JP3212820B2 - Catalyst composition for metathesis reaction, activation method and molding method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for obtaining a precursor of a molybdenum or tungsten catalyst useful as a precursor of an olefin metathesis catalyst. The present invention also relates to an olefin metathesis catalyst system useful for a simple olefin metathesis reaction, a non-cyclic diene metathesis reaction, ring-opening metathesis polymerization of a cyclic olefin, and the like.

[0002]

BACKGROUND OF THE INVENTION The process of olefin metathesis reaction is defined as a process in which a portion of the alkylidene undergoes recombination to give a mixture of olefins. For example, propylene changes to ethylene and butylene. The simplest examples are:

[0003]

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In this reaction, a catalyst having a metal carbene double bond (M = CHR; metal alkylidene complex)
The olefin is added to give a metal cyclobutane ring, which then proceeds on the principle of leaving the olefin to regenerate the metal alkylidene complex. Typical olefins that undergo a metathesis reaction in the presence of a suitable catalyst include oleic acid esters, cis CH ₃ (CH ₂ ) ₇ CH ＝ CH (C
H ₂ ) ₇ CO ₂ H and the like.

Ring-opening metathesis polymerization of cyclic olefins with olefin metathesis catalyst (hereinafter referred to as ROMP)
Is a very important reaction in the synthesis of thermosetting resins and thermoplastic resins. Heretofore, all of monocyclic olefins, substituted monocyclic olefins, polycyclic olefins, and substituted polycyclic olefins have been used for the synthesis of unsaturated polymers. In many cases, the cyclic olefin can be polymerized even when it has a polar group or a reactive group.

[0006] Norbornene is a typical olefin that does ROMP in the presence of a metathesis catalyst having a metal carbene double bond.

[0007] The third type of olefin metathesis reaction is the metathesis reaction of acyclic dienes (hereinafter ADMET). ADMET chemistry has been used to form dimers, oligomers and polymers. ADMET polymerization is a useful method for synthesizing high molecular weight polymers and copolymers, but is more complex than ROMP, a chain addition type polymerization reaction caused by ring strain relaxation. The polymerization by ADMET is a stepwise condensation reaction, and is an equilibrium reaction in which a product is formed by removing an olefin from the reaction system out of the system. In ADMET and simple olefin metathesis reaction of styrene and monoolefin, dimer of trans-stilbene which is expected to be formed by metathesis chemistry in quantum chemistry has been studied. Further, polymerization of 1,9-decadiene (α, ω-diolefin) by ADMET gives polyoctylene when the conversion is high. However, about 99% polymerization
If it is stopped before the conversion of is reached, it will be an oligomer of α, ω-diolefin. This is because the reaction is a step polymerization and produces high molecular weight polymers only at high conversions. Most importantly, the functionality of the ester or ether often does not change during the polymerization reaction, and a polymer is obtained that is not directly available with ROMP. On the other hand, since ADMET is a stepwise condensation reaction, there is an opportunity to bias the equilibrium between the monomer and the polymer. For example, unsaturated polymers such as polynorbornene and polybutadiene decompose and combine with ethylene to form low molecular oligomers and α, ω-
It is known to be an alkadiene.

The olefin metathesis reaction is also used as a method for producing a cyclic or acyclic olefin by ring-forming metathesis of an acyclic diene ether (Fu &
Grubbs, J.A. Am. Chem. Soc. , 1
992, vol. 114, p. 5426-27). For example, various diallyl ethers can be converted to Mo (= CHCMe ₂ Ph) (NC ₆ H ₃ −
Treatment with 2,6-i-Pr ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ produced various ring-closed compounds such as cyclic ethers, amines and amides.

Conjugated polymers useful for various applications, such as nonlinear optical devices, electro-optical devices, and wave guiding devices, are synthesized by an olefin metathesis reaction. Fox and S
clock is a cyclic polymer of diproparyl derivative, Mo
It is stated that when (= CHR) (NAr) (OC (CF ₃ ) ₂ CH ₃ ) ₂ is used as a catalyst, a polyene is obtained in high yield. Grubbs can also be obtained from a substituted cyclooctatetraene by using Mo (= CHCMe ₃ ) (NAr) (O
Polyene is obtained by a ring opening reaction using C (CF ₃ ) ₂ CH ₃ ) ₂ . Here, Me is a methyl group and Ar is an aryl group.

In order to take advantage of the features of metathesis reaction, ring-opening metathesis polymerization, ring-closing chemistry, cyclization polymerization and the above-mentioned ADMET chemistry of olefins having a functional group, transition metals such as tungsten and molybdenum are variously changed, Development of useful catalysts with low acidity is underway. Such catalysts must be easily synthesized, of which structure is already known, and whose reactivity can be easily controlled. Some of these types have already been reported to be capable of olefin metathesis reactions in a manner that modulates reactivity by the choice of aryloxy or alkoxy ligands (eg, JM Basset et al. AngewChem.,
1992, Vol. 104, p. 622-664;
A. Osborn et al. Chem. Soc. , Ch
em. Commun. 1989, p. 1062-10
63, R.C. R. Schrock. U.S. Pat. No. 4,68
No. 1,956, 4,727,215; R. Sch
See US Pat. No. 5,142,073 to Rock et al.).

A tungsten or molybdenum catalyst M (= CH
R ³ ) (NR ¹ ) (OR ² ) ₂ are employed in all the fields of olefin metathesis described above. The following molybdenum alkylidene complexes are particularly useful: Mo (C
HCMe ₂ Ph) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (O
CMe (CF ₃ ) ₂ ) ₂ , Mo (CHCMe ₃ ) (NC ₆ H ₃
−2,6-i-Pr ₂ ) (OCMe ₃ ) ₂ and Mo (CHC
Me ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (OCMe
(CF _{3) 2) 2.}

These transition metal alkylidene complexes having a distinct structure have high resistance to functional groups and temperatures. However, these catalysts are generally tedious to go through a multi-step synthesis route, and often require expensive reagents.

US Pat. No. 5,142,073 discloses complexes of the structure M (R ¹ ) ₂ (NR ² ) (R ³ ) _x . Where M is tungsten or molybdenum, R
¹ is halogen, R ² is phenyl or substituted phenyl (typically mono- or di-C ₁ -C ₆ alkyl-substituted phenyl), R ³ is a Lewis base having at least one pair of electrons, x Is 0, 1, or 2. This compound is a compound useful as a precursor of an M (= CHR ³ ) (NR ¹ ) (OR ² ) ₂ catalyst, and is used in an olefin metathesis reaction. In U.S. Pat. No. 5,142,073, M
A four-step process is shown for the synthesis of o (= CHR ⁴ ) (NR ¹ ) (OR ² ) ₂ , for example ([NH ₄ ] [M
o ₂ O ₇ ]) to the intermediate Mo
It is shown to be obtained via (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl ₂ (DME). Where DME
Is dimethoxyethane. However, this multi-step synthesis involves dangerous and expensive trifluorosulfonic acid (CF ₃ SO ₃₎ along with lithium alkoxides and aryloxides.
H). In general, reactions using these reagents need to be performed at a low temperature (-30 ° C).

A simple olefin metathesis reaction or ring-opening metathesis polymerization reaction of a special polymer using an M (= CHR ³ ) (NR ¹ ) (OR ² ) ₂ catalyst is carried out by reacting an olefin with an alkylidene in a solvent. Done in M
AD using (= CHR ³ ) (NR ¹ ) (OR ² ) ₂ catalyst
MET is performed both in solution and in bulk.

In the production of a thermosetting polymer, it is preferable to use a solvent-free system since the solvent does not enter the polymer matrix. However, the well-known alkylidene complex M (= CHR ⁴ ) (NR ¹ ) (O
R ² ) ₂ has two drawbacks: the use of an inert solvent and the immediate reaction upon contact with the metathesis polymerizable monomer.

Reaction injection molding (hereinafter referred to as RIM) of polyolefins using ring-opening metathesis polymerizable monomers in the presence of an alkylidene complex is a particularly important olefin metathesis reaction. In RIM technology, a system using two or more compositions is used to form an alkylidene complex, for example, a reaction with a metal halide and an alkylating agent. For example, K
losiewicz (U.S. Pat. No. 4,400,340)
No. 4,520,181) report that polydicyclopentadiene (hereinafter referred to as poly-DCPD) can be obtained by combining streams of a plurality of reactants. The first stream contains the metathesis catalyst precursor and the second stream contains the metathesis system activator. At least one of the streams contains dicyclopentadiene (hereinafter referred to as DCPD), and after mixing the streams to form a metathesis catalyst, the mixture is injected into a mold and a polymerization reaction occurs. Although this catalyst is very effective in polymerizing reactions, residual chlorine, solvents for dissolving the catalyst precursor and activator, and the metals resulting from the catalyst and activator can reduce the formation of thermoset products. It is not preferable because it remains inside. In addition, alkyl tins such as tetramethyl tin, alkyl aluminums such as diethyl aluminum chloride, which are sensitive to air and potentially dangerous
Alkylating agents, such as alkyl zincs, for example diethyl zinc, are often used to maximize the effectiveness of the catalyst.

[0017]

A series of olefin metathesis catalyst precursors have been found which have very mild activity and require only water and oxygen stable activators. The metathesis catalysts made from these metathesis catalyst precursors are very active, and the resulting olefin metathesis catalyst can be formed in situ in a monomer or solvent capable of olefin metathesis reaction, or if necessary. , Can also be isolated as pure.

In particular, the present invention relates to (a) M (NR ¹ ) (N
At least one catalyst precursor having the structure of R ² ) (R ³ ) (R ⁴ ) (Structural Formula I) and (b) at least one activator for activating the catalyst precursor The present invention relates to a catalyst composition containing the same and to the production of an olefin metathesis catalyst (olefin metathesis polymerizable compound) using the catalyst composition. Where M is Mo or W, R ¹ ,
R ² , R ³ , R ⁴ are alkyl, cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups and similar groups including silicon, Selected from the group consisting of
The same or different groups.

Generally, the activator is an alcohol (RO)
H), phenol (ArOH), silanol (R ₃ Si
OH), diols (HO-Z-OH), thiols (RS
H) or thiophenol (ArSH) or a combination thereof. Activation takes place in a solvent or in a monomer capable of an olefin metathesis reaction.

According to the present invention, the catalyst precursor of the structural formula I is obtained by reacting M (NR ¹ ) (NR ² ) X ₂ Ls with an alkylating agent containing R ³ and R ⁴ . Where X
Is a halogen, triflate (CF ₃ SO ₃ ⁻ ) or a leaving group, L is a Lewis base, s is 0, 1 or 2, and R ¹ , R ² , R ³ and R ⁴ have the structure As in the case of the catalyst precursor compound of the formula I. Compound M (NR ¹ ) (NR ² )
For X ₂ Ls, several methods have been proposed for synthesis. Throughout the specification, unless otherwise specified, the structural formulas of the catalyst precursor of the present invention and the olefin metathesis catalyst (olefin metathesis polymerizable compound) synthesized from the catalyst precursor of the present invention include L
The description of s may be omitted.

These olefin metathesis catalyst precursors have proven to be useful in ROMP and ADMET in a homogeneous system in the absence of a solvent. The catalyst precursor can of course be used in a suitable solvent. These are used in ring-opening metathesis polymerization of mono- or polycyclic olefins. Particularly, norbornene, substituted norbornene, DCPD and cyclic olefins having more rings are useful. Also, even at very low catalyst precursor concentrations, high rates of conversion from monomer to polymer can be achieved. Furthermore, in the case of poly DCPD, the heat distortion temperature and the glass transition temperature are sufficiently improved, and a very low concentration of halogen and metal can be obtained. Both thermosetting and thermoplastic polymers are also obtained. In this system, a Lewis base as a rate modifier is optionally used.

Further, the present invention provides a method for producing a compound (R) by bringing a compound of the structural formula I, M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ), into contact with a proton source in a solvent. ⁷ CH
=) M (NR ¹ ) (GR ⁵ ) (GR ⁶ ) (NH ₂ R ² ) A novel synthesis method of an olefin metathesis catalyst (olefin metathesis polymerizable compound) having the structure (Structural Formula II) is also included. Here, M is molybdenum or tungsten, and R ¹ , R ² , R ⁵ , and R ⁶ are alkyl, cycloalkyl, polycycloalkyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups, and silicon. And the same or different groups selected from the group consisting of: R ₇ is an alkyl, substituted or unsubstituted aryl or aralkyl group or a similar group containing silicon. Further, G comprises an oxygen, sulfur or amide (NH) group. Compounds having the structure of Structural Formula II can catalyze the metathesis reaction of general olefins in a homogeneous layer, and particularly the metathesis reaction of olefins having functional groups. This method is excellent in that it is the most economical among the conventional synthesis reactions, the reaction time is short, and the cost of starting materials is low. Further, according to the present method, (R ⁷ CH =) M in the presence of an olefin capable of metathesis reaction
(NR ¹ ) (GR ⁵ ) (GR ⁶ ) (NH ₂ R ² ) compounds can be easily synthesized.

It is an object of the present invention to provide an olefin metathesis catalyst precursor that requires only a very mild activator. Another advantage of this catalyst precursor is that (i) the olefin metathesis catalyst (olefin metathesis polymerizable compound) can be synthesized in situ in a monomer capable of olefin metathesis reaction or, if necessary, in a solvent, (ii) The catalyst precursor can be easily synthesized using inexpensive materials in a short step without requiring a low temperature. (Iii) From this catalyst precursor, (R ⁷ CH =) M (NR) can be obtained in a safe, simple and inexpensive manner. ¹ ) (GR
⁵ ) that (GR ⁶ ) (NH ₂ R ² ) compound can be synthesized;
(Iv) A thermosetting, thermoplastic product of olefin metathesis having extremely low metal and halogen concentrations can be obtained.

The catalysts of the present invention have broad benefits in olefin metathesis chemistry. The prior art does not have such a broad benefit and it is stated that only certain special ligand combinations are useful.

[0025]

Means for Solving the Problems] olefin metathesis catalyst composition in the catalyst precursor present invention,
(A) at least one catalyst precursor having a structure of M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) (structural formula I);
(B) a catalyst composition comprising at least one activator for activating the catalyst precursor, wherein M is Mo or W;
¹ , R ² , R ³ , R ⁴ are alkyl, cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups, and the like, including silicon. The same or different groups selected from the group consisting of

The term "polycycloalkyl" means having two or more carbon atoms and having two or more rings, such as norbornene and adamantane. "Cycloalkenyl"
Means a cyclic compound having an unsaturated bond. For example, cyclopentinyl. "Polycycloalkenyl" refers to two or more carbon atoms in common and two or more rings,
It means a compound having an unsaturated bond. For example, dicyclopentynyl. R ¹ , R ² , containing silicon;
Groups similar to the carbon-containing groups listed for R ³ and R ⁴ include those in which one or more carbon atoms have been replaced with silicon atoms. For example, a neopentyl group (Me ₃ C
A similar group containing silicon in CH ₂ —) corresponds to a methylsilyl group (Me ₃ SiCH ₂ —).

The terms "aryl" and "aralkyl" are as follows:
Here, it means a radical formed by removing hydrogen from an aromatic hydrocarbon. For example, an aryl group is phenyl,
2,6-diisopropylphenyl, 2,6-diphenylphenyl and 2,4,6-trimethylphenyl. Aralkyl groups are benzyl and triphenylmethyl.

When R ¹ , R ² , R ³ and R ⁴ in the above structural formula have a phenyl ring, mono-substituents at positions 2, 3 and 4 are included. In the case of a disubstituted phenyl group, 2,6,
Substitutions can be made at 2, 5, 2, 4, 2, 3, or 3, 4, 3, 5 positions. The substituents may be the same or different. In the case of a trisubstituted phenyl group, 2,3,4,
2,3,5,2,3,6 or 3,4,5,2
Substitutions can be made at positions 4, 5, 2, 4, and 6.
The substituents may be the same or different. In the case of a tetra-substituted phenyl group, 2,3,4,5,2,3,4,6 or 2,
Substitutions can be made at positions 3, 5, and 6. The substituents may be the same or different. In the case of a pentasubstituted phenyl group,
Substitution can be made at positions 2, 3, 4, 5, and 6.
The substituents may be the same or different. The following is a list of those that can be substituted for aromatic nuclei: Br, Cl, F, I, C
H ₃ , CN, OCH ₃ , SCH ₃ , COCH ₃ , OCOCH
_{3, COOCH 3, OC 2 H} 5, cyclo -C ₃ H _5, CF _{3,
OCF 3, NMe 2, COC 6} H 5, SO 2 Me, C 6 H 5,
CH ₂ C ₆ H ₅ , OC ₆ H ₅ , SC ₆ H ₅ and C _1-20 alkyl groups (Me represents a methyl group).

More preferred substituents include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, isopropenyl, phenyl, bromo, chloro , Fluoro, ethoxy, methoxy, butoxy, octyloxy, hexadecyloxy, tetradecyloxy, octadecyloxy, pentoxy, phenoxy, cyclopropyl, trifluoromethyl (CF ₃ ), trifluoromethoxy (OCF ₃ ), 1,
1,2,2-tetrafluoroethoxy (OCF ₂ CF
₂ H), nitro, ester, haloalkyl, cyano (-
CN), isocyano (-NC), amino (NH _2), methylamino (CH ₂ NH _2), dimethylamino (-NMe
₂ ), methylsulfonyl (SO ₂ Me), trifluoromethylsulfonyl (SO ₂ CF ₃ ), arylsulfonyl (SO ₂ Ar), and benzyl (CH ₂ C ₆ H ₅ ).

Preferred substituted phenyl groups include:
2,6-dimethylphenyl, 2,6-dichlorophenyl, 2,6-diisopropylphenyl, 2,6-dibromophenyl, 2,6-difluorophenyl, 2,6-bis (trifluoromethyl) phenyl, 2,6- Bis (trifluoromethoxy) phenyl, 3,5-bis (trifluoromethoxy) phenyl, 2,6-dimethoxyphenyl, 2-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,3,4 , 5,6-pentabromophenyl, 2-bromo-4,6-dimethylphenyl, 4-methylphenyl, 4-methoxy-2-methylphenyl, 2
-Tert-butyl-6-methylphenyl, 2-chloro-6
-Methylphenyl and 2-methoxy-5-chlorophenyl.

For compounds of structural formula I, preferred R ¹ and R ² are 2-bromo-4,6-dimethylphenyl,
2-chloro-4,6-dimethylphenyl, 2-chloro-
4-methylphenyl, 2-chloro-5-methoxyphenyl, 2-chloro-5-trifluorophenyl, 2-chloro-6-methoxyphenyl, 2-chloro-6-methylphenyl, 2-chlorophenyl, 2-ethylphenyl , 2
-Isopropylphenyl, 2-methoxybenzyl, 2-
Methoxyphenyl, 2-methoxy-5-methylphenyl, 2-methyl-2-phenylpropyl, 2-tert-butyl-6-methylphenyl, 2-tert-butylphenyl, 2-trifluoromethylphenyl, 2-trifluoro Phenyl, 4-methoxy-2-methylphenyl, 4-
Methoxyphenyl, 4-methylbenzyl, 4-methylphenyl, 4-phenylphenyl, 4-trifluoromethoxyphenyl, 2,3-dimethylphenyl, 2,4-dichloro-6-methylphenyl, 2,4-dimethoxyphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,5-di-tert-butylphenyl, 2,6-
Bis (trifluoromethoxy) phenyl, 2,6- (trifluoromethyl) phenyl, 2,6-bis (trifluoromethoxy) phenyl, 2,6-dibromo-4-chlorophenyl, 2,6-dibromo-4-methyl Phenyl,
2,6-dibromo-4-tert-butylphenyl, 2,6
-Dibromo-4-tert-octylphenyl, 2,6-dibromophenyl, 2,6-dichloro-4-methylphenyl, 2,6-dichloro-4-methylsulfonylphenyl, 2,6-dichloro-4-tert- Butylphenyl,
2,6-dichloro-4-tert-octylphenyl, 2,
6-dichlorophenyl, 2,6-diisopropylphenyl, 2,6-dimethoxybenzyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl, 2,6-diphenylphenyl, 3,4-diethoxyphenyl, 3,4 −
Dimethoxyphenyl, 3,4-dimethylphenyl, 3,
5-bis (trifluoromethoxy) phenyl, 3,4
5-trimethoxyphenyl, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-trimethylphenyl, 4-dimethylaminobenzoyl, 4-sec-butylphenyl, 4-ethylphenyl, 5-fluoro-2 -Methylphenyl, adamantyl, benzyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclopropyl, dodecylphenyl, ethyl, hexafluoro-tert
-Butyl, isopropyl, methyl, naphthyl, norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, perfluoro-2-methyl-2-pentyl, perfluoro-tert-butyl, phenyl, tert-butyl, tert-octyl, C ₁₂ -C ₁₄ tert
-Alkyl, C ₁₆ -C ₂₂ tert-alkyl, tri-tert-
It is selected from butylsilyl, trifluoro-tert-butyl, trimethylsilyl, triphenylsilyl, and triphenylmethyl groups.

