USH1388H - Polyolefin polymer and method of making same - Google Patents

Abstract

A polyolefin composition comprises repeating units of a metathesis polymerizable olefin monomer, a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and at least one member selected from the group consisting of: (i) a Lewis acid catalyst and a Lewis acid cocatalyst, effective to obtain a residual metathesis polymerizable olefin monomer level of from 0 to 0.25 weight percent, based on the weight of the polyolefin; (ii) an anionic polymerization catalyst; (iii) a free radical polymerization initiator; and (iv) a hydrosilation polymerization catalyst. The method for making the composition is also disclosed. The use of metathesis polymerization in conjunction with another type of polymerization can achieve a variety of beneficial effects, including a very low level of residual metathesis polymerizable monomer.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention pertains to processes for the polymerization of olefins, notably strained ring polycyclic olefins, particularly dicyclopentadiene, as well as to the corresponding polymeric reaction product. The invention utilizes metathesis polymerization in combination with one or more of a variety of other catalysts selected from the group consisting of: a Lewis acid catalyst and cocatalyst, an anionic catalyst, a free radical initiator, and a hydrosilation catalyst. The processes of the present invention are particularly suited to manufacturing plastic articles via reaction injection molding (i.e. "RIM").

2. Background and Relevant Information

Preparation of thermoset cycloolefin polymers via metathesis catalysis is a relatively recent development in the polymer art. Klosiewicz, in U.S. Pat. Nos. 4,400,340 and 4,520,181, teaches preparation of cycloolefins via a twostream reaction injection molding technique wherein a first stream, comprising a metathesis polymerizable olefin (such as dicyclopentadiene) in admixture with a metathesis catalyst, and a second stream, comprisihg a metathesis polymerizable olefin (such as dicyclopentadiene) in admixture with metathesis catalyst activator, are combined in a mix head and immediately injected into a mold where, within a matter of seconds, polymerization and molding to a permanently fixed shape take place simultaneously. Klosiewicz also teaches the use of a reaction rate moderator in the activator stream to delay the catalyst activation until the reaction mass is totally within the mold. Klosiewicz states that the catalyst can be a tungsten halide or a tungsten oxyhalide, and that the activator can be tetrabutyl tin, or an alkylaluminum compound, and that the reaction rate moderator can be an ester, ether, ketone or nitrile.

U.S. Pat. No. 4,835,230 (to N.P. KHASAT et al.) relates to the use of a cationic polymerization initiator in the preparation of a thermoset polymer. Cationic polymerization initiators disclosed include protonic acids, Lewis acids and other cation generators such as alkyl perchlorates and ionizing radiation, and it is further disclosed that the cationic polymerization initiator can be used alone or in conjunction with a cocatalyst. KHASAT et al. utilizes a plurality of reactant streams in the polymerization of dicyclopentadiene, especially for RIM. KHASAT et al. states that the number of applications for thermoset polydicyclopentadiene has been somewhat limited because of the distinctive odor of the residual dicyclopentadiene monomer. Finally, KHASAT et al. states that the use of a cationic polymerization initiator can increase the glass transition temperature (T_g) and polymer heat deflection temperature (HDT) of thermoset dicyclopentadiene polymers and copolymers, and reduce residual monomer content without reducing impact strength.

U.S. Pat. No. 4,481,344, to Newburg (NEWBURG), relates to a method for making thermoset poly(dicyclopentadiene), and to the product so produced. NEWBURG states that although thermoset poly(dicyclopentadiene) is well suited for a wide variety of applications, particularly as an engineering plastic, there are a number of applications in which its use has been somewhat limited due to the distinctive odor of the residual dicyclopentadiene monomer. NEWBURG describes a twopart metathesis catalyst system in which the first part comprises a metathesis catalyst, and the second part comprises an activator, and wherein at least one part comprises a halogen-containing hydrocarbyl additive. The hydrocarbyl additive contains at least one trihalogen-substituted atom or at least one activated halogen atom. NEWBURG's Table I discloses various hydrocarbyl additives, and Table II provides results in terms of residual dicyclopentadiene monomer in various poly(dicyclopentadiene) products produced using various hydrocarbyl additives.

European Patent Application 0,374,997 relates to the polymerization of cyclic olefins in the presence of a catalyst comprising (a) a transition metal compound, (b) a co-catalyst, and (c) a boron halide compound. This application states that this catalyst has been found to exhibit high activity in the polymerization of dicyclopentadiene, and high conversion in a reaction injection molding process having a short induction time and relatively low polymerization temperature.

SUMMARY OF THE INVENTION

The present invention relates to a composition comprising: (A) a polyolefin comprising repeating units of a metathesis polymerizable olefin; (B) a metathesis polymerization procatalyst and a metathesis polymerization procatalyst activator; and (c) at least one member selected from the group consisting of:

i. a Lewis acid catalyst and a Lewis acid cocatalyst, effective to obtain a residual metathesis polymerizable olefin monomer level of from about 0 to 0.25 weight percent, based on the weight of the polyolefin;

ii. an anionic polymerization catalyst;

iii. a free radical polymerization initiator; and

iv. a hydrosilation polymerization catalyst and a monomer comprising a hydrosilane (.tbd.Si--H) group.

The present invention also relates to a method for making the composition of the present invention. The method comprises combining a metathesis polymerizable olefin monomer with a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and at least one member selected from the group consisting of:

i. a Lewis acid catalyst and a Lewis acid cocatalyst, effective to obtain a residual metathesis polymerizable olefin monomer level of from 0 to 0.25 weight percent, based on the weight of the polyolefin;

ii. an anionic polymerization catalyst;

iii. a free radical polymerization initiator; and

iv. a hydrosilation polymerization catalyst and a monomer comprising a hydrosilane (.tbd.Si--H) group.

The method is preferably carried out by providing a plurality of reactant streams which are mixed together to form a reaction mixture. The reaction mixture is formed into a desired shape before the polymerization of the metathesis polymerizable olefin.

Although the present invention relates to the polymerization of olefins in general, and more particularly to the polymerization of cycloolefins, the present invention is concerned with achieving one or more of a variety of effects. One of the most significant effects is achieving a low level of residual metathesis polymerizable olefin monomer in a polymeric reaction product comprising repeating units of a metathesis polymerizable olefin. Other effects include increasing polymer T_g, increasing polymer impact strength, improving polymer stiffness, improving polymer heat distortion temperature, improving polymer oxidative heat stability, and reducing polymer odor.

