems of the prior art.

[0006]

Means for Solving the Problems The present inventors diligently studied a method for producing a hydrogenated cyclic olefin-based ring-opening metathesis polymer which solved the above problems, and completed the present invention.

That is, the present invention relates to a monocyclic olefin or a compound represented by the general formula [1]:

[0008]

Embedded image [1] (wherein, R ^{1 to} R ⁴ may be the same or different and each represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen, a carbon atom of 1 ~ 12 halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups,
x represents an integer of 0 to 3. The ring-opening metathesis polymer obtained by ring-opening polymerization of the cyclic olefin-based monomer represented by the formula (2) with a ring-opening metathesis catalyst is represented by the general formula [2]:

[0009]

Embedded image [2] (In the formula, M represents a rare earth metal element, and L ¹ and L ² are a cyclopentadienyl group or a cyclopentadienyl group substituted with an alkyl group or a silicon-containing alkyl group, The groups may each be the same or different and may be directly bonded to each other to form the same cyclic hydrocarbon substituent, or L ¹ and L ^1
2 is an indenyl group or a fluorenyl group, Q is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom or a silicon-containing alkyl group,
L ¹ and L ² may be the same or different. Wherein the ring-opening metathesis polymer is contacted with hydrogen in the presence of a rare earth metal complex represented by formula (1) to hydrogenate the carbon-carbon double bond in the main chain of the ring-opening metathesis polymer. This is a method for producing a hydrogenated product.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin monomer represented by the general formula [1] in the present invention is a derivative of bicycloheptoene where x is 0, a derivative of tetracyclododecene where x is 1, A derivative of hexacycloheptadecene where x is 2 and a derivative of octacyclodcocene where x is 3, and R ^{1 to} R ⁴ may be the same or different. R ^{1 to} R ⁴ are hydrogen, C ^{1 to} C 1
2, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and cyclohexyl; aryl groups such as phenyl and naphthyl; benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-
Aralkyl groups such as naphthylethyl and 2-naphthylisopropyl; alkoxy groups such as methoxy, ethoxy and mentoxy; halogens such as chlorine, bromine, iodine or fluorine, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, A halogenated alkyl group such as trifluoromethyl, trichloromethyl, and tribromomethyl; a nitrile group; a carboxyl group; or an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, and mentoxycarbonyl; and particularly, at least ^one of R ^{1 to} R ⁴ . One in which one is a nitrile group is preferably used.

As specific examples, 5-cyanobicyclo [2.2.1] hept-2-ene, 5-cyano-5-methylbicyclo [2.2.1] hept-2-ene, 5-dicyanobicyclo [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-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-cyano-6-carboxybicyclo [2.2.1] hept-
2-ene, 5-cyano-6-cyanobicyclo [2.2.
1] Hept-2-ene, 5-cyano-6-trifluoromethylbicyclo [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-phenylbicyclo [2.2.1] hept-2-ene, 5-cyano-6-benzylbicyclo [2.2.1] hept-2- Ene, 5-cyano-6-cyclohexylbicyclo [2.
2.1] cyano bicyclo f hept ene such as hept-2-ene, 8-cyano-tetracyclo [4.4.0.1 ^2.5.
1 ^7.10] -3-dodecene, 8-cyano-8-methyl-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10] -3-dodecene, 8-dicyano tetracyclo [4.4.0.1 ^2.5.
1 ^7.10] -3-dodecene, 8-cyano-9-methyl-tetracyclo [4.4.0.1 ^{2.5. 17.10} ] -3-dodecene, 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-carboxy-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10 ]-
3-dodecene, 8-cyano-9-cyano-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10 ] -3-dodecene, 8-
Cyano-9-trifluoromethyltetracyclo [4.
4.0.1 ^2.5 . 1 ^7.10] -3-dodecene, 8-cyano-9-fluoro-tetracyclo [4.4.0.1 ^2.5. 1
^7.10] -3-dodecene, 8-cyano-9-difluoro-tetracyclo [4.4.0.1 ^{2.5. 17.10} ] -3-dodecene, 8-cyano-9-phenyltetracyclo [4.
4.0.1 ^2.5 . 1 ^7.10] -3-dodecene, 8-cyano-9-benzyl-tetracyclo [4.4.0.1 ^2.5. 1
^7.10] -3-dodecene, 8-cyano-9-cyclohexyl-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10 ] -3-
Cyanotetracyclododecenes such as dodecene, 11-cyanohexacyclo [6.6.1.1 ^3.6 . 1 ^10.13 . 0
^2.7 . 0 ^9.14 ] -4-heptadecene, 11-cyano-1
1-methylhexacyclo [6.6.1.1 ^3.6 . 1
^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene, 11-
Dicyanohexacyclo [6.6.1.1 ^3.6 . 1
^10.13 . 0 ^2.7. 0 ^9.14] -4-heptadecene, 11-
Cyano-12-methylhexacyclo [6.6.1.1
^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene, 11-cyano-12-methoxyhexacyclo [6.
6.1.1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene, 11-cyano-12-carboxymethyl hexa cyclo [6.6.1.1 ^3.6. 1 ^10.13 . 0 ^2.7 .
0 ^9.14] -4-heptadecene, 11-cyano-12-carboxymethyl hexamethylene cyclo [6.6.1.1 ^3.6. 1
^{10.1 3} . 0 ^2.7 . 0 ^9.14] -4-heptadecene, 11-
Cyano-12-cyanohexacyclo [6.6.1.1
^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene, 11-cyano-12-trifluoromethyl hexa cyclo [6.6.1.1 ^3.6. 1 ^10.13 . 0 ^2.7 .
0 ^9.14] -4-heptadecene, 11-cyano-12-fluoro-hexamethylene cyclo [6.6.1.1 ^3.6. 1 ^10.13 .
0 ^2.7 . 0 ^9.14] -4-heptadecene, 11-cyano -
12-difluoro-hexa-cyclo [6.6.1.1 ^{3. 6.}
1 ^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene, 11
-Cyano-12-phenylhexacyclo [6.6.1.
1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene, 11-cyano-12-benzylhexacyclo [6.
6.1.1 ^3.6. 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene, 11-cyano-12-cyclohexylhexacyclo [6.6.1.1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0
^9.14 ] Cyanohexacycloheptadecenes such as 4-heptadecene, and 14-cyanooctacyclo [8.8.
1 ^2.9 . 1 ^4.7 . 1 ^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.1
7 ] -5-docosene, 14-cyano-14-methyloctacyclo [8.8.0.1 ^2.9 . 1 ^4.7 . 1 ^11.18 . 1
^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-docosene, 14-dicyanooctacyclo [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-methyloctacyclo [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
- methoxy octa cyclo [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-carboxymethyloctacyclo [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-carboxyoctacyclo [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-cyanooctacyclo [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-trifluoromethyloctacyclo [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-fluorooctacyclo [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-difluorooctacyclo [8.8.0.1 ^2.9 . 1 ^4.7 . 1
^11.18 . 1 ^{13.1 6.} 0 ^3.8 . 0 ^12.17 ] -5-docosene, 14-cyano-15-phenyloctacyclo [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-15-cyclohexyloctacyclo [8.8.0.1 ^2.9 . 1 ^4.7 . 1 ^11.18 . 1
^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-docosene and the like.

