JP2001151869A - Method for producing hydride of ring-opening metathesis polymer of cyclic olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for performing a ring-opening metathesis polymerization of a cyclic olefin monomer and then hydrogenating the obtained polymer, having a wide utility for the cyclic olefin monomers and capable of hydrogenating the produced polymer with a small amount of a catalyst in a good efficiency and stably. SOLUTION: This method for producing a hydride is provided by performing the ring-opening metathesis polymerization of the cyclic olefin monomer by using a transition metal compound belonging to the 4-8th group in the Periodic table, and then hydrogenating carbon-carbon unsaturated bond in the obtained polymer in the presence of a newly added catalyst consisting of a transition metal belonging to the 8th or 9th group in the Periodic table-carbene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for efficiently producing a ring-opened polymer hydride of a cyclic olefin,
The present invention relates to a production method applicable to a wide range of cyclic olefins.

[0002]

2. Description of the Related Art Ring-opening metathesis polymers of cyclic olefins and their hydrides have attracted attention as resins having excellent optical, electrical and mechanical properties, and various ring-opening metathesis polymers and their hydrides have been studied. Manufacturing methods have been proposed. A method of ring-opening metathesis polymerization of cyclic olefins using a polymerization catalyst such as a titanium compound, a tungsten compound, a molybdenum compound, a rhenium compound, and a ruthenium compound has been well known. The ring-opened polymer obtained by this method has insufficient thermal stability due to a double bond in the main chain, and various methods for hydrogenating the ring-opened polymer have been proposed as an improvement method.

[0003] Heterogeneous catalysts or homogeneous catalysts have been used to hydrogenate carbon-carbon unsaturated bonds in cyclic olefin ring-opening metathesis polymers. For example, as a heterogeneous catalyst, a supported metal catalyst in which a metal such as palladium, platinum, and nickel is supported on a carrier such as carbon, silica, alumina, and diatomaceous earth is known. Homogeneous catalysts include Ziegler type catalysts such as nickel naphthenate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, cobalt octenoate / diethylaluminum chloride, titanocene dichloride / n-butyllithium, and noble metal complexes such as rhodium and ruthenium It has been known. However, the method using a supported hydrogenation catalyst has a problem that a large amount of catalyst is required to obtain a high hydrogenation rate. In addition, the method using a Ziegler-type catalyst has a problem in that the catalyst is inactivated by water, air, a polar compound or the like, so that the handling is complicated and a solvent having a large polarity cannot be used. Furthermore, the method of using a noble metal complex such as rhodium or ruthenium,
There are problems that the complex is expensive and the activity of the hydrogenation catalyst is not always high.

As a measure for solving these problems, a method for improving the catalytic activity of hydrogenation of a ruthenium complex is disclosed in, for example, JP-A-7-2929 and JP-A-7-149823.
JP-A-11-158256, JP-A-11-193
323 and JP-A-11-209460. However, the method of JP-A-7-2929 has a problem that a large excess of an alkyl metal compound and an organoaluminum compound is required with respect to a ruthenium complex, and the method of JP-A-7-149823 is extremely inefficient. There is a problem that a stable ruthenium hydride complex is used, and JP-A-11-158256 and JP-A-1
The method of 1-193323 has a problem that a large excess of an organoaluminum compound or an amine compound is required for the ruthenium complex. Also, Japanese Patent Application Laid-Open
The methods of 1-193323 and JP-A-11-209460 still had a problem that the activity was not always sufficiently improved. Therefore, with high activity,
A hydrogenation catalyst that does not require an activator and that is easy to handle has been desired.

On the other hand, JP-A-10-195182 discloses a modified polymerization catalyst in which a cyclic olefin is subjected to ring-opening metathesis polymerization using a ruthenium-carbene compound as a catalyst, and then a modifier is added to the reaction system. A method for hydrogenating a ring-opened polymer as it is in the presence of is reported. According to this method, there is an advantage that the polymerization step and the hydrogenation step can be performed continuously. However, as described in this patent, when a ruthenium-carbene compound is used as a polymerization catalyst and the reformed product is subsequently used as a hydrogenation catalyst, the obtained polymer and its hydride are converted into a main chain. Because the cis-trans structure and stereoregularity of the carbon-carbon double bond are limited, for example, in ring-opening metathesis polymerization of dicyclopentadiene or tetracyclododecene, the produced polymer is not dissolved at all in a general solvent, and thereafter, There is a problem that the hydrogenation reaction is extremely difficult.

