CA2005688A1 - Oxide cocatalysts in ring opening polymerization of polycycloolefins - Google Patents

Abstract

ABSTRACT OF DISCLOSURE

This invention pertains to the use of a novel cocatalyst in ring opening polymerization of a cycloolefin containing a norbornene moiety in conjunction with a metathesis catalyst, said cocatalyst is selected from siloxalanes, stannoxalanes, germoxalanes, plumbosalanes, aluminoxanes, and mixtures thereof.

0456E/la

Description

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N()VE1 OXIDE COCATP,LYSTS
IN RI~aG OPENIN~; POL1~ERIZATION OF POI.YCYCLOOLEFINS

Ring opening polymerization with a 5 metathesis catalyst system o cycloolefins is well known. The cycloolefins for purposes herein are monomers which contain a norbornene group and generally include norbornene compounds, dicyclopentadiene, and similar polycycloolefin monomers. The metathesis catalyst system includes a catalyst and a cocatalyst. The catalyst i5 generally selected from molybdenum and tungsten compounds whereas the cocatalyst is selected from organometallics such as alkylaluminums and al~ylalumlnum halides.
U.S. patent 4,400,340 to Klosiewicz describes a tungsten-containing catalyst such as tungsten halide or tungsten oxyhalide. The catalyst is suspended in a solvent to prevent it from prepolymerizing a monomer to which is added an alcoholic or a phenolic compound to facilitate solubilization of the tungsten catalyst in the monomer and a Lewis base or a chelant to prevent premature polymeri~ation of the solution of the tungsken compound and the monomer. Amount of the tungsten compound is 0.1 t:o 0.7 mole per liter of solvent. ~eight ratio of the tungsten compound to the alcoholic or phenolic compound is 1:1 to 1:3, and amount of th~ Lewis base or chelant is 1 to 5 moles thereof per mole of the tungsten compound. Treatment of the tungsten compound should be carried out in the absence of moisture and air to prevent deactivation of the tungsten compound catalyst. The catalyst must be treated in the manner outlined above in order to render it soluble in the cycloolefin monomer. The cocatalyst in this patent is disclosed as being 5~

selected rom tetrabutyltin and alkylaluminum compounds such as alkylaluminum dihalide or dialkylaluminum halide where the alkyl group contains 1 to 1~ carbon atoms. The preferred alkyl group is ethyl with diethylaluminum chloride being the most preferred cocatalyst. These cocatalysts are sensitive to air and moisture but are readily soluble in the cycloolefin monomers.
U.S. patent 4,380,617 to Minchak et al discloses metathesis catalyst systems for polymerizing cycloolefins. The catalysts are defined as organoammonium isopolymolybdates and organoammonium isopolytungstates and these catalysts are soluble in cycloolefins and are insensitive to air and mois~ure. The cocatalysts in this patent are similar to the cocatalysts disclosed in USP 4,400,340 and are generally selected from organometallics, particularly alkylaluminum halides although in a less preferred embodiment, other metals can ~e used in place o~ aluminum such as lithium, magnesium, boron, lead, zinc, tin, silicon, and germanium. Also, metallic hydrides can be used in whole or in part for the organometallic cocatalysts. Alkylaluminum and the corresponding organom6~talllc compounds can also be used as cocatalysts herein.
U.S. patent 4,426,502 discloses the use of alko~yalkylaluminum halides or arylo~yalkylaluminum halides as cocatalysts in metathesis catalyst systems to polymerize cycloolefin monomers. These cocatalysts are disclosed as especially useful in conjunction with organoammonium isopolytungstate and isopolymolybdate catalysts in polymerization of cycloolefins or norbornene-type monom~rs. By modifying the alkylaluminum halide cocatalysts to alko~y or arylo~y alkylaluminum halides, the reducing ~56~

power of the cocatalysts is thus lowered to provide adequate pot life for mi~ing various ingre~ients at room temperature, and for work interruptions, before initiation of polymerization and subsequent rapid S polymerization.

SUMMARY
Polymerization of cycloolefins containing a norbornene group is carried out in the presence of a metathesis catalyst sy~tem composed of a metathesis catalyst and a metathesis cocatalyst selected from silo~alane, stanno~alane, germosalane, plumboxalane, and alumino~ane cocatalysts. These cocatalysts are generally soluble in inert solvents and in the cycloolefins but are sensitive to o~ygen and moisture.