Furthermore, bicyclo [2.2.1] hept
-2-ene, 5-methylbicyclo [2.2.1] hept
-2-ene, 5-ethylbicyclo [2.2.1] hept
-2-ene, 5-carboxybicyclo [2.2.1] f
Put-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-ethoxybishi
Black [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 ^7.10] -3-dodecene, 8-methyltet
Lacyclo [4.4.0.1^2.5 . 1^7.10] -3-Dodece
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-
Carboxymethyltetracyclo [4.4.0.1^2.5 .
1^{7. Ten}] -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-Dodece
8-ethoxytetracyclo [4.4.0.1^2.5 .
1^7.10] -3-dodecene, 8-methyl-9-methyltet
Lacyclo [4.4.0.1^2.5 . 1^7.10] -3-Dodece
8-methyl-9-carboxymethyltetracyclo
[4.4.0.1^2.5 . 1^7.10] -3-dodecene, 8-
Phenyltetracyclo [4.4.0.1 ^2.5 . 1^7.10]
Tetracyclododecene derivatives such as -3-dodecene;
Sacyclo [6.6.1.1^3.6 . 1^10.13 . 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-heptadecene, 11-ethylhexacyclo [6.
6.1.1^3.6 . 1^10.13 . 0^2.7 . 0^9.14] -4-F
Ptadecene, 11-carboxyhexacyclo [6.6.
1.1^3.6 . 1^10.13 . 0^2.7 . 0^9.14] -4-hepta
Decene, 11-benzylhexacyclo [6.6.1.1
^3.6 . 1^10.13 . 0^2.7 . 0^9.14] -4-heptadece
, 11-carboxymethylhexacyclo [6.6.
1.1^3.6 . 1^{10.1 Three} . 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-heptadece
, 11-ethoxyhexacyclo [6.6.1.1
^3.6 . 1^10.13 . 0^2.7 . 0^9.14] -4-heptadece
, 11-methyl-12-carboxymethylhexacyclo
B [6.6.1.1^3.6 . 1^10.13 . 0^2.7 . 0^9.14]
Hexacycloheptadecene derivatives 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
-Docosene, 14-ethyloctacyclo [8.8.0.
1^2.9 . 1^4.7 . 1^11.18 . 1 ^13.16 . 0^3.8 . 0
^12.17 ] -5-docosene, 14-carboxyoctacyclic
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-b
Ndyl octacyclo [8.8.0.1^2.9 . 1^4.7 . 1
^{11.1 8} . 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-Docosene, 14-methoxyoctacyclo
[8.8.0.1^2.9 . 1 ^4.7 . 1^11.18 . 1^13.16 .
0^3.8 . 0^12.17 ] -5-Docosene, 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 Octacyclodoko such as -5-docosene
Cene derivatives. As a monocyclic olefin,
Cyclobutene, cyclopentene, cycloheptene, cyclo
Cycloolefins such as looctene;
Mention may be made of pentadiene dimers. Especially d
What contains a tolyl group as a ring-opening metathesis polymer
And good physical properties.