[0006] Also, J.I. Am. Chem. Soc. , 1
18, 100-110 (1996), it has been reported that some ruthenium-carbene compounds are easily decomposed in solution depending on the catalyst, and some ruthenium-carbene compounds are converted during the polymerization. Since it is deactivated, it does not show sufficient hydrogenation catalyst activity during the hydrogenation reaction. Therefore, according to the study of the present inventors, the hydrogenation reaction activity greatly fluctuates due to the difference in polymerization conditions such as polymerization temperature, reaction time, and catalyst concentration during the polymerization step, and sometimes the hydrogenation reaction does not progress. It turned out to be.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a hydrogenated ring-opening metathesis polymer, comprising subjecting a cyclic olefin monomer to ring-opening metathesis polymerization and then hydrogenating the resulting polymer. Can be applied to a wide range of cyclic olefin monomers, can be polymerized using a wide range of polymerization catalysts, and the obtained cyclic olefin ring-opening metathesis polymer can be efficiently and stably hydrogenated with a small amount of hydrogenation catalyst. To provide a method that can be

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the periodic table Nos. 4 to 4 have been obtained.
A ring-opening metathesis polymerization of a cyclic olefin monomer using a Group VIII transition metal compound as a polymerization catalyst, and then a newly added hydrogenation catalyst comprising a Group VIII or Group IX transition metal-carbene compound of the periodic table. It was found that when the obtained polymer was hydrogenated in the presence, the hydrogenation reaction proceeded with extremely high activity, and based on this finding, the present invention was completed.

Thus, according to the present invention, the periodic tables Nos. 4 to 8
Ring-opening metathesis polymerization of a cyclic olefin monomer using a group IV transition metal compound as a catalyst, and then in the presence of a newly added catalyst comprising a transition group VIII or IX transition metal-carbene compound. The carbon in the resulting polymer
A method for producing a hydrogenated cyclic olefin ring-opening metathesis polymer characterized by hydrogenating a carbon unsaturated bond is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below. Ring Opening Metathesis Polymerization of Cyclic Olefin The process for producing a hydrogenated cyclic olefin ring opening metathesis polymer of the present invention comprises a polymerization step of ring opening metathesis polymerization of a cyclic olefin monomer, and a hydrogenation step of hydrogenating the obtained polymer. It consists of steps.

[0011] The catalyst used in the polymerization stage is the fourth to eighth periodic tables.
Any group transition metal compound may be used as long as the cyclic olefin monomer is a ring-opening metathesis polymerization catalyst,
For example, Olefin Metathesis (Ken
neth J, Irvin, Academic Pre
ss, New York 1983), a ring-opening metathesis catalyst system based on 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 or titanium. Organic aluminum compounds as co-catalysts,
A ring-opening metathesis catalyst comprising an organotin compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium, or boron can be used.

Specific examples of the transition metal halide include:
MoBr_Two, MoBr_Three, MoBr_Four, MoCl_Four, MoC
l_Five, MoF_Four, MoOCl_Four, MoOF_FourSuch as molybdenum
Halide, WBr_Two, WBr_Four, WCl_Two, WC
l_Four, WCl_Five, WCl₆, WF _Four, WI_Two, WOBr_Four, W
OCI_Four, WOF_Four, WCl_Four(OC₆H_FourCl_Two)_TwoSuch as
Tungsten halide, VOCl_Three, VOBr_ThreeSuch
Vanadium halide, TiCl_Four, TiBr_FourSuch
And the like.

Specific examples of the organometallic compound as a promoter include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride, -N-butylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, organic aluminum compounds such as ethylaluminum dichloride, tetramethyltin, diethyldimethyltin,
Tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride , Organic tin compounds such as butyltin trichloride, butyltin tribromide, butyltin triiodide, organic lithium compounds such as n-butyllithium, organic sodium compounds such as n-pentyl sodium, methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide , N-
Propyl magnesium bromide, t-butyl magnesium chloride, organic magnesium compounds such as aryl magnesium chloride, organic zinc compounds such as diethyl zinc, organic cadmium compounds such as diethyl cadmium,
Organic boron compounds such as trimethylboron, triethylboron, and tri-n-butylboron are exemplified.