DETAILED DESCRIPTION OF THE INVENTION

In general, the metathesis polymerizable olefin monomer may be any monomer which can be polymerized in the presence of one or more metathesis catalysts. Cycloolefins comprise a preferred group of metathesis polymerizable olefinic monomers. Metathesis-polymerizable, strained-ring, non-conjugated polycyclic cycloolefins comprise a group of still more preferred olefins useful in the process of the present invention. Most strained-ring, non-conjugated, polycyclic cycloolefins are metathesis polymerizable.

More specifically, preferred metathesis polymerizable monomers include cycloolefins of the norbornene type, defined by the following formulas: ##STR1## where R and R¹ are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated hydrocarbon cyclic groups formed by R and R¹ together with the two ring carbon atoms. R² and R³ are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms.

Preferably, the metathesis polymerizable olefin comprises a norbornene group. Preferred monomers include, for example, dicyclopentadiene, higher cyclopentadiene oligomers (such as trimers and higher oligomers of cyclopentadiene), norbornenes, norbornadiene, 4-alkylidene norbornene, dimethanooctahydronaphthalene, and dimethanohexahydronaphthalene, as well as substituted derivatives of these compounds.

The most preferred cyclic olefin monomer for use in the present invention is dicyclopentadiene, i.e. most preferably the polyolefin comprises repeating units of dicyclopentadiene. Preferably, the polyolefin comprises repeating units of dicyclopentadiene in an amount of from about 1 to 100 weight percent, based on the weight of the polyolefin. Still more preferably, repeating units of dicyclopentadiene are present in an amount of from about 10 to 100 weight percent, based on the weight of the polyolefin. Most preferably, repeating units of dicyclopentadiene are present in an amount of from about 75 to 100 weight percent, based on the weight of the polyolefin.

Dicyclopentadiene may be used as the sole monomer in the polymerization, or the polymerization may be carried out using a mixture of dicyclopentadiene with other strained-ring hydrocarbons in ratios of 1 to 99 mole percent of either monomer, preferably about 75 to 100 mole percent dicyclopentadiene.

The most preferred dicyclopentadiene for preparing polymers according to the process of the present invention is commercially available endo-dicyclopentadiene (i.e., 3a,4,7,7a-tetrahydro-4,7-methano-1H-indene). The exo-isomer, while not commercially available, can be used just as well. In fact, it is present in commercially-available dicyclopentadiene at a relatively low level, e.g. 0.5% by weight. The preferred commercially available monomer normally has a purity of at least 97 weight percent and preferably at least 99 weight percent. The preferred commercially available monomer further comprises tricyclopentadiene (i.e. cyclopentadiene trimer) in an amount of from about 0 to 2 weight percent, as well as from about 0 to 2 weight percent of still other norbornene-group containing cycloolefins. The exo-isomer of dicyclopentadiene is generally present in commercially available dicyclopentadiene at a relatively low level, e.g. about 0.5 weight percent, based on the weight of the dicyclopentadiene.

Commercially available dicyclopentadiene should have a purity high enough to prevent impurities from inhibiting the polymerization. The low boiling fraction should be removed. This can be done by stripping away several percent of the unsaturated four to six carbon atom volatiles, i.e., the volatiles distilled below 100° C. at about 90±3 torr absolute pressure. It is often desirable to purify the starting material even further by treatment with an absorbent such as molecular sieves, alumina or silica gel. Additionally, the water content of the starting material should be below about 100 ppm. The presence of water interferes with polymerization by hydrolysis of both the catalyst and the activator components of the catalyst system. Water can be removed by azeotropic distillation under reduced pressure.

The metathesis polymerizable olefin, alone or in combination with other monomers present in the reaction mixture, polymerizes to form one or more polymers. The resulting polyolefin (or polyolefins) preferably comprises repeating units of the metathesis polymerizable olefin in an amount of from about 1 weight percent to 100 weight percent, based on the weight of the polyolefin. More preferably, repeating units of the metathesis polymerizable olefin monomer are present in the polyolefin in an amount of from about 10 weight percent to 100 weight percent, based on the weight of the polyolefin. Most preferably, repeating units of the metathesis polymerizable monomer are present in the polyolefin in an amount of from about 75 to 100 weight percent, based on the weight of the polyolefin.

The process of the present invention may also be carried out by the polymerization of a plurality of monomers. Each of the monomers may be metathesis polymerizable, or only one of the monomers may be metathesis polymerizable. The additional monomer (or monomers) may polymerize to form a copolymer, a graft copolymer, a homopolymer, and/or an interpenetrating polymer network (IPN).

Any one or more of the following cycloolefins may be used as additional monomers, e.g. monomers used in combination with dicyclopentadiene. Such monomers include: norbornene-type comonomers such as norbornene, methylnorbornene, vinylnorbornene, ethylidenenorbornene, 5-ethylidene-2-norbornene, as well as m-diisopropenylbenzene, polyisoprene, styrene, α-methylstyrene, β-pinene, p-diisopropenyl-benzene, diisobutylene, polyindane, dimethanohexahydronaphthalene, tetracyclododecene(1,4,5,8-dimethano-1,2,4a,5,8,8a-octahydronaphthalene), methyltetracyclododecene, tetracyclododecadiene, 1,5,9-cyclododecatriene, 4-methylstyrene, dimethanohexahydronaphthalene, dimethanooctahydronaphthalene, and cyclopentadiene oligomers such as cyclopentadiene trimer (i.e. tricyclopentadiene, "CPT"), tetracyclopentadiene, and higher cyclopentadiene oligomers. In addition, compounds which can be alkylated, such as naphthalene, can be included.

Preferably the additional monomer is at least one member selected from the group consisting of: tricyclopentadiene, norbornene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, α-methylstyrene, pinene, 5-ethylidene-2-norbornene, β-pinene, polyisoprene, diisobutylene, polyindane, acenaphthylene, 5,5'-sulfonyl-bis(2-norbornene), hexamethylene-bis(5-norbornene-2-carboxylate), 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, hexamethylcyclotrisiloxane, 4-methylstyrene, and poly(vinylbenzyl chloride).

Most preferably the additional monomer is 5-ethylidene-2-norbornene.

