JPH11209460A - Preparation of hydrogenated product of ring opening metathesis polymer based on cyclic olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily hydrogenate at a high hydrogenation ratio a ring-opening metathesis polymer of a monocyclic olefin or a specific cyclic olefinic monomer by hydrogenation in the presence of hydrogen using a ruthenium metal complex. SOLUTION: A ring-opening metathesis polymer of a monocyclic olefin or a cyclic olefinic monomer of formula I [wherein R<1-4> are each H, 1-12C (halogenated)alkyl, aryl, aralkyl, halogen, nitrile, carboxyl or alkoxycarbonyl; and x is 0-3] is subjected to a hydrogenation reaction using a ruthenium metal complex of formula II [wherein Ru is a ruthenium metal atom; H is a hydrogen atom; CO is carbonyl; Q is halogen; Z is an organic phosphorous compound of the formula: PR'<1> R'<2> R'<3> (wherein P is a phosphorus atom; R<11> -R<3> are each linear, branched or cyclic alkyl, alkenyl, aryl, alkoxy or aryloxy); m and p are each 1 or 2; and q is 2-4] at a hydrogen pressure of an ordinary pressure to 30 MPaG, preferably 0.5-20 MPaG, at 0-300 deg.C, preferably at room temperature to 250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a hydrogenated ring-opening metathesis polymer of a cyclic olefin monomer.

[0002]

2. Description of the Related Art Ring-opening metathesis polymers of cyclic olefin monomers and hydrogenated products of ring-opening metathesis copolymers are attracting attention as resins having excellent optical properties, electrical properties, high rigidity, heat resistance and weather resistance. Various ring-opening metathesis polymers and methods for producing hydrogenated polymers have been proposed.

As a method for hydrogenating a carbon-carbon double bond in the main chain of a cyclic olefin-based ring-opening metathesis polymer, for example, a heterogeneous catalyst is used to convert a metal such as palladium, platinum, rhodium, ruthenium, nickel or the like to carbon, silica or the like. A method using a supported metal catalyst supported on a carrier such as alumina, titania, magnesia, diatomaceous earth, and synthetic zeolite is known, and JP-A-3-174406, JP-A-4-363312, etc. A method for producing a hydrogenated ring-opening metathesis polymer using them is exemplified.

In addition, homogeneous catalysts include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triisobutylaluminum, cobalt / n-butyllithium octanoate, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, dichlorobis (triphenylphosphine). ) Palladium, chlorohydride carbonyl tris (triphenylphosphine)
Ruthenium, chlorotris (triphenylphosphine)
A method using rhodium or the like is known, and is disclosed in JP-A-5-23.
No. 9124, JP-A-7-41549, etc.
A method for producing a hydrogenated ring-opening metathesis polymer using them is exemplified.

However, the method using a supported metal catalyst has a problem that it is necessary to use a large amount of a catalyst in order to obtain a high hydrogenation rate because the hydrogenation reaction is not uniform. I have. On the other hand, a homogeneous catalyst has the characteristic that the hydrogenation reaction proceeds with a small amount of catalyst, but a Ziegler-type catalyst consisting of organic acid salts such as nickel, cobalt, and titanium and organic metal compounds such as aluminum, lithium, magnesium, and tin. However, there is a problem that handling is complicated and a solvent having a large polarity cannot be used because it is deactivated by water, air, polar compounds and the like.

In addition, metal complexes such as rhodium have the problems that they are expensive and that the activity of the hydrogenation reaction is not always sufficiently high. These hydrogenation catalysts, especially the hydrogenation reaction of cyclic olefin-based ring-opening metathesis polymers, are based on the presence of a bulky tricyclododecene ring near the carbon-carbon double bond in the ring-opening metathesis polymer. It is considered difficult to hydrogenate at a high hydrogenation rate with large steric hindrance. In particular, when the ring-opening metathesis polymer has a polar substituent such as a hydroxy, carboxyl, carbonyl, alkoxy, alkoxycarbonyl or nitrile group, it has been difficult to hydrogenate at a high hydrogenation rate.

Therefore, even a cyclic olefin-based ring-opening metathesis polymer having a polar substituent such as hydroxy, carboxyl, carbonyl, alkoxy, alkoxycarbonyl or nitrile group can be easily hydrogenated at a high hydrogenation rate. The development of a method was desired.

[0008]

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.

[0009]

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 method for producing a hydrogenated cyclic olefin-based ring-opening metathesis polymer of the present invention comprises a monocyclic olefin or a compound represented by the general formula [1]:

[0011]

Embedded image (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,
Selected from halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups of from 1 to 12, and x represents an integer of from 0 to 3. The ring-opening metathesis polymer of a cyclic olefin monomer represented by the general formula [2] in the presence of hydrogen

[0012]

Embedded image RuH _m CO _p Z _q (where Ru represents a ruthenium metal atom, H represents a hydrogen atom, CO represents a carbonyl group, H represents a hydrogen atom, Q represents a halogen atom, , Z is PR ' ¹ R'
² R ′ ³ (P represents a phosphorus atom, and R ′ ¹ , R ′ ² , and R ′ ³ each represent the same or different linear, branched, or cyclic alkyl, alkenyl, aryl, alkoxy, or allyloxy group. Wherein m is 1 or 2, p is 1 or 2, and q is an integer of 2 to 4. ) Is hydrogenated using a ruthenium metal complex represented by the formula (1).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the cyclic olefin-based monomer represented by the general formula [1] in the present invention, a derivative of bicycloheptoene where x is 0 and a derivative of tetracyclododecene where x is 1 , X is 2 and the derivative of hexacycloheptadecene, x is 3 and the derivative of octacyclodcocene. R ^{1 to} R ⁴ may be the same or different, and each represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t
-Butyl, an alkyl group such as cyclohexyl, phenyl,
Aryl groups such as naphthyl, aralkyl groups such as benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-naphthylethyl, and 2-naphthylisopropyl;
Alkoxy groups such as methoxy, ethoxy, t-butoxy and menthoxy, halogens such as chlorine, bromine, iodine and fluorine, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, trichloromethyl A halogenated alkyl group having 1 to 12 carbon atoms such as bromomethyl, a nitrile group, a carboxyl group or an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and mentoxycarbonyl;
Those in which at least one of R ^{1 to} R ^{4 is} an alkoxycarbonyl or nitrile group are preferably used.