These cyclic olefin monomers need not necessarily be used alone, and ring-opening copolymerization can be carried out by using two or more kinds at an arbitrary ratio.

The ring-opening metathesis used in the present invention
If the catalyst is a catalyst that performs ring-opening metathesis polymerization,
Any type may be used, but specific examples of the ring-opening metathesis catalyst
As an example, W (N-2,6-C₆ H_Three Prⁱ _Two) (CH
Bu^t ) (OBu^t )_Two , W (N-2,6-C₆ H_Three P
rⁱ _Two) (CHBu^t ) (OCMe_Two CF_Three )_Two , W (N
−2,6-C₆ H_Three Prⁱ _Two) (CHBu^t ) (OCMe
_Two (CF_Three )_Two )_Two , W (N-2,6-C₆ H_Three P
rⁱ _Two) (CHCMe_Two Ph) (OBu^t )_Two , W (N-
2,6-C₆ H_Three Prⁱ _Two) (CHCMe_Two Ph) (OC
Me_Two CF_Three )_Two , W (N-2,6-C₆ H_Three Prⁱ _Two)
(CHCMe_Two Ph) (OCMe_Two CF_Three ) _Two )_Two ,
(Pr in the formulaⁱ Is an iso-propyl group, Bu^t Is ter
t-butyl group, Me represents a methyl group, and Ph represents a phenyl group.
You. ) And other tungsten-based alkylidene catalysts, W (N-
2,6-Me_Two C₆ H_Three ) (CHCHCMePh) (O
-Bu^t)_Two (PMe_Three ), W (N-2,6-Me)_Two C₆
 H_Three ) (CHCHMe_Two ) (O-Bu^t )_Two (PMe_Three
 ), W (N-2,6-Me)_Two C₆ H_Three ) (CHCHC
Ph_Two ) (O-Bu^t )_Two (PMe_Three ), W (N−2,
6-Me_Two C₆ H_Three ) (CHCHCMePh) (OCM
e_Two (CF_Three ))_Two (PMe_Three ), W (N-2,6-M)
e_Two C₆ H_Three ) (CHCHCMe_Two ) (OCMe_Two (C
F_Three ))_Two (PMe _Three ), W (N-2,6-Me)_Two C₆ 
H_Three ) (CHCHCPh_Two ) (OCMe_Two (CF_Three ))
_Two (PMe_Three ), W (N-2,6-Me)_Two C₆ H_Three )
(CHCHCMe) (OCMe (CF_Three )_Two )_Two (PM
e_Three ), W (N-2,6-Me)_Two C₆ H _Three ) (CHCH
CMe_Two ) (OCMe (CF_Three )_Two )_Two (PMe_Three ),
W (N-2,6-Me_Two C₆ H_Three ) (CHCHCPh
_Two ) (OCMe (CF_Three )_Two )_Two (PMe_Three ), W (N
−2,6-Prⁱ _TwoC₆ H_Three ) (CHCHCMePh)
(OCMe_Two (CF_Three ))_Two (PMe_Three ), W (N-
2,6-Prⁱ _TwoC₆ H_Three ) (CHCHCMePh) (O
CMe (CF_Three )_Two )_Two (PMe_Three ), W (N-2, 6)
-Prⁱ _TwoC₆ H_Three ) (CHCHCMePh) (OPh)
_Two (PMe_Three ), (Pr in the formulaⁱ Is iso-propyl
Group, Bu^t Is a tert-butyl group, Me is a methyl group, P
h represents a phenyl group. ), Etc.
Den catalyst, Mo (N-2,6-Pr)ⁱ _TwoC₆ H_Three ) (CH
Bu^t ) (OBu^t )_Two , Mo (N-2,6-Prⁱ _TwoC
₆ H_Three ) (CHBu^t ) (OCMe_Two CF_Three )_Two , Mo
(N-2,6-Prⁱ _TwoC₆ H_Three ) (CHBu^t ) (OC
Me (CF_Three )_Two )_Two , Mo (N-2,6-Prⁱ _TwoC₆ 
H_Three ) (CHCMe_Two Ph) (OBu^t )_Two , Mo (N
−2,6-Prⁱ _TwoC₆ H_Three ) (CHCMe_Two Ph) (O
CMe_Two CF_Three )_Two , Mo (N-2,6-Prⁱ _TwoC₆ H
_Three ) (CHCMe_Two Ph) (OCMe (CF_Three )_Two )
_Two , (Pr in the formulaⁱ Is an iso-propyl group, Bu^t Is t
ert-butyl group, Me is methyl group, Ph is phenyl group
Represents ) And other molybdenum alkylidene catalysts, Re
(CBu^t ) (CHBu^t ) (O-2,6-Prⁱ _TwoC₆ 
H_Three )_Two , Re (CBu ^t ) (CHBu^t ) (O-2,
6-Bu^t C₆ H_Four )_Two , Re (CBu^t ) (CHBu
^t ) (OCMe_Two CF_Three )_Two , Re (CBu^t ) (CH
Bu^t ) (OCMe (CF_Three )_Two )_Two , Re (CBu
^t ) (CHBu^t ) (O-2,6-Me_Two C ₆ H_Three )
_Two , (Bu in the formula^t Represents a tert-butyl group. )etc
Rhenium-based alkylidene catalyst, Ta [C (Me) C
(Me) CHMe_Three ] (O-2,6-Pr ⁱ _TwoC₆ H_Three )
_Three Py, Ta [C (Ph) C (Ph) CHMe_Three ] (O
−2,6-Prⁱ _TwoC₆ H_Three )_Three Py, (Me in the formula is
A tyl group, Ph represents a phenyl group, and Py represents a pyridine group.
You. ) And other tantalum-based alkylidene catalysts, Ru (CHC
HCPh _Two ) (PPh_Three )_Two Cl_Two , (Where Ph in the formula is
Represents a phenyl group. ) And other ruthenium-based alkylidene catalysts
And titanacyclobutanes. Ring-opening metathe above
The cis catalysts may be used alone or in combination of two or more.