[0014] Further, other catalysts include Periodic Table Nos. 4 to
Group VIII transition metal-carbene complexes and metallacyclobutene complexes
And the like. Specific examples of these include:
W (N-2,6-C₆H_ThreePrⁱ _Two) (CHBu^t) (OB
u^t)_Two, W (N-2,6-Prⁱ _TwoC₆H_Three) (CHB
u^t) (OCMe_TwoCF_Three)_Two, W (N-2,6-Prⁱ _TwoC
₆H_Three) (CHBu^t) (OCMe_Two(CF_Three)_Two)_Two, W
(N-2,6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh)
(OBu^t)_Two, W (N-2,6-Prⁱ _TwoC₆H_Three) (CH
CMe_TwoPh) (OCMe_TwoCF_Three), W (N-2,6-
Prⁱ _TwoC₆H_Three) (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. same as below. ) Such as tungsten-based alk
Lidene catalyst, Mo (N-2,6-Pr)ⁱ _TwoC ₆H_Three) (CH
Bu^t) (OBu^t)_Two, Mo (N-2,6-Prⁱ _TwoC₆H
_Three) (CHBu^t) (OCMe_TwoCF_Three)_Two, Mo (N-
2,6-Prⁱ _TwoC₆H_Three) (CHBu^t) (OCMe_Two(C
F_Three)_Two)_Two, Mo (N-2,6-Prⁱ _TwoC₆H_Three) (CH
CMe _TwoPh) (OBu^t)_Two, Mo (N-2,6-Prⁱ
_TwoC₆H_Three) (CHCMe_TwoPh) (OCMe_TwoCF_Three), M
o (N-2,6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh)
(OCMe_Two(CF_Three)_Two)_Two, Mo (N-2,6-Prⁱ _Two
C₆H_Three) (CHCMe_TwoPh) (BIPHEN), Mo
(N-2,6-Prⁱ _TwoC₆H_Three) (CHCMe_TwoPh)
(BINO) (THF), where BIPHEN is 5,
5 ', 6,6'-tetramethyl-3,3'di-tert
-Butyl-1,1'biphenyl-2,2'-dioxy
Group, BINO is 1,1'-dinaphthyl-2,2'-geo
The xy group, THF, represents tetrahydrofuran. Hereinafter the same
Same. ), Molybdenum alkylidene catalysts such as Re (C
Bu^t) (CHBu^t) (O-2,6-Prⁱ _TwoC
₆H_Three)_Two, Re (CBu^t) (CHBu^t) (O-2-B
u^tC₆H_Four)_Two, Re (CBu^t) (CHBu^t) (OCM
e_TwoCF_Three)_Two, Re (CBu^t) (CHBu^t) (OCM
e (CF_Three)_Two)_Two, Re (CBu^t) (CHBu^t) (O
−2,6-Me_TwoC₆H_Three)_TwoRhenium-based alkylide
Catalyst, Ta [C (Me) C (Me) CHMe_Three] (O
−2,6-Prⁱ _TwoC₆H_Three)_ThreePy, Ta [C (Ph) C
(Ph) CHMe_Three] (O-2,6-Prⁱ _TwoC₆H_Three)_ThreeP
y, (Py in the formula represents a pyridine group; the same applies hereinafter).
Any tantalum-based alkylidene catalyst, Ru (CHCHCP
h_Two) (PPh_Three)_TwoCl_Two, Ru (CHPh) (PC
y_Three)_TwoCl_Two, Bis (1,3-diisopropyl-imida
Sol-2-ylidene) benzylidene ruthenium dichloro
Lido, (Cy in the formula represents a cyclohexyl group.
Same. ) And other ruthenium-based alkylidene catalysts and titanashi
Clobutanes. The above ring-opening metathesis catalyst
May be used alone or in combination of two or more.

Of these, the use of a transition metal group 4-6 transition metal-carbene complex or a metallacyclobutene complex is preferred because a cocatalyst is not required and the activity is high.
The molar ratio of the cyclic olefin-based monomer to the ring-opening metathesis catalyst is such that in the ring-opening metathesis catalyst comprising the transition metal halide and the organometallic compound per 100 moles of the cyclic olefin monomer, the metal halide to be transferred is 0.1 mol. The amount is 001 to 5 mol, preferably 0.01 to 3 mol, and the amount of the organometallic compound as the promoter is 0.005 to 10 mol, preferably 0.02 to 5 mol. In the case of an alkylidene catalyst such as tungsten, molybdenum, rhenium, tantalum or ruthenium or titanacyclobutane, 0.0
It is 1 to 10 mol, preferably 0.1 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, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, and trichlorobenzene. These may be used in combination of two or more. Further, to control the molecular weight, ethylene, propylene, 1-butene, isobutene,
Ring-opening metathesis polymerization may be performed in the presence of an olefin such as styrene, 1-hexene, 4-methylpentene, and hexadiene.

The cyclic olefin monomers include (1) polycyclic olefins having a norbornene ring such as norbornenes, dicyclopentadienes, and tetracyclododecenes; (2) monocyclic olefins; Diolefins. These cyclic olefins may have a non-polar substituent such as an alkyl group or an alkenyl group, or a polar group such as an ester group, a carboxyl group, an acid anhydride group, an epoxy group, or a hydroxyl group. These cyclic olefin monomers can be used alone or in combination of two or more. In view of the heat resistance of the ring-opening polymer and the solubility in a solvent, the cyclic olefin is preferably a cyclic to hexacyclic cyclic olefin monomer having a norbornene ring, and among these, a cyclic olefin monomer such as dicyclopentadiene is preferred. Particularly preferred are cyclic cyclic olefin monomers and tetracyclic cyclic olefin monomers such as tetracyclododecenes.