Any metathesis polymerizable olefin may also be polymerized alone or in combination with any one or more additional metathesis polymerizable olefins, whether listed above or not. In addition, other monomers which will vary with the type of the additional polymerization, may be utilized, such as: styrenes, vinyl-substituted aromatic compounds, and methacrylates, which are subject to free radical polymerization; caprolactone, hexaalkylcyclotrisiloxane, methacrylates, and styrenes, which are subject to anionic polymerization; styrenes, divinylbenzene, α-methylstyrene, terpenes (such as β-pinene), diisopropenyl-benzenes, diisobutylene, polyisoprene, polybutadienes, polystyrenes, copolymers of styrene and dienes, polyindanes, which are subject to polymerization by the combination of a Lewis Acid catalyst and a Lewis Acid cocatalyst; and polysiloxanes and siloxysilanes polymerizable by a hydrosilation polymerization catalyst. In addition, aromatic molecules which can be alkylated, such as hindered phenols, aromatic amines, and hydrocarbons (such as naphthalene), can be included.

The additional monomer is used in the process of the present invention (hence present in the composition) in an amount of from about 1 to 99 weight percent, based on the weight of the polyolefin. More preferably, the additional monomer is used in the process in an amount of from about 1 to 50 weight percent, based on the weight of the polyolefin. Most preferably, the additional monomer is present used in the process in an amount of from about 1 to 25 weight percent, based on the weight of the polyolefin.

Suitable metathesis polymerization procatalysts include molybdenum halides and tungsten halides, and their corresponding oxyhalides, especially those having two valences satisfied by oxygen rather than halogen. Such procatalysts are herein referred to as "standard procatalysts". Halides and oxyhalides of still other transition metals such as rhenium, tantalum, and niobium are also suitable for use as metathesis polymerization procatalysts.

Tungsten halides and oxyhalides are among the preferred procatalysts. Still more preferred are mixtures or complexes of tungsten hexachloride (WCl₆) and a tungsten oxytetrachloride (WOCl₄) in a molar ratio of WOCl₄ to WCl₆ of about 1:9 to 2:1. Such mixtures or complexes can be prepared by contacting essentially pure WCl₆ with a controlled portion of an oxygen donor. Useful oxygen donors include, e.g., a hydrated salt, water, a wet molecular sieve and alkyl alcohols. The most preferred oxygen donor is t-butanol. Details of a catalyst preparation can be found in Klosiewicz, U.S. Pat. Nos. 4,400,340 and 4,568,660, and U.S. Pat. No. 4,696,585, to Martin, each of which is hereby incorporated, in its entirety, by reference thereto. In particular, U.S. Pat. No. 4,696,585 describes, in column 16, line 35, through Column 19, line 22, the preparation of a metathesis catalysts which can serve as the metathesis procatalyst.

The tungsten or molybdenum compound is not normally soluble in the methathesis polymerizable olefin monomer, but can be solubilized by complexing it with a phenolic compound. The tungsten or molybdenum compound is first suspended in a small amount of an inert diluent such as benzene, toluene, xylene or chlorinated benzene, to form a 0.1 to 1 mole per liter slurry. The phenolic compound is added to the slurry in a molar ratio of about 1:1 to 1:3 catalyst compound to phenolic compound, followed by passing a stream of dry inert gas through the agitated solution to remove hydrogen chloride gas that is formed. Alternatively, a phenolic salt, such as a lithium or sodium phenoxide, can be added to a tungsten compound/organic solvent slurry, the mixture stirred until essentially all of the tungsten compound is dissolved, and the precipitated inorganic salt removed by filtration or centrifugation.

All of these steps should be carried out in the absence of moisture and air to prevent deactivation of the procatalyst. Preferred phenolic compounds include phenol, alkyl phenols, halogenated phenols or phenolic salts such as lithium or sodium phenoxide. The most preferred phenolic compounds are t-butyl phenol, t-octyl phenol and nonyl phenol.

A particularly preferred procatalyst complex is described in U.S. Pat. No. 4,981,931, to Bell, which is hereby incorporated in its entirety, by reference thereto. This patent describes a tungsten catalyst complex having the formula: ##STR2## where X is Cl or Br, n is 2 or 3, R¹ is H, a Cl, an alkyl group having 1-10 carbons, an alkoxy group having 1 to 8 carbons, or a phenyl group; R² is H, a halogen, or an alkyl group having 1 to 9 carbon atoms; and R³ is a H, or an alkyl group having 1 to 10 carbon atoms together with a tin activator compound having the formula R₃ SnH, where R is an alkyl group having 1 to 10 carbon atoms, or a phenyl group.

The alkoxy groups R₁ can correspond to the following formulas: ##STR3## wherein m is between 0 and 7, n₁, n₂, and n₃ are integers, equal or different, between 0 and 5, wherein the sum of the three integers is between 0 and 5 inclusive, ##STR4## wherein the numbers n₄, n₅, n₆, and n₇ are equal or different, between 0 and 4 inclusive and the sum of the four numbers is between 0 and 4 inclusive. The bulky alkyl groups of R₂ can be for example isopropyl, isobutyl, tert-butyl, iso-amyl, tert-amyl or similar groups. The structure may be for example: ##STR5## where n₈, n₉, and n₁₀ represent integers, equal or different between 0 and 6 with the sum of the three numbers no greater than 6. Other examples of R₂ may be represented by the formula: ##STR6## wherein n₁₁, n₁₂, n₁₃, and n₁₄ are integral numbers the sum of which is no greater than 5. The two R² groups are generally bulky but do not have to be identical. The R² be methyl groups.

U.S. Pat. No. 5,082,909, which is hereby incorporated in its entirety by reference thereto, also relates to "Bell catalysts" for the metathesis polymerization of polyolefins.

The tungsten catalyst complex can be prepared in a manner similar to the method disclosed by Bassett et al. in The Journal of Inorganic Chemistry, Vol. 26, No. 25, pp. 4272-4277, (1987) and European Patent Appl. EP No. 259,215, Mar. 9, 1988, both of which are hereby incorporated, in their entireties, by reference thereto. Among the tungsten catalyst complexes that may be employed in this invention are WCl₂ (4-ethoxyphenoxy)₄, WCl₂ (4-butoxyphenoxy)₄, WCl₃ (2,6-di-tertbutylphenoxy) ₃, WCl₂ (phenoxy)₄, WCl₂ (3-methylphenoxy)₄, WCl₂ (4-methylphenoxy), WCl₂ (3,5-dimethylphenoxy)₄, WCl₂ (4-butylphenoxy)₄, WCl₂ (4-chlorophenoxy)₄, WCl₃ (2,6-dimethylphenoxy)₃, WCl₃ (2,4,6-trimethylphenoxy)₃, WCl₂ (4-phenylphenoxy)₄, WCl₂ (4-methoxyphenoxy)₄, and WCl₃ (2,6-diisopropylphenoxy)₃.

