JPH02283721A - Ring opening polymerization of cycloolefin and catalyst used therein - Google Patents

Abstract

PURPOSE: To obtain a cycloolefin polymer being soluble in a cycloolefin monomer and inert to air or moisture and having an improved pot life by polymerizing a norbornene-group-containing cycloolefin monomer in the presence of a metathesis catalyst and a specified metathesis cocatalyst.

CONSTITUTION: A norbornene-group-containing cycloolefin monomer of formula I or II [wherein R and R' are each H, a 1-20C alkyl or an aryl, or they together with the two ring carbon atoms may form a 4-7C (un)saturated cycluc group; and R² and R³ are each H or a 1-20C alkyl] is polymerized through ring opening at 0-100°C for 2 hr or below in an inert solvent in the presence of a metathesis catalyst and at least one metathesis cocatalyst selected among siloxalanes, stanoxalanes, germoxalanes, bromboxalanes and aluminoxanes.

COPYRIGHT: (C)1990,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for ring-opening polymerization of norbornene group-containing cycloolefin monomers in the presence of a metathesis catalyst and a metathesis cocatalyst, and a catalyst system used for this polymerization. .

[Conventional technology]

Ring-opening polymerization of cycloolefins using metathesis catalyst systems is well known. Here, the term "cycloolefin" refers to a monomer having a norbornene group, and generally includes norbornene compounds, synchropentadiene, and polycyclic cycloolefins similar to these. Metathesis catalyst systems include a catalyst and a cocatalyst, the catalyst generally selected from molybdenum and tungsten compounds, and the cocatalyst selected from organometallic compounds such as alkyl aluminums and alkyl aluminum halides.

U.S. Pat. No. 4,400,340 to Klozywicz et al. discloses tungsten-containing catalysts such as tungsten halides and tungsten oxyhalides. This catalyst prevents prepolymerization of the monomer by suspending it in a solvent, promotes solubilization in the monomer by adding an alcohol or phenol compound, and dissolves tungsten compounds by adding a Lewis base or a chelating agent. This prevents premature polymerization of the 7-mer solution. The amount of tungsten compound is from 0.1 to 0.7 mol per 12 of the solvent, the weight ratio of tungsten compound to alcohol or phenolic compound is from l:1 to 1:3, and the amount of Lewis base or chelating agent is Compound 1
1 to 5 moles per mole.

The tungsten compound is handled in the absence of moisture or air to prevent deactivation of its catalytic activity.

In order to solubilize the catalyst in the cycloolefin monomer, treatment as described above is necessary.

The above-mentioned US patent discloses tetrabutyltin and alkylaluminum compounds such as alkylaluminum cybarides and dialkylaluminum halides (the alkyl group has 1 to 10 carbon atoms) as cocatalysts. The preferred alkyl group is the ethyl group, and diethylaluminium chloride is the most preferred cocatalyst. These cocatalysts are sensitive to air and moisture, but are easily soluble in cycloolefin monomers.

U.S. Pat. No. 4,380,617 to Minchinatsuta et al. discloses a metathesis catalyst system for cycloolefin polymerization. The catalysts used here are organic ammonium isoborimolybdate and organic ammonium isopolytungstate, which are soluble in cycloolefins and are not sensitive to air or moisture. The cocatalysts used in this patent are similar to those described in the aforementioned U.S. Pat. No. 4,400,340 and are generally selected from organometallic compounds, particularly alkyl aluminum halides. Although somewhat less effective, lithium, magnesium, boron, lead, zinc, tin, silicon, and germanium can be used in place of aluminum, and metal hydrides can be used in place of all or part of the organometallic compound. You can also do it. Alkylaluminiums and corresponding organometallic compounds can also be used as cocatalysts.

U.S. Pat. No. 4,426,502 discloses the polymerization of cycloolefin monomers using a metathesis catalyst system cocatalyst with an alkoxyalkylaluminum halide or an aryloxyalkylaluminum halide. It is stated that it is particularly preferred to use these cocatalysts in combination with organic ammonium isopolycungestate and isoborimolybdate in the polymerization of cycloolefins, ie norbornene-based monomers. By modifying the alkylaluminum halide cocatalyst to an alkoxy or aryloxyalkylaluminum halide, the reducing power of the cocatalyst is reduced, allowing sufficient pot life for mixing the various components at room temperature and for work interruptions. become.