(I) Dicyclopentadiene: Specific examples of the dicyclopentadiene include dicyclopentadiene and methyl-dicyclopentadiene, which saturate the double bond of the 5-membered ring portion of dicyclopentadiene. tricyclo [4.3.1 ^{2, 5.} 0] -dec-3-ene and the like.

(Ii) Tetracyclododecenes: tetracyclododecenes are (a) those having no double bond other than the norbornene ring, (b) those having a double bond other than the norbornene ring, (c) A) having an aromatic ring, (d) having a polar group, and the like, and any monomer can be used.

(A) Specific examples of compounds having no double bond other than the norbornene ring include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, and 8-cyclohexyltetracyclododecene. And tetracyclododecenes such as 8-cyclopentyltetracyclododecene, and those having a substituent in the above tetracycldodecenes.

(B) Specific examples of the compound having a double bond other than the norbornene ring include 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene,
Examples thereof include 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene. (C) Specific examples of those having an aromatic ring include 8-phenyltetracyclododecene.

(D) Specific examples of the compound having a polar group include 8-methoxycarbonyltetracyclododecene,
8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8
-Carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-
Tetracyclododecenes having a substituent containing an oxygen atom such as 8,9-dicarboxylic anhydride; including nitrogen atoms such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide Tetracyclododecenes having a substituent; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; containing a silicon atom such as 8-trimethoxysilyltetracyclododecene And tetracyclododecene having a substituent.

(Iii) Other cyclic olefin monomer having a norbornene ring: Specific examples of the other cyclic olefin monomer having a norbornene ring include (a) a bicyclic monomer having one norbornene ring. Are norbornenes such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene, and oxanorbornene corresponding thereto. And 5-ethylidene norbornene,
Vinyl norbornene, 5-propenyl norbornene, 5
-Norbornenes having a double bond outside the ring, such as -cyclohexenylnorbornene and 5-cyclopentenylnorbornene; and oxanorbornenes corresponding thereto.

(B) Specific examples of one having one norbornene ring and one six-membered ring include hexacycloheptadecene, 12-methylhexacycloheptadecene,
Ethylhexacycloheptadecene, 12-butylhexacycloheptadecene, 12-hexylhexacycloheptadecene, 12-decylhexacycloheptadecene, 1
2-cyclohexylhexacycloheptadecene, 12-
Such as cyclopentylhexacycloheptadecene, and 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacyclohepta And hexacycloheptadecenes such as decene.

(C) having a norbornene ring and an aromatic ring
Specific examples thereof include 5-phenylnorbornene,
-Phenyloxanorbornene, tetracyclo [6.
5.1 ^2,5. 0^1,6. 0^8,13] Trideca-3,8,10,
12-tetraene (1,4-methano-1,4,4a, 9
a-tetrahydrofluorene), tetracyclo
[6.6.1^2,5. 0^1,6. 0^8,13] Tetradeca-3,
8,10,12-tetraene (1,4-methano-1,
4,4a, 5,10,10a-Hexahydroanthrace
).

(D) Specific examples of those having a polar group include 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl- 2-methylpropionate, norbornenyl-2-methyloctanoate, norbornene-5,6-dicarboxylic anhydride, 5-
Hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6- Norbornenes having an oxygen-containing polar group such as carboxynorbornene, and oxanorbornenes having an oxygen-containing polar group corresponding thereto; 5-cyanonorbornene, norbornene-5,6-
Examples include norbornenes having a nitrogen-containing polar group such as dicarboxylic acid imide, and oxanorbornenes having a nitrogen-containing polar group corresponding thereto.

Among them, those having a norbornene ring and an aromatic ring, for example, 4-methano-1,4,4a, 9
When tetrahydrofluorenes such as a-tetrahydrofluorene are copolymerized with the above-mentioned dicyclopentadiene, tetracyclododecene or the like, a polymer having excellent heat resistance and the like can be obtained.

(Iv) Monocyclic cyclic olefin monomer and cyclic diolefin monomer: Monocyclic cyclic olefin monomer and cyclic diolefin monomer are C _{4 to} C ₂₀ cyclic olefin and cyclic diolefin monomer. Olefins and their substituted products, preferably C _{4 to} C ₁₀ cyclic olefins and cyclic diolefins and their derivatives. Specific examples of the monocyclic cycloolefin monomer and cyclic diolefin monomer include JP-A Nos. 64-66, such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene.
No. 216 and the like; and JP-A-7-25 such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene and phenylcyclooctadiene.
And cyclic diolefin monomers described in No. 8318 and the like.