When used in conjunction with a procatalyst activator (described below), the "Bell-type" procatalyst acts to delay gelation and polymerization of the metathesis-polymerizable cycloolefins, for a time sufficient to at least charge the reaction mixture to a mold. Both the Bell-type procatalyst and the procatalyst activator have good stability, with resistance to oxygen and moisture. As reported in the '931 patent, the Bell-type procatalyst and the procatalyst activator are easily isolated, without requiring the addition of a rate moderator compound to obtain the desired delay in gel and cure time.

If necessary to prevent premature polymerization of the procatalyst component/monomer solution, which could occur within a matter of hours, about 1 to 5 moles of a Lewis base or a chelating agent can be added per mole of procatalyst compound. Preferred chelatants include acetylacetones, dibenzoyl methane and alkyl acetoacetates, where the alkyl group contains from 1 to 10 carbon atoms. Preferred Lewis bases are nitriles and ethers such as benzonitrile and tetrahydrofuran. The improvement in stability and shelf-life of the procatalyst component/monomer solution is obtained regardless of whether the complexing agent is added before or after the phenolic compound. When this complexed procatalyst component is added to purified cycloolefin, for example dicyclopentadiene, it forms a solution which is stable and has a shelf-life of several months in the absence of an activator.

The molar ratio of the procatalyst to metathesis polymerizable monomer (e.g. dicyclopentadiene) in the reaction mixture is generally from about 1:500 to 1:15,000, more preferably from about 1:2000 to 1:5,000. Still more preferably, the molar ratio of the procatalyst to monomer is from about 1:1000 to 1:3000, most preferably from about 1:1500 to 1:3000.

A lower amount of procatalyst not only results in a cost savings, but also a lower amount of procatalyst in the final product. It has been found that the lower amount of procatalyst in the final product provides a polymer which has less color and is less corrosive than its non-additive containing counterpart.

Metathesis polymerization procatalyst activators include alkylaluminum compounds, alkylzinc compounds, alkyltin compounds, alkylmagnesium compounds, alkyllithium compounds, and tin hydrides. Alkylaluminum compounds, such as trialkylaluminum compounds and dialkylaluminum halides, are preferred. Particularly preferred activators include dialkylaluminum halides containing an alkyl moiety of from 1 to 12 carbon atoms and iodide as the halide. Exemplary procatalyst activators include trialkylaluminum compounds, a dialkylaluminum halide, an alkylaluminum dihalide wherein the alkyl groups contain from 1 to 12 carbon atoms, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum chloride n-propoxide, a mixture of tri-n-octylaluminum:dioctyl-aluminum iodide:diglyme, tributyltin hydride, and tetrabutyl tin. The most preferred procatalyst activator is an 85:15:100 mixture (molar basis) of tri-n-octylaluminum: dioctylaluminum iodide:diglyme, in toluene.

The procatalyst activator can be prepared by mixing, for example, an alkyl aluminum compound or mixture of alkyl aluminum compounds with a Lewis base or chelating agent at a 1:1 to 1:5 molar ratio. While either order of addition, i.e., Lewis base to alkyl aluminum compound or alkyl aluminum compound to Lewis base, can be used, it is preferred to add the Lewis base to the alkyl aluminum compound, with agitation. The reaction is highly exothermic, and it is desirable to control the rate of Lewis base addition to the alkyl aluminum compound so as to maintain the temperature at less than approximately 50° C. to prevent decomposition of the rate moderator complex. In the case of solid Lewis bases, the base can be added as the solid or dissolved in a suitable nonreactive solvent such as toluene. The activator can also be prepared by dissolving or suspending the Lewis base in the cycloolefin and adding the alkyl aluminum component. Diglyme [i.e. bis(2-methoxyethyl) ether], may also be added to the activator solution.

The procatalyst activator is readily soluble in the cycloolefin, and is preferably in solution with the metathesis polymerizable olefin, which is preferably dicyclopentadiene. The solution of procatalyst activator and dicyclopentadiene monomer is storage stable (unlike the tungsten compound/monomer solution), and therefore needs no additives to prolong its shelf life, unlike the tungsten compound/monomer solution. If, however, an unmodified activator/monomer solution is mixed with the procatalyst/monomer solution, the polymerization reaction would initiate instantaneously, and the polymer could then set up in the mixing head.

The amount of procatalyst activator to be used differs with the particular procatalyst being used. For a "standard procatalyst" (i.e., procatalysts other than Bell procatalysts), the molar ratio of Al:W is generally from about 2:1 to 4:1, and is preferably from about 2.5:1 to 3.5:1, and is most preferably from about 2.75:1 to 3.25:1. For Bell procatalysts, the molar ratio of Sn:W is generally from about 1.5:1 to 9:1, preferably from about 2:1 to 6:1, and most preferably from about 2:1 to 3:1.

The onset of gelation or viscosity build-up of metathesis polyymerizable cycloolefins can be delayed by the addition one or more reaction rate moderators.

U.S. Pat. No. 4,458,037, to Leach, which is hereby incorporated in its entirety, by reference thereto, discloses extending the gelation time to as much as ten minutes at room temperature by the use of a dialkylaluminum iodide activator moderated by di-n-butyl ether.

U.S. Pat. No. 4,882,401, to Bell, which is hereby incorporated in its entirety, by reference thereto, discloses the use of alkylzinc activators instead of the alkylaluminum compounds usually used as activators in metathesis polymerization. The alkylzinc activators also serve to significantly increase gel and cure times, and may be used used in conjunction with tungsten or molybdenum compounds to which a phenolic compound has been added.

U.S. Pat. No. 4,883,849, to Matlack, which is hereby incorporated, in its entirety, by reference thereto, discloses certain nitrogen-containing compounds which act as moderators which significantly delay the onset of gelation or viscosity build-up of metathesis polymerizable cycloolefins, at temperatures up to at least about 80° C. These compounds may be added either to the catalyst-containing feedstream or to the activator-containing feedstream, provided that the components remain stable in the presence of these compounds.