~ETAI~E~ ~ES~RI~TION O~ TH~ INVENTION
This invention resides in the use of modified cocatalysts in the ring opening polymerization of cycloolefins containing a norbornene group. These cocatalysts ars soluble in hydrocarbon solvents and in the cycloolefin monomers which contain a norbornenel group. Metathesis catalyst~, particularly th~ose selected from mol~bdenum and tungsten compounds, together with other ingredients, can be used in conjunction with the modified cocatalysts described herein to polymerize cyclooleEins containing a nor~ornene group by solution or bulk polymerization.
Suitable cocatalysts herein are define~ by the following formula:

(Rnk!O) aRb~lXc where: ~ is silicon (Si), t;n (Sn), germanium SGe), lead ~Pb), or aluminum ~Al);

3~

R and Rl are individually selected from alkyl, alkylene, alkynyl, aryl, aralkyl, aral~ylene, and aralkynyl groups containing l-lB carbon atoms, preferably, R and Rl are individually selected from i alkyl groups of 1 to 3 carbon atoms and phenyl groups, however, when M is aluminum, one o~ th~ R
groups can be a halide;
X is selected from chlorine, fluorine, bromine, or iodinA, but preferably chlorine;
a = 1/2 to 2 1/2, preferably 1 to 3/4 b = 1/4 to 2, preferably 1/2 to 1 c = 0 to 2, preferably 3/4 to 1 1/4 a t b ~ c = 3 n = 3 e~cept n is 2 when M is aluminum Alcohols and phenols are described as cocatalyst modifiers by the Minchak USP 4,426,502 in polymerization of cycloolefins containing norbornene group. These cocatalysts are defined as ~RO)aRlAlXC, where the various parameters are de~ined above. Replacing the (OR) group with a silo~y group (OSiR3) also generates an active cocatalyst system in combination with a metathesis catalyst component. The ~silo~alane~, dascribed herein a~ suitable cocatalysts, can be prepared by reacting an appropriate silyl alcohol with an alkyl aluminum. A general reaction shown below for triethyl aluminum and trimethysilyl alcohol demonstrates preparation of a silosalane cocatalyst:

2 5 3 ~ 3)3SioH ~ (C2H5)2Al-~-Si(CH ) The resulting cocatalyst is diethylaluminum tri-methylsilosalane. Alternatively, a triethylaluminum can be reacted with octamethylcyclotetrasilane to produce disthylaluminum dimethylethyl silo~alane.

;~0~

Other pref~rred cocatalysts include trimethyl diethylsiloxalalle, dimethylethyl diethylsilo~alane, methylethyl diethylsilo~alane, and methyl isobutylsiloxalane.
A preparation of the silo~alanes is described in USP 3,969,332, which is incorporated herein by reference.
Similarly, stanno~alane cocatalysts can be synthesized by reacting an alkyltin hydro~ide, such as trimethyl or triphenyltin hydro~ide, with an alkylaluminum, such as triethylaluminum, to produce a stannosalane cocatalyst, in the following manner:

3 ( 2H5)3A~ (C2H5)2Al-o-snR3 The cocatalysts containing germanium or lead are prepared in the same way as the si:Lo~alanes and stanno~alanes. The cocatalysts containing another alurninum atom, the alumino~anes, are prepared differently by reacting an alkyl aluminum or an alkyl aluminum halide, as follows:

C2H5 ~ C2H5 HOH ~ (C2H5)3Al ~ Al-O-Al C2~5 C2H~

Ths new cocatalysts are particularly efficient and allow for th~ us~ of halogen-free cocatalysts in combination with metathesis catalysts.
The catalysts suitable herein are metathesis catalysts which include halides, osyhalides, and o~ides of molybdenum, tungsten, and tantalum compounds, and organoammonium molybdates and tungstates. The latter catalysts are insensitive to oxygen and moisture in the environment.