The molecular weight of the cyclic olefin ring-opening metathesis polymer obtained in the polymerization step is determined by considering the hydrogenation reaction.
The number average molecular weight (Mn) is preferably from 1,000 to 500,000, more preferably from 5,000 to 400,000, as measured by gel permeation chromatography (in terms of polystyrene).

Hydrogenation of cyclic olefin ring-opening polymer The cyclic olefin ring-opening metathesis polymer obtained in the above-mentioned polymerization step is subjected to a hydrogenation step using a transition metal group VIII or ninth group transition metal-carbene compound as a catalyst. It is newly added and hydrogenated. Examples of the transition metal of Group 8 or Group 9 of the periodic table in the transition metal-carbene compound include Fe,
Ru, Os, Co, Rh, and Ir can be mentioned.
Among them, Ru and Rh are preferable, and Ru is particularly preferable.

When a transition metal-carbene compound of Group 8 of the periodic table is used as a catalyst in the polymerization step and the same compound is used as a catalyst in the hydrogenation step,
It is important to add the same compound again in the hydrogenation stage. That is, when the hydrogenation is performed without adding the same catalyst newly under the remaining catalyst used in the polymerization stage, or after the remaining catalyst used in the polymerization stage is treated with a modifier or the like, a new catalyst is obtained. If hydrogenation is carried out without addition, sufficient activity for the hydrogenation reaction cannot be obtained. As the transition metal-carbene compound that is a hydrogenation catalyst, any compound having a metal-carbene [M = C (M is a transition metal of Group 8 or 9 of the periodic table)] can be used. Although it is possible, compounds represented by the following formulas (1) and (2) are preferable.

[(L ₁ ) _p (Y ₁ ) _q M ₁ = C (R ₁ ) _m ] _x (1) (where M ₁ represents a transition metal of Group 8 or 9 of the periodic table;
L ₁ represents an electron-donating ligand neutral independently, Y ₁
And independently represent anionic ligands. R ₁ independently represents hydrogen or a C _{1 to} C ₂₀ hydrocarbon group which may contain a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom. m represents 1 or 2, p represents 0 or an integer of 1 to 4, q represents 0, 1 or 2, and x represents 1 or 2. )

[(L ₂ ) _r (Y ₂ ) _s M ₂ = C (R ₂ ) _n ] (X) _y (2) (where M ₂ represents a transition metal of Group 8 or 9 of the periodic table;
L ₂ represents an electron-donating ligand neutral independently, Y ₂
And independently represent anionic ligands. R ₂ independently represents hydrogen or a C _{1 to} C ₂₀ hydrocarbon group which may contain a halogen atom, nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. X represents a counter anion. n represents 1 or 2, r represents 0 or an integer of 1 to 4, s represents 0, 1 or 2, and x represents 1 or 2. )

Here, the anionic ligand Y₁And Y_TwoIs
Ligands with a negative charge when separated from the central metal
Anything may be used. Neutral electron donating configuration
Child L ₁And L_TwoIs neutral when separated from the central metal
A ligand with a charge of
It may be. The counter anion X is a ruthenium cation
Any anion that forms an ion complex with
May be.

Specific examples of the anionic ligands Y ₁ and Y _{2 in} the above formulas (1) and (2) include F, Br,
Halogen atoms such as Cl and I; hydrogen, acetylacetone, diketonate groups, cyclopentadienyl groups, allyl groups, alkenyl groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups,
Examples include an arylcarboxyl group, a carboxyl group, an alkyl or arylsulfonate group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group. Among them, a halogen atom, a cyclopentadienyl group, an allyl group, an alkyl group and an aryl group are excellent in hydrogenation catalytic activity.

Specific examples of the neutral electron donating ligands L ₁ and L _{2 in} the above formulas (1) and (2) include oxygen, water, carbonyls, amines, pyridines,
Ethers, nitriles, esters, phosphines,
Examples include phosphinite, phosphite, stibine, sulfoxide, thioether, amide, aromatic hydrocarbon, cyclic diolefin, olefin, isocyanide, thiocyanate, and heterocyclic carbene compound. . Among them, pyridines, phosphines,
Carbonyls and heterocyclic carbene compounds are preferred because they form stable compounds.