The nitrogen compounds which can be employed include anilines, N-alkylanilines, alkyl arylamines, and related compounds. These nitrogen compounds may be represented by the general formula: ##STR7## wherein X represents aryl, alkaryl or haloaryl groups, Y represents hydrogen or an alkyl group, and Z represents alkyl, aralkyl, cycloalkyl groups or hydrogen. When neither Y nor Z represents hydrogen, X, Y and Z all must represent an alkyl group. Useful compounds include aniline, N-ethylaniline, indoline, triethylamine, ethylpiperidine, and methylpiperidine.

Preferred additives include N-ethylaniline and indoline. These preferred additives have been chosen as being readily available in the commercial marketplace, and as being effective in lower concentrations, thus minimally affecting the properties of the polymer being produced.

U.S. Pat. No. 4,727,125, to Nelson, which is also hereby incorporated in its entirety, by reference thereto, discloses delaying the onset of gelation or viscosity build-up at temperatures up to at least about 80° C., by employing, as a reaction rate moderator, a sterically unhindered or partially unhindered nucleophilic Lewis base. Sterically unhindered or partially unhindered nucleophilic Lewis bases which can be employed as moderators include unsaturated cyclic amines such as, e.g., pyridine, 2-,3-,4-, or 3,4-disubstituted pyridines, 2-,2,3,-di-, or 2,5-di-substituted pyrazines, quinoline and quinoxaline and cyclic saturated polycyclic amines such as hexamethylene tetramine and 1,4-diazabicyclo[2.2.2]octane, as well as still other nucleophilic Lewis bases including phenanthridine, pyrimidine, isoquinoline and substituted derivatives of these materials.

The sterically unhindered or partially unhindered nucleophilic Lewis bases can be employed in conjunction with conventional metathesis catalysts to polymerize any metathesis polymerizable olefin. A cycloolefin reaction mixture moderated by a sterically unhindered or partially unhindered Lewis base according to this invention remains fluid for a relatively long time at room temperature prior to forming a gel. As long a time as 1 to 4 hours can be required for gel formation at room temperature. Thus, the catalyst components need not be mixed and immediately injected into a mold. While the RIM technique can be employed, processing is not limited to the RIM technique. Moreover, the RIM technique can be used with a premixed reactive solution (i.e., cycloolefin containing both catalyst and activator) and materials can be charged directly into the heated mold without using a mix head on the molding machine.

The sterically unhindered or partially hindered moderators extend the gel time at convenient molding temperatures, i e , about 80° C. at which temperature the gel time can be extended to as long as three minutes or more. Solutions containing conventional rate moderators gel within 15 to 20 seconds at most. The extended gel time, during which the reaction mixture remains highly fluid, allows the reaction mixture to be used in techniques where molds are filled slowly, as is the situation, for example, in rotational molding, where centrifugal force is employed to distribute the mixture and where the polymerization reaction cannot start until uniform distribution is achieved. These moderators are also useful in preparing polymer articles filled with glass or other fibrous mat reinforcement where the mixture must remain fluid until it has completely impregnated the mat. Manufacture of large objects, where the volume of the mold, per se, necessitates long filling time, can also be facilitated by using these moderators.

U.S. Pat. No. 4,933,402, to Matlack, which is hereby incorporated in its entirety, by reference thereto, discloses the use of phosphorous-containing compounds as reaction rate moderators. These compounds are disclosed as delaying the onset of gelation at temperatures up to at least about 80° C. These compounds may be added either to the procatalystcontaining feedstream or to the procatalyst activatorcontaining feedstream, provided that the components remain stable in the presence of these compounds.

The phosphorus compounds suitable as moderators include trialkyl phosphites (especially tributylphosphites), norbornene phosphites, norbornene phosphates, trialkyl phosphates, triaryl phosphates, and related compounds. Phosphorus compounds suitable as moderators include those represented by the general formula: ##STR8## wherein X, Y and Z represent alkyl, cycloalkyl, alicyclic, aryl, aralkyl, alkaryl, alkoxy, alkylthio, aryloxy, arylthio, halogen or thiophene groups. X and Y may form a ring in which the phosphorus atom is included which is alicyclic, benzo or benzoalicyclic or X, Y and Z may form two rings which includes the phosphorus atom. Q represents oxygen, sulfur or nothing. Useful compounds include trimethyl phosphite, tris(2-chloroethyl)phosphite, ethyl dichlorophosphite, triisopropylphosphite, triisobutylphosphite, diethyl chlorophosphite, triethyl phosphite, isooctyldiphenyl phosphite, triisooctylphosphite, tris(5-norbornenyl-2-methyl)phosphate, triethyl phosphate, tributylphosphate, triphenylphosphate, tricresylphosphate, butylated triphenyl phosphate, diethylphenyl phosphonite, diisopropyl phenylphosphonite, ethyl diphenylphosphonite, tetraethyl pyrophosphite, 1,2-phenylenephosphorochloridite, ethylene chlorophosphite, diethyl ethylenepyrophosphite, diisodecylpentaerythritol diphosphite, tripentyl phosphite, trihexylphosphite, triheptylphosphite, trineodecylphosphite, tridodecyl trithiophosphite, tributylphosphine, triphenylphosphine, and tris(5-norbornenyl-2-methyl)phosphite.

Preferred additives include tris(5-norbornenyl-2-methyl)phosphite, tris(5-norbornenyl-2-methyl)phosphate, trimethyl phosphite, trialkyl phosphites, tributyl phosphate, trialkyl phosphates, trineodecyl phosphite, diethyl phenyl phosphonite, and diisodecylpentaerythritol diphosphite.

These preferred additives are readily available in the commercial marketplace, and are effective in relatively low concentrations, and thereby minimally affect the properties of the polymer being produced. Cycloolefin reaction mixtures moderated by phosphorus containing compounds remain fluid for a relatively long time at room temperature prior to forming a gel. By varying the amount of moderator, procatalyst, and procatalyst activator, it is possible to delay the gel time over a wide time period. Thus, the catalyst components need not be mixed and immediately injected into a mold. While the RIM technique can be employed, processing is not limited to the RIM technique. Moreover, the RIM technique can be used with a premixed reactive solution (i.e. cycloolefin containing both catalyst and activator) and materials can be charged directly into the heated mold without using a mix head on the molding machine.