Preferred catalysts are organoammonium isopolymolybdates and tungstates that are selected from those defined as follows:

4 ~(2y-6~ y or ~R3NH~(2 6 ~
whsre O represents o~ygen; M repre~ents either molybdenum or tungsten; ~ and y represent the number of M and O atoms in the molecule based on the valence of ~6 for molybd~num, ~6 or tungsten, and -2 for o~ygen; and the R and Rl radicals can be same or different and are selected from hydrogen, alkyl, and alkylene groups each containing from 1 to 20 carbon atoms, and cycloaliphatic groups each containing from 5 to 16 carbon atoms. All of t~e R and Rl radicals cannot be hydrogens nor be small in the number of carbon atom~ since such a condition will render the mo].ecule essentially insoluble in hydrocarbons and mo~t organic solvents. In a preferred embodiment, the ~ radicals are selected from alkyl groups each containing 1 to 18 carbon atoms wherein the sum of carbon atoms on all the R radicals is from 20 to 72, more preferably rom 25 to 48. In a preferred embodiment, the Rl radica:L~ are selected from alkyl groups each containing from 1 to 18 carbon atoms wherein tha sum of carbon atoms on all of the Rl radicals i~ ~rom lS to 54, more preferably from 21 to 42.
The norbornene-type monomers or cycloolefins 3Q that can be polymerized in accordance with the process described herein are characterized by the presence of the norbornene group, defined structurally by the following formula I:

~ (I) 3~

Pursuant to this definition, suitable norbornene-type monomers include substituted and unsubstituted norbornenes, dicyclopentadienes, dihydrodicyclopentadienes, trimers of s cyclopentadiene, and tetracyclododecenes.
Contemplated herein are also lower alkyl norbornenes and lower allcyl tetracyclododecenes wherein the lower alkyl group contains 1 to about 6 carbon atoms.
Preferred monomers of the norhornene-type are those defined by the following formulas II and III:

~ Rl ~ ~ ~ R3 (II)1 (III) where R and R are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated hydrocarbon cyclic groups formed by R and Rl to~ether with the two ring carbon atoms connected thereto containing 4 to 7 carbon atoms. In a preferred embodiment, R and are independently selected from hydrogen, alkyl groups of 1 to 3 carbon atoms, and monounsaturated hydrocarbon cyclic groups containing 5 carbon atoms, the cyclic group being ormed by R and Rl as well as by the two carbon atom~ connected to R and ~1 In reference to formula III, R2 and R3 are independen~ly selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, preferably 1 to 3 carbon atoms. E~amples of pref2rred monomers referred to herein include dicyclopentadiene, trimers and tetramers of cyclopentadiene:
methyltetracyclododecene; 2-norbornene and other norbornene monomers such as 5-methyl-2-norbornene, ~0~

5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hesyl-2-norbornene, 5-octyl-2-norbornene, and 5-dodecyl-2-norbornene;
vinyl norbornene, and ethylidene norbornene.
The monomer or mixture of norbornene-type monomers can contain up to about 20% by weight thereof of at least one other polymerizable monomer.
Such other polymerizable monomers are preferably selected from monocycloolefins containing 4 to 12 carbon atoms, preferably 4 to 8 carbon a~oms, e~amples of which include cyclobutene, cyclopentene, cyclopentadiena, cycloheptene, cyclooctane, 1,5-cyclooctadiene, cyclodecene, cyclododecene, cyclododecadiene, and cyclododecatriene~ As should be apparent, cycloolefins that cannot be polymerized hy ring opening, i.e., cyclohe~ene and derivatives thereof, are not employed in the polymerization process o this invention e~cept as solvents.
In solution pol~nerization, a hydrocarbon reaction solvent is mised with a cycloolefin monom~r or a misture thereof, with or without other polymeri2able monomers, and the mi~ture of the monomer and solvent is charged into a reactor. A
molecular weight modi~ier selected from nonconjugated acyclic olefins is then charged into ~he reactor ollowed by ths cocatalyst of the pres~nt invention and at least one molybdate or tungstate compound catalyst that is soluble in the cocatalyst and the monomer~ The reaction can be conducted at 0 to 100C, preferably ~0 to 80C, or at ambient temperature an~ carried out to completion in less than two hour~ and shortstopped by addition of an alcohol. The resulting product is a smooth, viscous polymer cement. Upon removal of the solvent, the polymer is ~ thermoplastic, solid material.