In addition to the above, "Olefin Metathesis" (Kenneth J. Ivin, Academic
Press, New York 1983), a ring-opening metathesis catalyst system comprising a combination of a transition metal compound and a Lewis acid as a co-catalyst, for example, a transition metal halide such as molybdenum, tungsten, vanadium, titanium or the like. A ring-opening metathesis catalyst comprising an organoaluminum compound, an organotin compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium, boron or the like can be used as a promoter.

Specific examples of the transition metal halide include:
MoBr_Two , MoBr_Three , MoBr _Four , MoCl_Four , M
oCl_Five , MoF_Four , MoOCl_Four , MoOF_Four , Etc.
Molybdenum halide, WBr_Two , WBr_Four , WCl
_Two , WCl_Four , WCl_Five , WCl₆ , WF_Four , WI_Two ,
WOBr_Four , WOCl_Four , WOF_Four , WCl_Four (OC ₆ 
H_Four Cl_Two )_Two Halides such as VOC
l_Three , VOBr_Three Halides such as TiC
l_Four , TiBr_Four And the like titanium halides
You.

Specific examples of the organometallic compound as a promoter include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride, -Organic aluminum compounds such as 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,
Organic tin compounds such as dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, and butyltin triiodide;
Organic lithium compounds such as n-butyllithium, organic sodium compounds such as n-pentyl sodium, methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesium bromide, t-butylmagnesium chloride, allylmagnesium chloride and the like Examples thereof include organic magnesium compounds, organic zinc compounds such as diethyl zinc, organic cadmium compounds such as diethyl cadmium, and organic boron compounds such as trimethyl boron, triethyl boron, and tri-n-butyl boron.

The molar ratio of the cyclic olefin-based monomer to the ring-opening metathesis catalyst is such that an alkylidene catalyst such as tungsten, molybdenum, rhenium, tantalum or ruthenium, or titanacyclobutane is used per 100 moles of the cyclic olefin monomer. In this case, it is 0.01 to 10 mol, preferably 0.1 to 5 mol. In a 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 to 1 mol. 0.005 to 10 mol, preferably 0.02 to 5 mol.

Solvents used in ring-opening metathesis polymerization include 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, heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane and decalin, methylene dichloride, dichloroethane And halogenated hydrocarbons such as dichloroethylene, tetrachloroethane, chlorobenzene and trichlorobenzene. These may be used in combination of two or more.

Further, in order to control the molecular weight, ethylene, propylene, 1-butene, isobutene, styrene,
Ring-opening metathesis polymerization may be performed in the presence of an olefin such as 1-hexene, 4-methylpentene, and hexadiene.

In the ring-opening metathesis polymerization, although it depends on the reactivity of the monomer and the solubility in the polymerization solvent, the concentration of the monomer / ring-opening metathesis and the solvent is 0.1 to 100 mol / mol.
L is preferable, and the reaction is usually performed at a reaction temperature of −30 to 150 ° C. for 1 minute to 10 hours, and aldehydes, ketones,
The reaction is stopped with a deactivator such as an alcohol to obtain a ring-opening metathesis polymer.

In the hydrogenation reaction in the present invention, a rare earth metal complex represented by the above general formula [2] is used as a catalyst. In the general formula [2], M is a rare earth metal element. Specific examples of rare earth metal elements include scandium,
Examples include yttrium, lanthanum, samarium, ytterbium, and lutetium.

L ¹ and L ² are a cyclopentadienyl group, an alkyl-substituted or silicon-containing alkyl-substituted cyclopentadienyl group (substituents may be the same or different, and are bonded to each other to form the same cyclic carbon A hydrogen group), an indenyl group or a fluorenyl group, and specific examples thereof include cyclopentadienyl, pentamethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl group, and fluorenyl group. .