Reaction rate moderators are generally used in conjunction with aluminum alkyl and tin alkyl-activated metathesis catalyst systems. If an alkylaluminum procatalyst activator is used, the onset of polymerization can be delayed by adding a reaction rate moderator selected from the group consisting of ethers, esters, ketones and nitriles. Ethyl benzoate and butyl ether are preferred. Particularly preferred is the dimethyl ether of diethylene glycol (diglyme), and butyl diglyme.

In general, the moderator can be used in an amount within the range of from about 0.1 moles of moderator per mole of tungsten, up to 5 mole percent, based on total metathesis polymerizable monomer content of the reaction mixture. Preferably the moderator is used in an amount of from about 0.5-2 mole percent based on the total metathesis polymerizable monomer content of the reaction mixture. Amine-containing moderators are preferably used in an amount of about 0.5 mole amine moderator per mole of tungsten compound. Phosphorus-containing moderators are preferably used in an amount of from about 1-2 moles phosphorus compound per mole tungsten compound. A preferred ratio of the "standard" procatalyst activator (e.g. an alkylaluminum compound) to moderator is from about 1:1.5 to about 1:5, on a molar basis.

In the instance in which a Lewis Acid catalyst and a Lewis Acid cocatalyst are used, most of the oxygen or nitrogen compound (i.e. the moderator) is tied up with the Lewis acid. In this instance, it is most preferred that the moderator is present in a 1:1 molar ratio with the sum of the amount of metathesis polymerization procatalyst (e.g. WOCl₆) and Lewis acid catalyst (e.g. BF₃). If boron trifluoride is used as the Lewis Acid catalyst, it is preferred to use a dialkylaniline moderator, instead of an alkylaniline moderator. If a Lewis Acid catlayst is not present, it is most preferred that the moderator is present in a molar ratio of from about 1:1 to 2:1, with the metathesis polymerization procatalyst.

In general, the Lewis acid catalysts suitable for use in the present invention include all compounds which act as Lewis Acids, other than compounds and complexes which serve as metathesis polymerization procatalysts. Lewis Acid catalysts include metal halides (other than metal halides which act as metathesis polymerization procatalysts). Such metal halides include boron halides, tin halides, aluminum halides, titanium halides, antimony halides, bismuth halides, iron halides, zinc halides, and zirconium halides. A group of preferred Lewis acids includes boron trifluoride etherate, boron trifluoride-N,N-diethylaniline, boron trifluoride-tetrahydrofuran, tin (IV) chloride, tin (IV) bromide, boron trifluoride quinuclidine, and a polymeric Lewis acid, a protonic acid, a cation generator, and ionizing radiation. Still more preferably, the Lewis acid comprises at least one member selected from the group consisting of boron trifluoride etherate, tin (IV) bromide and tin (IV) chloride. The most preferred Lewis acid catalyst is boron trifluoride etherate. Many other Lewis acid catalysts are known, and/or can be envisioned by those of ordinary skill in this art.

The Lewis acid catalyst is generally added in an amount of from about 0.1 to 5 weight percent, preferably from about 0.25 to 2 weight percent, and most preferably from about 0.5 to 1 weight percent, based on weight of monomer polymerizable with a Lewis Acid catalyst.

The Lewis acid catalyst can be added as such or can be formed in situ, for example, by adding the Lewis acid catalyst in the form of a complex that will subsequently decompose. The Lewis acid catalyst can be added to a solution comprising the metathesis polymerizable olefin and the procatalyst (e.g. a solution of the procatalyst in dicyclopentadiene). As disclosed above, most preferably from about 1 to about 5 moles of a Lewis base or a chelating agent are added to the dicyclopentadiene/procatalyst solution per mole of procatalyst, in order to prevent premature polymerization. The amount of Lewis base or chelating agent present is not sufficient, however, to prevent polymerization of the dicyclopentadiene in the presence of the Lewis acid catalyst, if they are left in contact for more than 24 hours. Thus, it may be found desirable to add the Lewis acid catalyst to the mixing head as a separate reactant stream. Regardless of the length of the time of contact of the Lewis acid catalyst with the metathesis polymerizable olefin monomer, the Lewis acid catalyst is preferably dissolved in the monomer before addition to the reaction mixture.

The Lewis acid cocatalyst may in general be any alkyl halide and/or aryl halide. The alkyl halide may be a primary, secondary, and/or tertiary alkyl halide. A preferred group of Lewis acid cocatalysts includes isobutyl chloride, tert-butyl chloride, benzyl chloride (i.e., α-chlorotoluene), vinylbenzyl chloride, 1-bromodecane, 2-ethylhexyl chloride, 2-ethylhexyl bromide, t-butyl acetate, chlorodiphenylmethane, and polymeric chlorides, such as poly(chloroprene) and poly(vinylbenzyl chloride). This listing of preferred Lewis acid cocatalysts is merely for purposes of illustrating the large group of compounds and polymers which may serve this function, and is in no way intended to restrict the choice of the Lewis acid cocatalyst in the present invention. However, the most preferred Lewis acid cocatalysts are t-butyl chloride and isobutyl chloride.

The Lewis acid cocatalyst may, in general, be used in the process of the present invention in an amount of from about 0.05 weight percent to 5 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst. Preferably the Lewis acid cocatalyst is present in the reaction mixture in an amount of from about 0.2 weight percent to 2 weight percent. Most preferably the Lewis acid cocatalyst is present in the reaction mixture in an amount of about 0.25 to 0.5 weight percent.

The anionic polymerization catalysts include any compounds or complexes capable of catalyzing the anionic polymerization of any one or more of a variety of cationically-polymerizable monomers, so long as the anionic polymerization catalyst is compatible with the metathesis procatalyst and procatalyst activator. Compatible anionic catalysts do not have hydroxy groups which interfere with the function of the aluminum alkyl metathesis procatalyst activator. Suitable anionic polymerization catalysts include metal alkyls such as n-butyllithium and dibutylzinc. Many other suitable anionic polymerization catalysts are known to those of skill in the art of anionic polymerization.