[Problem to be solved by the invention]

It is an object of the present invention to provide a cocatalyst that is soluble in cycloolefin monomers, is not sensitive to air or moisture, and provides a catalyst system with excellent pot life when used in combination with a metathesis catalyst for the polymerization of cycloolefin monomers. is to provide.

[Means to solve the problem]

The present invention provides at least one member selected from siloxalane, stanoxalane, germoxalane, plumboxalane, and aluminoxane as a metathesis cocatalyst when performing ring-opening polymerization of a cycloolefin monomer having a norbornene group in the presence of a metathesis catalyst and a metathesis cocatalyst. It is characterized by the use of the following compounds.

In the present invention, the polymerization of cycloolefins having norbornene groups is carried out using a metathesis catalyst system consisting of a metathesis catalyst and a specific metathesis cocatalyst, namely a metathesis cocatalyst selected from siloxalane, stanoxalane, germoxalane, plumboxalane, aluminoxane. carried out in the presence of These cocatalysts are generally soluble in inert solvents and cycloolefin monomers. These cocatalysts are used in the solution or bulk polymerization of cycloolefins in combination with metathesis catalysts, especially those selected from molybdenum and tungsten compounds.

The preferred cocatalyst used is shown by the following formula.

(R, MO), R', ^IXc where M is silicon (St), tin (Sn), germanium (
Ge), lead (Pb) or aluminum (A1),
R and R1 are each selected from an alkyl group having 1 to 1 B carbon atoms, an alkylene group, an alkynyl group, an aryl group, an aralkyl group, an aralkylene group, and aluminum, preferably an alkyl group having 1 to 3 carbon atoms, and a phenyl group. Ru. When M is aluminum, one of R may be a halogen.

X is chlorine, fluorine, bromine or iodine, preferably chlorine, and a is 1/2 to 2·1/2, preferably 1 to 1·3/4
, b is 1/4 to 2, preferably 1/2 to 1, C is θ to 2, preferably 3 to 4 to 1·1/4,
The total of a, b, and c is 3. n is 3, but 2 when M is aluminum.

U.S. Patent No. 4.426.502 for minced jutsuta:
Cocatalysts modified with alcohols or phenols have been disclosed in the polymerization of cycloolefins having norbornene groups. These cocatalysts are (RO), R'AIX
The symbol in the 0 formula, denoted by c, is the same as above.
Substitution of the (OR) group in the formula by a siloxy group (O5iR,) also produces an active catalyst system when combined with a metathesis catalyst component. The preferred cocatalyst, siloxalane, is obtained by reacting a suitable silyl alcohol with an aluminum alkyl. It is aluminum trimethylsiloxalane.

(CJs) x^1 + (CH3) 5sioll→(
CtHs) JI OSi (C)13) sAlso,
When triethylaluminum and octamethylcyclotetrasilane are reacted, diethylaluminum dimethylethylsiloxalane is obtained.

Examples of other preferred cocatalysts include trimethyldiethylsiloxalane, dimethylethyldiethylsiloxalane, methylethyldiethylsiloxalane, methylisobutylsiloxalane, and the like. A method for synthesizing siloxalane is disclosed in US Pat. No. 3,969,332.

Similarly, a stanoxalane cocatalyst can be obtained according to the following formula by reacting an organotin hydroxide such as trimethyltin hydroxide or triphenyltin hydroxide with an alkyl aluminum such as triethylaluminum.

RsS, OR+ (Calls) s^l→(C!)l
s) tAl 0 S, R3 Cocatalysts containing germanium and lead can be obtained in the same manner as siloxalane and stanoxalane. Separately, the method for synthesizing the cocatalyst (aluminoxane) having an aluminum atom is different, and is obtained by reacting an alkyl aluminum or an alkyl aluminum halide as shown in the following formula.

This new cocatalyst is effective and allows the use of halogen-free cocatalysts.

The catalyst used in the present invention is a metathesis catalyst, for example,
Examples include halides, oxyhalides and oxides of molybdenum, tungsten and tantalum, organic ammonium molybdate, and organic ammonium tungstate. Among them, organic ammonium molybdate and tungstate have the advantage of not being sensitive to surrounding oxygen and moisture.