As a specific example, 5-t-butoxycarbo
Nilbicyclo [2.2.1] hept-2-ene, 5-t
-Butoxycarbonyl-5-methylbicyclo [2.2.
1] hept-2-ene, 5-di-t-butoxycarbonyl
Bicyclo [2.2.1] hept-2-ene, 5-t-bu
Toxylcarbonyl-6-methylbicyclo [2.2.1]
Hept-2-ene, 5-t-butoxycarbonyl-6
Methoxybicyclo [2.2.1] hept-2-ene, 5
-T-butoxycarbonyl-6-carboxymethylbis
Black [2.2.1] hept-2-ene, 5-t-butoki
Cycarbonyl-6-carboxybicyclo [2.2.1]
Hept-2-ene, 5-t-butoxycarbonyl-6
Cyanobicyclo [2.2.1] hept-2-ene, 5-
t-butoxycarbonyl-6-trifluoromethylbis
Black [2.2.1] hept-2-ene, 5-t-butoki
Cicarbonyl-6-fluorobicyclo [2.2.1]
Put-2-ene, 5-t-butoxycarbonyl-6-di
Fluorobicyclo [2.2.1] hept-2-ene, 5
-T-butoxycarbonyl-6-phenylbicyclo
[2.2.1] Hept-2-ene, 5-t-butoxyca
Rubonyl-6-benzylbicyclo [2.2.1] hept
-2-ene, 5-t-butoxycarbonyl-6-cyclo
Hexylbicyclo [2.2.1] hept-2-ene and the like
Alkoxycarbonylbicycloheptoenes, 8-t-
Butoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-cyano-8-t
-Butoxycarbonyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-di-t-butoxyca
Rubonyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-t-butoxycarbonyl-9-me
Tyltetracyclo [4.4.0.1^{2, Five}. 1^7,10] -3
-Dodecene, 8-cyano-9-t-butoxycarbonyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-tert-butoxycarbonyl-9-tert-butoki
Cycarbonyltetracyclo [4.4.0.1^2,5. 1^7,1
0] -3-dodecene, 8-t-butoxycarbonyl-9
-Trifluoromethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-t-butoxycal
Bonyl-9-fluorotetracyclo [4.4.0.1
^2,5. 1^7,103-dodecene, 8-t-butoxycarbo
Nyl-9-difluorotetracyclo [4.4.0.1
^2,5 1^7,10] -3-dodecene, 8-t-butoxycarbo
Nyl-9-phenyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-t-butoxyca
Rubonyl-9-benzyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-t-butoxycal
Bonyl-9-cyclohexyltetracyclo [4.4.
0.1^2,5. 1^7,10Alkoxyca such as -3-dodecene
Rubonyltetracyclododecenes, 11-t-butoxy
Carbonylhexacyclo [6.6.1.1^3,6.
1^10,13. 0^2,7. 0^9,14] -4-heptadecene, 11-
t-butoxycarbonyl-11-methylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4
-Heptadecene, 11-di-tert-butoxycarbonylhexene
Sacyclo [6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,14] -4-Heptadecene, 11-t-butoxycarbo
Nyl-12-methylhexacyclo [6.6.1.
1^3,6. 1^{1 0,13}. 0^2,7. 0^9,14] -4-heptadece
11-t-butoxycarbonyl-12-methoxy
Xacyclo [6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,14] -4-Heptadecene, 11-t-butoxycarbo
Nyl-12-carbonoxymethylhexacyclo [6.
6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-hep
Tadecene, 11-t-butoxycarbonyl-12-cal
Boxyhexacyclo [6.6.1.1^3,6. 1^10,13. 0
^2,7. 0^9,14] -4-Heptadecene, 11-t-butoki
Cycarbonyl-12-cyanohexacyclo [6.6.
1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-Heptade
Sen, 11-t-butoxycarbonyl-12-trifluoro
Oromethylhexacyclo [6.6.1.1^3,6.
1^10,13. 0^2,7. 0^{9,1 Four}] -4-heptadecene, 11-
t-butoxycarbonyl-12-fluorohexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4
-Heptadecene, 11-t-butoxycarbonyl-12
-Difluorohexacyclo [6.6.1.1,^3,6. 1
^10,13. 0^2,7. 0^9,14] -4-heptadecene, 11-t
-Butoxycarbonyl-12-phenylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0 ^2,7. 0^9,14] -4
-Heptadecene, 11-t-butoxycarbonyl-12
-Benzylhexacyclo [6.6.1.1^3,6.
1^10,13. 0^2,7. 0^9,14] -4-heptadecene, 11-
t-butoxycarbonyl-12-cyclohexylhexa
Cyclo [6.6.1.1^3,6. 1^10,13. 0^2,7.
0^9,14] Alkoxycarbonyl such as -4-heptadecene
Hexacycloheptadecenes, 14-t-butoxycal
Bonyl octacyclo [8.8.0.1^2,9. 1^4,7. 1
^11,18. 1^13,16. 0^3,8. 0^{12, 17}] -5-docosene, 1
4-t-butoxycarbonyl-14-methyloctacycl
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-di-t-butoxy
Carbonyloctacyclo [8.8.0.1^2,9. 1^4,7.
1,^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docose
, 14-t-butoxycarbonyl-15-methyloctane
Tacyclo [8.8.0.1^2,9. 1^4,7. 1 ^11,18. 1
^13,16. 0^3,8. 0^12,17] -5-docosene, 14-t-
Butoxycarbonyl-15-methoxyoctacyclo
[8.8.0.1^2,9. 1^4,7. 1^11,18. 1^{1 3,16}. 0
^3,8. 0^12,17] -5-docosene, 14-t-butoxyca
Rubonyl-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-t-butoxycarboni
-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-t-butoxycarbonyl-15-si
Anooctacyclo [8.8.0.1^2,9. 1^4,7. 1
^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docosene, 1
4-t-butoxycarbonyl-15-trifluoromethyl
Luoctacyclo [8.8.0.1^2,9. 1^4,7.
1^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docosene,
14-t-butoxycarbonyl-15-fluoroocta
Cyclo [8.8.0.1^2,9. 1^4,7. 1^11,18.
1^13,16. 0^3,8. 0^12,17] -5-docosene, 14-t
-Butoxycarbonyl-15-difluorooctacyclo
[8.8.0.1^2,9. 1^4,7. 1^11,18. 1^13,16. 0
^3,8. 0^12,17] -5-docosene, 14-t-butoxyca
Rubonyl-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-t-butoxycarbonyl-15-
Benzyloctacyclo [8.8.0.1^2,9. 1^4,7. 1
^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docosene, 1
4-t-butoxycarbonyl-15-cyclohexylo
Kutacyclo [8.8.0.1^2,9. 1^4,7. 1^{11 , 18}. 1
^13,16. 0^3,8. 0^12,17Alkoxide such as -5-docosene
Cicarbonyl octacyclodcocenes and the like may be mentioned.
it can.