Further, specific examples of the C ₁ -C ₂₀ hydrocarbon groups R ₁ and R ₂ which may contain a halogen atom and the like in the above formulas (1) and (2) include hydrogen, alkenyl group and alkynyl group. , Alkyl group, aryl group, carboxyl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, alkenylthio group, arylthio group, alkylsulfonyl group, alkylsulfinyl group, alkylsilyl group And an arylsilyl group. Among them, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group are preferred because of their high hydrogenation catalytic activity.

Specific examples of the above-mentioned hydrogenation catalyst include the following.
Things can be mentioned. Examples where the transition metal is Ru
Then, (PCy_Three)_Two(Cl)_TwoRu = CH (OEt)
[Cy represents a cyclohexyl group. The same applies hereinafter), (PC
y_Three)_Two(Cl)_TwoRu = CH (Ph) [Ph is phenyl
Represents a group. The same applies hereinafter), (PCy_Three)_Two(Cl)_TwoRu =
CH (SiMe_Three[Me represents a methyl group. Hereinafter the same
)], (PiPr _Three)_Two(Cl)_TwoRu = CH (SPh)
[IPr represents an isopropyl group. The same applies hereinafter), (PC
y_Three) (Py) (Cl)_TwoRu = CH (Ph) [Py is
Indicates lysine. The same applies hereinafter), (PPh_Three)_Two(Cl)_TwoR
u = CH = CH (Ph), bis (1,3-diisopropyl)
Ru-imidazole-2-ylidene) benzylidene luteni
Um dichloride, (PCy_Three)_Two(Cl)_TwoRu = C = C
H (Ph), (PCy_Three)_Two(Cl)_TwoRu = C = CH
(TBu) [tBu is tert. Indicates a butyl group. Less than
Same), (PiPr_Three)_Two(Cl)_TwoRu = C = CH (P
h), bis (1,3-diisopropyl-imidazole-)
2-ylidene) phenylvinylidene ruthenium dichloride
And the like.

Examples of the case where the transition metal is Fe include tetracarbonyl (ethoxyphenylmethylene) iron, tetracarbonyl ((dimethylamino) phenylmethylene) iron,
Tetracarbonyl (bis (dimethylamino) methylene)
Iron, tetracarbonyl ((dimethylamino) methylene)
Iron, tetracarbonyl (diaminomethylene) iron, tetracarbonyl ((dimethylamino) ethoxymethylene)
Iron, tetracarbonyl (1,3-dioxolan-2-ylidene) iron, tetracarbonyl (4,4,5,5-tetramethyl-1,3-dioxolan-2-ylidene) iron,
Tetracarbonyl (1,3-benzodioxolan-2-
(Ylidene) iron, tetracarbonyl (2-oxazolidinylidene) iron, tetracarbonyl (1,3-dimethyl-2)
-Imidazolidinylidene) iron, tetracarbonyl (1,
3-dihydro-1,3-dimethyl-2H-imidazole-
2-ylidene) iron, tetracarbonyl (1,4-dimethyltetrazoline-5-ylidene) iron, tetracarbonyl (3,4-dimethyl-2 (3H) -thiazolylidene)
Iron, tricarbonyl (triphenylphosphine) (1-
Ethoxyethylidene) iron, tricarbonyl (triphenylphosphine) (ethoxyphenylmethylene) iron, tricarbonyl (triphenylphosphite) (1-ethoxyethylidene) iron, tricarbonyl (triphenylphosphite) (ethoxyphenylmethylene) iron, Carbonyl (ethoxyphenylmethylene) dinitrosyliron, carbonyl ((dimethylamino) ethoxymethylene) dinitrosyliron, carbonyl (1,3-dimethyl-2-imidazolidinylidene) dinitrosyliron, ((dimethylamino) ethoxymethylene) dinitrosyl (triphenyl (Phosphine) iron.

Examples of the transition metal being Os include carbonyldichloro (dichloromethylene) bis (triphenylphosphine) osmium, dicarbonyl (difluoromethylene) bis (triphenylphosphine) osmium,
Examples include dicarbonyl ((4-methyl-2,5-cyclohexadiene-1-ylidene) methylene) bis (triphenylphosphine) osmium and tetracarbonyl (3,4-dimethyl-2 (3H) -thiazolylidene) osmium. An example in which the transition metal is Co is dicarbonyl (1,3-dimethyl-2-imidazolidinylidene).
Nitrosyl cobalt, carbonyl (cyclopentadienyl) (1,3-dimethyl-2-imidazolidinylidene)
Cobalt, cyclopentadienyl (1,3-dimethyl-
2-imidazolidinylidene) diiodocobalt.