Q is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, or an alkyl-substituted silyl group. Specific examples include hydrogen, methyl, ethyl, isopropyl, t-butyl, and fluorine. , Chlorine, bromine,
Examples thereof include iodine and bis (trimethylsilyl) methyl.

The rare earth metal complex represented by the general formula [2]
It may be a monomer or a multimer. Specific examples include ScH
(Cp)_Two , ScMe (Cp)_Two , ScBu^t (Cp)
_Two , ScCl (Cp)_Two , ScCH [Si (Me)_Three ]
_Two (Cp)_Two , YH (Cp)_Two, YMe (Cp)_Two , Y
Bu^t (Cp)_Two , YCl (Cp)_Two , YCH [Si
(Me)_Three ]_Two (Cp)_Two , [YH (Cp)_Two ]_Two ,
[YMe (Cp)_Two ]_Two , [YCl (Cp)_Two ]_Two , L
aH (Cp)_Two , LaMe (Cp)_Two , LaBu^t (C
p)_Two , LaCl (Cp)_Two , LaCH [Si (Me)
_Three ]_Two (Cp)_Two , SmH (Cp)_Two , SMMe (C
p)_Two , SmBu^t (Cp)_Two , SmCl (Cp)_Two ,
SmCH [Si (Me)_Three ]_Two (Cp)_Two , [SmH
(Cp)_Two ]_Two , [SMMe (Cp)_Two ]_Two , [SmC
l (Cp)_Two ]_Two , YbH (Cp)_Two , YbMe (C
p), YbBu^t (Cp)_Two , YbCl (Cp)_Two , Y
bCH [Si (Me)_Three ]_Two (Cp)_Two , LuH (C
p)_Two , LuMe (Cp)_Two , LuBu^t(Cp)_Two ,
LuCl (Cp)_Two , LuCH [Si (Me)^Three ]_Two 
(Cp)_Two , ScH (CP^* )_Two , ScMe (Cp^* )
_Two , ScBu^t (Cp^* )_Two , ScCl (Cp^* )_Two ,
ScH (Cp^**)_Two , ScMe (Cp^*** )_Two , ScC
H [Si (Me)_Three ]_Two (Cp^* )_Two , YH (Cp^* )
_Two , YMe (Cp^* )_Two , YBu^t (Cp^* )_Two , YC
l (Cp^* )_Two , YCH [Si (Me)_Three ]_Two (C
p^*)_Two , [YH (Cp^* )_Two ]_Two , [YMe (Cp
^* )_Two ]_Two , [YCl (Cp^*)_Two ]_Two , YH (C
p^**)_Two , YMe (Cp^**)_Two , YBu^t (Cp^**)
_Two , YCl (Cp^**)_Two , YCH [Si (Me)_Three ]_Two 
(Cp^**)_Two , YH (Cp^***)_Two , YMe (Cp
^*** )_Two , YBu^t (Cp^*** )_Two , YCl (Cp
^*** )_Two, YCH [Si (Me)_Three ]_Two (Cp^*** )
_Two , [YH (Cp^**)_Two ]_Two , [YMe (Cp^**)_Two ]
_Two , [YCl (Cp^**)_Two ]_Two , [YH (Cp^*** )
_Two ]_Two, [YMe (Cp^*** )_Two ]_Two , [YCl (Cp
^*** )_Two ]_Two , LaH (Cp^*)_Two , LaMe (Cp
^* )_Two , LaBu^t (Cp^* )_Two , LaCl (Cp^* )
_Two, LaCH [Si (Me)_Three ]_Two (Cp^* )_Two , La
Me (Cp^**)_Two , LaH (Cp^*** )_Two , SmH (C
p^* )_Two , SMMe (Cp^* )_Two , SmBu^t (Cp
^* )_Two , SmCl (Cp^* )_Two , SmCH [Si (M
e)_Three ]_Two (Cp^* )_Two, [SmH (Cp^* )_Two ]_Two ,
[SMMe (Cp^* )_Two ]_Two , [SmCl (Cp ^* )
_Two ]_Two , SmH (Cp^**)_Two , SMMe (Cp^*** )
_Two , [SmH (Cp^{** *} )_Two ]_Two , YbH (Cp^* )
_Two , YbMe (Cp^* )_Two , YbBu^t (Cp^*)_Two ,
YbCl (Cp^* )_Two , YbCH [Si (Me)_Three ]_Two 
(Cp^* )_Two , YbCl (Cp^**)_Two , YbMe (Cp
^*** )_Two , LuH (Cp^* )_Two , LuMe (Cp^* )
_Two , LuBu^t (Cp^* )_Two , LuCl (Cp^* )_Two ,
LuCH [Si (Me)_Three ]_Two (Cp^* )_Two , LuCl
(Cp^*** )_Two , LuMe (Cp^***)_Two , ScH (I
nd)_Two , ScMe (Ind)_Two , ScBu^t (In
d)_Two , ScCl (Ind)_Two , ScCH [Si (M
e)_Three ]_Two (Ind)_Two , YH (Ind)_Two , YMe