Also, 5-cyanobicyclo [2.2.1]
Hept-2-ene, 5-cyano-5-methylbicyclo
[2.2.1] Hept-2-ene, 5-dicyanobic
B [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-ca
Ruboxibicyclo [2.2.1] hept-2-ene, 5
-Cyano-6-cyanobicyclo [2.2.1] hept-
2-ene, 5-cyano-6-trifluoromethylbisic
B [2.2.1] hept-2-ene, 5-cyano-6
Fluorobicyclo [2.2.1] hept-2-ene, 5
-Cyano 6-difluorobicyclo [2.2.1] hep
To-2-ene, 5-cyano-6-phenylbicyclo
[2.2.1] Hept-2-ene, 5-cyano-6-b
Ndylbicyclo [2.2.1] hept-2-ene, 5-
Cyano-6-cyclohexylbicyclo [2.2.1] f
Cyanobicycloheptoenes such as pt-2-ene, 8-
Cyanotetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 8-cyano-8-methyltetracyclo
[4.4.0.12, 5.1^7,10] -3-dodecene, 8
-Dicyanotetracyclo [4.4.0.1.
^2,51^7,10] -3-dodecene, 8-cyano-9-methyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 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-cal
Bonoxytetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-cyano-9-cyanotetracyclo
[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-fluorotetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-cyano-9-difluorote
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 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-cyclohexyl
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Cyanotetracyclododecenes such as dodecene;
Anohexacyclo [6.6.1.1^3,6. 1^{Ten, 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-c
Ano-12-methoxyhexacyclo [6.6.1.1
^3,6. 1^10,13. 0^2,7. 0^9,14-4-heptadecene,
11-cyano-12-carboxymethylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4
-Heptadecene, 11-cyano-12-carboxyhex
Sacyclo [6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,144-Heptadecene, 11-cyano-12-cia
Nohexacyclo [6.6.1.1^3,6. 1^10,13.
0^2,7. 0^9,14] -4-Heptadecene, 11-cyano-
12-trifluoromethylhexacyclo [6.6. 1.
1^3,6. 1^10,13. 0^2,7. 0^{9,1 Four}] -4-heptadece
, 11-cyano-12-fluorohexacyclo [6.
6.1.1^3,6. 1^10,13. 0.^2,70^9,14] -4-hep
Tadecene, 11-cyano-12-difluorohexacyclo
B [6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14]-
4-heptadecene, 11-cyano-12-phenylhex
Sacyclo [6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,144-Heptadecene, 11-cyano-12-ben
Zylhexacyclo [6.6.1.1^3,6. 1^10,13. 0
^2,7. 0^9,14] -4-heptadecene, 11-cyano-1
2-cyclohexylhexacyclo [6.6. 1.
1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-Heptadecene
Cyanohexacycloheptadecenes such as 14-cyano
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-si
Ano-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. 113,16.0^3,8. 0
^12,17] -5-Docosene, 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-docosene, 14-si
Ano-15-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-cyano-15-carboxymethylo
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-sia
No-15-carboxyoctacyclo [8.8.0.1
^2,9. 1^4,7. 1^11,18. 1^{1 3,16}. 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. 14, 7.1^11,18. 1^13,16. 0^3,8.
0^12,17] -5-Docosene, 14-cyano-15-fur
Orooctacyclo [8.8.0.1^2,9. 1^4,7. 1^11,1
8. 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. 1^13,16. 0^3,8. 0^{12, 17}]-
5-docosene, 14-cyano-15-phenyloctacy
Black [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-docosene,
14-cyano-15-cyclohexyloctacyclo
[8.8.0.1^2,9. 1^4,7. 1^11,18. 1^13,16. 0
^3,8. 012,17] -5-docosene and other cyanoocta
Cyclodcocenes and the like can be mentioned.