Preferred catalysts are organoammonium isoborimolybdates and tungstates, which are represented by the formula:

(R4N) +2y-&xl MXO, or (R'J
H) (2y-Ax)MxOy where 0 represents oxygen, M represents molybdenum or tungsten, X and y are the number of M atoms and oxygen atoms in the molecule, respectively, and for M atoms A valence of +6 is given, and a valence of -2 is given to an oxygen atom. R and R1 may be the same or different and are selected from hydrogen, alkyl groups and alkylene groups having 1 to 20 carbon atoms, and alicyclic groups having 5 to 16 carbon atoms. If all of R and R1 are hydrogen or the total number of carbon atoms is too small, it will not dissolve in hydrocarbons or many organic solvents. Preferred specific examples include R being selected from alkyl groups having 1 to 18 carbon atoms, and the total number of all carbon atoms being 20 to 72;
More preferably, it is 25 to 48, and R' is selected from alkyl groups having 1 to 18 carbon atoms, and the total number of carbon atoms of all R1 is 15 to 54, more preferably 21 to 42.
belongs to.

The norbornene monomer, ie, cycloolefin, used in the present invention has a norbornene group represented by the following formula (r).

0...(1) Specific examples of preferable norbornene monomers include norbornene, synclopentadiene, dihydrocinclopentadiene, cyclopentadiene dimer, cyclopendadiene tetramer, tetracyclododecene, alkyls thereof, Examples include alkenyl, alkylidene, and aryl substituents (for example, norbornene and tetracyclododecene having a lower alkyl group having 1 to 6 carbon atoms).

Preferred norbornene monomers have the following formulas (II) and (
In).

In the formula, R and R1 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, and a cyclic saturated or unsaturated hydrocarbon having 4 to 7 carbon atoms formed by R and R1 together with two carbon atoms in the ring. selected from the group. Preferred R and R1 are each independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a monounsaturated hydrocarbon cyclic group having 5 carbon atoms formed by R and R' and 02 carbon atoms in the ring. . R2 and R of formula (I[)
3 is each independently hydrogen, carbon number 1-20, preferably 1-20
3 alkyl groups.

Specific examples of preferred monomers include synchlopentadiene, cyclopentadiene trimer, cyclopentadiene tetramer, methyltetracyclododecene, 2-norbornene, 5-methyl-2-norbornene, 5.6-cymethyl-2- norbornene, 5-ethyl-2-norbornene,
Examples include 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, vinylnorbornene, and ethylidene norbornene.

The norbornene-based monomer or monomer mixture may contain up to about 20% by weight of at least one other polymerizable monomer. These other polymerizable monomers are selected from cycloolefins having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, specific examples of which include cyclobutene, cyclopentene, cyclopentadiene, cycloheptene, cyclooctene, 1.5-cyclo Examples include octadiene, cyclodecene, cyclododecene, cyclododecadiene, and cyclododecatriene.

However, cycloolefins without ring-opening polymerizability, ie, cyclohexene and its derivatives, can be used as solvents, but cannot be used as monomers.

When performing solution polymerization, first, a cycloolefin monomer and a hydrocarbon reaction solvent are mixed, and the mixture is charged into a reactor. A molecular N modifier selected from non-conjugated acyclic olefins is then added followed by the co-catalyst of the invention and at least one molybate or tungstate compound catalyst. These catalysts are soluble in cocatalyst and monomer. The reaction is usually carried out at 0 to 100°C, preferably 20 to 8°C.
It is carried out at 0°C1 or room temperature and is completed within 2 hours. Polymerization is stopped by adding alcohol. The product is a smooth, viscous polymer solution, and upon removal of the solvent a thermoplastic solid polymer is obtained.

Specific examples of preferred solvents used in solution polymerization include aliphatic and alicyclic hydrocarbon solvents having 4 to 10 carbon atoms such as pentane, hexane, heptane, octane, cyclohexane, cyclohexene, cyclooctane, etc.; benzene, toluene, Liquid or easily liquefiable aromatic hydrocarbon solvents having 6 to 14 carbon atoms, such as naphthalene; substituted hydrocarbon solvents having inert substituents, such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene, and the like. Among these, cyclohexane was found to be an excellent solvent. Although there is no particular restriction on the timing of addition of the solvent, a portion of the solvent, preferably 0.1 to 10% by weight of the total, is used to dissolve the catalyst, and the remainder is added prior to addition of the catalyst solution.

Generally, the amount of solvent used is 172 g/100 g of monomer.
~21.

An activator for solution polymerization can be added, but is not necessary for boat fishing. Specific examples of activators include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, phenol, ethyl mercaptan, 2-chloroethanol, 1,3-dichloropropanol, p-
Examples include bromophenol, epichlorohydrin, ethylene oxide, cyclopentene-2-hydroperoxide, cumyl hydroperoxide, t-butyl peroxide, benzoyl peroxide, air or oxygen. The activator is generally used in a proportion of 0 to about 3 moles, preferably 0 to about 1 mole, per mole of cocatalyst.