(Ind)_Two , YBu^t (Ind)_Two , YCl (In
d)_Two , YCH [Si (Me)_Three ]_Two (Ind)_Two ,
[YH (Ind)_Two ]_Two , [YMe (Ind)_Two ]_Two ,
[YCl (Ind)_Two ]_Two , LaH (Ind)_Two , La
Me (Ind)_Two , LaBu^t (Ind)_Two , LaCl
(Ind)_Two , LaCH [Si (Me)_Three ]_Two (In
d)_Two , SmH (Ind)_Two , SMMe (Ind)_Two ,
SmBu^t (Ind)_Two , SmCl (Ind)_Two , Sm
CH [Si (Me)_Three ] _Two (Ind)_Two , [SmH (I
nd)_Two ]_Two , [SMMe (Ind)_Two ]_Two , [SmC
l (Ind)_Two ]_Two , YbH (Ind)_Two , YbMe
(Ind)_Two , YbBu^t (Ind)_Two , YbCl (I
nd)_Two , YbCH [Si (Me)_Three ]_Two (Ind)
_Two , LuH (Ind)_Two , LuMe (Ind)_Two , Lu
Bu^t (Ind)_Two , LuCl (Ind)_Two , LuCH
[Si (Me)_Three ] (Ind)_Two , ScH (Flu)
_Two , ScMe (Flu)_Two , ScBu^t (Flu)_Two ,
ScCl (Flu)_Two , ScCH [Si (Me)_Three ]_Two 
(Flu)_Two , YH (Flu)_Two , YMe (Flu)
_Two , YBu^t (Flu)_Two , YCl (Flu)_Two , YC
H [Si (Me)_Three ]_Two (Flu)_Two , [YH (Fl
u)_Two ]_Two , [YMe (Flu) _Two ]_Two , [YCl (F
lu)_Two ]_Two , LaH (Flu)_Two , LaMe (Fl
u) _Two , LaBu^t (Flu)_Two , LaCl (Flu)
_Two , LaCH [Si (Me) _Three ]_Two (Flu)_Two , Sm
H (Flu)_Two , SMMe (Flu)_Two , SmBu
^t(Flu)_Two , SmCl (Flu)_Two , SmCH [S
i (Me)_Three ]_Two (Flu)_Two , [SmH (Flu)
_Two ]_Two , [SMMe (Flu)_Two ]_Two , [SmCl (F
lu)_Two ]_Two , YbH (Flu)_Two , YbMe (Fl
u)_Two , YbBu^t (Flu)_Two , YbCl (Flu)
_Two , YbCH [Si (Me)_Three ]_Two (Flu)_Two, Lu
H (Flu)_Two , LuMe (Flu)_Two , LuBu^t 
(Flu)_Two , LuCl (Flu)_Two , LuCH [Si
(Me)_Three ]_Two (Flu)_Two Etc. can be exemplified,
Furthermore, tetrahydrofuran or the like is added to the above-mentioned rare earth metal complex.
With the coordination of ethers of
Phosphines such as pyridine, or pyridine
And the like to which amines are coordinated. (In the formula
Me is a methyl group, Bu^t Is a tert-butyl group, Cp
Is a cyclopentadienyl group, Cp^* Is pentamethylsic
Lopentadienyl group, Cp^**Is di-tert-butyl
Clopentadienyl group, Cp^*** Is trimethylsilylpe
Antadienyl group, Ind is indenyl group, Flu is full
Represents an enyl group. ) Used in hydrogenation reactions of ring-opening metathesis polymers
As a solvent, the ring-opening metathesis polymer is dissolved and the solvent itself is dissolved.
Can be any non-hydrogenated
For example, tetrahydrofuran, diethyl ether,
Ethers such as dibutyl ether and dimethoxyethane,
Benzene, toluene, xylene, ethylbenzene, etc.
Fats such as aromatic hydrocarbons, pentane, hexane and heptane
Aromatic hydrocarbon, cyclopentane, cyclohexane, methyl
Cyclohexane, dimethylcyclohexane, decalin, etc.
Aliphatic cyclic hydrocarbons, methylene dichloride, dichloro
Ethane, dichloroethylene, tetrachloroethane, chloro
Halogenated hydrocarbons such as benzene and trichlorobenzene
And these may be used in combination of two or more.
Good.