Examples where the transition metal is Rh include chlorobis (triisopropylphosphine) vinylidene rhodium, chlorobis (triisopropylphosphine) propenylidene rhodium, chlorobis (triisopropylphosphine) phenylvinylidene rhodium, and chlorobis (triphenylphosphine). Thiocarbonylrhodium, carbonylchloro (triphenylphosphine) (1,3-diethyl-2-imidazolidinylidene) rhodium, carbonyl (cyclopentadienyl) (1,3-dimethyl-2)
-Imidazolidinylidene) rhodium, cyclopentadienyl (phenylvinylidene) (triisopropylphosphine) rhodium, dicarbonyldi-μ-chlorotetrachlorobis ((dimethylamino) methylene) dirhodium. Examples where the transition metal is Ir include chlorobis (triisopropylphosphine) vinylideneiridium, chlorobis (triisopropylphosphine) propylideneiridium, and chlorobis (triisopropylphosphine) phenylvinylideneiridium.

The hydrogenation reaction conditions differ depending on the hydrogenation catalyst used, and the hydrogenation temperature is usually -20 ° C to 25 ° C.
0 ° C, preferably -10 to 220 ° C, more preferably 0 ° C.
~ 200 ° C and hydrogen pressure is usually 0.1 ~ 100k
g / cm ² , preferably 0.5 to 70 kg / cm ² , more preferably 1 to 50 kg / cm ² . If the hydrogenation temperature is too low, the reaction rate is low, and if it is too high, side reactions occur. On the other hand, if the hydrogen pressure is too low, the hydrogenation rate becomes slow, and if it is too high, a high pressure reactor is required. The hydrogenation reaction time is usually 0.1 to 10 hours.

The hydrogenation reaction is usually carried out in an inert organic solvent. The organic solvent can be arbitrarily selected depending on the solubility of the produced hydride. Examples of the organic solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and n-hexane; alicyclic hydrocarbons such as cyclohexane and decalin;
Ethers such as tetrahydrofuran and ethylene glycol dimethyl ether are exemplified. Among them, hydrocarbon solvents and ethers are preferable because of excellent solubility of the hydrogenated cyclic olefin ring-opening polymer. Among the hydrocarbon solvents, alicyclic hydrocarbon solvents are particularly preferred. The organic solvent may usually be the same as the polymerization reaction solvent,
What is necessary is just to add a hydrogenation catalyst to a polymerization reaction liquid as it is, and to make it react.

According to the hydrogenation reaction of the present invention, 70% or more, preferably 90% or more, more preferably 95% or more of the carbon-carbon double bonds of the main chain in the polymer are hydrogenated. Can be. After completion of the hydrogenation reaction, known methods for removing the polymerization catalyst and the hydrogenation catalyst include a method of adsorbing and separating with an adsorbent and a method of washing with water or a lower alcohol in the presence of an organic acid and / or an inorganic acid. Is separated and recovered from the reaction solution.

The number average molecular weight of the hydride of the obtained polymer is preferably 5,000 or more, more preferably 7.0 or more.
00 or more, particularly preferably 10,000 or more, preferably 1,000,000 or less, more preferably 500,0 or less.
00 or less, particularly preferably 200,000 or less.
If the number average molecular weight is too small, the mechanical properties are poor, and if it is too high, the production becomes difficult.

[0046]

The present invention will be described more specifically below with reference to examples and comparative examples. (1) The molecular weight of the ring-opened polymer is determined by gel permeation chromatography using tetrahydrofuran as a solvent.
The molecular weight of the hydrogenated ring-opened polymer was measured by gel permeation chromatography (GP) using cyclohexane as a solvent.
It was measured as a polyisoprene conversion value according to C). (2) The hydrogenation rate was measured by a ¹ H-NMR spectrum. The description of “parts” in the examples is based on weight.

Example 1 (Synthesis of cyclic olefin ring-opening metathesis polymer) 2,6-diisopropylphenylimide neophylidenemolybdenium (VI) bis (hexafluoro-t-butoxide) was added to a glass reactor equipped with a stirrer. After adding 0.1116 parts, cyclohexane 40 parts, dicyclopentadiene 1
0 parts and 0.092 parts of 1-hexene were added to carry out a polymerization reaction at room temperature. After reacting for 3 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at 40 ° C. for 40 hours. The yield of the obtained ring-opened polymer was 9.2 parts, and the molecular weight (in terms of polystyrene) was such that the number average molecular weight (Mn) was 8,900 and the weight average molecular weight (Mw) was 17,000.

(Hydrogenation reaction) Into an autoclave equipped with a stirrer, 5.0 parts of the obtained ring-opening metathesis polymer and 35 parts of cyclohexane were added. Then, (PCy ₃ ) ₂ (Cl)
A hydrogenation catalyst solution obtained by dissolving 6.0 × 10 ⁻³ parts of ₂ Ru = CH (OEt) in 10 parts of tetrahydrofuran was added, and a hydrogenation reaction was performed at a hydrogen pressure of 8 kg / cm ² and 120 ° C. for 10 hours. The hydrogenation reaction mixture was poured into a large amount of isopropanol to completely precipitate the polymer.
It dried under reduced pressure for 0 hours. The hydrogenation rate was over 99%.