Most preferred R ¹ and R ² are 2-chlorophenyl, 2-methoxyphenyl, 2-methyl-2-phenylpropyl, 2-tert-butylphenyl, 4-methoxyphenyl, 4-methylphenyl, 4-phenyl Phenyl, 4-trifluoromethoxyphenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 2,6-diisopropylphenyl, 2,6-dimethoxyphenyl,
2,6-dimethylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, adamantyl,
Benzyl, cyclohexyl, ethyl, hexafluoro-
tert-butyl, isopropyl, methyl, naphthyl, norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, perfluoro-2-methyl-2-pentyl, perfluoro-tert-butyl, phenyl, tert-butyl, trifluoro- tert-butyl,
It is selected from trimethylsilyl and triphenylsilyl groups.

R ³ and R ⁴ are preferably neopentyl (C
H ₂ CMe _3), neophyl (CH ₂ CMe ₂ Ph), trimethylsilylmethyl (CH ₂ SiMe _3), benzyl, substituted benzyl, e.g., 4-methylbenzyl (CH ₂ C ₆ H
₃ -4-CH _3), 2- methoxybenzyl (CH ₂ C ₆ H ₄
-2-OMe), 2,6- dimethoxybenzyl (CH _{2
C 6 H 3 -2,6- (OMe)} 2), 4- dimethylamino-benzyl _{(CH 2 C 6 H 4 -N} (CH 3) 2), cyclopentyl, cyclohexyl, methyl, cyclopropyl, cyclobutyl, substituted or non Selected from substituted phenyl, norbornenyl, and dicyclopentenyl groups.

The catalyst precursor M (NR ¹ ) (NR ² )
For certain combinations of (R ³ ) (R ⁴ ), R ¹ , R ² , R ³ and R ⁴ may be different. R ¹ and R ^{2 in} this case are
Preferably, 2-bromo-4,6-dimethylphenyl,
2-chloro-4,6-dimethylphenyl, 2-chloro-
4-methylphenyl, 2-chloro-5-methoxyphenyl, 2-chloro-5-trifluoromethylphenyl, 2
-Chloro-6-methoxyphenyl, 2-chloro-6-methylphenyl, 2-chlorophenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-methoxyphenyl, 2-methoxy-5-methylphenyl, 2-methyl-
2-phenylpropyl, 2-tert-butyl-6-methylphenyl, 2-tert-butylphenyl, 2-trifluoromethylphenyl, 2-trifluorophenyl, 4-methoxy-2-methylphenyl, 4-methoxyphenyl,
4-methylphenyl, 4-phenylphenyl, 4-trifluoromethoxyphenyl, 2,3-dimethylphenyl, 2,4-dichloro-6-methylphenyl, 2,4-
Dimethoxyphenyl, 2,4-dimethylphenyl, 2,
5-dimethylphenyl, 2,5-di-tert-butylphenyl, 2,6-bis (trifluoromethoxy) phenyl, 2,6-bis (trifluoromethyl) phenyl,
2,6-dibromo-4-chlorophenyl, 2,6-dibromo-4-methylphenyl, 2,6-dibromo-4-te
rt-butylphenyl, 2,6-dibromo-4-tert-octylphenyl, 2,6-dibromophenyl, 2,6-
Dichloro-4-methylphenyl, 2,6-dichloro-4
-Methylsulfonylphenyl, 2,6-dichloro-4
-Tert-butylphenyl, 2,6-chloro-4-tert-
Octylphenyl, 2,6-dichlorophenyl, 2,6
-Diisopropylphenyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl, 2,6-diphenylphenyl, 3,5-bis (trifluoromethoxy) phenyl, 3,4-diethoxyphenyl, 3,4-dimethoxy Phenyl, 3,4-dimethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 3,4,5-trimethoxyphenyl, 2,4,6-trimethylphenyl,
-Sec-butylphenyl, 4-ethylphenyl, 5-fluoro-2-methylphenyl, adamantyl, benzyl, cyclobutyl, cyclohexyl, cyclopentyl,
Cyclopropyl, dodecylphenyl, ethyl, hexafluoro-tert-butyl, isopropyl, methyl, naphthyl, norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, perfluoro-2-methyl-2-pentyl, perfluoro-tert- Butyl, phenyl, tert-butyl, tert-octyl, C ₁₂
—C ₁₄ tert-alkyl, C ₁₆ -C ₂₂ tert-alkyl, tri-tert-butylsilyl, trifluoro-tert-butyl, trimethylsilyl, triphenylsilyl, triphenylmethyl group.

R ³ and R ⁴ are preferably selected from substituted or unsubstituted benzyl, norbornenyl, substituted or unsubstituted phenyl, neopentyl, neophyl or trimethylsilyl groups.

M when R ¹ , R ² , R ³ and R ⁴ are different
A typical example of (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) is Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-P
r ₂ ) (CH ₂ CMe ₃ ) (CH ₂ CMe ₂ Ph), W (N
CMe ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ C
Me ₃ ) (CH ₂ CMe ₂ Ph), Mo (NCMe ₃ ) (N
_{C 6 H 3 -2,6-i-} Pr 2) (CH 2 CMe 2 Ph)
(CH ₂ Ph), W (NCMe ₃ ) (NC ₆ H ₃ -2,6-
i-Pr ₂ ) (CH ₂ CMe ₂ Ph) (CH ₂ Ph), W
_{(N-1-adamantyl) (NC 6 H 3 -2,6-} i-P
r ₂ ) (CH ₃ ) (CH ₂ Ph), Mo (NCMe ₃ ) (N
_{C 6 H 3 -2,6-Cl 2} ) (CH 2 SiMe 3) (CH 2 C
Me ₂ Ph), Mo (NC ₆ H ₃ -2,6-Me ₂ ) (NC
Me ₃ ) (CH ₃ ) (CH ₂ CMe ₂ Ph), Mo (NC _{6
H 3 -2,6-Me 2) (} NCMe 3) (CH 3) (CH 2
SiMe ₃ ), W (NC ₆ H ₃ -2,6-i-Pr ₂ ) (N
CMe ₃ ) (CH ₃ ) (CH ₂ CMe ₂ Ph), W (NC _{6
H 3 -2,6-Me 2) (} NCMe 3) (CH 3) (CH 2
CMe ₂ Ph), Mo (NC ₆ H ₃ -2,6-i-Pr ₂ )
(NCMe ₃ ) (CH ₃ ) (CH ₂ CMe ₂ Ph).
Here, Me represents a methyl group, i-Pr represents an isopropyl group, and Ph represents a phenyl group. N-1-adamantyl represents 1-adamantylamine.

When R ¹ and R ² are the same but R ³ and R ⁴ are different, preferred examples of M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) are
Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) (CH ₂ P
h), W (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) (CH ₂
CMe ₃ ), Mo (NC ₆ H ₃ -2,6-i-Pr ₂ )
₂ (CH ₂ CMe ₂ Ph) (CH ₂ CMe ₃ ), W (NC ₆ H
_{3 -2,6-i-Pr 2)} 2 (CH 2 CMe 2 Ph) (CH 2
CMe ₃ ), Mo (NCMe ₃ ) ₂ (CH ₃ ) (CH ₂ CM
e ₂ Ph), Mo (NC ₆ H ₃ -2,6-i-Pr ₂ )
₂ (CH ₃ ) (CH ₂ CMe ₂ Ph), Mo (NCMe ₃ ) _{2
(CH 3) (CH 2 CMe} 3), W (NCMe 3) 2 (C
H ₃ ) (CH ₂ CMe ₂ Ph), Mo (NCMe ₃ ) ₂ (C
H ₂ SiMe ₃ ) (CH ₃ ), Mo (NCMe ₃ ) ₂ (CH ₂
Ph) (CH ₃ ), Mo (NC ₆ H ₃ -2,6-i-P
_{r 2) 2 (CH 2 SiMe} 3) (CH 3), W (NC 6 H 3 -
_{2,6-i-Pr 2) 2} (CH 3) (CH 2 CMe 2 Ph)
And W (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ (CH ₂ SiM
e ₃ ) (CH ₃ ).

When R ³ and R ⁴ are the same and R ¹ and R ² are different, preferred examples of M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) are
Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ )
(CH ₂ CMe ₂ Ph) ₂ , W (NCMe ₃ ) (NC ₆ H ₃ −
2,6-i-Pr ₂ ) (CH ₂ CMe ₂ Ph) ₂ , Mo (N
-1-adamantyl) (NC ₆ H ₃ -2,6-i-P
r ₂ ) (CH ₂ CMe ₂ Ph) ₂ , W (N-1-adamantyl) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ CMe ₂
Ph) ₂ , Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-
Pr ₂ ) (CH ₃ ) ₂ , W (NCMe ₃ ) (NC ₆ H ₃ -2,
6-i-Pr ₂ ) (CH ₃ ) ₂ , Mo (NC ₆ F ₅ ) (NC ₆
H ₃ -2,6-i-Pr ₂ ) (CH ₂ CMe ₂ Ph) ₂ , M
o (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (C
H ₃ ) ₂ , Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-C
l ₂ ) (CH ₂ CMe ₂ Ph) ₂ , Mo (NC ₆ F ₅ ) (NC
Me ₃ ) (CH ₂ CMe ₂ Ph) ₂ , W (NC ₆ F ₅ ) (NC
_{6 H 3 -2,6-i-Pr} 2) (CH 2 Ph) 2, Mo (N
_{C 6 H 3 -2,6-i-} Pr 2) (N-1- _{adamantyl) (CH 3) 2, Mo} (NC 6 H 5) (N-1- _{adamantyl) (CH 3) 2, Mo} (NC ₆ H ₅₎ (NCMe ₃₎
(CH ₃ ) ₂ , W (NC ₆ H ₃ -2,6-Me ₂ ) (NCM
_{e 3) (CH 3) 2} , Mo (NC 6 H 3 -2-tert-CM
_{e 3) (NCMe 3) (} CH 3) 2, Mo (NC 6 H 3 -2,
6-Cl ₂ ) (NCMe ₃ ) (CH ₃ ) ₂ , Mo (NC
_{6 F 5) (NCMe 3)} (CH 3) 2, Mo (NCMe 3)
(NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₃ ) ₂ , Mo
(NC ₆ H ₃ -2,6-Me ₂ ) (NCMe ₃ ) (C
H ₃ ) ₂ , W (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-P
r ₂ ) (CH ₃ ) ₂ , Mo (NC ₆ H ₃ -2,6-i-P
r ₂ ) (N-1-adamantyl) (CH ₂ Ph) ₂ , Mo
(NC ₆ H ₅ ) (N-1-adamantyl) (CH ₂ P
h) ₂ , Mo (NC ₆ H ₅ ) (NCMe ₃ ) (CH ₂ P
h) ₂ , W (NC ₆ H ₃ -2,6-Me ₂ ) (NCMe ₃ )
(CH ₂ Ph) ₂ , Mo (NC ₆ H ₃ -2,6-Cl ₂ )
_{(NCMe 3) (CH 2 CMe} 3), Mo (NC 6 H 4 -2
-Tert-CMe ₃ ) (NCMe ₃ ) (CH ₂ Ph) ₂ , Mo
_{(NC 6 H 3 -2,6-Cl} 2) (NCMe 3) (CH 2 P
h) ₂ , Mo (NC ₆ F ₅ ) (NCMe ₃ ) (CH ₂ P
h) ₂ , Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-P
r ₂ ) (CH ₂ Ph) ₂ , Mo (NC ₆ H ₃ -2,6-M
e ₂ ) (NCMe ₃ ) (CH ₂ Ph) ₂ and W (NCMe ₃ )
(NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ Ph) ₂ .

Synthesis of Catalyst Precursor M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) is represented by (a) M (N
A compound having a structure of R ¹ ) (NR ² ) X ₂ Ls; and (b)
It is synthesized by reacting an alkylating agent having R ³ and R ⁴ or a mixture of alkylating agents, preferably in an inert gas. Here, M is Mo or W, and R ¹ , R ² , R ³ , R ⁴
Is alkyl, cycloalkyl, polycycloalkyl,
Same or different groups selected from the group consisting of haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups, and similar groups containing silicon. X is preferably halogen,
L is a Lewis base, s is 0, 1 or 2; chlorine, bromine, triflate or a leaving group. `` Leaving group ''
Is defined as a free radical formed by the reaction of a high electron density reagent with a relatively low electron density site in a nucleophilic substitution reaction, replacing a group with an extra lone pair of electrons. Preferred leaving groups include halide, aryloxide, alkoxide, tosylate (CH ₃ C ₆ H ₄
SO ₃ ⁻ ) and triflate (CF ₃ SO ₃ ⁻ ).

Preferred alkylating agents include alkyl lithium (R ³ Li, R ⁴ Li), Grignard reagent (R
³ MgCl, R ⁴ MgCl), dialkyl magnesium ((R ³ ) ₂ Mg, (R ⁴ ) ₂ Mg) and dialkyl zinc ((R ³ ) ₂ Zn, (R ⁴ ) ₂ Zn). Most preferred are Grignard reagents (R ³ MgCl; R ⁴ M
gCl) and alkyl lithium (R ³ Li; R ⁴ Li) or a mixture thereof.

A Lewis base is a compound that can donate an electron pair. These ligands can be easily replaced by metathesisable olefins. Preferred Lewis bases are tetrahydrofuran, 4,4 ′
- dimethyl-2,2'-bipyridine, 1,10-phenanthroline, 2,2'-bipyridine, pyridine, dimethoxyethane, quinuclidine, PR ₃ or R ₂ PCH ₂ C
A phosphorus compound having a structure of H ₂ PR ₂ (where R is an alkyl or aryl group), diglyme, RN = CH—CH
= Diazabutadiene having the structure NR where R is an alkyl or aryl group or a substituted, unsubstituted aryl or aralkyl group.

In a preferred embodiment, R ¹ and R ² are different. In this case, R ¹ and R ² are preferably 2-bromo-
4,6-dimethylphenyl, 2-chloro-4,6-dimethylphenyl, 2-chloro-4-methylphenyl, 2-
Chloro-5-methoxyphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6-methoxyphenyl, 2-chloro-6-methylphenyl, 2-chlorophenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-methoxyphenyl, 2-methoxy-5-methylphenyl, 2-methyl-2-phenylpropyl, 2-
tert-butyl-6-methylphenyl, 2-tert-butylphenyl, 2-trifluoromethylphenyl, 2-trifluorophenyl, 4-methoxy-2-methylphenyl, 4-methoxyphenyl, 4-methylphenyl, 4-
Phenylphenyl, 4-trifluoromethoxyphenyl, 2,3-dimethylphenyl, 2,4-dichloro-6
-Methylphenyl, 2,4-dimethoxyphenyl, 2,
4-dimethylphenyl, 2,5-dimethylphenyl,
2,5-di-tert-butylphenyl, 2,6-bis (trifluoromethoxy) phenyl, 2,6-bis (trifluoromethyl) phenyl, 2,6-dibromo-4-chlorophenyl, 2,6-dibromo -4-methylphenyl,
2,6-dibromo-4-tert-butylphenyl, 2,6
-Dibromo-4-tert-octylphenyl, 2,6-dibromophenyl, 2,6-dichloro-4-methylphenyl, 2,6-dichloro-4-methylsulfonylphenyl, 2,6-dichloro-4-tert- Butylphenyl,
2,6-dichloro-4-tert-octylphenyl, 2,
6-dichlorophenyl, 2,6-diisopropylphenyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl, 2,6-diphenylphenyl, 3,5-bis (trifluoromethoxy) phenyl, 3,4-diethoxy Phenyl, 3,4-dimethoxyphenyl, 3,4-dimethylphenyl, 3,5-bis (trifluoromethyl)
Phenyl, 3,4,5-trimethoxyphenyl, 2,
4,6-trimethylphenyl, 4-sec-butylphenyl, 4-ethylphenyl, 5-fluoro-2-methylphenyl, adamantyl, benzyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclopropyl, dodecylphenyl, ethyl, hexafluoro-tert -Butyl,
Isopropyl, methyl, naphthyl, norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, perfluoro-2-methyl-2-pentyl, perfluoro-tert-butyl, phenyl, tert-
Butyl, tert-octyl, C ₁₂ -C ₁₄ tert-alkyl,
C ₁₆ -C ₂₂ tert-alkyl, tri-tert-butylsilyl, trifluoro-tert-butyl, trimethylsilyl,
It is selected from triphenylsilyl and triphenylmethyl groups.

When R ¹ and R ² are different, M (N
R ¹ ) (NR ² ) X ₂ Ls is preferably Mo (NC ₆ H ₃
−2,6-i-Pr ₂ ) (NCMe ₃ ) Cl ₂ (DM
E), Mo (NC ₆ H ₃ -2,6-Me ₂ ) Cl ₂ (DM
E), W (NC ₆ H ₃ -2,6-i-Pr ₂ ) (NCM
e ₃ ) Cl ₂ (DME), Mo (NC ₆ F ₅ ) (NCM
e ₃ ) Cl ₂ (DME), W (NC ₆ F ₅ ) (NCMe ₃ )
Cl ₂ (DME), W (NC ₆ H ₃ -2,6-i-Pr ₂ )
(N-1-adamantyl) Cl ₂ (DME), W (NC ₆
H ₃ -2,6-Cl ₂ ) (NCMe ₃ ) Cl ₂ (DME),
_{W (NC 6 H 3 -2,6-} Cl 2) (NCMe 3) Cl
_{2 (DME), Mo (NC} 6 H 4 -2-tert-CMe 3)
(NCMe ₃ ) Cl ₂ (DME) and Mo (NC ₆ H ₃ −
2,6-Cl ₂ ) (NCMe ₃ ) Cl ₂ (DME). DME is dimethoxyethane.

As a specific example when M is tungsten,
M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) (Structural Formula I)
It is synthesized by reacting (a) a compound having the structure of W (NR ¹ ) (NR ² ) X ₂ Ls with (b) an alkylating agent having R ³ and R ⁴ or a mixture of alkylating agents. Where R ¹ ,
R ² , R ³ and R ⁴ are selected from the group consisting of alkyl, cycloalkyl, polycycloalkyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups, and similar groups including silicon. The same or different groups. X is an alkoxide or aryloxide; L is a Lewis base;
s is 0, 1 or 2.

Good alkylating agents and Lewis bases are as described above. More preferred Lewis bases are te
rt-butylamine. Advantageous alkoxide groups, aryloxides include 2,6-diisopropylphenoxide, 2,6-diphenylphenoxide, triphenylsiloxide, tert-butoxide. Compounds of structural formula I are preferably W (NCMe ₃ ) ₂ (OC
₆ H ₃ -2,6-Ph ₂ ) ₂ , W (NCMe ₃ ) ₂ (OC ₆ H ₃
−2,6-i-Pr ₂ ) ₂ , W (NCMe ₃ ) ₂ (OSi
(C ₆ H ₅ ) ₃ ) ₂ and W (NCMe ₃ ) ₂ (OCMe ₃ ) ₂ .

[0046] used in the synthesis of ^{M (NR 1) (NR 2} ) X 2 Synthesis M (NR ¹⁾ of ^{Ls (NR 2) (R 3} ) (R 4), M (NR 1) (NR 2) X One method of synthesizing ₂ Ls is to use an amine having a structure of H ₂ NR ² and M (NR ¹ ) ₂ X ₂ L
reaction with s. This reaction is preferably performed in a solvent. Good solvents include toluene, dichloromethane, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and diethyl ether.