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] hept
-2-ene, 5-benzylbicyclo [2.2.1] hep
To-2-ene, 5-chlorobicyclo [2.2.1] hep
To-2-ene, 5-bromobicyclo [2.2.1] hep
To-2-ene, 5-methoxybicyclo [2.2.1]
Put-2-ene, 5-ethoxybicyclo [2.2.1]
Hept-2-ene, 5-methyl-6-methylbicyclo
[2.2.1] Bicycloheptoe such as hept-2-ene
Derivative, tetracyclo [4.4.0.1.
^2,51^7,10] -3-dodecene, 8-methyltetracyclo
[4.4.0.1^2,5. 1]^7,10-3-dodecene, 8-
Ethyltetracyclo [4.4.0.1^2,5. 17,1
0] -3-dodecene, 8-carboxytetracyclo
[4.4.0.1^2,5. 1]^7,10-3-dodecene, 8-
Benzyltetracyclo [4.4.0.1.^2,51^{7 ,Ten}]
-3-dodecene, 8-chlorotetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-bromotet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8-methoxytetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-ethoxytetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-9-methyltetracyclo [4.4.0.
1^2,5. 1^7,103-Dodecene, 8-methyl-9-ka
Ruboxymethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-phenyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-Dodecene
Tracyclododecene derivative, hexacyclo [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-heptadecene, 11-ethyl
Xacyclo [6.6.1.1^3,6. 1^10,13. 0.
^2,70]^{9,1 Four}-4-heptadecene, 11-carboxy
Xacyclo [6.6.1.1^3,6. 1 ^10,13. 0^2,7. 0
^9,14] -4-Heptadecene, 11-benzylhexacyclo
B [6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14]-
4-heptadecene, 11-methoxyhexacyclo [6.
6.1.1^3,6. 1^10,13. 02,7.0^9,14] -4-F
Ptadecene, 11-ethoxyhexacyclo [6.6.
1.1^3,6. 1^10,13. 0^{2, 7}. 0^9,14] -4-Heptade
Sen, 11-methyl-12-carboxymethylhexa
Black [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^{Four , 7}. 1
^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docosene, 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-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-do
Cocene, 14-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-benzyloctacyclo [8.8.
0.1^2,9. 1^4,7. 1^11,18. 113, 16.03,
8.0^12,17] -5-docosene, 14-methoxyocta
Cyclo [8.8.0.1^2,9. 1^4,7. 1^11,18.
1^13,16. 0^3,8. 0^12,17] -5-docosene, 14-d
Toxioctacyclo [8.8.0.1^2,9. 1^4,7. 1
^11,18. 1^13,16. 0.^3,80^12,17] -5-docosene, 1
4-methyl-15-carboxymethyloctacyclo
[8.8.0.1^2,9. 1^4,7. 1^11,18. 113,1
6.0^{Three , 8}. 0^12,17Octacyclo such as -5-docosene
Docosene derivatives.

As the monocyclic olefin, cycloolefins such as cyclobutene, cyclopentene, cycloheptene and cyclooctene, and a dimer of cyclopentadiene can be used. In particular, when a compound containing an alkoxycarbonyl or nitrile group is used as a ring-opening metathesis polymer, physical properties are good and preferable.