The hydrogenated cyclic olefin ring-opening polymer of the present invention can be produced by isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution and then dissolving it in a solvent. A method of performing hydrogenation by adding the above-mentioned hydrogenation catalyst without separation can also be adopted.

The hydrogenation reaction of the ring-opening metathesis polymer is as follows:
The hydrogen pressure is usually normal pressure ~300kg / cm ^2, preferably carried out in the range of 20 to 200 kg / cm ^2, the reaction temperature is a temperature of usually 0 to 200 ° C., a temperature of preferably from room temperature to 150 DEG ° C. Range.

Generally, the weight ratio of the ring-opening metathesis polymer to the hydrogenation catalyst is from 100: 0.005 to 100: 100, preferably from 100: 0.01 to 100: 10. The hydrogenation rate in the hydrogenation reaction of the ring-opening metathesis polymer can be measured from ¹ H-NMR or IR spectra belonging to olefins.

[0029]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The physical properties of the polymers obtained in the examples were measured by the following methods.

Average molecular weight: GPC was used to dissolve the obtained hydrogenated cyclic olefin-based ring-opening metathesis polymer in chloroform, and as a detector, 830-R manufactured by JASCO Corporation
I and UVIDEC-100-VI, S as column
hodex k-805,804,803,802.5
Was used to calibrate the molecular weight with a polystyrene standard at room temperature with a flow rate of 1.0 ml / min.

Glass transition temperature: DSC-5 manufactured by Shimadzu Corporation
0, 3.5 mg at a rate of 10 ° C./min in nitrogen
Was measured using a powder of a hydrogenated cyclic olefin-based ring-opening metathesis polymer.

Example 1 [Synthesis of hydrogenation catalyst] Bis (cyclopentadienyl)
[Bis (trimethylsilyl) methyl] samarium was synthesized as follows. In a 200 ml one-neck flask under a nitrogen atmosphere, cyclopentadienyl lithium (1.
122 g, 15.58 mmol) was dissolved in 80 ml of dry tetrahydrofuran, and the resulting solution was stirred at room temperature under stirring with samarium trichloride (2.00 g, 7.79 mmol).
l) was gradually added, and the mixture was allowed to react overnight, and then tetrahydrofuran was distilled off. 80 ml of dried toluene was added to the obtained solid and stirred, and a hexane solution of bis (trimethylsilyl) methyllithium (0.91 M, 8.
56 ml) was gradually added, and the mixture was allowed to react overnight. Next, after removing by-produced salts by filtration, the filtrate was concentrated and cooled at -25 ° C overnight to obtain orange crystals (2.49 g, 62.4%). The analytical values of this compound are shown below.

[0034]¹H-NMR (90 MHz, C₆ D₆ ) Δ
(CH) 12.25 (s, 1H), δ (C_Five H_Five ) 9.
76 (s, 10H), δ (CH_Three Si) -0.63
(S, 18H), δ (THF) -1.44 (m, 4
H), δ (THF)-2.08 (m, 4H); Elemental analysis
Calculated value: C, 39.87, H, 5.71, Analysis value: C,
39.92, H, 5.69 [Ring-opening metathesis polymerization] Using a magnetic stirrer under a nitrogen atmosphere
8-cyanotetracyclo in a 50 ml flask equipped with
[4.4.0.1^2.5 . 1^7.10] -3-dodecene (3.
0 g, 16.26 mmol) in tetrahydrofuran 12
It was dissolved in 0 ml and stirred. Ring-opening metathesis weight
Mo (N-2,6-C)₆ H_Three Prⁱ _Two) (C
HCMe _Two Ph) (OBu^t ) 2 (90 mg, 0.16
2 mmol) and reacted at room temperature for 1 hour. afterwards,
Benzaldehyde (84 mg, 0.162 mmol)
The mixture was reacted at room temperature for 1 hour. Then Benzardehi
(84 mg, 0.810 mmol) and stirred for 30 minutes.
The reaction was stopped by stirring.

This ring-opening metathesis polymer solution is added to a large amount of methanol to precipitate a ring-opening metathesis polymer,
After filtration and separation, the product was further washed with methanol and dried under vacuum to obtain 2.997 g of a ring-opening metathesis polymer powder as a white powder.

[Hydrogenation reaction] Thereafter, this ring-opening metathesis polymer powder (2.
997 g) and bis (cyclopentadienyl) {bis (trimethylsilyl) methyl} samarium (0.06 g, 0.117 mmol) as a hydrogenation catalyst were dissolved in tetrahydrofuran (147 g), and the hydrogen pressure was 70 kg / cm.
^2. After a hydrogenation reaction at 100 ° C. for 5 hours, the temperature was returned to room temperature, and hydrogen gas was released. This reaction solution is added to a large amount of a methanol / hydrochloric acid solution to precipitate a hydrogenated ring-opening metathesis polymer, separated by filtration, washed with methanol, and dried in vacuo to form a white powdered ring-opening metathesis polymer. An additive was obtained. The hydrogenation rate calculated from the obtained ring-opening metathesis polymer hydrogenated product ¹ H-NMR was 31.4% from the peak attributed to protons of the olefin in the main chain, and was measured by GPC. The weight average molecular weight Mw is 18600, and the number average molecular weight Mn is 18
Mw / Mn was 1.00. Also DS
The glass transition temperature measured at C was 231 ° C.