Comparative Example 1 Hydrogenation catalyst (PCy ₃ ) ₂ (Cl) ₂ Ru = CH (OE
t) 6.0 × 10 ^-3 parts of (PPh ₃ ) ₃ (Cl) ₂ Ru
A hydrogenation reaction was carried out in the same manner as in Example 1 except that 7.3 × 10 ⁻³ part was used. The hydrogenation rate was 24%.

Example 2 (Synthesis of Cyclic Olefin Ring-Opening Metathesis Polymer) In an autoclave equipped with a stirrer, 21 parts of dicyclopentadiene and 9 parts of 8-ethyltetracyclododecene were used as a cyclic olefin monomer, and 1-chain was used as a chain transfer agent. 0.17 parts of hexene was added, and a catalyst solution obtained by dissolving 0.020 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride in 10 parts of cyclohexane was added, and a polymerization reaction was carried out at 100 ° C. After reacting for 3 hours, a part of the polymerization solution was collected and its molecular weight (in terms of polystyrene) was measured.
The number average molecular weight (Mn) was 13,200 and the weight average molecular weight (Mw) was 31,200.

(Hydrogenation reaction) Then, (PiPr_Three)
_Two(Cl)_TwoRu = CH (SPh)
Add hydrogenation catalyst solution dissolved in 10 parts of hydrofuran
And hydrogen pressure 8kg / cm ^TwoHydrogenation at 120 ° C for 10 hours
The reaction was performed. Use a large amount of isopropanol
And the polymer was completely precipitated.
It dried under reduced pressure at 40 degreeC for 40 hours. Hydrogenation of the resulting ring-opened polymer
The product is 29 parts and its molecular weight (polyisoprene conversion) is measured.
As a result, the number average molecular weight (Mn) was 17,100, and the weight was
The average molecular weight (Mw) was 39,100. Hydrogenation rate
Was over 99%.

Comparative Example 2 After polymerization was carried out in the same manner as in Example 2, 0.2 parts of ethyl vinyl ether was added, and then hydrogen was supplied at a hydrogen pressure of 8 kg / cm ² and hydrogenated at 120 ° C. for 10 hours. The reaction was performed. The hydrogenation rate was 10% or less.

Comparative Example 3 (Synthesis of Cyclic Olefin Ring-Opening Metathesis Polymer) The cycloolefin monomer was 30 parts of dicyclopentadiene,
Polymerization was carried out in the same manner as in Example 2 except that the polymerization temperature was changed to room temperature. After the polymerization, a part of the polymerization solution was collected. As a result, the polymer was precipitated and was in the form of white agar. Since this polymer did not dissolve in tetrahydrofuran, the molecular weight could not be measured by GPC. (Hydrogenation reaction) Ethyl vinyl ether (0.2 part) was added, and then hydrogen was supplied so that hydrogen pressure was 8 kg / cm ² , 12
The hydrogenation reaction was performed at 0 ° C. for 10 hours. Hydrogenation rate is 10%
It was below.

[0054]

According to the present invention, a cyclic olefin monomer is subjected to ring-opening metathesis polymerization using a transition metal compound belonging to Group 8 or 9 of the periodic table as a polymerization catalyst, and then to Group 8 or 9 of the periodic table. According to the method of hydrogenating a polymer by newly adding a transition metal-carbene compound as a hydrogenation catalyst, a wide range of cyclic olefin monomers can be polymerized using a wide range of polymerization catalysts, and the obtained The obtained polymer can be efficiently and stably hydrogenated with a small amount of a hydrogenation catalyst.

Continuation of the front page (72) Inventor Yasuo Kakurei 2-1-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in the Zeon Corporation General Development Center (reference) 4J032 CA22 CA23 CA24 CA27 CA33 CA34 CA35 CA36 CA38 CA45 CB01 CB04 CB05 CB12 CC02 CC03 CD02 CD03 CD04 CD05 CD09 CE03 CF03

Claims (1)

[Claims] 1. A cyclic olefin monomer is subjected to ring-opening metathesis polymerization using a transition metal compound of Groups 4 to 8 of the periodic table as a catalyst, and then a newly added transition group 8 or 9 of the periodic table is added. A method for producing a hydrogenated cyclic olefin ring-opening metathesis polymer, comprising hydrogenating a carbon-carbon unsaturated bond in an obtained polymer in the presence of a catalyst comprising a metal-carbene compound.