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

Further, as the polymerization catalyst used in the present invention,
Is any catalyst capable of ring-opening metathesis polymerization.
However, specific examples of the ring-opening metathesis catalyst include:
W (N-2,6-C₆H_ThreePrⁱ _Two) (CHBu^t) (OB
u^t)_Two, W (N-2,6-C₆H_ThreePrⁱ _Two) (CHB
u^t) (OCMe_TwoCF_Three)_Two, W (N-2,6-C₆H_ThreeP
rⁱ _Two) (CHBu^t) (OCMe_Two(CF_Three)_Two)_Two, W
(N-2,6-C₆H_ThreePrⁱ)_Two(CHCMe_TwoPh)
(OBu^t)_Two, W (N-2,6-C₆H_ThreePrⁱ _Two) (CH
CMe_TwoPh) (OCMe_TwoCF_Three)_Two, W (N-2,6-
C₆H_ThreePrⁱ _Two) (CHCMe_TwoPh) (OCMe_Two(CF
_Three)_Two)_Two, (Pr in the formulaⁱIs an iso-propyl group, Bu^t
Is a tert-butyl group, Me is a methyl group, and Ph is phenyl.
Represents a hydroxyl group. ) And other tungsten-based alkylidene catalysts,
W (N-2,6-Me_TwoC₆H_Three) (CHCHCMeP
h) (O-Bu^t)_Two(PMe_Three), W (N-2,6-M)
e_TwoC₆H_Three) (CHCHCMe_Two) (O-Bu^t)_Two(PM
e_Three), W (N-2,6-Me)_TwoC₆H_Three) (CHCHCP
h_Two) (O-Bu^t)_Two(PMe_Three), W (N-2,6-M)
e_TwoC₆H _Three) (CHCHCMePh) (OCMe_Two(CF
_Three))_Two(PMe_Three), W (N-2,6-Me)_TwoC₆H_Three)
(CHCHCMe_Two) (OCMe_Two(CF_Three))_Two(PMe
_Three), W (N-2,6-Me)_TwoC₆H_Three) (CHCHCPh
_Two) (OCMe_Two(CF_Three)) _Two(PMe_Three), W (N-
2,6-Me_TwoC₆H_Three) (CHCHCMe_Two) (OCMe
(CF_Three)_Two)_Two(PMe_Three), W (N-2,6-Me)_TwoC₆
H_Three) (CHCHCMe_Two) (OCMe (CF_Three)_Two)
_Two(PMe_Three), W (N-2,6-Me)_TwoC₆H_Three) (CH
CHCPh_Two) (OCMe (CF_Three)_Two)_Two(PMe_Three),
W (N-2,6-Prⁱ _TwoC₆H_Three) (CHCHCMeP
h) (OCMe_Two(CF_Three))_Two(PMe_Three), W (N-
2,6-Prⁱ _TwoC₆H_Three) (CHCHCMePh) (OC
Me (CF_Three)_Two)_Two(PMe_Three), W (N-2,6-Pr)
ⁱ _TwoC₆H_Three) (CHCHCMePh) (OPh)_Two(PM
e_Three), (Pr in the formulaⁱIs an iso-propyl group, Bu^tIs
tert-butyl group, Me is methyl group, Ph is phenyl
Represents a group. ) And other tungsten-based alkylidene catalysts, M
o (N-2,6-Prⁱ _TwoC₆H_Three) (CHBu^t) (OB
u^t)_Two, Mo (N-2,6-Prⁱ _TwoC₆H_Three) (CHBu
^t) (OCMe_TwoCF_Three)_Two, Mo (N-2,6-Prⁱ _TwoC
₆H_Three) (CHBu^t) (OCMe (CF_Three)_Two)_Two, Mo
(N-2,6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh)
(OBu^t)_Two, Mo (N-2,6-Prⁱ _TwoC₆H_Three) (C
HCMe_TwoPh) (OCMe_TwoCF_Three)_Two, Mo (N-2,
6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh) (OCMe
(CF_Three)_Two)_Two, (Pr in the formulaⁱIs an isopropyl group,
Bu^tIs a tert-butyl group, Me is a methyl group, and Ph is
Represents a phenyl group. ) And other molybdenum-based alkylidene
Medium, Re (C) Bu ^t(CHBu^t) (O-2,6-Pr
ⁱ _TwoC₆H_Three)_Two, Re (CBu^t) (CHBu^t) (O-2
-Bu^tC₆H_Four)_Two, Re (CBu^t) (CHBu^t) (O
CMe_TwoCF)_Three)_Two, Re (CBu^t) (CHBu^t)
(OCMe (CF_Three)_Two)_Two, Re (CBu^t) (CHBu
^t) (O-2,6-MeC)₆H_Three)_Two, (Bu in the formula^tIs t
represents an tert-butyl group. ) And other rhenium-based alkylides
Catalyst, Ta [C (Me) C (Me) CHMe_Two] (O
−2,6-Prⁱ _TwoC₆H_Three)_ThreePy, Ta [C (Ph) C
(Ph) CHMe_Two] (O-2,6-Prⁱ _TwoC₆H_Three)_ThreeP
y, (where Me is a methyl group, Ph is a phenyl group, Py
Represents a pyridine group. ) And other tantalum-based alkylidene
Medium, Ru (CHCHCPh)_Two) (PPh_Three)_TwoCl_Two,(formula
Ph in the above represents a phenyl group. ), Etc.
Examples include a kylidene catalyst and titanacyclobutanes. Up
The ring-opening metathesis catalyst may be used alone or as a mixture of two or more.
You may. In addition, Japanese Patent Application No. 09-167488 and Japanese Patent Application No.
The above transition as described in 09-167489
Metallic alkylidene complexes and unsaturated bonds as chain transfer agents
Ring opening metathesis by combination with a compound having
It is also possible to employ a medium system.

Examples of the compound having an unsaturated bond as a chain transfer agent include ethylene, propylene, butene,
Α-olefins such as pentene, hexene, and octene;
Silicon-containing olefins such as vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane, dienes such as pentadiene, hexadiene, heptadiene, styrene, aromatic vinyl such as divinylbenzene, methyl methacrylate,
(Meth) acrylic acid esters such as methyl acrylate.

Further, 0lefin Metathesis (Kenneth J I
vin, Academic Press, New York, 1983)
Of a transition metal compound with a Lewis acid as a co-catalyst
Ring opening metathesis catalyst system by combination, e.g., molybdenum
Transition metals such as tungsten, vanadium, titanium, etc.
Organoaluminum compound as a co-catalyst
Tin compound or lithium, sodium, magnesium
Organic metal compounds such as metals, zinc, cadmium and boron
A ring-opening metathesis catalyst comprising transition
Specific examples of metal halides include MoBr_Two, Mo
Br_Three, MoBr_Four, MoCl_Four, MoCl_Five, MoF_Four,
MoOCl_Four, MoOF_FourMolybdenum halides, such as
Object, WBr_Two, WBr_Four, WCl_Two, WCl_Four, WCl_Five,
WCl₆, WF _Four, WI_Two, WOBr_Four, WOCl_Four, WO
F_Four, WCl_Four(OC₆H_FourCl_Two)_Two, Etc.
Logenide, VOCl_Three, VOBr_Three, Etc. vanadium
Logenide, TiCi_Four, TiBr_Four, Etc. titanium halide
And the like.

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, etc. 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 monomer to the ring-opening metathesis catalyst is such that tungsten, molybdenum, rhenium, tantalum,
Alternatively, 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 case of a reaction system in which a compound having an unsaturated bond as a chain transfer agent is added, the amount used is such that the molar ratio of the compound having an unsaturated bond to the cyclic olefin monomer is And the molar ratio of the compound having an unsaturated bond to the transition metal complex is 1 equivalent of the alkylidene of the transition metal alkylidene complex. 0.1 to 1000, preferably 1 to 50
It is in the range of 0.

Further, 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 co-catalyst is used. Is 0.005
The range is from 10 to 10 mol, preferably from 0.02 to 5 mol.