The anionic polymerization catalyst should be present in the stream comprising the metathesis polymerization procatalyst activator, or in a separate stream, but in any event should not be present in the stream comprising the metathesis polymerization procatalyst. In general, the anionic polymerization catalyst can be present in an amount of from about 0.05 to 10 weight percent, based on the weight of the anionic polymerizable monomer. Preferably the anionic polymerization catalyst is present in an amount of from about 0.1 to 5 weight percent, most preferably 0.3 to 2 weight percent.

The free radical polymerization initiators include any compounds, complexes, or other means (such as ionizing radiation) capable of catalyzing free radical polymerization of any one or more of a variety of monomers, while also being compatible with the metathesis procatalyst and procatalyst activator system. Compatible free radical polymerization initiators will not interfere with the functioning of the metathesis polymerization procatalyst activator. Suitable free radical polymerization initiators include a wide variety of azo and peroxide compounds. Such compounds include: 2,2'-azobis(2-methylpropionitrile); dimethyl 2,2'-azobisisobutyrate; 2,2'-azobis(2-methylbutyronitrile); tertbutylperoxyoctoate; 1,1'-azobis(cyclohexanecarbonitrile); 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 2,2'-azobis(2,4,4-trimethylpentane); dicumyl peroxide; 2,5-di(tert-butylperoxy)-2,5-dimethylhexane; tert-butylperoxide. Free-radical initiation by ultraviolet light or electron beam or gamma rays may also be utilized. If ultraviolet light is used, a photoinitiator should also be used.

The azo or peroxy compounds or photoinitiators, which act as free-radical initiators, can be used in a stream comprising a metathesis polymerizable olefin together with the metathesis procatalyst, or in a stream comprising a metathesis polymerizable olefin together with the metathesis procatalyst activator, or in a separate stream. The amount of azo or peroxy compound could be from about 0.05 to 10 percent, based on the weight of the free-radical polymerizable monomer. Preferably the amount of azo or peroxy compound is from 0.25 to 5 weight percent, most preferably from about 0.5 to 2 weight percent, based on the weight of the free radical polymerizable monomer.

U.S. Pat. No. 4,900,779, which is hereby incorporated in its entirety by reference thereto, describes the use of hydrosilation catalysts for making organosilicon polymers. The organosilicon polymers comprise alternating polycyclic hydrocarbon residues, and residues of monomers comprising at least one hydrosilane group, i.e., cyclic polysiloxane or tetrahedral siloxysilane residues linked through carbon-silicon bonds. The cyclic polysiloxane or tetrahedral siloxysilane monomers contain at least two hydrosilane groups. The ratio of carbon-carbon double bonds in the ringls of the polycyclic polyene to hydrosilane groups in the cyclic polysiloxane or tetrahedral siloxysilane monomers is in the range of from about 0.5:1 up to about 1.8:1. The polycyclic polyene and/or the cyclic polysiloxane or tetrahedral siloxysilane has more than two reactive sites (i.e., carboncarbon double bonds of the rings of the polycyclic polyene or hydrosilane groups in the cyclic polysiloxane or tetrahedral siloxysilane).

Any cyclic polysiloxane, tetrahedral siloxysilane, or linear polysiloxane containing two or more hydrogen atoms bound to silicon will enter into the reaction. Cyclic polysiloxanes useful in forming the products of this invention have the general formula: ##STR9## wherein R is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms.

The tetrahedral siloxysilanes are represented by the general structural formula: ##STR10## wherein R is as defined above and is hydrogen in at least two silicon atoms in the molecule.

Examples of reactants of Formula (I) include, e.g., trimethyl cyclotrisiloxane, tetramethyl cyclotetrasiloxane, pentamethyl cyclopentasiloxane, hexamethyl cyclohexasiloxane, tetraethylcyclotetrasiloxane, cyclotetrasiloxane, tetraphenyl cyclotetrasiloxane, tetraoctyl cyclotetrasiloxane and hexamethyl tetracyclosiloxane.

The most commonly occurring members of this group are the tetra-, penta-, and hexacyclosiloxanes, with tetramethyl tetracyclosiloxane being a preferred member. In most cases, however, the material is a mixture of a number of species wherein n can vary widely. Generally, commercial mixtures contain up to about 20% (in purer forms as low as 2%) low molecular weight linear methylhydrosiloxanes, such as heptamethyltrisiloxane, octamethyltrisiloxane, etc.

Examples of reactants of Formula (II) include, e.g., tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane. The tetrakisdimethylsiloxysilane is the best known and preferred species in this group.

Cyclic polyenes which can be employed are polycyclic hydrocarbon compounds having at least two nonaromatic carboncarbon double bonds in their rings. Exemplary compounds include dicyclopentadiene, methyl dicyclopentadiene, cyclopentadiene oligomers, norbornadiene, norbornadiene dimer, hexahydronaphthalene, dimethanohexahydronaphthalene, and substituted derivatives of any of these.

If prepolymers are being formed (see discussion below), cyclic polysiloxanes with three or more hydrogen atoms bound to silicon are generally used. Mixtures of cyclic polysiloxanes are also useful. Cyclic polysiloxanes useful in fcrming the products of this invention include those having the general formula I (above), wherein R is hydrogen, or substituted or unsubstituted alkyl or aromatic radical, n is an integer from 3 to about 7, and R is hydrogen on at least three of the silicon atoms in the molecule.

Examples of cyclic polysiloxanes suitable for the formation of prepolymers include, e.g., tetra and pentamethylcyclotetrasiloxanes, tetra-, penta-, hexa- and heptamethylcyclopentasiloxanes, tetra-, penta- and hexamethylcyclohexasiloxanes, tetraethyl cyclotetrasiloxanes and tetraphenyl cyclotetrasiloxanes. Preferred are 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,7,9,11-hexamethylcyclohexasiloxane, or blends thereof.

U.S. Pat. No. 4,877,820, which is hereby incorporated in its entirety by reference thereto, relates to crosslinked organosiloxane polymers, preferably poly(organohydrosiloxane) of the general formula: ##STR11## wherein R is a substituted or unsubstituted, saturated alkyl radical or a substituted or unsubstituted phenyl radical, and about 1% to about 50%, preferably 5 to about 50%, of the R's are hydrogen, and m is an integer from about 5 to 1000, preferably 5 to 100, and the maximum value of m is desirably 40. A preferred linear poly(organohydrosiloxane) defined by the above general formula is trimethylsiloxy-terminated methylhydropolysiloxane.