The activator may be added at any point in the preparation of the reaction solution, but
Preferably, it is added last or together with the catalyst.

molecule! As a regulator, a carbon number of 2 to 12, preferably 3 to
Non-conjugated acyclic olefins can be used in which the carbon atoms forming the double bond each have at least one hydrogen. Specific examples of preferred acyclic olefins include 1-olefin, 2-olefin, 3-olefin, non-conjugated triolefin, and more preferred non-conjugated acyclic olefins include 1-butene, 3-methyl-
It is selected from 1-olefins and 2-olefins having 3 to 8 carbon atoms, such as 1-butene, 2-pentene, 4-methyl-2-pentene, and the like. Compounds that do not have hydrogen on the carbon atoms that form double bonds are inactive as molecular weight modifiers.

The non-conjugated acyclic olefin is approximately 0.0 per mole of monomer.
001 to about 1 mole. Such a non-conjugated acyclic olefin may be added at any point in the preparation of the reaction solution, but is preferably added together with the monomer. If added at the end, it is preferably added before polymerization begins.

Although the timing of adding the monomer is not particularly limited, it is usually charged into the reactor first together with the solvent and the non-conjugated acyclic olefin. Each of these components may be added separately or as a mixture. The cocatalyst and catalyst are then added separately. These are commonly used as hydrocarbon solvents as described above. The order of addition can also be reversed so that the catalyst and cocatalyst are added in that order. The monomer in the reaction solution is detected by gas chromatography, and when it disappears, the polymerization reaction is complete.

Bulk polymerization is carried out by polymerizing cycloolefin monomers in the absence of solvent using a metathesis catalyst system consisting of a molybdate or tungstate compound catalyst and a cocatalyst of the present invention.

Reaction injection molding (RIM), in which polymerization is carried out in a mold, allows solid molded articles to be obtained from monomers in one step. Examples of molded products include housings for office equipment, furniture, window frames, and parts for automobiles and leisure vehicles. Since the above metathesis catalyst is soluble in norbornene monomers, polymerization is carried out in the absence of solvents and other additives used in solution polymerization. The cocatalyst is also heptamer soluble, which facilitates bulk polymerization and enables the polymerization of norbornene-based monomers by RIM.

The catalyst is generally used in an amount of 0.01 to 50 mmol, preferably 0.1 to 10 mmol, per mole of monomer. Although the molar ratio of cocatalyst to catalyst is not necessarily critical, the ratio of metal in the cocatalyst to molybdenum or tungsten in the catalyst is typically from 1 to 1:10, preferably from 10:1 to 2:1. be.

A halogen source is used if the cocatalyst does not contain halogen or if it is desired to contain more halogen. The preferred halogen source is a halosilane, which is typically 0. ．．
It is used in a proportion of 0.05 to 10 mmol, preferably 0.1 to 2 mmol. Preferred halogen sources include:
Examples include chlorosilanes such as dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, and tetrachlorosilane. In bulk polymerizations such as RIM, conversions of 95% or more (measured by thermobalance) are obtained, preferably 98% or more.

[Examples] The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples in any way.

This example demonstrates the preparation of a siloxalane cocatalyst believed to have the formula:

(C, +1.). , s ((CJs)ssio) +
The monomer mixture used in 5A1c1 consisted of 92.5 parts by weight of synchropentadiene (DCPD) and 7.5 parts by weight of ethylidene norbornene (ENB).

Liquid triethylsilanol ((Calls)
:+5iOH) to obtain a 1 molar solution (A
liquid). Diethylaluminum chloride (DEAC) was dissolved in the DCPD/ENB monomer mixture to obtain a 0.5 molar solution (solution B). Then 0.9 d of liquid A and D
25.41 d of the CPD/ENB monomer mixture was mixed to obtain liquid C, and 1.2 tails of liquid B was added to this to obtain a colorless cocatalyst monomer solution. When this solution was mixed, the temperature rose, and ethane gas was generated as the reaction progressed.

1 Plate I This example demonstrates the preparation of a stanoxalane cocatalyst believed to have the formula:

(C2H5)0.11 ((Cbls):+5nO)
1. The monomer mixture using ZAIcl is DCPD/E
NB = 92.5/7.5 (weight ratio).