R ¹ and R ² are preferably 2-bromo-
4,6-dimethylphenyl, 2-chloro-4,6-dimethylphenyl, 2-chloro-4-methylphenyl, 2-
Chloro-5-methoxyphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6-methoxyphenyl, 2-chloro-6-methylphenyl, 2-chlorophenyl, 2-ethylphenyl, 2-isopropylphenyl, 2-methoxyphenyl, 2-methoxy-5-methylphenyl, 2-methyl-2-phenylpropyl, 2-
tert-butyl-6-methylphenyl, 2-tert-butylphenyl, 2-trifluoromethylphenyl, 2-trifluorophenyl, 4-methoxy-2-methylphenyl, 4-methoxyphenyl, 4-methylphenyl, 4-
Phenylphenyl, 4-trifluoromethoxyphenyl, 2,3-dimethylphenyl, 2,4-dichloro-6
-Methylphenyl, 2,4-dimethoxyphenyl, 2,
4-dimethylphenyl, 2,5-dimethylphenyl,
2,5-di-tert-butylphenyl, 2,6-bis (trifluoromethoxy) phenyl, 2,6-bis (trifluoromethyl) phenyl, 2,6-dibromo-4-chlorophenyl, 2,6-dibromo -4-methylphenyl,
2,6-dibromo-4-tert-butylphenyl, 2,6
-Dibromo-4-tert-octylphenyl, 2,6-dibromophenyl, 2,6-dichloro-4-methylphenyl, 2,6-dichloro-4-methylsulfonylphenyl, 2,6-dichloro-4-tert- Butylphenyl,
2,6-chloro-4-tert-octylphenyl, 2,6
-Dichlorophenyl, 2,6-diisopropylphenyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl, 2,6-diphenylphenyl, 3,5-bis (trifluoromethoxy) phenyl, 3,4-diethoxyphenyl , 3,4-dimethoxyphenyl, 3,4-dimethylphenyl, 3,5-bis (trifluoromethyl)
Phenyl, 3,4,5-trimethoxyphenyl, 2,
4,6-trimethylphenyl, 4-sec-butylphenyl, 4-ethylphenyl, 5-fluoro-2-methylphenyl, adamantyl, benzyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclopropyl, dodecylphenyl, ethyl, hexafluoro-tert -Butyl,
Isopropyl, methyl, naphthyl, norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, perfluoro-2-methyl-2-pentyl, perfluoro-tert-butyl, phenyl, tert-
Butyl, tert-octyl, C ₁₂ -C ₁₄ tert-alkyl,
C ₁₆ -C ₂₂ tert-alkyl, tri-tert-butylsilyl, trifluoro-tert-butyl, trimethylsilyl,
It is selected from triphenylsilyl and triphenylmethyl groups.

When R ¹ and R ² are different, the amine H ₂
NR ² is preferably an alkyl or arylamine. To make R ¹ an alkyl group, the amine reagent H ₂ NR ²
May be an alkyl or arylamine. In this case, the amine reagent H ₂ NR ² is preferably tert-butylamine,
It is selected from adamantylamine, isopropylamine, cyclohexylamine, benzylamine, 2,6-dimethylaniline, 2,6-dichloroaniline, pentafluoroaniline, and 2,6-diisopropylaniline. R
^{When 1} is an aryl group, the preferred amine is an arylamine. More preferred amines are 2,6-dimethylaniline, 2,6-dichloroaniline, pentafluoroaniline, and 2,6-diisopropylaniline.

The amine is chosen according to its acidity. Acidity is defined by the degree of ease of electron separation. p
The Ka scale is a convenient measure of the strength of the acid-base. As the value of pKa increases, the acid weakens. The definitions of Ka and pKa are “pKa, P
redaction for Organic Aci
ds and Bases ", DD Perrin,
B. Demspeyand E.A. P. Serjean
t, Chapman and Hall (1981). Amine H ₂ NR ² for a typical reaction
Is preferably more acidic than H ₂ NR ¹ . Here, H ₂ NR ¹ is the first imide bond, M =
An amine derived from NR ^1. In general, simple arylamines are more acidic than alkylamines and are therefore preferred reagents. Although the reaction can be carried out using only an amine, it is more preferable to use a solvent.

As a preferred specific example, Mo (NC ₆ H ₃
−2,6-Cl ₂ ) (NCMe ₃ ) Cl ₂ (DME)
2,6-Dichloroaniline is converted to Mo (NCMe ₃ ) ₂ Cl ₂
(DME) and dimethoxyethane (DME). M (NC ₆ H ₃ -2,6-i-P
r ₂ ) (NCMe ₃ ) Cl ₂ (DME) converts 2,6-diisopropylaniline to Mo (NCMe ₃ ) ₂ Cl ₂ (DM
It is obtained by reacting E) with dimethoxyethane.

Alternatively, M (NR ¹ ) (NR ² ) X ₂
Ls (R ¹ and R ² are different from each other) is M (NR ¹ ) ₂ X ₂ L
It is synthesized by reacting s with M (NR ² ) ₂ X ₂ Ls in a solvent. Coordinating solvents are preferred. In this system, convenient solvents include toluene, dichloromethane, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and diethyl ether. X is preferably chlorine or bromine. M (NR ¹ ) ₂ X ₂ Ls and M (NR ² ) ₂ X ₂ Ls are preferably W (NCMe ₃ )
₂ Cl ₂ (DME), Mo (NCMe ₃ ) ₂ Cl ₂ (DM
E), W (NCMe ₃ ) ₂ Br ₂ (DME), Mo (NC
Me ₃ ) ₂ Br ₂ (DME), Mo (NC ₆ H ₃ -2,6-
i-Pr ₂ ) ₂ Cl ₂ (DME), W (NC ₆ H ₃ -2,6
-I-Pr ₂ ) ₂ Cl ₂ (DME), Mo (NC ₆ H ₃ −
2,6-i-Pr ₂ ) ₂ Br ₂ (DME), W (NC ₆ H ₃
−2,6-i-Pr ₂ ) ₂ Br ₂ (DME), Mo (NC _{6
H 4 -2-tert-CMe 3} ) Cl 2 (DME), W (NC 6
_{H 4 -2-tert-CMe 3} ) 2 Cl 2 (DME), Mo (N
_{C 6 H 4 -2-tert-} CMe 3) 2 Br 2 (DME), W
_{(NC 6 H 4 -2-tert} -CMe 3) is selected from among ₂ Br ₂ (DME).

Preferred Product M (NR ¹ ) (NR ² ) X ₂
Ls is expressed as Mo (NC ₆ H ₃ -2,6-i-Pr ₂ ) (NC
Me ₃ ) Cl ₂ (DME), Mo (NC ₆ H ₃ -2,6-i
-Pr ₂ ) (NCMe ₃ ) Br ₂ (DME), W (NC ₆ H
_{3 -2,6-i-Pr 2)} (NCMe 3) Cl 2 (DM
E), Mo (NC ₆ H ₃ -2,6-Cl ₂ ) (NCMe ₃ )
_{Cl 2 (DME), W (} NC 6 H 3 -2,6-Cl 2) (N
−1-adamantyl) Cl ₂ (DME), Mo (NC ₆ H)
₅ ) (NCMe ₃ ) Cl ₂ (DME), Mo (NC ₆ H ₃ −
2,6-i-Pr ₂ ) (N-1-adamantyl) Cl
₂ (DME), Mo (NC ₆ F ₅ ) (NCMe ₃ ) Cl
₂ (DME) or _{Mo (NC 6 H 4 -2-} tert-CM
e ₃ ) (NCMe ₃ ) Cl ₂ (DME).

A third method for synthesizing M (NR ¹ ) (NR ² ) X ₂ Ls is to use molybdate and (1) NH ₂ R ¹
Or a 1: 1 mixture of an amine of NH ₂ R ² or an amine compound having a structural formula selected from trimethylsilylamine derivatives of (CH ₃ ) ₃ SiNHR ¹ and (CH ₃ ) ₃ SiNHR ² , (2) It is carried out by mixing with a dehydrogenating agent, (3) a trifluoroting agent or a halogenating agent and (4) a solvent, and heating the resulting mixture to complete the reaction. The molybdate is preferably sodium, ammonium or alkyl ammonium molybdate, more preferably [HN (C ₁₂ H ₂₅ ) ₃ ] ₄ (Mo ₈
O ₂₆ ) or [CH ₃ N (C ₁₂ H ₂₅ ) ₃ ] ₄ (Mo
₈ O ₂₆ ). In this system, the amines R ¹ NH ₂ and R ² NH ₂ are adamantylamine, cyclohexylamine, tert-butylamine, trimethylsilylmethylamine, aniline, pentafluoroaniline, 2,6-dichlorophenylaniline, 2,6-diisopropylaniline , 2,6-dimethylaniline and 2-tert-butylaniline are preferred, and R ₁ and R ₂ are preferably different.

Useful dehydrogenating agents are triethylamine, pyridine and substituted pyridine. A preferred fluorinating agent is Me ₃ SiSO ₃ CF ₃ , where Me is a methyl group. Preferred halogenating agents are trimethylsilyl chloride and trimethylsilyl bromide.

As a solvent for the reaction, a Lewis base such as tetrahydrofuran, pyridine, 4,4'-dimethyl-2,2'-bipyridine, 1,10-phenanthroline, 2,2'-dipyridine, quinuclidine, PR ₃ or A phosphorus compound having a structure of R ₂ PCH ₂ CH ₂ PR ₂ (where R is an alkyl group or a substituted or unsubstituted aryl or aralkyl group), diglyme, RN = CH—C
1,4-diaza-1,3-butadiene having a structure of H = NR (where R is an alkyl group or a substituted or unsubstituted aryl or aralkyl group), or a non-coordinating compound such as toluene, dichloromethane or trichloromethane An aprotic solvent can be used.

The tungsten imide complex W (NR ¹ ) (N
R ² ) X ₂ Ls cannot be easily synthesized from tungstate. However, these compounds are prepared by reacting the arylimide complex W in the presence of a dehydrogenating agent, a Lewis base and a solvent.
(NR ¹ ) X ₄ (where X is a halogen) and amine R ² NH ₂
Can be synthesized by reacting X is preferably chlorine or bromine.

For example, [W (NC ₆ H ₃ -2,6-i-P
r ₂₎ Cl _{4] 2} is in diethyl ether, dimethoxyethane presence tert- butylamine (NH ₂ CMe ₃₎ reacting at room _{temperature, W (NC 6 H 3 -2,6} -i-Pr 2) (NC
Me ₃ ) Cl ₂ (DME) is provided. R ¹ is preferably phenyl, a substituted phenyl group, or a fused aromatic hydrocarbon. Phenyl, naphthyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, pentafluorophenyl, 2,6-dichlorophenyl or 2-
Tert-butylphenyl is most preferred. H ₂ NR ² can be selected from aromatic or alkylamine;
² is adamantyl, tert-butyl, cyclohexyl,
Phenyl, naphthyl, 2,6-dimethylphenyl, 2,
6-Diisopropylphenyl, pentafluorophenyl, 2,6-dichlorophenyl or 2-tert-butylphenyl is preferred.

Preferred Lewis bases include tetrahydrofuran, dimethoxyethane, pyridine, 4,4'-dimethyl-2,2'-bipyridine, 1,10-phenanthroline, 2,2'-dipyridine, quinuclidine, PR ₃
Or a phosphorus compound having a structure of R ₂ PCH ₂ CH ₂ PR ₂ (where R is an alkyl or aryl group), diglyme, 1,4-diaza-1,3-butadiene having a structure of RN = CH—CH = NR (Where R is an alkyl or a substituted or unsubstituted aryl or aralkyl group), for example, N, N'-di-tert-butylethylenediimine.

Although any dehydrogenating agent can be used, triethylamine, t-butylamine, adamantylamine,
Pyridine and substituted pyridine are preferred.

Convenient solvents include, for example, diethyl ether, toluene, tetrahydrofuran, dimethoxyethane.

(R ⁷ CH =) M (NR ¹ ) (GR ⁵ ) (G
Synthesis of R ⁶ ) (NH ₂ R ² ) In the present invention, a novel synthesis of an M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) compound (Structural Formula I) as a compound capable of olefin metathesis reaction The use of the method is also included. These compounds capable of olefin metathesis reaction (olefin metathesis catalyst) are (R ⁷ CH =) M (NR ¹ ) (GR
⁵ ) having the structure of (GR ⁶ ) (NH ₂ R ² ) (Structural Formula II); Where M is tungsten or molybdenum; N is nitrogen; R ¹ , R ² , R ⁵ , and R ⁶ are alkyl, cycloalkyl,
Polycycloalkyl, haloalkyl, haloaralkyl,
A substituted or unsubstituted aryl or aralkyl group,
And the same or different groups selected from the group consisting of: G is
An oxygen, sulfur or amide (NH) group, wherein R ⁷ is selected from alkyl, substituted or unsubstituted aryl or aralkyl groups, and similar groups including silicon. When M is molybdenum and R ¹ and R are the same, R ³ and R ⁴ are preferably different.

Compounds of structural formula II can be prepared by (a) M (N
R ¹ ) (NR ² ) (R ³ ) (R ⁴ ) (where R ¹ , R ² , R ³
And R ⁴ are the same or different and are selected from the group consisting of alkyl, cycloalkyl, polycycloalkyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl groups, and similar groups including silicon. Group. ) Is converted to the imide group N of M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) in the solvent (b).
Synthesized by contacting one of R ¹ or NR ² with a hydrogen source capable of hydrogenating to form an amine R ¹ NH ₂ or R ² NH ₂ . Preferred as hydrogen sources are alcohols, anilines, phenols,
Silanols, thiols, thiophenols, diols or mixtures thereof are used. When the hydrogen source is alcohol, perfluoro-tert-butanol, hexafluoro-tert-butanol, perfluoro-2-methyl-2-pentanol and hexafluoroisopropanol are preferred.

When the hydrogen source is phenol, 2-chloro-4-nitrophenol, 2-chloro-phenol,
2-ethylphenol, 2-methoxy-4-nitrophenol, 2-naphthol, 2-tert-butylphenol, 2-trifluoromethylphenol, 3-iodophenol, 4-fluorophenol, 4-chloro-3-
Nitrophenol, 4-chlorophenol, 4-iodophenol, 4-methoxyphenol, 4-methylsulfonylphenol, 4-nitrophenol, 4-phenylphenol, 4-trifluoromethoxyphenol, 4-trifluoromethylphenol, 6- Bromo-
2-naphthol, 1,6-dibromo-2-naphthol,
2,3-dimethylphenol, 2,4-dichloro-6
Methylphenol, 2,4-dichlorophenol, 2,
6-bis (trifluoromethyl) phenol, 2,6-
Dibromo-4-methylphenol, 2,6-dibromo-
4-tert-butylphenol, 2,6-dibromo-4-
tert-octylphenol, 2,6-dibromophenol, 2,6-dichloro-4-methylphenol, 2,6
-Dichloro-4-methylsulfonylphenol, 2,
6-dichloro-4-nitrophenol, 2,6-dichloro-4-tert-butylphenol, 2,6-dichloro-
4-tert-octylphenol, 2,6-dichlorophenol, 2,6-difluorophenol, 2,6-diisopropylphenol, 2,6-dimethyl-4-nitrophenol, 2,6-diphenylphenol, 3,5-
Bis (trifluoromethyl) phenol, 2,4,6-
Trimethylphenol, pentabromophenol, pentachlorophenol, pentafluorophenol, phenol, tert-octylphenol, and nonylphenol are preferred.

When the hydrogen source is thiophenol, thiophenol, 2,4,6-triisopropylbenzenethiol, 2,6-diisopropylbenzenethiol,
2,6-dichlorobenzenethiol and 2,6-dichlorothiophenol are preferred.

Suitable solvents include, for example, pentane,
Hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, cyclooctane,
Decalin, benzene, chlorobenzene and toluene are mentioned.

In the compound of structural formula II, R ⁵ , R
⁶ is tert-butyl, phenyl, 2,4-dichlorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-
Methoxyphenyl, 2,6-diisopropylphenyl,
2,4,6-trimethylphenyl, pentafluorophenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-difluorophenyl, tert-octylphenyl, pentachlorophenyl, 4-methylsulfonylphenyl, 2- Chloro-4-nitrophenyl, 4-
Iodophenyl, 4-trifluoromethoxyphenyl,
A 4-trifluoromethylphenyl, 4-phenylphenyl, 2-naphthylphenyl or 3,5-bis (trifluoromethyl) phenyl group is preferred.

In the compound of formula II, R ¹ , R
² is tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, perfluoro-tert-butyl, neophyl, perfluoro-2-methyl-2-pentyl, phenyl, 2,6-dimethylphenyl, 2,6
-Diphenylphenyl, 2,4,6-trimethylphenyl, pentafluorophenyl, trimethylsilyl, tri-tert-butylsilyl, triphenylsilyl, 2,6-
A diisopropylphenyl group is preferred. R ³ and R ⁴ are preferably a methyl, benzyl, substituted benzyl, cyclohexyl, cyclopentyl, norbornyl, neophyl or trimethylsilylmethyl group.

[0068] Specifically, in the compound of structural formula II, in G is oxygen, when R ^1, R ² are different, R ^1, R
² is tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, perfluoro-tert-butyl, neophyl, perfluoro-2-methyl-2-pentyl, phenyl, 2,6-dimethylphenyl, 2,6
-Dichlorophenyl, 2,6-diphenylphenyl,
2,4,6-trimethylphenyl, pentafluorophenyl, trimethylsilyl, tri-tert-butylsilyl,
Triphenylsilyl and 2,6-diisopropylphenyl groups are preferred.

R ³ and R ⁴ are preferably methyl, benzyl, neopentyl, neophyl and trimethylsilyl,
R ⁵ and R ⁶ are phenyl, pentafluorophenyl, tert-
Butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, perfluoro-tert-butyl, neophyl, perfluoro-2-methyl-2-pentyl, 3,
5-bis (trifluoromethyl) phenyl, 2-chlorophenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-dichlorophenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, Trimethylsilyl, tri-tert-butylsilyl, triphenylsilyl and 2,6-diisopropylphenyl groups are preferred.

M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ )
Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ )
(CH ₂ CMe ₃ ) (CH ₂ CMe ₂ Ph), W (NCMe)
₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ CMe ₃ )
(CH ₂ CMe ₂ Ph), Mo (NCMe ₃ ) (NC ₆ H ₃
−2,6-i-Pr ₂ ) (CH ₂ CMe ₂ Ph) (CH ₂ P
h), W (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-P
r ₂ ) (CH ₂ CMe ₂ Ph) (CH ₂ Ph), W (N−1)
-Adamantyl) (NC ₆ H ₃ -2,6-i-Pr ₂ )
(CH ₃ ) (CH ₂ Ph), Mo (NCMe ₃ ) (NC ₆ H
_{3 -2,6-Cl 2) (CH} 2 SiMe 3) (CH 2 CMe 2
Ph), Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) (C
H ₂ Ph), W (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph)
(CH ₂ CMe ₃ ), Mo (NC ₆ H ₃ -2,6-i-Pr
₂ ) ₂ (CH ₂ CMe ₂ Ph) (CH ₂ CMe ₃ ), W (NC
_{6 H 3 -2,6-i-Pr} 2) 2 (CH 2 CMe 2 Ph) (C
H ₂ CMe ₃ ), Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6
-I-Pr ₂ ) (CH ₂ CMe ₂ Ph) ₂ , W (NCM
e ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ CMe ₂
Ph) ₂ , Mo (N-1-adamantyl) (NC ₆ H ₃ −
2,6-i-Pr ₂ ) (CH ₂ CMe ₂ Ph) ₂ , W (N-
1-adamantyl) (NC ₆ H ₃ -2,6-i-Pr ₂ )
(CH ₂ CMe ₂ Ph) ₂ , Mo (NCMe ₃ ) (NC ₆ H ₃
−2,6-i-Pr ₂ ) (CH ₃ ) ₂ , W (NCMe ₃ )
(NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₃ ) ₂ , Mo
(NC ₆ F ₅ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH _{2
CMe 2 Ph) 2, Mo (} NCMe 3) (NC 6 H 3 -2,
6-i-Pr ₂ ) (CH ₃ ) ₂ , Mo (NCMe ₃ ) (NC
_{6 H 3 -2,6-Cl 2)} (CH 2 CMe 2 Ph) 2, Mo
(NC ₆ F ₅ ) (NCMe ₃ ) (CH ₂ CMe ₂ Ph) ₂ or W (NC ₆ F ₅ ) (NC ₆ H ₃ -2,6-i-Pr ₂ )
(CH ₂ Ph) ₂ is preferred.