Solvents used in the ring-opening metathesis polymerization include tetrahydrofuran, diethyl ether,
Dibutyl ether, ethers such as dimethoxyethane, benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, pentane, hexane, aliphatic hydrocarbons such as heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane,
Examples include aliphatic cyclic hydrocarbons such as decalin, and halogenated hydrocarbons such as methylene dichloride, dichloroethane, 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 carried out in the presence of an olefin such as l-hexene, 4-methylpentene, hexadiene and the like.

In the ring-opening metathesis polymerization, the concentration of the monomer / ring-opening metathesis catalyst and the solvent varies from 0.1 to 100 m, although it depends on the reactivity of the monomer and the solubility in the polymerization solvent.
ol / L is preferable, and the reaction is usually carried out at a reaction temperature of -30 to 150 ° C. for 1 minute to 10 hours, the reaction is stopped with a deactivator such as aldehydes, ketones, alcohols, etc., and the ring-opening metathesis polymer is obtained. A solution can be obtained.

After the completion of the ring-opening metathesis polymerization reaction, the ring-opening metathesis catalyst remaining in the polymer can be removed by a known method. Examples of a method for removing a metal and a metal compound component from the ring-opening polymer solution include, for example, trimethylene diamine, aniline, pyridine, ethanediamide, and water in the ring-opening metathesis polymer solution or slurry under an atmosphere such as nitrogen or hydrogen gas. After the contact treatment with a basic compound such as sodium oxide, or simultaneously with the contact treatment, a method of contacting with an acidic compound such as acetic acid, citric acid, benzoic acid, hydrochloric acid or the like can be employed.

The hydrogenation reaction of the ring-opening metathesis polymer of the cyclic olefin monomer of the present invention is carried out by hydrogenation using a ruthenium metal complex represented by the general formula [2] in the presence of hydrogen. It is possible to improve the hydrogenation rate.

In the present invention, in the ruthenium metal complex represented by the general formula [2], H represents a hydrogen atom, CO represents a carbonyl group, and Z represents an organic compound represented by PR ′ ¹ R ′ ² R ′ ^3. Represents a phosphatized rod, P represents a phosphorus atom,
R ′ ¹ , R ′ ² , R ′ ³ are the same or different linear, branched or cyclic alkyl, aryl or alkoxy groups, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, C1-C12 (cyclo) alkyl groups such as cyclohexyl; C6-C20 aryl groups such as phenyl and naphthyl; C1-carbon atoms such as methoxy, ethoxy, t-butoxy and mentoxy;
To 12 alkoxy groups.

Specific examples of the organic phosphorus compound include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-propylphosphine, tri-t
-Butylphosphine, triisobutylphosphine, trin-butylphosphine, tricyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, trio-tolylphosphine, trim-tolylphosphine, trip-tolylphosphine, diethylphenyl Examples thereof include phosphine, dichloro (ethyl) phosphine, dichloro (phenyl) phosphine, chlorodiphenylphosphine, trimethylphosphite, triisopropylphosphite, and triphenylphosphite.

Specific examples of the ruthenium metal complex represented by the general formula [2] include hydridocarbonyltris (triphenylphosphine) ruthenium, hydridecarbonyltetrakis (triphenylphosphine) ruthenium, and dihydridocarbonyltris (triphenylphosphine).
Ruthenium, hydridodicarbonyltris (triphenylphosphine) ruthenium, dihydridodicarbonylbis (triphenylphosphine) ruthenium, hydridecarbonyltris (trimethylphosphine) ruthenium,
Hydridecarbonyltetrakis (trimethylphosphine) ruthenium, dihydridocarbonyltris (trimethylphosphine) ruthenium, hydridedicarbonyltris (trimethylphosphine) ruthenium, dihydridodicarbonylbis (trimethylphosphine) ruthenium, hydridecarbonylcarbonyltris (triethylphosphine) ruthenium, hydride Carbonyltetrakis (triethylphosphine) ruthenium, dihydridocarbonyltris (triethylphosphine) ruthenium, hydridedicarbonyltris (triethylphosphine) ruthenium, dihydridodicarbonylbis (triethylphosphine) ruthenium, hydridecarbonylcarbonyltris (tricyclohexylphosphine) ruthenium, hydride Carbonyl tetrakis (Trisik Hexylphosphine) ruthenium, dihydridocarbonyltris (tricyclohexylphosphine) ruthenium, hydridedicarbonyltris (tricyclohexylphosphine) ruthenium, dihydridodicarbonylbis (tricyclohexylphosphine) ruthenium, hydridecarbonylcarbonyltris (methyldiphenylphosphine) ruthenium, hydride Carbonyltetrakis (methyldiphenylphosphine) ruthenium, dihydridocarbonyltris (methyldiphenylphosphine) ruthenium, hydridedicarbonyltris (methyldiphenylphosphine) ruthenium, dihydridodicarbonylbis (methyldiphenylphosphine) ruthenium, hydridecarbonylcarbonyltris (dimethylphenylphosphine) ) Ruthenium, hydride carboni Tetrakis (dimethylphenylphosphine) ruthenium, dihydridocarbonyltris (dimethylphenylphosphine) ruthenium, hydridedicarbonyltris (dimethylphenylphosphine) ruthenium, dihydridodicarbonylbis (dimethylphenylphosphine) ruthenium, hydridecarbonyltris (trio-tolyl) (Phosphine) ruthenium, hydridecarbonylcarbonyltetrakis (tri-tolylphosphine) ruthenium, dihydridocarbonyltris (trio-tolylphosphine) ruthenium, hydridedicarbonyltris (trio-tolylphosphine) ruthenium, dihydridodicarbonylbis (trio) -Tolylphosphine) ruthenium, hydride carbonyl tris (dichloroethylphosphine) ruthenium,
Hydridocarbonyltetrakis (dichloroethylphosphine) ruthenium, dihydridocarbonyltris (dichloroethylphosphine) ruthenium, hydridedicarbonyltris (dichloroethylphosphine) ruthenium,
Dihydridodicarbonylbis (dichloroethylphosphine) ruthenium, hydridecarbonylcarbonyltris (dichlorophenylphosphine) ruthenium, hydridecarbonyltetrakis (dichlorophenylphosphine) ruthenium, dihydridocarbonyltris (dichlorophenylphosphine) ruthenium, hydridodicarbonyltris (dichlorophenylphosphine) ruthenium, Dihydridodicarbonylbis (dichlorophenylphosphine) ruthenium, hydridecarbonylcarbonyltris (trimethylphosphite) ruthenium, hydridecarbonyltetrakis (trimethylphosphite) ruthenium, dihydridocarbonyltris (trimethylphosphite) ruthenium, hydridedicarbonyltris (trimethylphosphite) ) Ruthenium, dihydrido di Rubonirubisu can be mentioned (trimethyl phosphite) ruthenium, significant improvement in the hydrogenation rate, especially when using a dihydride carbonyl tris (triphenylphosphine) ruthenium.