This cocatalyst was prepared similarly to the siloxalane cocatalyst of Example 1. First, solid triphenyltin hydroxide was dissolved in a DCPD/ENB mixture under a nitrogen atmosphere to form a 1 molar solution (liquid A). Then D.E.A.
C was dissolved in the DCPD/ENB monomer mixture to give 0.5
A molar solution was prepared (solution B).

0.9 d of solution A and DCPD/ENB monomer mixture 2
5.4td was mixed to make liquid C, and finally liquid C and liquid B1.
The two components were mixed under stirring to obtain a colorless cocatalyst monomer solution. When mixed with this solution, the temperature rose and ethane gas was generated as the reaction progressed.

This example uses DCPD/E using a siloxalane cocatalyst.
NB = 92.5/7.5 (weight ratio) Polymerization of a monomer mixture is shown.

Triethylsilanol (abbreviated as SiOH), silicon tetrachloride (SiC14), (N(C+1llz7)
) II) Tris(tridecyl)ammonium molybdate (abbreviated as AM) and DI, denoted by 3MosOzb
Three polymerizations were performed using EAC. The addition order and usage amount (d) of each component are as follows.

DCPD/ENB SiOII, 1.0 M DEAC, 0.5 M SiC14, 0.25 M AM, 0.1 N SiO)1/DEAC (weight ratio) 12.7 25.4 0.333 0.84 0.6 1. 2 0.6 1.2 0.75 1.5 1.1/ 1 1.4/ 25.4 0.84 1.2 1.2 1.5 1 1.4/1 The above components are DCPD/ENB Prepared as a solution of monomer mixture. It will be clear that the first three steps prepare the cocatalyst of the invention.

Each ingredient was added in the given order to a 7 oz bottle with a pouring cap. Each component was added in rapid succession with vigorous stirring after each step.

Bottle A was kept at room temperature, and bottle B was left at room temperature for about 10 minutes and then placed in an oven at 140°C. The contents of Bottle A polymerized immediately to form a dark brown polymer. The contents of bottle B were placed in an oven at 140°C2.
Polymerization occurred after ~3 minutes. No polymerization occurred in Bottle C even after being left at room temperature for 3 hours, but when placed in an oven at 140° C., polymerization occurred within 2 to 3 minutes to obtain a solid product. This example shows that the catalyst system of the present invention has an excellent pot life.

This example is a DCPD using a stanoxalane cocatalyst.
/ENB =92.5/7.5 (weight ratio) The polymerization of the monomer mixture is shown.

25.4jd of CPD/ENB monomer mixture in a bottle
and then 1 molar concentration of triphenyltin hydroxide ((Calls)ssnOH) 0.72id
, 0.5 molar DHAC solution 1.2 d! added. This procedure is the same as the method for preparing the inventive cocatalyst shown in Example 2.

Subsequently, 1.2 ml of a 0.25 molar silicon tetrachloride solution and 1.5 ml of a 0.1 normal tris(tridecyl)ammonium molybdate catalyst solution were added. The weight ratio of triphenyltin hydroxide to DHAC was 1.2/1.

When the molybdate catalyst is added, the reaction solution polymerizes immediately,
It turned into a dark brown solid.

This example demonstrates the preparation of an aluminoxane cocatalyst and its use in the polymerization of a DCPD/ENB = 92.5/7.5 (weight ratio) monomer mixture.

DCPD/I in the reaction bottle! Nu monomer mixture 28
．． Then, 6.0 μm (0.33 mmol) of distilled water was added. After shaking well to ensure thorough mixing, a 0.5 molar DHAC monomer solution was added.

The produced aluminoxane cocatalyst is thought to have the following structure.

To the above solution in the bottle was added 1.25 m (0.31 mmol) of a 0.25 molar monomer solution of silicon tetrachloride. When 1.6 m of a 0.1 N amine molybdate catalyst monomer solution was added with shaking, polymerization occurred instantly. It was clear that polymerization had occurred because the contents turned dark brown, a strong exotherm occurred, and the contents thickened. The contents quickly changed to a solid substance.

For comparison, when unmodified DEAC was used in the same manner as above, the reaction was too fast and the catalyst was trapped inside the polymer, resulting in insufficient monomer conversion.