When R ⁵ and R ⁶ are the same, R ⁵ and R ⁶ are
Phenyl, pentafluorophenyl, tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, perfluoro-tert-butyl, neophyl, perfluoro-2-methyl-2-pentyl, 3,5-bis ( (Trifluoromethyl) phenyl, 2-chlorophenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-dichlorophenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, trimethylsilyl, tri- Preferred are tert-butylsilyl, triphenylsilyl and 2,6-diisopropylphenyl groups.

A specific example of a process for synthesizing a compound of structural formula II is that M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) is Mo
(NCMe ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH
₂ CMe ₂ Ph) ₂ , the hydrogen source is pentafluorophenol, and the compound to be isolated is (PhMe ₂ C)
CH =) Mo (NC ₆ H ₃ -2,6-i-Pr ₂ ) (OC ₆
F ₅ ) ₂ (NH ₂ CMe ₃ ) or M (NR ¹ )
(NR ² ) (R ³ ) (R ⁴ ) is Mo (NCMe ₃ ) ₂ (CH ₂
CMe ₂ Ph) ₂ , the hydrogen source is pentafluorophenol, and the compound to be isolated is (PhMe ₂ CC)
H =) Mo (NCMe ₃ ) (OC ₆ F ₅ ) ₂ (NH ₂ CM
e ₃ ). The reaction product may be in the solvent as it is, or may be isolated as a solid by removing the solvent by distillation.

Activation of Catalyst Precursor The conversion of the catalyst precursor (Structural Formula I) to an active olefin metathesis catalyst (Olefin Metathesis Polymerizable Compound) can be accomplished by converting the catalyst precursor (Structural Formula I) to a suitable acidic hydrogen supply. Occurs when mixed with a source activator. In this system, an activator is a compound that, when combined with a catalyst precursor, directly provides an olefin metathesis catalyst without further chemical separation or manipulation. Generally, as a hydrogen source, an alcohol (ROH) capable of hydrogenating one of the imide groups of M (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ),
Phenol (ArOH), Silanol (R ₃ SiO
H), thiol (RSH), thiophenol (ArS
H) and diols (HO-Z-OH) such as catechol (HOArOH), dialcohol, bisphenol ((HOArArOH), or binaphthol, where Z is an organic radical), many substituted phenols, halogenated Alcohols hydrogenate imide ligands to promote their elimination, causing the elimination of α-hydrogen and the formation of alkylidene ([M] = CHR ⁷ ) .Olefin metathesis catalyst (olefin metathesis polymerizable compound)
A preferred way to vary the rate of formation of is to select an activator for the catalyst precursor based on acidity. Also, the reaction rate can be controlled using activator mixtures with different acidities. The choice of activator can also be based on the size of the substituents, in addition to the acidity. In the case of phenol, there is no substituent at the 2,6 position, or only one of the 2,6 positions is substituted, or even if it is substituted, a small substituent such as F is
Any of the substituents at positions 2 and 6 of the aromatic ring is preferred. The most preferred phenol reagent is 3,
It is substituted at the 4- and 5-positions. Examples of this type include 2-chlorophenol, 3-chlorophenol, 4-fluorophenol, 2,6-difluorophenol, 4-chlorophenol, 4-trifluoromethoxyphenol, 4-trifluoromethylphenol,
There are 4-methylsulfonylphenol, 4-nitrophenol, pentafluorophenol and 3,5-bis (trifluoromethyl) phenol.

While acidity is the preferred method of choosing an activator, it may be necessary to adjust the reaction temperature to achieve the required conversion and reactivity. The pKa value of the activator is desirably 11 or less.
It is more preferably at most 6, and most preferably at most 6. Higher pKa values of the activator require higher temperature conditions. The exact temperature and reaction conditions required for the system of catalyst precursor and activator can be readily determined by one skilled in the art.

Preferred alcohols and phenols have electron withdrawing groups and are highly acidic compounds. Any substituent can be used as long as it does not cause an interaction with the newly formed alkylidene.
Preferred alcohols and phenols include 2-chloro-4-nitrophenol, 2-chlorophenol, and 2-chlorophenol.
Ethylphenol, 2-methoxy-4-nitrophenol, 2-naphthol, 2-tert-butylphenol, 2
-Trifluoromethylphenol, 3-iodophenol, 4-fluorophenol, 4-chloro-3-nitrophenol, 4-chlorophenol, 4-iodophenol, 4-methoxyphenol, 4-methylsulfonylphenol, 4-nitrophenol , 4-phenylphenol, 4-trifluoromethoxyphenol, 4-
Trifluoromethylphenol, 6-bromo-2-naphthol, 1,6-dibromo-2-naphthol, 2,3-
Dimethylphenol, 2,4-dichloro-6-methylphenol, 2,4-dichlorophenol, 2,6-bis (trifluoromethyl) phenol, 2,6-dibromo-4-methylphenol, 2,6-dibromo- 4-tert
-Butylphenol, 2,6-dibromo-4-tert-octylphenol, 2,6-dibromophenol, 2,
6-dichloro-4-methylphenol, 2,6-dichloro-4-methylsulfonylphenol, 2,6-dichloro-4-nitrophenol, 2,6-dichloro-4-
tert-butylphenol, 2,6-dichloro-4-tert
-Octylphenol, 2,6-dichlorophenol,
2,6-difluorophenol, 2,6-diisopropylphenol, 2,6-dimethyl-4-nitrophenol, 2,6-diphenylphenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6- Trimethylphenol, pentabromophenol, pentachlorophenol, pentafluorophenol, phenol,
There are tert-octylphenol and nonylphenol,
Preferred thiols include 2,4,6-triisopropylbenzenethiol, 2,6-diisopropylbenzenethiol, and 2,6-dichlorobenzenethiol.

The diol ligand (O—Z—O) (where Z
Is an organic radical) can replace (OR ⁵ ) (OR ⁶ ) of the compound of structural formula II when G is oxygen. These ligands include, for example, bisphenolate, catecholate, binaphthalate and dialcolate ligands. 3,5-di-tert-butylcatechol,
Catechol, binaphthol, pinacol (HOC (CH
₃ ) ₂ C (CH ₃ ) ₂ OH), perfluoropinacol (H
_{OC (CF 3) 2 C (} CF 3) 2 OH), benzopinacol, 2,2'-biphenol, 2,2'-methylenebis (4-chlorophenol) and 2,2'-thiobis (4-
Chlorophenol) is preferred.

The activation reaction can be carried out over a wide temperature range and is carried out between about -40 ° C and about 200 ° C. More preferably between about 0 ° C. and about 150 ° C., even more preferably between about 40 ° C. and about 120 ° C., which can be selected depending on the pKa value of the rate regulator.

The molar ratio of activator to metal of the catalyst precursor is from about 0.5 to about 6, more preferably 2 to 6.
~ 3. More preferably, it is approximately 2. If a diol is used as the activator, the molar ratio of catalyst precursor to activator can be between 1: 0.5 and 1: 2, preferably from 1: 0.75 to 1: 0.75. 1: 1.5, more preferably between 1: 0.9 and 1: 1.1.

The olefin metathesis catalyst (olefin metathesis polymerizable compound) is used as the catalyst precursor M (NR ¹ )
A metathesis reaction can be generated by simply mixing (NR ² ) (R ³ ) (R ⁴ ) with the activator to form a reaction product, and immediately mixing with the olefin. Also,
This olefin metathesis catalyst (olefin metathesis polymerizable compound) can be stored in an inert solvent and used later. Olefin metathesis catalysts (olefin metathesis polymerizable compounds) can also be formed in situ by mixing the catalyst precursor with the olefin or solvent in a test tube and immediately adding the activator. An advantage of the method of preparing an olefin metathesis catalyst (olefin metathesis polymerizable compound) in advance is that the amount of the generated catalyst can be determined before the olefin metathesis reaction. This reaction can also be controlled by the addition of a suitable Lewis base.

Whether the catalyst precursor is generated in situ or the catalyst precursor is prepared in advance, the reaction flow containing neither the catalyst precursor nor the olefin metathesis catalyst (olefin metathesis polymerizable compound) is Can be heated to a temperature higher than the decomposition temperature.
This method is superior to other methods because higher temperatures accelerate the olefin metathesis reaction. The lowest temperature limit of the reaction stream is determined by the freezing point of the composition used. The limit of the maximum temperature of the reaction stream is determined by the thermal stability of the monomers used.

Olefin Metathesis Reaction The catalyst composition of the present invention comprises a single olefin or
Useful for mixed olefin metathesis reactions. The term "metathesis reaction" includes metathesis reactions of simple olefin compounds, ADMET, ROMP, ring closure, and decomposition reactions of polymers.

In selecting an olefin metathesis catalyst precursor in the ADMET field, the molar ratio of monomer to catalyst precursor is about 50: 1 to 10,000: 1,
The most preferred range is from about 100: 1 to 1,000: 1.
It is. In the case of a metathesis reaction of a simple olefin compound such as methyl olefin or cis-2-pentene,
The smaller the molar ratio of monomer to olefin metathesis catalyst precursor, the better, for example, about 50:
1 to 500: 1.

The catalyst precursor M (NR ¹ ) (NR ² )
In the structure of (R ³ ) (R ⁴ ), R ¹ and R ² are 2-chlorophenyl, 2-methoxyphenyl, 2-methyl-2-
Phenylpropyl, 2-tert-butylphenyl, 4-methoxyphenyl, 4-methylphenyl, 4-phenylphenyl, 4-trifluoromethoxyphenyl, 2,6-
Dibromophenyl, 2,6-dichlorophenyl, 2,6
-Diisopropylphenyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, adamantyl, benzyl, cyclohexyl, ethyl, hexafluoro-tert-butyl, isopropyl , Methyl, naphthyl,
Norbornenyl, pentabromophenyl, pentachlorophenyl, pentafluorophenyl, pentafluoro-
It is preferably selected from 2-methyl-2-phenyl, perfluoro-tert-butyl, tert-butyl, phenyl, trifluoro-tert-butyl, trimethylsilyl, triphenylmethyl and triphenylsilyl groups.

R ³ and R ⁴ are methyl, substituted or unsubstituted benzyl, neophyl, neopentyl, cyclopentyl, cyclohexyl, cyclopropyl, cyclobutyl,
It is preferred to choose from substituted or unsubstituted phenyl, norbornenyl, dicyclopentenyl and trimethylsilyl groups.

As the catalyst precursor, Mo (NCM
e_Three)_Two(CH_Three)_Two, Mo (NCMe _Three)_Two(CH_TwoP
h)_Two, Mo (NCMe_Three)_Two(CH_TwoCMe_Three)_Two, Mo
(NCMe_Three)_Two(CH_TwoSiMe_Three)_Two, Mo (NCM
e_Three)_Two(CH_TwoCMe_TwoPh)_Two, W (NCMe_Three)_Two(C
H_TwoPh)_Two, W (NCMe_Three)_Two(CH_TwoCMe_Three)_Two, M
o (NCMe_Three)_Two(CH_TwoSiMe_Three)_Two, W (NCM
e_Three)_Two(CH_TwoCMe_TwoPh)_Two, Mo (NC₆H_Three−2,
6-i-Pr_Two) (NCMe_Three) (CH_TwoCMe_TwoP
h)_Two, W (NC₆H_Three−2,6-i-Pr_Two) (NCMe
_Three) (CH_TwoCMe_TwoPh)_Two, Mo (NC₆H_Three−2,6-
i-Pr_Two) (NCMe_Three) (CH_TwoPh)_Two, W (NC₆
H_Three−2,6-i-Pr_Two) (NCMe_Three) (CH_TwoPh)
_Two, Mo (NC₆H_Three−2,6-i-Pr_Two) (NCM
e_Three) (CH_TwoCMe_TwoPh)_Two, W (NC₆H_Three−2,6-
i-Pr_Two) (NCMe_Three) (CH_TwoCMe_Three)_Two, Mo
(NC₆H_Five)_Two(CH_Three)_Two, Mo (NC₆H_Three−2,6-
Cl_Two)_Two(CH_Three)_Two, Mo (N-1-adamantyl)_Two
(CH_Three)_Two, Mo (NC₆H_Three−2,6-i-Pr_Two)
_Two(CH_Three)_Two, W (NCMe_Three)_Two(CH_Three)_Two, W (NC₆
H_Three−2,6-i-Pr_Two)_Two(CH_Three)_Two, W (NC₆H_Three
−2,6-i-Pr_Two)_Two(CH_TwoCMe_TwoPh)_Two, Mo
(NC₆H_Three−2,6-i-Pr_Two)_Two(CH_TwoCMe_TwoP
h)_Two, W (NC₆H_Three−2,6-i-Pr_Two)_Two(CH_TwoC
Me_Three)_TwoAnd Mo (NC₆H_Three−2,6-i-Pr_Two) (N
CMe_Three) (CH_TwoCMe_TwoPh)_TwoTo choose from
preferable.

Activating agents include hexafluoroisopropanol, perfluoro-tert-butanol, hexafluoropropanol, 2,6-dichlorothiophenol,
2,6-diisopropylaniline, 2-chloro-4-nitrophenol, 2-chlorophenol, 2-ethylphenol, 2-methoxy-4-nitrophenol, 2-
Naphthol, 2-tert-butylphenol, 2-trifluoromethylphenol, 3-iodophenol, 4-
Fluorophenol, 4-chloro-3-nitrophenol, 4-chlorophenol, 4-iodophenol, 4
-Methoxyphenol, 4-methylsulfonylphenol, 4-nitrophenol, 4-phenylphenol, 4-trifluoromethoxyphenol, 4-trifluoromethylphenol, 6-bromo-2-naphthol, 1,6-dibromo-2- Naphthol, 2,3-dimethylphenol, 2,4-dichloro-6-methylphenol, 2,4-dichlorophenol, 2,6-bis (trifluoromethyl) phenol, 2,6-dibromo-4
-Methylphenol, 2,6-dibromo-4-tert-butylphenol, 2,6-dibromo-4-tert-octylphenol, 2,6-dibromophenol, 2,6-
Dichloro-4-methylphenol, 2,6-dichloro-
4-methylsulfonylphenol, 2,6-dichloro-4-nitrophenol, 2,6-dichloro-4-tert
-Butylphenol, 2,6-dichloro-4-tert-octylphenol, 2,6-dichlorophenol, 2,
6-difluorophenol, 2,6-diisopropylphenol, 2,6-dimethyl-4-nitrophenol,
2,6-diphenylphenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-trimethylphenol, pentabromophenol, pentachlorophenol, pentafluorophenol, phenol, tert
-It is preferred to choose between octylphenol and mixtures thereof.

Preferred materials for the olefin metathesis reaction include acyclic olefins, cyclic olefins, polycyclic olefins and α, ω-diolefins. Representative examples include ethylene, cis-2-pentene, trans-
2-pentene, cis-3-hexene, cis-5-decene, methyl oleate (cis-methyl-9-octadecenoate), ethyl oleate, 4-pentyl acetate, 1-pentadecene, 1-decene, -Methylbutylene, trimethylvinylsilane, allyltrimethylsilane and styrene.

The monomers which are convenient for ADMET include:
1,5-hexadiene, 1,9-decadiene, ethylenediundecenoate, bis (hexenyl) ether,
2,5-dihydrofuran, diallyl ether, diallyldimethylsilane, 4,4,7,7-tetramethyl-4,
7-disiladeca-1,9-diene, 1,4-bis (allyldimethylsilyl) benzene, 1,4-benzenedicarboxic bis (1-hexyl) ester, 1,4-
Benzenedicarboxylic bis (1-pentenyl) ester, 1,4-benzenedicarboxylic bis (1
-Butenyl) ester, 1-hexenyl-1-pentanoate, trivinylcyclohexane, divinylcyclohexane, 1,4-divinylbenzene.

The metathesis reaction can be carried out, for example, in a pentane, hexane, dichloromethane, methylcyclohexane, benzene, chlorobenzene or toluene solvent, and is carried out at a temperature between about 0 ° C. and about 200 ° C. This temperature is more preferably from about 25C to about 150C, even more preferably from about 40C to about 120C.

Metathesis Polymerization Reaction of Cyclic Olefin Using the catalyst composition of the present invention, cyclic olefins can be subjected to metathesis polymerization in high yield by bulk polymerization or solution polymerization. The metathesis polymer can be thermosetting or thermoplastic. The thermoplastic polymer can be repeatedly softened or hardened by increasing or decreasing the temperature, and can be shaped by pouring or extruding the softened state into a mold. Thermoplastic polymers have a linear or branched structure in their molecular structure, but generally dissolve in a specific solvent. Thermoset polymers do not melt or dissolve after being cured by heat or other methods. The crosslinked (or cured) polymer swells with the solvent but does not dissolve without decomposition.

When a comonomer is added to the metathesis polymerization of a cyclic olefin, (a) the glass transition temperature is increased without post-curing, (b) the amount of residual monomer is reduced, and (c) the impact resistance is increased. (D)
In some cases, advantages such as increasing hardness, (e) improving heat distortion temperature, (f) increasing oxidative stability, and (g) reducing odor may be obtained. Also, the freezing point of the monomer solution can be changed.

Preferred cyclic olefins and comonomers are norbornene-type monomers represented by the following structural formula. In the figure, R is hydrogen, C _1-20 alkyl, C
_1-20 alkenyl, aryl groups, and saturated or unsaturated cyclic hydrocarbon groups wherein two R groups are linked by a carbon atom.

[0093]

Embedded image

Specific examples of cyclic olefins and comonomers include endo- or exo-DCPD, symmetric or asymmetric cyclopentadiene trimers or tetramers, higher cyclopentadiene oligomers, 2-norbornene , 1-methyl-2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-butyl-2-norbornene,
5-hexyl-2-norbornene, 7-methyl-2-norbornene, vinylnorbornene, ethylidene norbornene, 5- (2-propenyl) -norbornene, norbornadiene, 5,8-methylene-5a, 8a-dihydrofluorene, exo-trans -Exo-pentacyclo [8.2.1.1.1 ^4,7 . 0 ^2,9 . [0 ^3,8 ] tetradeca-5,11-diene, 5,6-acenaphthalene norbornene, cyclohexenyl norbornene, dimethanohexahydronaphthalene, dimethanooctahydronaphthalene, alkyl-substituted derivatives of these cycloolefins and mixtures thereof.

Other preferred polymerizable olefin metathesisable substances include cyclobutene, cyclobutadiene, cyclopentene, cyclooctene, cycloheptene, cyclododecene, 1,5-cyclooctadiene, cyclododecadiene, cyclododecatriene.

Examples of the addition-polymerizable olefin metathesizable substance include R.I. R. Schrock et al. In Macrom
olecules, Vol. 24, 1991, p. 44
95-4502. R. Schrock is Acco
unts of Chemical Research
h, Vol. 23, 1990, p. 158-165 and T
he Stream Chemiker, Vol. XIV
(No. 1), October 1992, p. 1-
6 (Strem Chemicals Inc.). Monomers having other functional groups include 2-norbornene-5-carbonitrile,
5-norborn-2-yl acetate, 5-exo-methoxycarbonylnorbornene, endo, endo-
5,6-dimethoxynorbornene, 5-endo-methoxycarbonylnorbornene, endo, endo-
5,6-dimethoxynorbornene, 5,6-exo, e
ndo-bis (methoxycarbonyl) norbornene,
5,6-exo, exo-bis (methoxycarbonyl)
Norbornene, 5,6-endo, endo-bis (methoxycarbonyl) norbornene, endo, endo
-5,6-dimethoxynorbornene, endo, end
o-5,6-dicarbomethoxynorbornene, 2,3-
Dimethoxynorbornadiene, 5,6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene, 2,
3-endo-cis-diacetoxy-7-oxanorbornene, 2,3-bistrifluoromethyl-7-oxabicyclo [2.2.1] hepta-2,5-diene,
2,3-dicarbomethoxy-7-oxabicyclo [2.
2.1] Hepta-2,5-diene, 7-oxa-benzonorbornadiene, 2,3-trans-dicyano-7
-Oxanorbornene-5,5-tris (ethoxy) silylnorbornene, 2-dimethylsilylbicyclo [2.
2.1] Hepta-2,5-diene, 2,3-bistrifluoromethylbicyclo [2.2.1] hepta-2,5-
Diene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoroisopropyl-6- (trifluoromethyl) bicyclo [2.2.1] hepta-2-ene, 2,
3,3,4,4,5,5,6-octafluorotricyclo [5.2.1.0] de-8-cene, 2,3-bis (trifluoromethyl) -7-oxabicyclo [2 .2.
1] Hepta-2,5-diene and 5-trifluoromethylbicyclo [2.2.1] hepta-2,5-diene.