~0~

Suitable solvents for solution poly~erization include aliphatic and cycloaliphatic hydrocarbon solvents containing 4 to lO carbon atoms such as pentane, hesane, heptane, octane, cyclohe~ane, cyclohe~ene, cyclooctane and the like;
aromatic hydrocarbon solvents containing 6 to 14 carbon atoms which are liquid or easily liquified such as benzene, toluene, naphthalene and the like;
and substituted hydrocarbons wherein the substituents are inert, such as dichloromethane, chloro~orm, chlorobenzene, dichlorobenzene, and the like.
Cyclohesane was found to be an escellent solvent.
The polymer need not be soluble in the solvent. The solvent may be added at any point in the charging procedure, but a portion, preferably 0.1 to 10% of the total solvent, is used to dissolve the catalyst and the remainder added before the catalyst solution. Generally, 1/2 to 2 liters of solvent is used per lO0 grams of monomer.
A solution polymerization activator may be used but is not generally needed. Examples of activator~ include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, phenol, ~thyl mercaptan, 2-chloroethanol, 1,3-dichloropropanol, p-bromophenol, epichlorohydrin, ethylene 03ide, cyclopentene-2-hydropero~ide, cumyl hydropero~ide, tertiary butyl pero~ide, benzoyl pero~ide, and air or ogygen. The activator may be employed in a ranye from about 0 moles to ahout 3 moles per mole o~ the cocatalyst, more preferably from about 0 to about l mole per mole. The activator may be added at any point in the charge procedure but it is more preferably added last, or with the catalyst.
At least one nonconjugated acyclic olefin can be used as a molecular weight modifier ha~ing at least one hydrogen on each double-bonded carbon atom and containing 2 to 12 carbon atoms, more preerably 3 to 8 carbon atoms. E~amplas of suitable acyclic olefins include l-olefins, 2 olefins, 3-olefins, and nonconjugated triolefins. More preferably, the nonconjugated acyclic olefin is selected from the group consisting of l-olefins and 2-olefins containing 3 to 8 carbon atom~ such as l-butene, 3-methyl-1-butene, 2-pentene, 4-methyl-2-pentene, and the like. Compounds not having hydrogen atoms substituted on double-bonded carbons are unreactive in this invention.
The nonconjugated acyclic olefin can be used in a molar ratio to total monomer charge of from ~5 about O.Q001 to about 1 mole per mole of the monomer charge. The nonconjugated acyclic olefin can be charged directly or in solution at any point in the charge procedure, but it is more preferably charged along with the monomers. When charged last, the nonconjugated acyclic olefin is pre~erably charged before reaction begins.
The monomer can be added at any point in the charging procedure. Normally, however, the monomer, solvent and nonconjugated acyclic olefin are added first to the reactor vessel. These ingredients can be added separat~ly or as a mi~ture o ingredients.
~e~t, th~ cocatalyst and the catalyst are added separately, usually in the hydrocarbon solvent deseribed above. The metathesis catalyst component is added following addition of the cocatalyst component although the order can be reversed.
Completion of the polymerization reaction is indicated by the disappearance of the monomer in the charge, as monitored by gas chromatography.

~3~

Bulk polymerization is carried out in absence of a solvent by polymerizing cycloolefin monomer or a mixture thereof by means of a metathesis catalyst system wherein the catalyst component is a molybdate or tu~gstata compound and the cocatalyst component is a cocatalyst of this invention. The monomer can be formed into a hard object in a single step by means of reaction injection molding (RIM) process wherein polymerization takes place in a mold. E~amples of such objects include business machine housings, furniture, window frames, automobils and recreation vehicle parts, and the like.
Since the metathesis catalysts described herein are soluble in a norbornene-type monomer or a mi~ture thereo, the polymerization can be carried out in absence of a solvent and other additives used in solution polymerization. Since the cocatalysts ar~ also soluble in such monomers, this, of course, facilitates polymerization in bulk and makes it possible to polymerize the norbornene-type monomer(s) by reaction injection moltling process.
Ths catalysts, or mistures thereof, are employed at a level of 0.01 to 50 millimoles of the metal~s) per mole of totaL monomer(s), preferably 0.1 to 10 millimoles. The molar ratio of the cocatalyst to the catalyst is not critical and can range from about 200:1 or more to 1:10 , preferahly 10:1 to 2:1 of the matal(s) in the cocatalyst to the combined amount of molybdenum or tungsten in the catalyst.
If the cocatalyst does not contain any halide or if more halogen is desired, then a halogen source is used. Suitable halogen source is selected from halosilanes which are used in amount of 0.05 to 10 millimoles per mole of the norbornen~-type monomer, prefera~ly 0.1 to 2 millimoles per mole of 5~

the monomer. 5pecific e~amples of preferred halogen source are chlorosilanes such as dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, and the S like. In bulk polymeriYation such as reaction injection molding pro~sss, conversion of in e~cess of 95~, preferably in e~cess of 98~ can be attained, measured by the thermal gravimetric procedure.
In order to further illustrate the invention described herein, the following e~amples are presented that demonstrate certain aspects of the invention herein in greater dstail. It is to be understood, however, that the e~amples are presented for illustrative purposes and not in any sense are to limit the scope of the invention herein, the scope of which is defined by thc appended claims.