These ruthenium metal complexes can be used in combination of two or more kinds at any ratio.

The amount of the ruthenium metal complex to be added is 5 to 5 with respect to the ring-opening metathesis polymer of the cyclic olefin monomer.
50,000 ppm, preferably 10 to 10,000
ppm, particularly preferably 50 to 1000 ppm.

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

The hydrogenation reaction of the ring-opening metathesis polymer is as follows:
The hydrogen pressure is usually from normal pressure to 30 MPaG, preferably 0.1 MPa.
The reaction is carried out in the range of 5 to 20 MPaG, particularly preferably 2 to 15 MPaG, and the reaction temperature is usually 0 to 300 ° C, preferably room temperature to 250 ° C, particularly preferably 50 to 200 ° C. .

The production of hydrogenated cyclic olefin-based ring-opening metathesis polymer can be carried out by isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution and then dissolving it in a solvent again. Alternatively, a method of performing a hydrogenation reaction by adding the above-described ruthenium metal complex may be employed.

After the completion of the hydrogenation reaction, the hydrogenation catalyst remaining in the polymer can be removed by a known method. For example, an adsorption method using an adsorbent, a method in which an organic acid such as lactic acid, a poor solvent, and water are added to a solution using a good solvent, and the system is extracted and removed at room temperature or under heating. After contacting the solution or polymer slurry with a basic compound such as trimethylenediamine, aniline, pyridine, ethanediamide, sodium hydroxide or the like in an atmosphere of nitrogen or hydrogen gas, or simultaneously with the contacting treatment, acetic acid, citric acid, benzoic acid And contact removal with an acidic compound such as hydrochloric acid, followed by washing and removal.

The method for recovering the polymer hydride from the ring-opening metathesis polymer hydrogenated solution is not particularly limited, and a known method can be used. For example, the reaction solution is discharged into a poor solvent under stirring, the polymer hydride is coagulated and collected by a filtration method, a centrifugation method, a decantation method, or the like, and steam is blown into the reaction solution to form the polymer hydride. Examples thereof include a steam stripping method for precipitation, and a method for directly removing a solvent from a reaction solution by heating or the like.

When the hydrogenation method of the present invention is used, a hydrogenation rate of 90% or more can be easily attained, and 95% or more, particularly 9% or more.
9% or more, and the resulting hydrogenated cyclic olefin-based metathesis polymer hydrogenated product is not easily oxidized. Becomes

[0041]

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 ring-opening metathesis polymer obtained in the examples were measured by the following methods.

Average molecular weight: Using GPC, the obtained cyclic olefin-based ring-opening metathesis polymer or a hydrogenated polymer thereof was dissolved in chloroform, and 830-RI and UVIDEC-100-VI manufactured by JASCO Corporation were used as detectors. ,
Shodexk-805, 804, 80 as a column
3,802.5, flow rate 1.0 ml at room temperature
The molecular weight was calibrated by a polystyrene standard at / min.

Hydrogenation ratio: A powder of a hydrogenated cyclic olefin-based ring-opening metathesis polymer was dissolved in deuterated chloroform, and δ = 4.5 to 6.6 using 90 MHz-NMR.
The magnitude at which the peak attributable to the carbon-carbon double bond of 0 ppm in the main chain was reduced by the hydrogenation reaction was calculated.

Example 1 Under a nitrogen atmosphere, 8-t-butoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (2.82
g, 10.84 mmol) was dissolved in dry tetrahydrofuran (80 ml) and stirred. Mo to as ring-opening metathesis polymerization Sawacho _{(N-2,6-C 6 H} 3 Pr i 2)
^{_{(CHCMe 2 Ph) (0Bu t}} ) 2 (60mg, 0.1
08 mmol) and reacted at room temperature for 1 hour. Then, t-butyraldehyde (38.9 mg, 0.54 m
mol) was added and stirred for 30 minutes to stop the reaction.

Trimethylenediamine (120 mg, 1.62 mmol) was added to this ring-opening metathesis polymer solution, and the solution was transferred to a 200 ml autoclave under a nitrogen atmosphere, and stirred at a hydrogen pressure of 0.5 MPaG at 60 ° C. for 1 hour. , Methanol (400 ml) to precipitate a ring-opening metathesis polymer, which was separated by filtration, dried in vacuo, and then dried at 2.82.
g of ring-opening metathesis polymer powder was obtained.