[0037] Example 2 8-cyano-tetracyclo [4.4.0.1 ^2.5.
1 ^7.10 ] -3-dodecene (3.0 g, 16.26 mmol
8-methyltetracyclo [4.4.0.1] instead of l)
^2.5 . ^17.10 ] -3-dodecene (3.0 g, 17.05
mmol) and ring-opening metathesis polymerization and hydrogenation reaction were carried out in the same manner as in Example 1 except that toluene was used instead of tetrahydrofuran as a hydrogenation reaction solvent to obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer calculated from ¹ H-NMR was 30.6% from the peak attributed to protons of the olefin in the main chain.
, The number average molecular weight Mn was 17,040, and Mw / Mn was 1.01. The glass transition temperature measured by DSC is 165 ° C.
Met.

Example 3 [Synthesis of bis (cyclopentadienyl) @bis (trimethylsilyl) methyl) yttrium (tetrahydrofuran) Cyclopentadienyl lithium (1.122 g, 15.2 g) was placed in a 200 ml one-neck flask under a nitrogen atmosphere.
58 mmol) in dry THF (80 ml) and stirred at room temperature with yttrium trichloride (1.521).
g, 7.79 mmol) was added slowly, and the mixture was reacted overnight. After that, THF was distilled off, and dried toluene (80 ml) was added to the obtained solid, followed by stirring, to give a bis (trimethylsilyl) methyllithium hexane solution. (0.91
M, 8.56 ml) was added slowly, and the reaction was continued overnight. Then, by-produced salts were removed by filtration, and the filtrate was concentrated and cooled at -25 ° C overnight to obtain pale yellow crystals (1.27 g, 40.2%). The analytical values of this compound are shown below.

¹ H-NMR (90 MHz, C ₆ D ₆ ) δ
(CH) -0.52 (d, 1H ), δ (C 5 H 5) 6.
20 (s, 10H), δ (CH ₃ Si) 0.42 (s,
18H), δ (THF) 1.21 (m, 4H), δ (T
HF) 3.20 (m, 4H); elemental analysis, C21 H37 O1
Si2 Y1 (405.09), calculated; C, 62.2.
1, H9.13, analysis value; C, 61.98, H, 9.2
0 [Hydrogenation reaction] under a stream of nitrogen was synthesized as in Example 1 autoclave 200 ml 8- cyano-tetracyclo [4.4.0.1 ^2.5. 1 ^7.10] -3-dodecene of the ring-opening metathesis polymer powder (2.996G) and bis hydrogenation catalyst (cyclopentadienyl) {bis (trimethylsilyl) methyl} yttrium (tetrahydrofuran) (0.060 g, 0.148 mmol ) Was dissolved in tetrahydrofuran (147 g), and the hydrogen pressure was 70 kg /
After a hydrogenation reaction at 100 ° C. for 5 hours at a temperature of ² cm ² , the temperature was returned to room temperature, and hydrogen gas was released.

This reaction solution was added to a large amount of a methanol / hydrochloric acid solution to precipitate a hydrogenated ring-opening metathesis polymer, separated by filtration, washed with methanol and dried in vacuo to form a white powdery ring-opening metathesis polymer. A polymer hydrogenated product was obtained. The resulting hydrogenated ring-opening metathesis polymer ¹ H-
From the peak attributed to protons of the main chain olefin, the hydrogenation rate calculated from NMR was 29.
4%, and the weight average molecular weight Mw measured by GPC was 1
7200, the number average molecular weight Mn is 17130, and Mw /
Mn was 1.00. The glass transition temperature measured by DSC was 233 ° C.

[0041]

The process for producing a hydrogenated cyclic olefin ring-opening polymer of the present invention is particularly effective in hydrogenation under mild conditions even if the ring-opened polymer has a polar substituent. It is extremely valuable industrially.

Claims (2)

[Claims] 1. A monocyclic olefin or a general formula [1] [1] (wherein, R ^{1 to} R ⁴ may be the same or different and each represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a halogen, a carbon atom of 1 ~ 12 halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups,
x represents an integer of 0 to 3. The ring-opening metathesis polymer obtained by ring-opening polymerization of the cyclic olefin-based monomer represented by the formula (2) with a ring-opening metathesis catalyst is represented by the following general formula [2]: [2] (In the formula, M represents a rare earth metal element, and L ¹ and L ² are a cyclopentadienyl group or a cyclopentadienyl group substituted with an alkyl group or a silicon-containing alkyl group, The groups may each be the same or different and may be directly bonded to each other to form the same cyclic hydrocarbon substituent, or L ¹ and L ^1
2 is an indenyl group or a fluorenyl group, Q is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom or a silicon-containing alkyl group,
L ¹ and L ² may be the same or different. Wherein the ring-opening metathesis polymer is contacted with hydrogen in the presence of a rare earth metal complex represented by formula (1) to hydrogenate the carbon-carbon double bond in the main chain of the ring-opening metathesis polymer. Method for producing hydrogenated product. 2. A rare earth metal complex wherein M in the general formula [2] is yttrium or samarium, L ¹ and L ² are cyclopentadienyl groups, and Q is a hydrogen atom or a bis (trimethylsilyl) methyl group. The method of claim 1 for use.