Claims (1)

[Claims] 1. A method for producing a polymer by ring-opening polymerization in the presence of a metathesis catalyst system, which comprises polymerizing a cycloolefin monomer having a norbornene group in the presence of a metathesis catalyst and a metathesis cocatalyst, A method for producing a cycloolefin polymer, characterized in that at least one compound selected from siloxalane, stanoxalane, germoxalane, plumboxalane, and aluminoxane is used as a cocatalyst, 2. The metathesis catalyst is a molybdenum compound, a tungsten compound, and The method according to claim 1, wherein the tantalum is selected from halides, oxyhalides and oxides. 3. The production method according to claim 2, wherein the cocatalyst is a compound represented by the following formula. (R_mMO)_aR^1_bAlX_c In the formula, M is silicon, tin, germanium, lead, or aluminum, and R and R^1 are each an alkyl group having 1 to 18 carbon atoms, an alkylene group, an alkynyl group, an aryl group, or an aralkyl group. , aralkylene group, and aralkynyl group (however, when M is aluminum, one of R may be a halogen), X is fluorine, bromine, chlorine, or iodine, and a is 1/2 to 2・1/2, b is 1/4 to 2, c
is 0 to 2, and the total of a, b, and c is 3 (however,
When M is aluminum, n is 2). 4, R and R^1 are each selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, X is chlorine, and a is 1 to 1.
4. The manufacturing method according to claim 3, wherein 3/4, b is 1/2 to 1, and c is 3/4 to 1.1/4. 5. The method according to claim 4, wherein the catalyst is selected from solvent-soluble organic ammonium isopolymolybdate and organic ammonium isopolytungstate. 6. The production method according to any one of claims 1 to 5, wherein the cycloolefin monomer is a compound represented by the following formula or a mixture thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R and R^1 are each hydrogen, an alkyl group and an aryl group having 1 to 20 carbon atoms, and R and R^1 are two carbon atoms in the ring. 4. The method according to claim 3, wherein R^2 and R^3 are each selected from hydrogen and an alkyl group having 1 to 20 carbon atoms. 7. Cycloolefin monomers include norbornene, synclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, cyclopentadiene trimer, cyclopentadiene tetramer, alkyl-substituted products, alkenyl-substituted products, alkylidene-substituted products, and aryl-substituted products of these. 8. The method of claim 3, wherein a halogen source is used in addition to the catalyst and cocatalyst. 9. The method according to any one of claims 1 to 7, wherein the thermosetting polymer is obtained by carrying out the polymerization in bulk in a mold. 10, the following formula (R_nMO)_aR^1_bAlX_c [In the formula, M is silicon, tin, germanium, lead or aluminum, and R and R^1 are each an alkyl group having 1 to 18 carbon atoms, an alkylene group, an alkynyl group, selected from aryl, aralkyl, aralkylene and aralkynyl (provided that when M is aluminum, one of R may be a halogen), X is fluorine, bromine, chlorine or iodine, and a is 1/2~2・1/2, b is 1/4~2,
c is 0 to 2, and the total of a, b, and c is 3 (however, when M is aluminum, n is 2)] In coexistence with a metathesis catalyst consisting of a compound represented by A cocatalyst for polymerizing norbornene group-containing cycloolefin monomers. 11. Metathesis catalyst and the following formula (R_nMO)_aR^1_bAlX_c [In the formula, M is silicon, tin, germanium, lead or aluminum, and R and R^1 are each an alkyl group or an alkylene group having 1 to 18 carbon atoms. , alkynyl group, aryl group, aralkyl group, aralkylene group and aralkynyl group (when M is aluminum, one of R may be a halogen), X is fluorine, bromine, chlorine or iodine, a is 1/2~2・1/2, b is 1/4~2, c is 0
~2, and the total of a, b, and c is 3 (however, when M is aluminum, n is 2)] A catalyst system for polymerizing monomers. 12, the following formula (RnMO)_aR^1_bAlX_c [In the formula, M is silicon, tin, germanium, lead or aluminum, and R and R^1 are each an alkyl group having 1 to 18 carbon atoms, an alkylene group, an alkynyl group, selected from aryl, aralkyl, aralkylene and aralkynyl (provided that when M is aluminum, one of R may be a halogen), X is fluorine, bromine, chlorine or iodine, and a is 1/2~2・1/2, b is 1/4~2,
c is 0 to 2, and the total of a, b, and c is 3 (however, when M is aluminum, n is 2)] A metathesis cocatalyst and a norbornene group-containing cycloolefin monomer A reaction stock solution for bulk polymerization of cycloolefin consisting of.