The monomer used is desirably of high purity, for example, those having 2% by weight or less of impurities are preferable. DC used mainly in the following examples
PD had a purity of about 98-99% by weight. Other monomers or comonomers used in the experiments of the present invention need to be of similar purity. However, when a suitable tungsten or molybdenum catalyst composition is employed, the catalyst composition of the present invention can be polymerized even though the purity of the olefin metathesizable monomer is somewhat poor.

A preferred process for the solution polymerization reaction is to mix the olefin metathesis catalyst precursor (structural formula I) and the olefin metathesis-capable substance in a hydrocarbon solvent, and then add an activating agent. Preferred catalyst precursors and activators have already been mentioned in the description of the olefin metathesis reaction.

Preferred solvents in the solution polymerization include:
Examples include pentane, hexane, diethyl ether, tetrahydrofuran, dimethoxyethane, benzene and toluene. The resulting polymer need not be soluble in the solvent. The reaction is preferably carried out at about 0 ° C to about 200 ° C,
More preferably, it is carried out at about 25 ° C to about 150 ° C, even more preferably at about 40 ° C to about 120 ° C.

The bulk polymerization of the olefin monomer is carried out in the absence of a solvent. Olefin metathesis catalyst precursor M
By adding an activator to a mixture of (NR ¹ ) (NR ² ) (R ³ ) (R ⁴ ) and an olefin metathesis monomer, polymerization of a cyclic or acyclic olefin is achieved,
For example, it is used for films, fibers, molded products and the like.
M, R ¹ , R ² , R ³ , and R ⁴ are as described above. The polymerizable olefin and the olefin metathesis catalyst precursor are introduced into a mold by injection, resin transfer molding, casting, or adding as a solid. In the case of a solid, the olefin metathesis polymerization is formed by heating the physical mixture of the metathesis polymerizable olefin, the catalyst precursor activator and the olefin metathesis catalyst precursor above the melting temperature and melting to cause the metathesis reaction. You can also get things.

The catalyst precursor activator or olefin metathesis catalyst precursor can also be placed on a solid support before introduction into the mold. Preferred solid carriers include glass beads, glass fibers, molecular sieves or powders thereof, glass mats, carbon fibers. The olefin metathesis catalyst precursor can be introduced as a liquid or a solid in a capsule. When placed in a capsule, it dissolves in the polymerizable monomer or melts under external force.

RIM Conventionally, olefin metathesis polymerization, even when using a catalyst with a controlled reaction rate, is limited to two or more when utilizing the polymerization of a strained olefin because of the very fast reaction rate. RIM technology has been adopted. However, in RIM, the lack of control over the gel time often limits the use to relatively small, relatively simple products. Further, even if the polymerization is controlled such that casting, rotation, and resin transfer molding can be performed, the reaction rate of the monomer may decrease due to a relatively long mold filling time and curing time. Advantages of the catalyst system of the present invention include (i) high polymerization rate, (ii) conversion of monomer into polymer in high yield, (iii) excellent effect in controlling gel time and cure time. And (iv) monomers / catalyst precursors /
The tolerance of the ratio of activator is quite wide, and so on.

The RIM process involves mixing the catalyst system with two or more low-viscosity streams of a composition dissolved in a solvent or polymerizable monomer, and polymerizing the mixed stream with monomers. Injecting into a mold that becomes a solid molded article. Catalyst systems are required to be converted to polymers in high yields. In addition, the polymerization is allowed to mix at its ambient temperature and the polymerization is started at about
Preferably, it starts in a temperature range from about 90C to about 90C.

The RIM process consists of two reactant streams, wherein at least one stream may include a polymerizable monomer. However, if one stream contains the activator of the metathesis catalyst system, the second stream contains the catalyst precursor of the metathesis catalyst system and at least one stream uses a plurality of streams containing polymerizable monomers. Is preferred. The activator and catalyst precursor of the catalyst system may be present in a solvent, but are preferably in a polymerizable monomer or comonomer. Also, RIM
Is an olefin metathesis catalyst (olefin metathesis polymerizable compound) prepared by previously mixing a catalyst precursor and an activator in an inert medium, and a stream of one or more polymerizable monomers at the same time. It is also possible by injection. Solvents such as toluene, other hydrocarbons, waxes and low molecular weight rubbers can be used as the inert medium. Compositions containing catalyst precursors and activators may be sensitive to temperature and air entrainment. Therefore, rather than using a catalyst precursor / monomer or activator / monomer stream, a single stream containing an olefin metathesis catalyst (olefin metathesis polymerizable compound) is used in combination with one or more monomers. It is more advantageous to do so. Alternatively, a previously prepared olefin metathesis catalyst (olefin metathesis polymerizable compound) alone or on a solid support is placed in a mold and reacted with one or more streams of olefin metathesis-capable monomers. It is also possible to make it.

A preferred specific example of RIM is a polymerization reaction of DCPD monomer. This process for obtaining poly DCPD can use one or more streams. For example, in a two-stream process, a ring-opening metathesis polymerization reaction is caused by combining a olefin metathesis catalyst precursor / DCPD stream and an olefin metathesis activator / DCPD stream into a mold. To form a tough, tough thermosetting poly DCPD, a so-called cross-linked resin. The reaction is completed in a short time.
Generally, the mixing of the composition and the polymerization reaction can be performed in a few seconds. The polymerization reaction occurs spontaneously, resulting in a resin with low residual monomer (<1% by weight). The metathesis catalyst precursor and the metathesisable monomer can also be used as one or more streams. Alternatively, the olefin metathesis catalyst precursor can be dissolved in an inert solvent. Such solvents include low viscosity rubbers, for example, other polymers such as cis-1,4-butadiene and polymethylsiloxane.

Commercially available DCPDs are generally of the endo type. However, even with exo-DCPD, e
Even a mixture of ndo and exo can be used. Industrial DCPD is obtained by dimerization of cyclopentadiene. There are several DCPD grades of industrial DCPD, with the preferred purity of commercial DCPD being about 96
% To about 98% by weight. Low purity industrial DC
The advantage of using PD is that it is a common liquid at an ambient temperature of about 20 ° C.

Furthermore, the water content in DCPD should preferably be below 100 ppm. In RIM molding with two (or more) streams, the presence of water can hinder the polymerization reaction by hydrolyzing the composition comprising the catalyst precursor or activator of the catalyst system, or both. In the present invention, only the catalyst precursor is sensitive to water or oxygen. DCPD can be treated with silica, alumina, and / or molecular sieves to remove or reduce interfering impurities. In the present invention, strictly dried DCPD should be used to maximize the conversion of monomer to polymer. That is, the water content is desirably 5 ppm or less. By eliminating water, the molar ratio of monomer to catalyst precursor can be increased. A molar ratio of DCPD: catalyst precursor of 200,000: 1 is possible using this catalyst system.

In some of the current RIM processes, transition metal catalyst precursors using alkylaluminum compositions as cocatalysts require high purity monomers to sufficiently polymerize DCPD. When the catalyst precursor having an imide group and an alcohol or phenol activator according to the present invention are used, industrial DCPD is used.
(DCPD component of about 83% by weight to 95% by weight) can be used. The advantage of the catalyst system in the present invention is that it shows high reactivity even in relatively low-purity DCPD (DCPD component is about 90% to 95% by weight).

Mixtures of DCPD and other cyclic olefin comonomers can likewise be polymerized by the RIM process. In general, the polymerization can be carried out using a wide range of mixtures of these comonomers. Preferably, however, the mixture comprises from about 50% to about 99% by weight DCPD, based on a total weight of 100, and 1%.
% To about 50% comonomer.
The most preferred DCPD and comonomer system is from about 75% to about 99% of a mixture of DCPD and other olefinic hydrocarbon compounds having a strained ring.

In RIM of metathesis polymerizable olefin monomers, the molar ratio of monomer to catalyst precursor is 10
0: 1 to 200,000: 1, preferably 2
The ratio is from 00: 1 to 20,000: 1, and more preferably from 500: 1 to 5,000: 1. In the reaction of polycyclic cycloolefins such as DCPD, the molar ratio of monomer to olefin metathesis precursor is from 100: 1 to 200,000: 1, preferably from 100: 1 to 20,000: 1. And more preferably from 1500: 1 to 6,000: 1.

The RIM of the present invention may be, for example, a filler,
It can be carried out in the presence of additives such as fibers, antioxidants, flame retardants, reinforcing agents, pigments, plasticizers. Furthermore, in order to obtain desired properties, additives such as solvents, swelling agents, fillers, pigments, antioxidants, light stabilizers, plasticizers, foaming agents, reinforcing agents, reactive modifiers, viscosity modifiers, etc. It is also possible for various compositions, such as, to be present in the reaction mixture during the polymerization. In particular, it is preferred to add about 1 to 15% by weight of elastomer, based on the weight of monomer, to improve the impact resistance of the resin. These compositions comprise one or more reaction mixture streams in monomers as components of a stream.
It is most convenient to add it in the form of a liquid or a solution.

[0112] In some embodiments of the present invention, elastomers can be added to the reaction system to improve the impact resistance of the resin. The elastomer component is dissolved in one or more of the reaction mixture streams such that the loading is from about 1 to 15% by weight based on the weight of monomer. Suitable elastomers include, for example, saturated and unsaturated hydrocarbon elastomers, preferably raw rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene butadiene styrene-triblock rubber, random styrene butadiene rubber Styrene-isoprenestyrene-triblock rubber, ethylene-propylene-diene terpolymer, ethylene vinyl acetate, and nitrile rubber.
Also, other polar rubbers can be used. The amount of elastomer added is determined by its molecular weight and is limited by the viscosity of the final composition stream.

In one embodiment of the present invention, substantially,
A polymerized structural unit of DCPD polymerized by an olefin metathesis catalyst (olefin metathesis polymerizable compound);
At least 13 comprising a blend of a thermoplastic resin containing 1% to 10% by weight of a hydrocarbon elastomer.
A molded article having a heat distortion temperature of 5 ° C. is obtained. here,
The hydrocarbon elastomer may be a saturated or unsaturated elastomer.

In the RIM, the use of a Lewis base reaction rate regulator can be appropriately selected. With this use, the gelation time and the cure time can be controlled. The reaction rate regulator prevents the polymerization process from proceeding too fast,
Allows for thorough mixing of the catalyst precursor and activator. Further, the inside of the mold can be sufficiently filled. The reaction rate regulator in the present invention is preferably a Lewis base, and is disclosed in U.S. Pat. No. 4,727,125, 4,883,843.
9 and 4,933,402.

Preferred examples of Lewis base reaction rate regulators include tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dimethoxyethane, trimethylphosphine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine and methyl. Diphenyl phosphine, dimethyl phenyl phosphine, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, triphenyl phosphite, triisopropyl phosphine, tri-tert-
Butylphosphine, diethylphenylphosphonite, tribenzylphosphine, tert-butylamine,
Pyridine, pyrazine, 2,2'-bipyridine, 4,4 '
-Dimethyl-2,2'-bipyridine, 1,10-phenanthroline, quinonuclidine or RN = CH-CH
1,4-diaza-1,3-butadiene having the structure ＝ N—R (where R is an alkyl, substituted or unsubstituted aryl or aralkyl group), for example, N, N′-di-
t-butylethylenediimine. Phosphorus chelating agents include (R) ₂ P (CH ₂ ) _n P (R) ₂
Can also be used. Here, n is 1 or more and R is aryl or alkyl.

DCPD can be polymerized by RIM or other polymerization methods by using the activated catalyst precursor of the present invention. Resin monomers of the resins obtained by these molding methods are generally low (<1.0% by weight, preferably <0.5% by weight). 80% or more of the metathesis polymer composed of poly DCPD polymerized with the catalyst precursor of the present invention or the olefin metathesis catalyst (olefin metathesis polymerizable compound) is particularly molybdenum.
The amount of metal due to the catalyst can be about 8 ppm or less. A metathesis polymer of DCPD substantially consisting of polymerized structural units of DCPD polymerized by an olefin metathesis catalyst (olefin metathesis polymerizable compound) has a heat distortion temperature of at least 135 ° C and a glass transition point of at least 172 ° C. You can also. These polymers, particularly in the case of molybdenum, may have a total metal content from the catalyst of about 8 ppm or less and may contain little or no inorganic halogen such as chloride ions.

The following general procedure was employed in the polymerization examples. All operations were performed in a vacuum / Atomophers HE with a HE-393 Dri-Train in a dry nitrogen or argon atmosphere or in vacuum.
-43 or its equivalent (Vacuum / Atomo)
phers Co. , Hawthorne, CA, U
(Available from SA) or performed using Schlenk technology. Schlenk's technology is described in F. S
cherver & M. A. Drezdzon, Th
e Manipulation of Air-Sen
site Compounds, 2nd edition, John
Wiley and Sons. , Inc. , New
York, 1986. All liquid transfers were performed using cannulas or syringes to maintain an inert atmosphere. Unless otherwise noted, D
CPD (98-99% by weight) was used in the polymerization experiments. Polymerization experiments consisted of test tubes replaced with argon or nitrogen,
Performed using a capped bottle, glass bottle, reaction vessel, or other mold. Generally, polymerization experiments were performed by adding a solvent or a mixture of DCPD and a catalyst precursor to a mixture of DCPD and an activator. Mixing of these components was performed with a vibrating stirrer, magnetic stirrer, or rotary stirrer. The reaction mixture was placed at room temperature or in a controlled bath at a constant temperature of about 80 ° C. or higher. Gelation time (t
_gel ) is determined by the initial viscosity change and is the time from the start of mixing until the reaction mixture begins to change from fluid to non-fluid. In addition, time (t ₅₀ ° C, t ₁₀₀ ° C, t ₁₅₀ ° C,
t ₁₈₀ ° C), the exothermic temperature after the resin starts to generate heat,
50 ° C, 100 ° C, 150 ° C or 180 ° C, respectively
Is reached (depending on the initial temperature of the solution). The highest temperature reached during polymerization of the resin (T _max ) was similarly recorded. t _Tmax is the time from the start of heat generation to reaching T _max . Residual D in poly DCPD sample
The amount of CPD was determined by extracting DCPD by swelling the sample in toluene, and quantifying the amount by gas chromatography using dodecane as an internal standard. The swelling ratio was measured in addition to the measurement of the gel time, cure time, and residual monomer amount. A low swelling ratio indicates a high crosslinking density. To measure the swelling ratio, a resin sample was taken out of the polymerization vessel, carefully cut into small pieces, the fluff was removed, the pieces were weighed to the milligram level, immersed in toluene (50 ml of toluene per gram of resin), and then immersed for 16 hours ( Overnight), heat reflux, then cool, then remove each sample from the flask, place on a small dish with fresh toluene, remove the sample from it, pat it dry and weigh it. It was measured.
The swelling ratio is calculated as follows: swelling ratio (%) = (w ₂ −w ₁ ) / w ₁ × 100
% (Where w ₁ is the initial weight of the poly DCPD sample,
w ₂ was calculated in accordance with Equation poly DCPD by weight of the sample) after swelling by the solvent. The swelling ratio indicates the degree of crosslinking density, and a low swelling ratio is preferable.

[0118]

The following examples further illustrate the invention. These examples are for explanation, and the scope of the present invention is not limited to these examples.

Example 1 In this example, Mo (NC ₆ H ₃
The synthesis of -2,6-i-Pr ₂ ) ₂ (CH ₂ CMe ₂ Ph) ₂ will be described. Here, i-Pr is an isopropyl group, and Ph is a phenyl group.

The diethyl ether solution of neophyl magnesium chloride was stirred with Mo (NC ₆ H _3-
It was added dropwise to a solution of 2,6-i-Pr ₂ ) ₂ Cl ₂ (DME) in diethyl ether at -30 ° C. The color of the solution changed from red to orange as the reaction proceeded. In addition, MgC
l ₂ has precipitated out of the solvent. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The mixture was filtered with a Manville Celite® filter (Fisher Scientific, Fair)
(Purchasable from Lawn, NJ, USA) and the filtrate was concentrated under reduced pressure.

[Embodiment 2] In this example, Mo (NCMe)
₃ ) The synthesis of ₂ (CH ₂ CMe ₂ Ph) ₂ will be described. Here, Me is a methyl group.

A solution of neophyl magnesium chloride in diethyl ether was stirred with Mo (NC ₆ H _3-
It was added dropwise to a solution of 2,6-i-Pr ₂ ) ₂ Cl ₂ (DME) in diethyl ether at -30 ° C. The color of the solution changed from red to orange as the reaction proceeded. In addition, MgC
l ₂ has precipitated out of the solvent. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The mixture was filtered through a Manville Celite® filter and the filtrate was concentrated under reduced pressure. The reaction product was a pale yellow oily substance, and its structure was confirmed by proton NMR and carbon NMR. Generally, when stored at -35 ° C, the reaction product instantaneously becomes solid.

[Embodiment 3] In this embodiment, W (NC ₆ H ₃ −
The synthesis of 2,6-i-Pr ₂ ) ₂ (CH ₂ CMe ₃ ) ₂ will be described.

A solution of 2,2-dimethyl-propylmagnesium chloride in diethyl ether was stirred with W (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl ₂ (DME).
Was added dropwise at −30 ° C. to a diethyl ether solution. The color of the solution changed from red to orange as the reaction proceeded. Also, MgCl ₂ was precipitated from the solvent. The reaction mixture was allowed to warm to room temperature and was stirred overnight. Mix the mixture with Manville Celite
The solution was filtered through a (registered trademark) filter, and the filtrate was concentrated under reduced pressure.

[Embodiment 4] In this example, Mo (NCMe)
The synthesis of ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ will be described.

A diethyl ether solution of 2,2-dimethyl-propylmagnesium chloride was added dropwise at −30 ° C. to a stirring solution of Mo (NCMe ₃ ) ₂ Cl ₂ (DME) in diethyl ether. The color of the solution changed from red to orange as the reaction proceeded. Also, MgCl
₂ has precipitated out of the solvent. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The mixture was filtered through a Manville Celite® filter and the filtrate was concentrated under reduced pressure. The reaction product was a pale yellow oily substance, and its structure was confirmed by proton NMR and carbon NMR, and was sufficiently pure to be used in polymerization experiments. When stored at -35 ° C, the reaction product instantly became solid.

[Embodiment 5] In this example, W (NCM
The synthesis of e ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ will be described. The starting material W (NCMe ₃ ) ₂ (OSi (C ₆ H ₅ ) ₃ ) ₂ is
It was obtained by reacting W (NCMe ₃ ) ₂ (NHCMe ₃ ) ₂ with twice equivalent of triphenylsilanol (HOSi (C ₆ H ₅ ) ₃ ) in hexane at room temperature. (Nugent
Et al., Inorg. Chem. , Vol. 19,198
0, p. 777-779). W (NCMe ₃ ) ₂ (N
HCMe ₃ ) ₂ is tungsten hexachloride (WCl ₆ ),
Obtained by reaction with an excess of tert-butylamine in cyclohexane (Nugent et al., Inorg. Chem.,
Vol. 22, 1983, p. 965-969).

Trimethylsilylmethyllithium (LiC
A pentane solution of H ₂ SiMe ₃ ) was added dropwise to a stirring hexane solution in which a fixed amount of W (NCMe ₃ ) ₂ (OSi (C ₆ H ₅ ) ₃ ) ₂ was dissolved. The reaction was continued at room temperature for 2 hours while stirring, followed by filtration, and the solvent in the filtrate was distilled off and dried. This solid was dissolved in a small amount of pentane to give -35.
The lithium salt generated in the reaction was precipitated by storing at ℃ for 24 hours. This salt is filtered off from the pentane solution,
The solvent was distilled off from the solution to obtain a colorless and transparent oily substance. The structure was confirmed by proton NMR and carbon NMR.

W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ )
_2, a pentane solution of trimethylsilylmethyl lithium, stirring is _{W (NCMe 3) 2 (OC} 6 H 3 -2,
It can also be obtained by adding dropwise to a solution of 6-Ph ₂ ) ₂ in pentane. _{W (NCMe 3) 2 (OC} 6 H 3 -2,
6-Ph ₂ ) ₂ is obtained by reacting W (NCMe ₃ ) ₂ (NHCMe ₃ ) ₂ with a 2-fold equivalent of 2,6-diphenylphenol under hexane reflux (Rothwell et al., Inor).
g. Chem. , Vol. 28, 1989, p. 141
4-1418).