Then, in a 200 ml autoclave, 2.82 g of the ring-opening metathesis polymer powder was dissolved in dry tetrahydrofuran (108 ml), and dihydridocarbonyltris (triphenylphosphine) ruthenium (2.3 mg, 0 .0025mmo
1) A solution of dry tetrahydrofuran (12 ml) was added, a hydrogenation reaction was performed at 8.5 MPaG at 165 ° C. for 5 hours, and the temperature was returned to room temperature to release hydrogen gas.

The hydrogenated product of the ring-opening metathesis polymer was added to methanol (400 ml) with stirring to precipitate a hydrogenated product of the ring-opening metathesis polymer. 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 did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 25990, and the number average molecular weight Mn
Was 25970 and Mw / Mn was 1.00.

Example 2 Ring-opening metathesis polymerization was carried out in the same manner as in Example 1 to obtain a ring-opening metathesis polymer solution. Dihydrogencarbonyl tris (triphenylphosphine) as a hydrogenation catalyst
A solution of ruthenium (2.3 mg, 0.0025 mmol) in dry tetrahydrofuran (12 ml) was added, a hydrogenation reaction was performed at 8.5 MPaG at 165 ° C. for 5 hours, and then the temperature was returned to room temperature and hydrogen gas was released. , Trimethylenediamine (120 mg, 1.62 mmol) were added, and the mixture was stirred at a hydrogen pressure of 0.5 MPaG and 60 ° C. for 1 hour, and then the temperature was returned to room temperature to release hydrogen gas.

The hydrogenated product of the ring-opening metathesis polymer was added to 400 ml of methanol with stirring to precipitate a hydrogenated product of the ring-opening metathesis polymer. 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 did not show a peak attributed to protons of olefins in the main chain, and the hydrogenation rate was 100%. The measured weight average molecular weight Mw is 26000, and the number average molecular weight Mn is
Was 25990 and Mw / Mn was 1.00.

Example 3 8-t-butoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (2.82 g, 1
0.84 mmol) instead of 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (2.
Example 1 except that the same amount was used.
Perform ring-opening metathesis polymerization and hydrogenation reaction in the same manner as
A white powdered hydrogenated ring-opening metathesis polymer was obtained.
1H-NM of the obtained hydrogenated ring-opening metathesis polymer
As for the hydrogenation rate calculated from R, no peak attributed to protons of the main chain olefin was observed, and the hydrogenation rate was 1%.
The weight average molecular weight Mw measured by GPC was 18100, the number average molecular weight Mn was 18080, and Mw / M
n was 1.00.

Comparative Example 1 Ring-opening metathesis polymerization was carried out in the same manner as in Example 1 to obtain a ring-opening metathesis polymer powder.

Thereafter, 1.00 g of the ring-opening metathesis polymer powder and dichlorotris (triphenylphosphine) ruthenium (2.3 mg, 0.0024 mmol) as a hydrogenation catalyst were dissolved in dry tetrahydrofuran (60 ml) in a 200 ml autoclave. And hydrogen pressure 8.
After performing a hydrogenation reaction at 5 MPaG and 165 ° C. for 5 hours, the temperature was returned to room temperature and hydrogen gas was released.

The hydrogenated product of the ring-opening metathesis polymer was added to methanol (400 ml) with stirring to precipitate a hydrogenated product of the ring-opening metathesis polymer. To obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of the obtained hydrogenated product of the ring-opening metathesis polymer was 2 calculated from 1H-NMR.
1.5%, and the weight average molecular weight Mw measured by GPC
Is 26020, number average molecular weight Mn is 26000, Mw /
Mn was 1.00.

[0055]

The method for producing a hydrogenated cyclic olefin-based metathesis polymer of the present invention can efficiently provide a heat-resistant hydrogenated ring-opening metathesis polymer, which is extremely valuable industrially. is there.

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[Procedure amendment]

[Submission date] January 28, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

[0012]

Embedded image _{RuH m CO p Z q [2} ] ( wherein, Ru represents a ruthenium metal atom, H represents a hydrogen atom, CO will display the carbonyl group, Z is PR '
¹ R ′ ² R ′ ³ (P represents a phosphorus atom, R ′ ¹ , R ′ ² ,
R ′ ³ represents the same or different linear, branched or cyclic alkyl group, alkenyl group, aryl group, alkoxy group or allyloxy group. ) Represents an organic phosphorus compound, m represents 1 or 2, p represents 1 or 2, and q represents an integer of 2 to 4. ) Is hydrogenated using a ruthenium metal complex represented by the formula (1).

Claims (2)

[Claims] 1. A monocyclic olefin or a general formula [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,
Selected from halogenated alkyl groups, nitrile groups, carboxyl groups or alkoxycarbonyl groups of from 1 to 12, and x represents an integer of from 0 to 3. The ring-opening metathesis polymer of a cyclic olefin monomer represented by the general formula [2] RuHmCOpZq [2] (where Ru represents a ruthenium metal atom; Represents a hydrogen atom, CO represents a carbonyl group, and Z represents PR ′
¹ R ′ ² R ′ ³ (P represents a phosphorus atom, R ′ ¹ , R ′ ² ,
R ′ ³ represents the same or different linear, branched or cyclic alkyl group, alkenyl group, aryl group, alkoxy group or allyloxy group. ) Represents an organic phosphorus compound, m represents 1 or 2, p represents 1 or 2, and q represents an integer of 2 to 4. A method for producing a hydrogenated cyclic olefin-based ring-opening metathesis polymer, comprising hydrogenating a ruthenium metal complex represented by the formula (1). 2. The method according to claim ¹ , wherein R ′ ¹ , R ′ ² and R ′ ³ are phenyl groups, m is 2, p is 1, and q is 3.