EXA~PLE 1 This e~ample demonstrates preparation of the ~ silo~alana cocatalyst which is ~elieved to have the following formula:

(~2H5)0.5 [(C2~5)3si]l 5 AlCl ~5 The monomer mixtulre used her~in was 92.5 weight parts dicyclopentadliene ~DCPD) and 7.5 weight parts ethylidene norbornene (E~
The preparation procedure involvPd dissolving liquid triethyl silanol [(C2H5)3SiOHl in a liquid DCPD/ENB monomer mi~ture in a bottle under nitrogen to give a 1 molar solution or solution(A~. Diethylaluminumchloride in solid form was dissolved in the DCPD/ENB mcnomer mi~ture to give a 0.5 molar solution or solutiontB).
Then, 0.9 ml of solution(A) was added with mixing to ~3~

25.4 ml of DCPD/ENB to make solution(c). Then, 1.2 ml of solution(s) was added with mixing to solution(C) which resulted in a colorless solution of the cocatalyst in the monomer mixture. The resul~ing cocatalyst ~olution became warm on mi~ing and tha reaction was accompanied by evolution of ethane gas.

This e~ample demonstrates preparation of the stanno~alane cocatalyst which is believed to have the following formula:

( 2H5)0.8 ~(C6H5)3sn]l 2 AlCl The monomer mi~ture used herein was that of dicyclopentadiene (DCPD~ and ethylidene norbornene (E~B) in 92.5/7.5 weight ratio.
This cocatalyst was prepared in a similar manner to that of the siloxalane cocatalyst of E~a~ple 1 by dissolving solid triphenyltin hydroxide in the DCPD/ENB mi~ture u,nder nitrogen to give a 1 molar solution or solution~A). Then, solid di~thylaluminum chloride ~was also dissolved in the ~CPD/E~B monomer mi~ture to give a 0.5 molar solution or solution(B). Then, 0.9 ml of solution(A) was added to 25.4 mls of the DCPD/ENB monomer mi~ture to yield ~olutiontC). Finally, 1.2 mls o~ solution(B) was added with agitation to solution~C) and a colorless cocatalyst solution in the monomer mi~ture was obtained. The solution became warm on mi~ing and the reaction was accompanied by evolution of ethane gas.

XAMP~E 3 This e~ample demonstrates polymerization of a monomer misture of dicyclopentadiene ~DCPD) and ethylidene norbornene ~ENB) in weight ratio of 92.5~7.5 with a ilosalane cocatalyst of this invention.
Three polymerizations were conducted with triethylsilanol, designated below as (SiOH), silicon tetrachloride (SiC14), tris(tridecyl)ammonium molybdate designated as AM below which has the formula t~t~ l3H27)H]3 M826;
diethylaluminum chloride (DEAC~. Order of addition of th~ materials and amounts in milliliters (mls~ is given below:
Order of Addition and Material ~ B C
DCPD/E~B 12.7 25.4 25.4 SiOH, 1.0M 0.333 0.84 0.84 DEAC, 0.5~ 0.6 1.2 1.2 SiCl~, 0.25M 0.6 1.2 1.2 AM, 0.1N 0.75 1.5 1.5 Wt. Ratio SiOH/DEAC 1.1/1 1.4/1 1.4/1 Ths materials given above in solution form, w~re prepared in the monomer mi~ture of DCPD~ENB, in which they are soluble.
It should ba apparent that the first three steps noted abo~e involve preparation of the cocatalyst of this in~ention.
The material~ were added in the given order to 7 oz. bottles provided wit}l injection caps~ The bottles were vigorously agitated after each addition and each addition was made in quick succession.
3S Bottl~ A was allowed to remain at room temperature ~5~