[0130] _{W (NCMe 3) 2 (CH} 2 SiMe 3) 2 also, a pentane solution of trimethylsilylmethyl lithium, stirring is _{W (NCMe 3) 2 (OC} 6 H 3 -2,
It can also be synthesized by a method of adding dropwise to a pentane solution of 6-i-Pr ₂ ) ₂ [NH ₂ CMe ₃ ]. W (NCMe ₃ ) _{2
(OC 6 H 3 -2,6-i} -Pr 2) 2 [NH 2 CMe 3]
Was obtained by refluxing a 2-fold equivalent of 2,6-diisopropylphenol with W (NCMe ₃ ) ₂ (NHCMe ₃ ) ₂ in pentane at room temperature.

[Embodiment 6] In this embodiment, W (NCMe)
₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor and 2,6-
Describes the polymerization of DCPD using dichlorophenol as an activator.

A bottle with a rubber cap containing 0.024 g of 2,6-dichlorophenol and 20 ml of DCPD (2
5 ml) to W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ )
₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: HOC ₆ H ₃ −
2,6-Cl ₂ = 1000: 1: 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. As it warmed to 80 ° C., the color of the solution changed from clear and colorless to pale yellow. The reaction mixture gelled after 185 seconds and reached 100 ° C. in 216 seconds. further,
180 ° C reached in 237 seconds, maximum temperature reached 2 in 268 seconds
44 ° C was reached. The residual DCPD in the resin was 0.48% by weight.

[Embodiment 7] In this embodiment, W (NCMe)
₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor and 2,6-
Describes the polymerization of DCPD using dichlorophenol as an activator. W (NCMe ₃ ) ₂ (CH ₂ S) was placed in a bottle (25 ml) containing 0.024 g of 2,6-dichlorophenol and 20 ml of DCPD with a rubber cap.
iMe ₃ ) ₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: H
OC ₆ H ₃ -2,6-Cl ₂ = 1000: 1: 2. The mixture was stirred at room temperature and left overnight. The reaction mixture began to thicken after 43 minutes and after curing became a firm mass peeled from the bottle with the rubber cap.

[Embodiment 8] In this embodiment, W (NCMe)
₃ ) Describes the polymerization of DCPD using ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor and pentafluorophenol as an activator. W (NCMe ₃ ) ₂ (CH ₂ SiM) was placed in a bottle (25 ml) containing 0.027 g of pentafluorophenol and 20 ml of DCPD with a rubber cap.
e ₃ ) ₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: HOC ₆
F ₅ = 1000: 1: was 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. As it warmed to 80 ° C., the color of the solution changed from clear and colorless to pale yellow after 85 seconds. The following parameters indicate the state of the polymerization reaction: t _gel = 116 seconds, t ₁₀₀ ° C. = 156 seconds, t ₁₈₀
° C = 159 seconds, _Tmax = 231 ° C, _tTmax = 203 seconds.
The residual DCPD in the resin was 0.78% by weight.

[Embodiments 9-10] In this embodiment, W (N
This describes polymerization of DCPD using CMe ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor, pentafluorophenol as an activator, and 2 and 3 equivalents of pentafluorophenol with respect to tungsten. is there.

A bottle with a rubber cap containing 0.027 g of pentafluorophenol and 20 ml of DCPD (25
ml) to W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ (0.
25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents was DCPD: W: HOC ₆ F ₅ = 1000:
1: 2 (Example 9). Similarly, W (NCMe ₃ ) was placed in a bottle (25 ml) containing 0.041 g of pentafluorophenol and 20 ml of DCPD with a rubber cap.
₂ (CH ₂ SiMe ₃ ) ₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCP
D: W: HOC ₆ F ₅ = 1000: 1: 3 (Example 10).

Immediately after mixing these polymerization raw materials at room temperature, they were placed in an oil bath at 80 ° C. Table 1 below details the polymerization experiments.

[0138]

[Table 1]

[Embodiment 11] In this embodiment, W (NCM
_{e 3) 2 (CH 2 SiMe} 3) 2 was used as a catalyst precursor, and perfluoro -tert- butanol with an activator, DC
Describes the polymerization of PD.

0.021 ml of perfluoro-tert
W (NCMe ₃ ) ₂ (CH ₂ SiM) was placed in a bottle (25 ml) containing butanol and 20 ml of DCPD with a rubber cap.
e ₃ ) ₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: HOC
(CF ₃ ) ₃ = 1000: 1: 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath.
The following parameters indicate the state of the polymerization reaction: t _gel = 15
1 second, t ₁₀₀ ° C. = 250 seconds, t ₁₈₀ ° C. = 270 seconds, T _max
= 223 ° C, t _Tmax = 294 seconds. Residual DCPD in resin
Was 0.53% by weight.

[Embodiment 12] In this embodiment, W (NCM
DCPD using e ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor and hexafluoro-t-butanol as an activator
This is a description of the polymerization of

W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ ) was placed in a bottle (25 ml) containing 0.021 ml of hexafluoro-t-butanol and 20 ml of DCPD with a rubber cap.
₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: HOC (CF
₃ ) ₂ CH ₃ = 1000: 1: 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath.
DCPD gelled after 11 minutes, and after curing, turned into a hard, transparent beige mass overnight at room temperature.

[Embodiment 13] In this embodiment, W (NCM
DCPD using e ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor and hexafluoroisopropanol as an activator
This is a description of the polymerization of

W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ ) was placed in a bottle with rubber cap (25 ml) containing 0.016 ml of hexafluoroisopropanol and 20 ml of DCPD.
₂ (0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: HOCH (C
F ₃ ) ₂ = 1000: 1: 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. DCP
D gelled after 11 minutes and 30 seconds, and after curing, became a soft, transparent, golden mass overnight at room temperature.

[Embodiment 14] In this embodiment, W (NCM
e ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor;
-Dichlorothiophenol (HSC ₆ H ₃ -2,6-Cl
_This describes polymerization of DCPD using ₂ ) as an activator.

W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ was placed in a bottle (25 ml) containing 0.026 g of 2,6-dichlorothiophenol and 20 ml of DCPD with a rubber cap.
(0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents was DCPD: W: HSC ₆ H ₃ −
2,6-Cl ₂ = 1000: 1: 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. DCPD gelled after about 30 minutes, and after curing, turned into a clear yellow lump overnight at room temperature.

[Embodiment 15] In this embodiment, W (NCM
e ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ as a catalyst precursor;
-Diisopropylaniline (H ₂ NC ₆ H ₃ -2,6-P
This describes polymerization of DCPD using r ₂ ) as an activator.

W (NCMe ₃ ) ₂ (CH ₂ SiMe ₃ ) ₂ was placed in a bottle (25 ml) containing 0.026 g of 2,6-diisopropylaniline and 20 ml of DCPD with a rubber cap.
(0.25 ml of a 0.296 M toluene solution) was added. The molar ratio of the reaction reagents is DCPD: W: H ₂ NC ₆ H _{3
-2,6-Cl 2 = 1000: 1} : was 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. The DCPD gelled after about 3 hours, and after curing, turned into a soft, transparent mass overnight at room temperature.

[Embodiment 16] In this example, Mo (NCM
e ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator (DCP
D: Mo: HOC ₆ F ₅ = 2000: 1: 2, molar ratio)
An embodiment in which a poly DCPD plate is formed by RIM will be described.

Using a laboratory level RIM machine, a plate of poly DCPD was prepared using an equal volume of DCPD monomer (> 98% pure by weight and 3% by weight ethylidene norbornene added as a freezing point depressant). The molding was performed using the two flows described above. The viscosity of each stream is 1.8% by weight of ROYALE
NE 301T (ethylene-propylene-diene rubber,
Uniroyal Chemical Co. , In
c. , Naugatuck, CT, USA). One stream contains pentafluorophenol and the other stream is molybdenum species Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ P
h) contained ₂ . The two streams are stored in separate tanks
Stored at 4 ° C. In the experiment, an equal volume of liquid containing the catalyst precursor and the activator was supplied to the mix head and mixed. The catalyst mixture formed instantaneously and was poured into a mold heated to about 70 ° C. The mixing of the components and the filling of the mold were performed within 2 seconds. After filling into 80/60 ° C mold, t
_Tmax was 8.7 seconds. After one minute, the rigid molding was removed from the mold. The composition of the two streams is shown in Table 2 below, and the physical property values of poly DCPD are shown in Table 3.

[0151]

[Table 2]

[0152]

[Table 3]

[Embodiment 17] In this example, Mo (NCM
An example in which a plate of poly DCPD was formed by RIM using e ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator will be described.

Using a laboratory RIM machine, plates of poly DCPD were molded from two equal volume streams under the same conditions as in Example 16. DCPD: Mo (NCMe
₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ : HOC ₆ F ₅ = 8000:
The molar ratio was 1: 2 (see Table 4 below). 80/60
After filling into a mold at ° C., t _Tmax was 24.3 seconds. In addition, t _Tmax when filled into a mold having a mold temperature of 95/75 ° C. was 14.3 seconds. The rigid molding was removed from the mold after one minute. The composition of the two streams is shown in Table 4 below, and the physical property values of poly DCPD are shown in Table 5.

[0155]

[Table 4]

[0156]

[Table 5]

[Embodiment 18] In this example, the stored M
An example relating to the polymerization of o (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ / DCPD solution will be described.

Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph)
₂ (0.093 g) was dissolved in 50 ml of DCPD (containing 3% by weight of ENB). The molar ratio of DCPD: Mo was 2000: 1. The catalyst precursor solution is 18
There was no increase in viscosity after storage for a time. An appropriate amount of a pentafluorophenol activator dissolved in a minimum amount of toluene (0.2 ml) was added to 10 ml of the stored solution to carry out polymerization. The molar ratio of the total reactants was 2000: 1: 2
= DCPD: Mo: HOC ₆ F ₅ The following parameters indicate the state of the polymerization reaction: t _gel = 9 seconds, t ₁₀₀ ° C. = 5
8 seconds, t ₁₈₀ ° C. = 61 seconds, T _max = 207 ° C., t _Tmax = 9
0 seconds. Residual DCPD in the resin was 0.12% by weight.

[Embodiment 19] In this example, the stored M
o (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ / D with rubber
An example relating to polymerization of a CPD solution will be described.

Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph)
₂ (0.093 g) in DCPD (3% by weight ENB,
1.75% by weight of ROYALENE 301T)
Dissolved in 50 ml. The molar ratio of DCPD: Mo is 20
00: 1. Even when the catalyst precursor solution was stored at room temperature for 18 hours, there was no significant increase in viscosity. An appropriate amount of a pentafluorophenol activator dissolved in a minimum amount of toluene (0.2 ml) was added to 10 ml of the stored solution to carry out polymerization. The molar ratio of the total reactants was 2000: 1:
2 = DCPD: Mo: HOC ₆ F ₅ The following parameters describe the state of the polymerization reaction at room temperature (28 ° C.): t
₁₀₀ ° C. = 42 seconds, t ₁₅₀ ° C. = 44 seconds, t ₁₈₀ ° C. = 50 seconds,
T _max = 211 ° C., t _Tmax = 78 sec. Residual DC in resin
PD was 0.06% by weight.

[Embodiment 20] In this embodiment, Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
D, using 2,6-diisopropylaniline as an activator
It describes the polymerization of CPD.

0.026 g of 2,6-diisopropylaniline and 20 ml of DCPD were added to Mo (NCMe ₃ ) ₂ (C
_{H 2 CMe 2 Ph) 2 (} 0.296M in toluene, 0.
25 ml) was added. The molar ratio of the reaction reagents was DCPD:
_{Mo: H 2 NC 6 H 3} -i-Pr 2 = 1000: 1: was 2. The mixture was mixed at room temperature and then placed in an 80 ° C. oil bath. DCPD gels after 3 hours and polymerizes by heating at 80 ° C. for 12 hours or more,
It became a transparent mass.

[Embodiment 21] This embodiment is directed to the case where Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
D, using 2,6-dichlorothiophenol as an activator
It describes the polymerization of CPD.

To 26 ml of 2,6-dichlorothiophenol and 20 ml of DCPD were added Mo (NCMe ₃ ) ₂ (C
_{H 2 CMe 2 Ph) 2 (} 0.296M in toluene, 0.
25 ml) was added. The molar ratio of the reaction reagents was DCPD:
Mo: HSC ₆ H ₃ -2,6-Cl ₂ = 1000: 1: 2
Met. This mixture is mixed at room temperature and then
Placed in an oil bath. DCPD gelled after 30 minutes, and polymerized by heating at 80 ° C. for 12 hours or more to form a transparent mass.

[Embodiment 22] In this example, Mo (NCM
e ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) Cl ₂ (DM
A method for synthesizing E) from 2,6-diisopropylaniline, tert-butylamine and sodium molybdate will be described.

To the stirring suspension of sodium molybdate (Na ₂ MoO ₄ ) in dimethoxyethane, (i)
A solution of triethylamine in dimethoxyethane, (ii) a solution of chlorotrimethylsilane in dimethoxyethane, (ii)
i) A dimethoxyethane solution of a 1: 1 mixture of 2,6-diisopropylaniline and tert-butylamine was added sequentially. The reaction mixture was then heated for 12 hours, producing an orange solution and a white precipitate. The solution was filtered to remove solids, the solvent was removed under reduced pressure and Mo (NCMe ₃ )
(NC ₆ H ₃ -2,6-i-Pr ₂ ) Cl ₂ (DME), M
o (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl ₂ (DME)
And Mo (NCMe ₃ ) ₂ Cl ₂ (DME). The exact composition of this mixture could be determined from the integrated value of the corresponding peak by proton NMR. Mo (NCMe ₃ ) (NC ₆ H ₃ −
_{2,6-i-Pr 2) Cl} 2 (DME) could be obtained by recrystallization in ether the reaction mixture.

[Embodiment 23] In this example, Mo (NCM
e ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) Cl ₂ (DM
E) was converted to Mo (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl
A method of synthesizing from ₂ (DME) and Mo (NCMe ₃ ) ₂ Cl ₂ (DME) will be described.

In a dimethoxyethane (DME) solution, equimolar amounts of Mo (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl ₂ (D
A mixture of (ME) and Mo (NCMe ₃ ) ₂ Cl ₂ (DME) was heated under reflux in a nitrogen atmosphere for 10 days. During this time, a part was taken out and analyzed. During the reaction, the reaction _{mixture, Mo (NCMe 3) (NC} 6 H 3 -2,6-i-P
r ₂₎ Cl ₂ and (DME), a small amount of Mo (NC ₆ H ₃ -2,
_{6-i-Pr 2) 2} Cl 2 (DME) and Mo (NCM
A final composition consisting of e ₃ ) ₂ Cl ₂ (DME) was provided.
The exact composition of this mixture could be determined from the integrated value of the corresponding peak by proton NMR. Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-
_{i-Pr 2) Cl 2 (} DME) could be obtained by recrystallization in ether the reaction mixture.

[Embodiment 24] In this example, Mo (NCM
e ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) Cl ₂ (DM
E) was converted to Mo (NCMe ₃ ) ₂ Cl ₂ (DME) and 2,6-
A method for synthesizing from diisopropylaniline will be described.

In a dimethoxyethane (DME) solution, Mo
An equivalent amount of 2,6-diisopropylaniline was added to (NCMe ₃ ) ₂ Cl ₂ (DME). The reaction mixture was stirred at room temperature for 16 hours under a nitrogen atmosphere. By distilling off the solvent and the reaction by-product tert-butylamine, the reaction mixture became Mo (NCMe ₃ ) (NC ₆ H ₃ ) as the main component.
−2,6-i-Pr ₂ ) Cl ₂ (DME) and a small amount of Mo
A final composition consisting of (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ Cl ₂ (DME) and Mo (NCMe ₃ ) ₂ Cl ₂ (DME) was provided. The exact composition of this mixture could be determined from the integrated value of the corresponding peak by proton NMR. Mo (NCMe ₃ ) (N
_{C 6 H 3 -2,6-i-} Pr 2) Cl 2 (DME) could be obtained by recrystallization in ether the reaction mixture.

As an alternative, Mo (NCMe ₃ ) ₂ Cl
The reaction of ₂ (DME) with an equivalent amount of 2,6-diisopropylaniline can also be carried out in diethyl ether at room temperature for at least 12 hours. If the saturated ether solution is cooled, Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i
—Pr ₂ ) Cl ₂ (DME) is obtained.

[Embodiment 25] In this example, Mo (NCM
e ₃ ) (NC ₆ H ₃ -2,6-i-Pr ₂ ) (CH ₂ CMe ₂
Ph) ₂ is converted to Mo (NCMe ₃ ) (NC ₆ H ₃ -2,6-i-
A method of synthesizing from Pr ₂ ) Cl ₂ (DME) will be described.

The diethyl ether solution of the neophyl magnesium Grignard reagent (PhCMe ₂ CH ₂ MgCl) was stirred with Mo (NCMe ₃ ) (NC ₆ H ₃ −
2,6-i-Pr ₂ ) Cl ₂ (DME) was added dropwise at −78 ° C. to a diethyl ether solution. The reaction mixture is
Stir for 16 hours, filter out the salts coming out of the reaction solution,
The solvent was removed under reduced pressure and pure Mo (NCMe ₃ ) (NC ₆ H
_{3 -2,6-i-Pr 2)} ( to obtain a CH ₂ CMe ₂ Ph) ₂ as an orange oil.

[Embodiment 26] In this example, Mo (NCM)
The polymerization of a rubber-containing DCPD solution using e ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ as a catalyst precursor and hexafluoro-2-propanol as an activator will be described.

3.5% by weight of ROYALENE 301
T rubber was dissolved, the DCPD solution 500ml containing ENB 2 _{wt%, Mo (NCMe 3) 2} (CH 2 CMe 3)
₂ (1.39 g dissolved in 1.5 g dry toluene) was added. ROYALENE 301T is Uni
Royal Chemical Co. , Inc. , N
available from Augatuck, CT, USA.
Similarly, hexafluoro-2-propanol (1.23 g) was added to 500 ml of a DCPD solution (containing ENB) in which the same rubber was dissolved. The polymerization reaction of the solution containing rubber is
This is performed by mixing 2 ml of each solution at room temperature.
Placed in an oil bath. The molar ratio of the total reactants is 200
0: 1: 2 = DCPD: Mo: hexafluoro-2-propanol. The next parameter is room temperature (28 ° C)
_Shows the state of the polymerization reaction at: t _gel = 15 seconds, t ₁₀₀ ° C. =
50 seconds, t ₁₈₀ ° C. = 65 seconds. The residual DCPD in the resin is
0.31% by weight. The swelling ratio was 135%.

[Embodiment 27] In this example, Mo (NCM
e ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ and 2 equivalents of hexafluoro-
An example in which an alkylidene bond is generated from 2-propanol will be described.

Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ (0.5%) dissolved in d ₆ -benzene (approximately 0.5 ml)
To 3 g), 2 equivalents of hexafluoro-2-propanol to Mo (0.046 g) dissolved in d ₆ -benzene (approximately 0.5 ml) were added. The proton NMR spectrum of this solution showed a strong signal at about 13 ppm. This indicates the presence of the molybdenum alkylidene species Mo = CHCMe ₃ .

[Embodiment 28] In this example, Mo (NCM
e ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ and 3 equivalents of hexafluoro-
An example in which an alkylidene bond is generated from 2-propanol will be described.

D6-Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ (0.4
To 5 g), 2 equivalents of hexafluoro-2-propanol to Mo (0.060 g) dissolved in d ₆ -benzene (approximately 0.5 ml) were added. The proton NMR spectrum of this solution showed a strong signal at about 13 ppm. This indicates the presence of the molybdenum alkylidene species Mo = CHCMe ₃ .

[Examples 29-37] In this example, pentafluorophenol, 2,6-dichlorophenol,
Mo (NCMe ₃ ) ₂ (CH ₂ C) activated by 2,6-diisopropylphenol, hexafluoroisopropanol or perfluoro-tert-butanol
The polymerization of DCPD using Me ₂ Ph ₂ ) ₂ will be described.

In the polymerization reaction, a molybdenum catalyst precursor Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂
Ph _{2) 2} (toluene 0.1ml of 0.152M)
4 m containing the above various phenols and alcohols
This was performed by adding to the 1DCPD solution (described in Table 6 below). The molar ratio of the total reactants was DCPD: M
o: ROH or ArOH = 2000: 1: 2. The water content of DCPD used here was 10 ppm or less.

[0182]

[Table 6]

[Examples 38-41] In this example, Mo (NCMe) activated by pentafluorophenol was used.
_{3) 2 (CH 2 CMe 3} ) using ₂ describes the polymerization of DCPD.

In the polymerization reaction, DCP having a purity of 98% by weight or more was used.
D was performed with activated 13X molecular sieves under nitrogen atmosphere at 35 ° C. to 39 ° C. for at least 12 hours. This DCP
D (40 ml) was stored in a bottle with a rubber cap under a nitrogen atmosphere. The molar ratio of the reactants is DCPD: Mo: H
OC ₆ F ₅ = 2000: 1: 2 to 12,500: 1: 2
Changed to These mixtures are allowed to reach room temperature (about 28 ° C to 29 ° C).
C). The conditions and results are shown in Table 7 below.

[0185]

[Table 7]

[Examples 42-43] In this example, Mo (NCMe) activated by pentafluorophenol was used.
_{3) 2 (CH 2 CMe 3} ) using ₂ describes the polymerization of DCPD.

In Example 42, a glass bottle containing 0.013 g of pentafluorophenol and 100 ml of DCPD was charged with Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₃ ) ₂ (0.1
0.25 ml of a 47M toluene solution) was added. The molar ratio of the reactants was DCPD: Mo: HOC ₆ F ₅ = 20,000
0: 1: 2. In Example 43, a glass bottle containing 0.020 g of pentafluorophenol and 100 ml of DCPD was placed in a glass bottle containing Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₃ ) _2.
(0.25 ml of a 0.147 M toluene solution) was added. The molar ratio of the reactants is DCPD: Mo: HOC ₆ F ₅ =
20,000: 1: 3. In both examples, the reactants were stirred at room temperature and placed under a nitrogen atmosphere. Next Table 8
Shows details of the polymerization experiment.

[0188]

[Table 8]

[Example 44] In this example, Mo (NCMe ₃ ) activated by pentafluorophenol was used.
The polymerization of DCPD using ₂ (CH ₂ CMe ₃ ) ₂ will be described.

The polymerization reaction is carried out under a nitrogen atmosphere at 35 ° C. to 3
13X activated for at least 12 hours in the range of 9 ° C
98% by weight treated with molecular sieve
The above was performed using DCPD. The water content in DCPD was 3 ppm or less. The polymerization reaction was carried out at 31 ° C. and the monomer: Mo (NCMe ₃ ) ₂ (CH ₂ CM
e ₃ ) ₂ : the molar ratio of pentafluorophenol is DCP
D: Mo: ArOH = 25,000: 1: 2. The results are shown in Table 9 below.

[0191]

[Table 9]

Examples 45-46 In this example, Mo (NCMe) activated by pentafluorophenol
₃ ) DCP using ₂ (CH ₂ CMe ₃ ) ₂ in a molar ratio of DCPD: catalyst precursor: activator = 50,000: 1: 2
The polymerization of D will be described.

The polymerization reaction is carried out under a nitrogen atmosphere at 35 ° C. to 3 ° C.
13X activated for at least 12 hours in the range of 9 ° C
98% by weight treated with molecular sieve
The above was performed using DCPD. The water content in DCPD was 3 ppm or less. The results are shown in Table 10 below.

[0194]

[Table 10]

Examples 47-48 In this example, Mo (NCMe) activated by pentafluorophenol
₃ ) ₂ (CH ₂ CMe ₃ ) ₂ was used in a DCPD: catalyst precursor: activator = 100,000: 1: 2 molar ratio;
The polymerization of PD will be described.

The polymerization reaction is carried out under a nitrogen atmosphere at 35 ° C. to 3
13X activated for at least 12 hours in the range of 9 ° C
98% by weight treated with molecular sieve
The above was performed using DCPD. The water content in DCPD was 3 ppm or less. The results are shown in Table 11 below.

[0197]

[Table 11]

[Embodiment 49] In this example, Mo (NC _{6
H 3 -2,6-Pr 2) (} NCMe 3) (CH 2 CMe 2 P
h) An example in which an alkylidene bond is formed from ₂ and 2 equivalents of pentafluorophenol is described.

Mo (NC ₆ H ₃ -2,6-) dissolved in d ₈ -toluene (approximately 0.5 ml) cooled to −35 ° C.
Pr ₂ ) (NCMe ₃ ) (CH ₂ CMe ₂ Ph) ₂ (0.0
60 g) solution, cooled to -35 ° C, 2
D of equivalent pentafluorophenol (0.036 g)
_{An 8} -toluene solution was added. The solution was then warmed to room temperature until the color changed from orange to dark red. The proton NMR spectrum of this solution showed a strong signal at about 13.8 ppm. This indicates the presence of a molybdenum alkylidene species ([Mo] = CHCMe ₂ Ph). In carbon-13 NMR, about 314 ppm (d
_The alkylidene resonance was observed in ( ₈ -toluene). Based on the spectroscopic resonance, the reaction product is (PhMe
₂ CCH =) Mo (NC ₆ H ₃ -2,6-Pr ₂ ) (OC ₆
F ₅ ) ₂ (H ₂ NCMe ₃ ).

[Embodiment 50] In this example, Mo (NC _{6
H 3 -2,6-Pr 2) (} NCMe 3) (CH 2 CMe 2 P
h) An example of the metathesis reaction of 1,9-decadiene using ₂ and 2 equivalents of pentafluorophenol is described.

In a solution of 1,9-decadiene (1.79 g) and pentafluorophenol (0.024 g), Mo (NC ₆ H ₃ -2,6-Pr ₂ ) (NCM
e ₃ ) (CH ₂ CMe ₂ Ph) ₂ (0.033 g) was added. The molar ratio of the reactants was 200: 1: 2 = 1,9-decadiene: Mo: pentafluorophenol. After stirring overnight, the viscosity of the sample increased. Carbon 13N
According to MR, the newly formed vinyl group (-CH = CH
-) And a peak indicating that about 25% of the starting material 1,9-decadiene was present. The presence of the newly formed vinyl group was also confirmed from the proton NMR spectrum.

Embodiment 51 In this embodiment, W (NC ₆ H ₃
This describes the polymerization of DCPD using -2,6-i-Pr ₂ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator.

W (NC ₆ H ₃ -2,6-i-Pr ₂ ) ₂ (C
H ₂ CMe ₂ Ph) ₂ (58 mg, 7.24 × 10 ⁻⁵ mo
pentafluorophenol (40 mg, 2.173 × 10 ⁻⁴ mol, DCPD5
(in ml). DCPD: W: pentafluorophenol = 1000: 1: 3 on a molar basis. The sample was placed in an 80 ° C. oil bath and turned into a thick gel after 4 seconds. During 16 hours, the temperature of the reaction mixture rose to a maximum of 86 ° C. in an 80 ° C. constant temperature oil bath.
After this, the DCPD mixture polymerized to an orange, rubbery mass.

As a comparison, W (NC ₆ H ₃ -2,6-i-
Pr ₂ ) ₂ (CH ₂ CMe ₂ Ph) ₂ (58 mg, 7.24
x10 ^-5 mol) without the activator (DCPD: W = 1000: 1 on a molar basis)
Heated in oil bath for 16 hours. The viscosity of the DCPD mixture did not increase.

[Embodiment 52] In this example, Mo (NCM
A method for synthesizing e ₃ ) ₂ (CH ₃ ) ₂ will be described.

Mo (NCMe ₃ ) ₂ Cl ₂ (−D at −78 ° C.)
To a solution of ME) in diethyl ether was slowly added 2 equivalents of methyl magnesium bromide. DME is dimethoxyethane. The reaction mixture was slowly warmed to room temperature, filtered, evaporated and dried. The purple powder is then dissolved in pentane, filtered and
Chilled. Purple crystal by recrystallization is carbon 13N
Mo (NCMe ₃ ) ₂ (CH
₃ ) It was identified as ₂ .

[Embodiment 53] In this embodiment, Mo (NCM
A method for synthesizing e ₃ ) ₂ (CH ₂ Ph) ₂ will be described.

Mo (NCMe ₃ ) ₂ Cl ₂ (-D at −78 ° C.)
To a solution of ME) in diethyl ether was slowly added 2 equivalents of benzylmagnesium chloride. The reaction mixture was slowly warmed to room temperature, filtered, evaporated and dried. The yellow powder was then dissolved in pentane, filtered and cooled to -35C. The yellow crystals by recrystallization were analyzed by carbon-13 NMR and proton NMR for Mo.
(NCMe ₃ ) ₂ (CH ₂ Ph) ₂ was identified.

[Embodiment 54] In this example, W (NC ₆ H ₃
−2,6-i-Pr ₂ ) (NCMe ₃ ) Cl ₂ (DME)
Will be described.

A fixed amount of [W (NC ₆ H ₃ -2,6-i-P
r ₂ ) Cl ₄ ] ₂ dissolved in diethyl ether,
One equivalent of dimethoxyethane (DM
E) and 3 equivalents of tert-butylamine were added at room temperature. The reaction mixture was stirred at room temperature for 2 hours. The by-product amine salt ([Me ₃ CNH ₃ ] Cl) was filtered and removed from the reaction system. The solvent was removed under reduced pressure and substantially pure W (NC ₆ H ₃ -2,6-i-Pr ₂ ) (NCMe ₃ ) Cl
₂ (DME) was obtained. This material was recrystallized from diethyl ether or pentane and further purified.

Alternatively, 3 equivalents of tert-butylamine can be replaced with 1 equivalent of tert-butylamine and 2 equivalents of triethylamine to remove hydrogen chloride (HCl) generated during the reaction.

[Embodiment 55] In this embodiment, W (NC ₆ H _{3
-2,6-i-Pr 2) (} N-1- adamantyl) Cl ₂
A method for synthesizing (DME) will be described.

A fixed amount of [W (NC ₆ H ₃ -2,6-i-P
r ₂ ) Cl ₄ ] ₂ dissolved in diethyl ether,
One equivalent of dimethoxyethane (DM
E) and 3 equivalents of 1-aminoadamantane were added at room temperature. The reaction mixture was stirred at room temperature for 2 hours. The amine salt (1-aminoadamantane hydrochloride) as a by-product was filtered and removed from the reaction system. Solvent under reduced pressure
The substantially pure W (NC ₆ H ₃ -2,6-i-Pr
₂₎ (yield N-1- adamantyl) Cl ₂ a (DME).
This material was recrystallized from diethyl ether or pentane and further purified. This material was identified by proton and carbon NMR.

[Embodiment 56] In this example, W (NC ₆ H ₃
A method of synthesizing -2,6-i-Pr ₂ ) (NCMe ₃ ) (CH ₂ Ph) ₂ will be described.

A fixed amount of W (NC ₆ H ₃ -2,6-i-Pr
₂₎ (NCMe ₃₎ Cl ₂ with (DME) and cooled to -78 ° C. was dissolved in diethyl ether. To this solution was added a solution of benzylmagnesium chloride (PhCH ₂ MgCl) in diethyl ether equivalent to 2 equivalents of tungsten. The reaction mixture was slowly warmed to room temperature and stirred for about 2 hours. The by-product magnesium chloride was filtered to obtain an orange solution. Evaporation of the solvent gave a brittle solid. The product was recrystallized from diethyl ether at -35 ° C to further increase the purity. By carbon 13 NMR and proton NMR, W (NC ₆ H ₃ -2,6-i-P
r ₂ ) (NCMe ₃ ) (CH ₂ Ph) ₂ .

[Embodiment 57] In this example, W (NC ₆ H ₃
−2,6-i-Pr ₂ ) (NCMe ₃ ) (CH ₂ CMe ₂ P
h) A method for synthesizing ₂ will be described.

A certain amount of W (NC ₆ H ₃ -2,6-i-Pr
₂₎ (NCMe ₃₎ Cl ₂ with (DME) and cooled to -78 ° C. was dissolved in diethyl ether. To this solution, a diethyl ether solution of 2 equivalents of neophyl magnesium chloride (PhMe ₂ CCH ₂ MgCl) with respect to tungsten was added. The reaction mixture was slowly warmed to room temperature,
Stir for about 2 hours. The by-product magnesium chloride was filtered to obtain an orange solution. Evaporation of the solvent gave an orange oil. Carbon 13 NMR, proton NM
The _{R W (NC 6 H 3 -2,6} -i-Pr 2) (NCM
e ₃ ) (CH ₂ CMe ₂ Ph) ₂ .

[Embodiment 58] This embodiment relates to the case where Mo (NC)
It describes polymerization of DCPD using Me ₃ ) ₂ (CH ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator.

A bottle with a rubber cap containing 0.026 g of pentafluorophenol and 20 ml of DCPD (25
ml) was added Mo (NCMe ₃ ) ₂ (CH ₂ Ph) ₂ (31 mg dissolved in a minimum amount of toluene). The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ F ₅ = 2000: 1: 2
Met. This mixture is mixed at room temperature and then
Placed in an oil bath. The following parameters are indicative of the nature of the polymerization reaction: t _gel = 4 seconds, t ₁₀₀ ° C = 6.
Second, t ₁₈₀ ° C. = 12 seconds, T _max = 207 ° C., t _Tmax = 32
Seconds. The residual DCPD in the resin was 0.88% by weight. The resin obtained by polymerization exhibited a swelling ratio of 44% in toluene.

[Embodiment 59] This embodiment relates to the case where Mo (NC)
It describes polymerization of DCPD using Me ₃ ) ₂ (CH ₂ Ph) ₂ as a catalyst precursor and a mixture of pentafluorophenol / 2,6-dichlorophenol as an activator.

0.013 g of pentafluorophenol, 0.012 g of 2,6-dichlorophenol and 20 m
1 bottle with DCPD and 25ml of DCPD
Was added Mo (NCMe ₃ ) ₂ (CH ₂ Ph) ₂ (31 mg dissolved in a minimum amount of toluene). The molar ratio of the reaction reagents is
DCPD: Mo: HOC ₆ F ₅ : HOC ₆ H ₃ -2,6-C
l ₂ = 2000: 1: 1: 1. This mixture is
They were mixed and polymerized at room temperature. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 2 seconds, t ₁₅₀ ° C = 1.
1 second, t ₁₈₀ ° C. = 14 seconds, T _max = 209 ° C., t _Tmax = 3
8 seconds. The residual DCPD in the resin was 2.50% by weight. The resin obtained by polymerization showed a swelling ratio of 30% in toluene.

[Embodiment 60] In this embodiment, Mo (NC)
It describes polymerization of crude DCPD using Me ₃ ) ₂ (CH ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator.

A 95% by weight nominal DCPD dried over a 13X molecular sieve is Mo (NCMe ₃ ).
Polymerization was carried out using ₂ (CH ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator. The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ F ₅ = 2000: 1: 2
Met. The mixture was mixed at 31 ° C and placed in an 80 ° C oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 33 seconds, t ₁₀₀ ° C. = 41
Second, t ₁₈₀ ° C. = 48 seconds, T _max = 210 ° C., t _Tmax = 66
Seconds. Residual DCPD in the resin obtained by polymerization is
It was 0.50% by weight.

[Embodiment 61] In this embodiment, Mo (NC)
Crude DCPD using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator
This is a description of the polymerization of

The nominal 95% by weight of DCPD dried by the 4A molecular sieve is Mo (NCMe ₃ ) ₂ (C
Polymerization was performed using H ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator. The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ F ₅ = 2000: 1:
It was 2. The mixture was mixed at 31 ° C and placed in an 80 ° C oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 35 seconds, t ₁₀₀ ° C = 41.
Second, t ₁₈₀ ° C. = 46 seconds, T _max = 201 ° C., t _Tmax = 61
Seconds. The residual DCPD in the resin was 1.1% by weight.

[Embodiments 62-65] This embodiment is directed to Mo
(NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor, pentafluorophenol as an activator, and Mo /
It describes the polymerization of DCPD with varying activator molar ratios.

DCPD (10 ml) was added to Mo (NCMe)
₃ ) Polymerization was carried out using ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor, pentafluorophenol as an activator, and changing the Mo / activator molar ratio from 1 to 4. The mixture was mixed at 31 ° C and placed in an 80 ° C oil bath. Table 12 below shows details of the polymerization reaction.

[0228]

[Table 12]

[Embodiment 66] This embodiment is based on the assumption that Mo (NC)
This describes polymerization of DCPD using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and phenol as an activator.

In a bottle containing 14 mg of phenol (0.2 ml of a toluene solution) and 20 ml of DCPD in a 25 ml bottle with a rubber cap, Mo (NCMe ₃ ) ₂ (CH ₂
CMe ₂ Ph) ₂ (37 mg dissolved in 0.5 ml toluene)
Was added. The molar ratio of the reaction reagents is DCPD: Mo: HO
C ₆ H ₅ = 2000: 1: 2. The mixture was mixed at room temperature and placed in an 80 ° C. oil bath. The following parameters are used to indicate the state of the polymerization reaction: t _gel = 7
Second, t ₁₀₀ ° C. = 146 seconds, t ₁₈₀ ° C. = 170 seconds, T _max =
212 ° C., t _Tmax = 192 seconds. Residual DCPD in resin
Was 0.11% by weight.

[Embodiment 67] In this embodiment, Mo (NC)
Using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
-Describes the polymerization of DCPD using methoxyphenol as an activator.

18 mg of 4-methoxyphenol (0.
2 ml of toluene solution) and 20 ml of DCPD in 25 m
l in a bottle with a rubber cap, add Mo (NCMe
₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ (3 in 0.5 ml toluene)
(7 mg dissolved). The molar ratio of the reaction reagents is DCP
D: Mo: HOC ₆ H ₄ -4-OMe = 2000: 1: 2
Met. The mixture was mixed at room temperature and placed in an 80 ° C. oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 6 seconds, t ₁₀₀ ° C = 198 seconds, t
₁₈₀ ° C. = 221 seconds, T _max = 212 ° C., t _Tmax = 248
Seconds. Residual DCPD in the resin was 0.11% by weight.

[Embodiment 68] This embodiment is directed to the case where Mo (NC)
Using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
-Describes the polymerization of DCPD using chlorophenol as an activator.

Mo (N) was added to 18.7 mg of 4-chlorophenol (0.2 ml of toluene solution) and 20 ml of DCPD in a 25 ml bottle with a rubber cap.
CMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ (37 mg dissolved in 0.5 ml toluene) was added. The molar ratio of the reactants is D
CPD: Mo: HOC ₆ H ₄ -4-Cl = 2000: 1:
It was 2. The mixture was mixed at room temperature and placed in an 80 ° C. oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 4 seconds, t ₁₀₀ ° C = 41 seconds, t
₁₈₀ ° C. = 63 seconds, T _max = 207 ° C., t _Tmax = 84 seconds. Residual DCPD in the resin was 0.15% by weight.

[Embodiment 69] This embodiment is directed to the case where Mo (NC)
Using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
-Describes the polymerization of DCPD using nitrophenol as an activator.

20.2 mg of 4-nitrophenol (0.2 ml of dimethoxyethane (DME) solution) and 2
Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ was added to 0 ml of DCPD in a 25 ml bottle with a rubber cap.
(37 mg dissolved in 0.5 ml toluene) was added. The molar ratio of the reaction _{reagent, DCPD: Mo: HOC 6 H} 4 -4-N
O ₂ = 2000: 1: 2. The mixture was mixed at room temperature and placed in an 80 ° C. oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 3
Second, t ₁₀₀ ° C. = 25 seconds, t ₁₈₀ ° C. = 37 seconds, T _max = 19
1 ° C., t _Tmax = 71 sec. Residual DCPD in the resin is 5.
It was 93% by weight.

[Embodiment 70] This embodiment is directed to the case where Mo (NC)
It describes polymerization of DCPD in which Me ₃ ) ₂ (CH ₂ Ph) ₂ is used as a catalyst precursor, pentafluorophenol is used as an activator, and tri-n-butyl phosphite is added as a reaction rate regulator. .