while bottle B was allowed to stand at room temperature or about 10 minutes and then was placed in an oven maintained at 140C.
The contents of bottle A polymerized immediately into a dark brown ma~s. Contents of bottle B polymerized within a few minutes after being placed in the 140C oven.
~ottle C was allowed to stand at amhient t~mperature for 3 hours after which time no reaction had occurred. The bottle was then placed in an oven at 140C after which polymerization to a solid mass occurred within a few minutes. This e~ampla serves to illustrate the e~cellent pot-life properties of the catalyst mi~tures of the current invention.
EX~MP~E_4 This example demonstrates polymerization of the monomer mi~ture of dicyclopentadiene (DCPD) and ethylidene norbornene (EN~) in weight ratio of 92.5/7.5 using tha stannosalane cocatalyst of this invention.
Procadure involve~d the addition of 25.4 mls of the DCPD/ENB monomer mi~ture to a bottle followed by 0.72 ml of a 1 molar solution of triphenyltin hydro~ide ~(C~H5)3SnOH], and 1.2 mls of a 0.5 molar solution of diethylaluminum chloride (DEAC).
This procedure is the same as that for pr2paration of the novel cocatalyst of this invention.
Preparation of the cocatalyst was followed by addition of 102 mls of 0.25M solution of silicon tetrachloride and 1.5 mls of a O.lN solution of tri(tridecyl)ammonium molybdate catalyst. Weight ratio of the triphenyltin hydro~ide to DEAC wa~ 1.2/l.
Upon addition of the amine molybdate catalyst, solution polymerized immediately into a solid mass of a dark brown color.

3 aJ fi ~ ~3 This e~ampls demonstrates preparation of the alumino2ane catalyst and polymerization therewith of a monomer mi~ture of dicyclopentadiene (DCPD) and ethylidene norbornene ~EN~) in weight ratio of 92.5~7.5. Preparation of the cocatalyst was under nitrogen.
To 28.59 of the monomer mi~ture of DCPD and ENB in a reaction bottle was added 6.0mg (0.33m mol) o~ distilled water. The resulting solution was shal~en to ensure good mi~ing and it was then added to a 0.5 molar solution of diethylaluminum chloride (DEAC) in the monomer misture. The resulting aluminosane cocatalyst is believed to have the ~5 following structural formula:

Cl Cl \ Al-O-Al C2H5 ~ C~H5 (diethyldichlorodialuminumo~ane) To the above solution in the reaction bottle was added 1.25 ml (0.31m mol) of a 0.25 molar solution of silicon tetrachloride in the monomer mi~tur~. On addition o 1.6 ml. o the 0.1 molar amine molybdate catalyst solution in the monomer mi~ture with shaking, polymerization in the reaction bottle ensued almost immediately. Polymerization was evident from the color change to dark brown of the polymerization mi~ture, a high esotherm, and thickening of the contents of the reaction bottle.
The oontents of the bottle was rapidly converted to a solid mass.

6fi~

When the above polymerization was run with unmodified DEAC, what was obtained was encapsulation of the catalyst and incompleke conversion of the monomers ~

Claims (16)

1. Process for preparing a polymer by ring opening polymerization in the presence of a metathesis catalyst system comprising the step of polymerizing a cycloolefin monomer containing a norbornene group, or a mixture thereof, in the presence of an effective amount of a metathesis catalyst component and an effective amount of a metathesis cocatalyst component, said cocatalyst component is salected from siloxalanes, stannoxalanes, germoxalanes, plumboxalanes, aluminoxanes, and mixtures of such cocatalysts.

2. Process of claim 1 wherein said norbornene group is defined as follows:

and said catalyst component is selected from molybdenum compounds, tungsten compounds, halides, oxyhalides, and oxides of tantalum compounds, and mixtures thereof.

3. Process of claim 2 wherein said cocatalysts are defined as follows:

where: M is silicon, tin, germanium, lead, or aluminum;
R and Rl are individually selected from alkyl, alkylene, alkynyl, aryl, aralkyl, aralkylene, and aralkynyl containing 1-18 carbon atoms, and when M is aluminum, one R group can also be selected from halides;

X is fluorine, bromine, chlorine or iodine a is 1/2 to 2 1/2 b is 1/4 to 2 c is 0 to 2, and a + b + c = 3 n = 3 except n is 2 when M is aluminum

4. Process of claim 3 wherein R and R1 are individually selected from alkyl groups containing 1 to 3 carbon atoms and phenyl groups;
X is chlorine; "a" is 1 to 1 3/4; "b" is 1/2 to 1;
and "c" is 3/4 to 1 1/4.