27 mg of pentafluorophenol (0.2 ml of toluene solution) and 18 mg of tri-n-
Mo (NCMe ₃ ) ₂ (CH ₂ Ph) ₂ (0.1 mL) was charged with butyl phosphite (0.2 ml of toluene solution) and 20 ml of DCPD in a 25 ml bottle with a rubber cap.
(31 mg dissolved in 5 ml toluene). The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ F ₅ = 2000:
1: 2. This mixture is mixed at room temperature and
Placed in an oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 6 seconds, t ₁₀₀ ° C = 12.
Sec, t ₁₈₀ ° C. = 18 seconds, T _max = 214 ° C., t _Tmax = 42
Seconds.

[Embodiment 71] This embodiment is directed to the case where Mo (NC)
DCP obtained by adding Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor, pentafluorophenol as an activator, and triphenylphosphite as a reaction rate regulator.
This is a description of the polymerization of D.

27 mg of pentafluorophenol (0.2 ml of a toluene solution), 23 mg of triphenylphosphite (0.2 ml of a toluene solution) and 20 mg of
ml of DCPD in a 25 ml bottle with a rubber cap, and Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph)
₂ (37 mg dissolved in 0.5 ml toluene) was added. The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ F ₅ = 20.
00: 1: 2. This mixture is mixed at room temperature,
Placed in an 80 ° C. oil bath. The following parameters are used to indicate the nature of the polymerization reaction: t _gel = 4 seconds, t ₁₀₀ ° C =
11 seconds, t ₁₈₀ ° C. = 19 seconds, T _max = 205 ° C., t _Tmax =
52 seconds.

[Embodiment 72] In this embodiment, Mo (N
CMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
Poly DC with pentafluorophenol as an activator
The formation of a PD plate by three-stream RIM will be described.

Using a laboratory size RIM machine, DC
Two streams of equal volume of PD monomer (DCPD having a purity of 98% by weight or more and 3% by weight of ethylidene norbornene added as a freezing point depressant) / pentafluorophenol and Mo (NCMe ₃ ) ₂ dissolved in toluene ( CH
A plate of poly DCPD was formed from a third stream containing ₂ CMe ₂ Ph) ₂ as a catalyst precursor. The viscosity is EPT407
0 (ethylidene norbornene (ENB) / ethylene-propylene-diene rubber (EPDM), available from Mitsui Petrochemical Industries, Ltd.) by adding 4.0% by weight. The two liquids containing DCPD have a temperature of 3
The catalyst precursor was separately placed in a tank at 1 to 34 ° C, and the toluene solution of the catalyst precursor was stored at room temperature. 3 before molding
The inside of the mold was replaced with nitrogen for 0 second. In the molding experiment, the three liquids containing the activator or catalyst precursor were led to a mix head and mixed, and the resulting mixture was immediately heated to about 75 ° C.
Was injected into a heated mold. The mixing of the raw materials and the injection into the mold were completed within 1.5 seconds. The mold was opened for 30 to 60 seconds after mixing the raw materials, and a rigid molded product could be immediately taken out. The residual DCPD in the poly DCPD was 0.18% by weight, and the heat resistant temperature (HD
T) was 116 ° C.

[Embodiment 73] In this embodiment, Mo (NC)
Poly DCPD boards are molded by three-stream RIM using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as catalyst precursor, pentafluorophenol as activator and 95% by weight of crude DCPD. What to do. D
The molar ratio was CPD: Mo: HOC ₆ F ₅ = 1500: 1: 2.

Using a laboratory-sized RIM machine, DC
PD monomer / pentafluorophenol (purity ~ 95
% By weight) and a third stream containing Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ dissolved in toluene as a catalyst precursor in a mixhead by mixing with a mixhead. Was molded. The viscosity is EPT
4070 (ethylidene norbornene (ENB) / ethylene-propylene-diene rubber (EPDM), available from Mitsui Petrochemical Industry Co., Ltd.) was added at 4.0% by weight to increase the viscosity. The two DCPD solutions were separately placed in tanks having a temperature of 31 to 34 ° C., and the toluene solution of the catalyst precursor was stored at room temperature. Before molding, the inside of the mold was replaced with nitrogen for 30 seconds. In a molding experiment, three liquids containing the activator or catalyst precursor were directed to a mixhead and the resulting mixture was injected into a mold heated to about 90 ° C. The mixing of the raw materials and the injection into the mold were completed within 1.5 seconds. The mold was opened within 2 to 3 minutes after mixing the raw materials, and a rigid molded product could be immediately taken out. The residual DCPD in the poly DCPD is 0.67% by weight,
The heat resistance temperature (HDT) was 113 ° C.

[Embodiment 74] In this embodiment, Mo (NC)
Poly DCP using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor and pentafluorophenol as an activator
The forming of the plate D by RIM will be described.

The olefin metathesis catalyst (olefin metathesis polymerizable compound) is Mo (NCMe ₃ ) ₂ (CH
₂ CMe ₂ Ph) ₂ (68.36 g) and 2 equivalents of pentafluorophenol (50.3 g) at about −370 at −35 ° C.
It was obtained by reacting in ml of toluene and then warming to room temperature. The molar ratio of the reaction reagents is Mo (NCMe
₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ : HOC ₆ F ₅ = 1: 2.

Using a laboratory-sized RIM machine, DC
PD monomer / pentafluorophenol (purity ~ 95
(% By weight) and a third stream containing an olefin metathesis catalyst (olefin metathesis polymerizable compound) dissolved in toluene using a mix head to form a poly DCPD plate. The viscosity is EPT4
070 (ethylidene norbornene (ENB) / ethylene-propylene-diene rubber (EPDM), which can be purchased from Mitsui Petrochemical Industries, Ltd.) was added by 4.0% by weight to increase the viscosity. The DCPD monomer solution was placed in a tank at a temperature of 31 ° C., and the olefin metathesis catalyst (olefin metathesis polymerizable compound) / toluene solution was stored at room temperature. Before molding, the inside of the mold was replaced with nitrogen for 30 seconds. In the molding experiments, all streams were directed to the mixhead and injected into a mold heated to about 75 ° C. Mixing of the raw materials and injection into the mold were completed within 2 seconds.
The mold was opened within 2 to 3 minutes after mixing the raw materials, and a rigid molded product could be immediately taken out. Poly D
The residual DCPD in the CPD was 1.53% by weight.

[Embodiment 75] In this embodiment, Mo (NC)
It describes polymerization of DCPD using Me ₃ ) ₂ (CH ₃ ) ₂ as a catalyst precursor and pentafluorophenol as an activator.

27 mg of pentafluorophenol and 2
In a bottle with rubber cap (25 ml) containing 0 ml of DCPD (dried by molecular sieve of 4A), Mo was added.
(NCMe ₃ ) ₂ (CH ₃ ) ₂ ( _{2 in} 0.5 ml of toluene
0 mg dissolved). The molar ratio of the reaction reagents is DCP
D: Mo: HOC ₆ F ₅ = 2000: 1: 2. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 5 seconds, t ₁₀₀ ° C = 10
Seconds, t ₁₈₀ ° C. = 20 seconds, T _max = 214 ° C., t _Tmax = 49
Seconds. Residual DCPD in the resin was 0.12% by weight. Poly DCPD showed a swelling ratio of 94% in toluene.

[Embodiment 76] In this embodiment, Mo (NC)
It describes polymerization of DCPD using Me ₃ ) ₂ (CH ₃ ) ₂ as a catalyst precursor and pentafluorophenol as an activator.

In a bottle (25 ml) containing a rubber cap containing 6.7 mg of pentafluorophenol and 20 ml of DCPD (dried by molecular sieve of 4A), Mo was added.
(NCMe ₃ ) ₂ (CH ₃ ) ₂ (4.9 mg dissolved in 0.5 ml toluene) was added. The molar ratio of the reactants is D
CPD: Mo: HOC ₆ F ₅ = 8000: 1: 2. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 5
Second, t ₁₀₀ ° C. = 18 seconds, t ₁₈₀ ° C. = 25 seconds, T _max = 21
0 ° C., t _Tmax = 50 sec. The residual DCPD in the resin is 0.
It was 11% by weight. Poly DCPD is 91% in toluene
% Swelling rate.

[Embodiment 77] This embodiment relates to the case where Mo (NC)
It describes polymerization of DCPD using Me ₃ ) ₂ (CH ₃ ) ₂ as a catalyst precursor and pentafluorophenol as an activator.

In a bottle with rubber cap (25 ml) containing 3.4 mg of pentafluorophenol and 20 ml of DCPD (dried by molecular sieve of 4A), Mo was added.
(NCMe ₃ ) ₂ (CH ₃ ) ₂ (2.5 mg dissolved in 0.5 ml toluene) was added. The molar ratio of the reactants is D
CPD: Mo: HOC ₆ F ₅ = 16,000: 1: 2. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 6 seconds, t ₁₀₀ ° C.
= 32 seconds, t ₁₈₀ ° C. = 37 seconds, T _max = 210 ° C., t _Tmax
= 59 seconds. Residual DCPD in the resin was 0.34% by weight. Poly DCPD showed 98% swelling in toluene.

[Embodiment 78] This embodiment relates to the case where Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
It describes the polymerization of DCPD using 2,3,4,5-tetrabromo-6-methylphenol as an activator.

62 mg of 2,3,4,5-tetrabromo-6-methylphenol (HOC ₆ -2,3,4,5-
Mo (NCMe ₃ ) ₂ (C) was placed in a bottle (25 ml) with a rubber cap containing Br _4-6 -CH ₃ ) and 20 ml of DCPD.
H ₂ CMe ₂ Ph) ₂ (37 mg, 7.24 × 10 ⁻⁵ mo
l) was added. The molar ratio of the reaction reagents was DCPD: Mo:
_{HOC 6 -2,3,4,5-Br 4 -6-} CH 3 = 200
0: 1: 2. This mixture was mixed at room temperature and polymerized. The following parameters describe the state of the polymerization reaction: t
_gel = 1 second, t ₁₀₀ ° C. = 15 seconds, t ₁₈₀ ° C. = 61 seconds, T _max
= 192 ° C, t _Tmax = 73 seconds.

[Embodiment 79] This embodiment is directed to the case where Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
Using 2,3,4,5-tetrabromo-6-methylphenol as an activator, tributyl phosphite (P (OB
u) describes polymerization of DCPD with addition of ₃ ) as a reaction rate regulator.

[0257] of 62mg 2,3,4,5- tetrabromo-6-methyl-phenol (HOC ₆ -2,3,4,5-
Br ₄ -6-CH _3), the rubber cap Tsukebin containing the DCPD tributyl phosphite and 20ml of 0.06ml (25ml), Mo (NCMe 3) 2 (CH 2 CMe 2
Ph) ₂ (37 mg, 7.24 × 10 ⁻⁵ mol) was added. The molar ratio of the reaction reagents was DCPD: Mo: HOC ₆ −
_{2,3,4,5-Br 4 -6-CH 3} : P (OBu) 3 =
2000: 1: 2: 3. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 5 seconds, t ₁₀₀ ° C = 37 seconds, t
₁₈₀ ° C. = 114 seconds, T _max = 192 ° C., t _Tmax = 122
Seconds.

[Embodiment 80] This embodiment is directed to the case where Mo (NC)
The polymerization of DCPD was described in which Me ₃ ) ₂ (CH ₂ Ph) ₂ was used as a catalyst precursor, pentafluorophenol was used as an activator, and tributyl phosphite (P (OBu) ₃ ) was added as a reaction rate regulator. Things.

27 mg of pentafluorophenol (H
OC ₆ F ₅ ), a bottle with rubber cap containing 0.06 ml of tributyl phosphite and 20 ml of DCPD (25
ml), Mo (NCMe ₃ ) ₂ (CH ₂ Ph) ₂ (31 m
g, 7.24 × 10 ⁻⁵ mol). The molar ratio of the reaction reagents is DCPD: Mo: HOC ₆ F ₅ : P (OBu) ₃
= 2000: 1: 2: 3. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 6 seconds, t ₁₀₀ ° C = 12 seconds, t ₁₈₀ ° C = 1
8 seconds, T _max = 214 ° C., t _Tmax = 42 seconds. The residual DCPD in the resin was 0.36% by weight. Poly DCPD
Showed a swelling ratio of 37.7% in toluene.

[Embodiment 81] This embodiment relates to the case where Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
This describes polymerization of DCPD using 2,6-dichloro-4-methylsulfonylphenol as an activator.

35 mg of 2,6-dichloro-4-methylsulfonylphenol (HOC ₆ H ₂ -2,6-Cl ₂
-4-SO ₂ Me), 18 mg of tributyl phosphite (P (OBu) ₃ ) and 20 ml of DCPD in a bottle (25 ml) with a rubber cap, and Mo (NCM
e ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ (37 mg, 7.24 ×
10 ^-5 mol). The molar ratio of the reaction reagents is DCP
D: Mo: HOC ₆ H ₂ -2,6-Cl ₂ -4-SO ₂ M
e: P (OBu) ₃ = 2000: 1: 2: 3.
This mixture was mixed at room temperature and polymerized. The following parameters indicate the nature of the polymerization reaction: t _gel = 3 seconds,
t ₁₀₀ ° C. = 19 seconds, t ₁₈₀ ° C. = 23 seconds, T _max = 211
° C, t _Tmax = 43 seconds. The residual DCPD in the resin is 1.5
It was 8% by weight. Poly DCPD was used in toluene.
The swelling ratio was 8%.

[Embodiment 82] This embodiment is directed to the case where Mo (NC
Using Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor, 2
-Describes the polymerization of DCPD using naphthol as an activator.

21 mg of 2-naphthol (C ₁₀ H ₇ O
H) and a bottle (25 ml) with a rubber cap containing 20 ml of DCPD were placed in a bottle of Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ P).
h) ₂ (37 mg) was added. The molar ratio of the reactants is D
CPD: Mo: C ₁₀ H ₇ OH = 2000: 1: 2. This mixture was mixed at room temperature and polymerized. The following parameters indicate the state of the polymerization reaction: t _gel = 3
Second, t ₁₀₀ ° C. = 211 seconds, t ₁₈₀ ° C. = 252 seconds, T _max =
189 ° C., t _Tmax = 312 seconds. Residual DCPD in resin
Was 0.76% by weight. Poly DCPD exhibited a swelling ratio of 90.2% in toluene.

[Embodiment 83] In this embodiment, Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
2,2′-biphenol [2,2 ′-(C ₆ H ₄ O
H) ₂ ] as an activator.

27 mg of 2,2'-biphenol and 20
bottle with 25ml DCPD (25ml)
In addition, Mo (NCMe ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ (37
mg, 7.24 × 10 ⁻⁵ mol). The molar ratio of the reaction reagent is DCPD: Mo: 2,2 ′-(C ₆ H ₄ OH)
₂ = 2000: 1: 1. The mixture was mixed at room temperature and placed in an 80 ° C. oil bath. The following parameters indicate the state of the polymerization reaction: t _gel = 382 seconds, t
₁₀₀ ° C. = 559 seconds, t ₁₈₀ ° C. = 588 seconds, T _max = 218
° C, t _Tmax = 629 sec. 3. Residual DCPD in the resin
It was 47% by weight.

[Embodiment 84] In this embodiment, Mo (NC)
Me ₃ ) ₂ (CH ₂ CMe ₂ Ph) ₂ as a catalyst precursor,
2,2'-methylenebis (4-chlorophenol)
_{[2,2'-CH 2 (C 6} H 3 -4-Cl) 2] was used as activating agent, those described for the polymerization of DCPD.

20 mg of 2,2'-methylenebis (4-
Chlorophenol) (dissolved in 0.2 ml of glyme) and 20 ml of DCPD were mixed with Mo (NCMe ₃ ) ₂ (C
H ₂ CMe ₂ Ph) ₂ (37 mg, 7.24 × 10 ⁻⁵ mo
l) was added. The molar ratio of the reaction reagents was DCPD: Mo:
_{2,2'-CH 2 (C 6 H} 3 -4-Cl) 2 = 2000:
1: 1. This mixture is mixed at room temperature and
Placed in an oil bath. The following parameters indicate the nature of the polymerization reaction: t _gel = 40 seconds, t ₁₀₀ ° C = 157 seconds,
t ₁₈₀ ° C. = 185 seconds, T _max = 201 ° C., t _Tmax = 265
Seconds.

[0268]

According to the present invention, an olefin metathesis catalyst precursor which has a very mild activity and can use an activator which is stable against water and oxygen can be used. Moreover, the olefin metathesis catalyst (olefin metathesis polymerizable compound) made from this is very active and can be produced in situ in a monomer or solvent capable of olefin metathesis reaction, or if necessary, a pure product. It can also be isolated as In addition, in the olefin metathesis reaction using these, it is possible to use raw materials and monomers having low purity, and it is also possible to extremely reduce the metal content and the inorganic halogen content in the product.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/06-61/08 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] (A) M (NR ¹ ) (NR ² ) (R ³ )
At least one catalyst precursor having a structure of (R ⁴ ); and (b) at least one catalyst precursor for activating the catalyst precursor.
A catalyst composition comprising at least one activator. Where M is Mo or W
Wherein R ¹ , R ² , R ³ , R ⁴ include alkyl, cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, haloalkyl, haloaralky, substituted or unsubstituted aryl or aralkyl groups, and silicon These are the same or different groups selected from the group consisting of groups similar to these. 2. The method according to claim 1, wherein the activator is alcohol, phenol,
The catalyst composition according to claim 1, wherein the catalyst composition is selected from the group consisting of silanols, thiols, thiophenols, diols, and mixtures thereof. 3. The method according to claim 1, further comprising a Lewis base reaction regulator.
A catalyst composition as described. 4. (a) Structural formula M (NR ¹ ) (NR ² ) (R
³ ) (R ⁴ ) (where R ¹ , R ² , R ³ and R ⁴ are alkyl,
A cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, haloalkyl, haloaralkyl, substituted or unsubstituted aryl or aralkyl group, and a group similar to these containing silicon; Different groups. ) In the solvent (b) in the presence of M (NR ¹ )
One of the imide groups NR ¹ or NR ² of (NR ² ) (R ³ ) (R ⁴ ) is hydrogenated to form an amine R ¹ NH ₂ or R ² N
By contact with a hydrogen source capable of forming H ₂ , the structural formula is (R ⁷ CH =) M (NR ¹ ) (GR ⁵ )
An olefin metathesis polymerizable compound (olefin metathesis catalyst) which is (GR ⁶ ) (NH ₂ R ² ) (where M
Is Mo or W; R ¹ , R ² , R ⁵ , R ⁶ are alkyl, haloalkyl, haloaralkyl, cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, substituted or unsubstituted aryl or aralkyl groups; And groups similar to these, including silicon,
And the same or different groups selected from the group consisting of G is an oxygen, sulfur or amide (NH) group, and R ⁷ is a group selected from the group consisting of alkyl, substituted or unsubstituted aryl and aralkyl groups, and similar groups including silicon. is there. ). 5. The method of claim 1, wherein (1) (a) at least an olefin monomer capable of metathesis polymerization and (b) a structural formula M (N
Polymerizing a reaction mixture comprising at least one catalyst precursor of R ¹ ) (NR ² ) (R ³ ) (R ⁴ ) and (c) an activator for activating at least one polymerization catalyst precursor A method of molding a polymer molded article containing a metathesis polymer, comprising: pouring the molded article into a mold where a reaction occurs; and (2) removing the molded article from the mold. Here, M is molybdenum or tungsten, and R ¹ , R ² , R ³ and R
⁴ consists of the same or different alkyl, haloalkyl, haloaralkyl, cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, substituted or unsubstituted aryl and aralkyl groups, and similar groups including silicon. A group selected from a group. 6. A method according to claim 1, wherein one stream comprises at least one metathesis polymerization catalyst precursor and the other stream comprises at least one activator for activating the polymerization catalyst precursor. (2) combining a plurality of reactive streams comprising a metathesis polymerizable olefin monomer or mixture of monomers to form a reaction mixture, and (2) forming a mold in which the polymerization reaction occurs. (3) A reaction injection molding method of a molded article containing a metathesis polymer, which comprises (3) removing a product from a mold.
Here, the catalyst precursor has the structural formula M (NR ¹ ) (NR ² )
Having the structural formula (R ³ ) (R ⁴ ), M is molybdenum or tungsten, and R ¹ , R ² , R ³ and R ⁴ are the same or different, alkyl, haloalkyl, haloaralky, cycloalkyl It is a group selected from the group consisting of alkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl, substituted or unsubstituted aryl or aralkyl groups, and similar groups containing silicon. 7. The method of claim 6, wherein the reaction mixture comprises an elastomer.