5. Process of claim 4 wherein said catalyst component is selected from organoammonium isopolymolybdates and organoammonium isopolytungstates defined as follows:
[R4N](2y-6x)Mx Oy or (2y-6x)Mx Oy where O represents oxygen; M represents either molybdanum or tungsten; s and y represent the number of M and O atoms in tha molecule based on the valence of +6 for molybdenum, +6 for tungsten, and -2 for oxygen; and the R and Rl radicals can be same or different and are selected from hydrogen, alkyl, and alkylene groups each containing from 1 to 20 carbon atoms, and cycloaliphatic groups each containing from 5 to 16 carbon atoms; the sum of carbon atoms in R
and Rl radicals is large enough to render to catalyst component soluble in hydrocarbons and organic solvents.

6. Process of claim 5 wherein in the formula for the catalyst components, R radicals are individually selected from alkyl groups of 1 to 18 carbon atoms and the sum of the carbons in all R
radicals is 20 to 72; and Rl radicals are individually selected from alkyl groups of 1 to 18 carbon atoms and the sum of the carbons in all radicals is 15 to 54.

7. Process of claim 6 wherein the sum of the carbons in all Rl radicals is 25 to 48 and the sum of the carbons in all Rl radicals is 21 to 42.

8. Process of claim 3 wherein said cycloolefin monomer is selected from the following monomers, and mixtures thereof:

where R and Rl ars independently selected from hydrogen, alkyl, and aryl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups containing 4 to 7 carbon atoms formed by R and and ths two ring carbon atoms connected thereto;
where R2 and R3 are independently selected from hydrogen and alkyl groups of 1 to 20 carbon atoms;
amount of said catalyst being 0.01 to 50 millimoles molybdenum or tungsten per mole of total cycloolefin monomer and the molar ratio of said cocatalyst as aluminum and silicon or tin to said catalyst as molybdenum or tungsten is in the range of about 200:1 to 1:10.

9. Process of claim 4 wherein said cycloolefin monomer is selected from the following monomers, and mixtures thereof:

where R and R1 are independently selected from hydrogen, alkyl, and aryl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups containing 4 to 7 carbon atoms formed by R and R1 and the two ring carbon atoms connected thereto;
where R2 and R3 are independently selected from hydrogen and alkyl groups of 1 to 20 carbon atoms;
amount of said catalyst being 0.01 to 50 millimoles molybdenum or tungsten per mole of total cycloolefin monomer and the molar ratio of said cocatalyst as aluminum and silicon or tin to said catalyst as molybdenum or tungsten is in the range of about 200:1 to 1:10.

10. Process of claim 9 wherein said cycloolefin monomer is selected from substituted and unsubstituted 2-norbornenes, dicyclopentadienes, dihydrodicyclopentadienes, trimers of cyclopentadienes, tetramers of cyclopentadienes, tetracyclododecenes, and mistures thereof.

11. Process of claim 9 wherein said cycloolefin monomer is selected from norbornene, methylnorbornene, vinyl norbornene, ethylidene norbornene, tetracyclododecene, methyltetracyclododecene, dicyclopentadiene, trimer of cyclopentadiene, tetramer of cyclopentadiena, and mixtures thereof; wherein amount of said catalyst is 0.1 to 10 millimoles; and wherein molar ratio of said cocatalyst to said catalyst is 10:1 to 2:1.

12. Process of claim 4 which also includes the step of adding a halogen source in amount of 0.1 to 2 millimoles per mol of said monomer(s), said halogen source is selected from chlorosilanes.

13. Process of claim 12 wherein said halogen source is selected from dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, and mixtures thereof.

14. Process of claim 13 which includes the step of mixing multiple streams containing said catalyst, said cocatalyst, said halogen source, and said monomer(s) to produce a reactive mixture, and the step of injecting said reactive mixture into a mold where said polymerization takes place to produce a thermoset polymer.

15. Process of claim 14 wherein conversion of said monomer(s) to said polymer is at least 95%, measured by thermal gravimetric procedure.

16. Process of claim 3 conducted in the presence of an effective amount of a solvent.