Other exemplary poly(organohydrosiloxanes) include: trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, dimethylsiloxy-terminated dimethylsiloxane methylhydrosiloxane copolymer, dimethylsiloxy-terminated polydimethylsiloxane, trimethylsiloxy-terminated methyloctylsiloxane methylhydrosiloxane copolymer, dimethylsiloxy-terminated phenylmethylsiloxane methylhydrosiloxane copolymer, trimethylsiloxy-terminated methylcyanopropylsiloxane methylhydrosiloxane copolymer, trimethylsiloxy-terminated 3,3,3-trifluoropropylmethyl siloxane methylhydrosiloxane copolymer, trimethylsiloxy-terminated 3-aminopropylmethylsiloxane methylhydrosiloxane copolymer, trimethylsiloxy-terminated 2-phenylethylmethylsiloxane methylhydrosiloxane copolymer, and trimethylsiloxy-terminated 2-(4-methylphenyl) ethylmethylsiloxane-methylhydrosiloxane copolymer.

The hydrosilation reaction proceeds readily in the presence of a platinum-containing catlayst. Metal salts and complexes of Group VIII elements can also be used. The preferred catalyst, in terms of both reactivity and cost, is chloroplatinic acid (H₂ PtCl₆.6H₂ O). Catalyst concentrations of 0.0005 to about 0.5% by weight, based on weight of the monomer, will effect smooth and substantially complete polymerization. Typical platinum concentrations are from about 0,001 to about 0.05 weight percent, preferably about 0.0025 to 0.03 weight percent, based on weight of the prepolymer. Other platinum compounds can also be used to advantage in some instances, such as PtCl₂ and dibenzonitrile platinum dichloride. Platinum on carbon is also effective for carrying out high temperature polymerizations. Other useful platinum catalysts are disclosed in, e.g., U.S. Pat. Nos. 3,220,972, 3,715,334, and 3,159,662, each of which is hereby incorporated in its entirety, by reference thereto. An exhaustive discussion of the catalysis of hydrosilation can be found in Advances in Organometallic Chemistry, Vol. 17, which is also incorporated in its entirety, by reference thereto. See especially page 407, et. seq. The polymerization reactions can be promoted thermally or by the addition of radical generators such as peroxides and azo compounds.

U.S. Pat. No. 4,902,731, which is hereby incorporated in its entirety, by reference thereto, relates to organosilicon prepolymers. These heat-curable prepolymers or oligomers are the partial reaction product of (a) a cyclic polysiloxane or a tetrahedral siloxysilane containing at least two hydrosilane groups and (b) a polycyclic polyene having at least two chemically distinguishable carbon-carbon double bonds, wherein the ratio of the carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is greater than 0.5:1 and up to 1.9:1 and at least one of the compounds (a) and (b) has more than two reactive sites.

The reactions for forming the prepolymers can be promoted thermally or by the addition of a hydrosilation catalyst, radical generators such as peroxides, and azo compounds, as described above. Hydrosilation catalysts include metal salts and complexes of Group VIII elements. The preferred hydrosilation catalysts contain the same platinum-containing catalysts described above with respect to hydrosilation polymers.

In one embodiment for preparing a prepolymer, a platinum-containing catalyst, preferably chloroplatinic acid, and a liquid polycyclic polyene are mixed and heated at 40° to 80° C. for one to two hours to form a platinum/olefin complex. The platinum/olefin complex solution is cooled to room temperature and then mixed with the other ingredients, i.e., cyclic siloxane, polycyclic polyene, chain extender, aliphatic hydrocarbon solvent and optional ingredients. This mixture is stirred at 20° C. to 40° C. in a water bath which serves as a heat sink. The level of solvent (from 5 to 50% by weight of the prepolymer solution), the catalyst level, and the temperature of the bath will all affect the rate of reaction. Conditions should be chosen such that the reaction temperature does not increase substantially above the bath temperature, as a sudden temperature rise may decrease the activity of the catalyst, which is needed for cure.

In a second embodiment, the polycyclic polyene-platinum catalyst complex can be mixed with solvent, polycyclic polyene, chain extender and optional ingredients. The mixture is heated to a temperature at which hydrosilation of reactive double bonds is facile, usually 40° to 80° C. Then, the cyclic siloxane is slowly dripped into the mixture.

Organosilicon prepolymers can also be made by heating siloxane and polyene reactants at lower temperatures, e.g., about 50° to about 80° C. The resulting prepolymer may be in the form of a solid or a flowable, heat-curable liquid, even though the ratio of carbon-carbon double bonds to hydrosilane groups is otherwise suitable for cross-linking. Such prepolymers can be recovered and subsequently transferred to a mold for curing, to form thermoset polymers. Temperatures of, for example, from about 100° to about 250° C., are utilized for curing such prepolymers.

U.S. Pat. No. 5,008,360, which is hereby incorporated in its entirety, by reference thereto, is directed to organosilicon materials which are prepregs comprising fiber reinforcement impregnated with the partial hydrosilation reaction product of a polyene, a polycyclic polyene, and at least one cyclic polysiloxane containing three or more .tbd.SiH groups.

The method of the present invention can be carried out by providing a plurality of reactant streams, wherein a first reactant stream comprises the metathesis polymerization procatalyst activator and a portion of the metathesis polymerizable olefin, and a second reactant stream comprises the metathesis polymerization procatalyst and a portion of the the metathesis polymerizable olefin. At least one reactant stream further comprises at least one member selected from the group consisting of: (i) a Lewis acid catalyst and a Lewis acid cocatalyst, present in separate reactant streams; (ii) an anionic polymerization catalyst; (iii) a free radical polymerization initiator; (iv) a hydrosilation polymerization catalyst. The reactant streams are then mixed together, whereby a reaction mixture is formed. The reaction mixture is then formed into a desired shape before the polymerization of the metathesis polymerizable olefin.

Reaction Injection Molding (RIM) is the preferred process for carrying out the method of the present invention. RIM is most conveniently accomplished by mixing equal parts of two solutions, one of which contains twice the desired concentration of procatalyst, and the other of which contains twice the desired concentration of the procatalyst activator. It is preferable, but not necessarily required, that at least one of the solutions contains a rate moderator, as described above. Since the reactive mixture does not gel immediately, the RIM process can frequently be carried out via the alternative process of adding one part of the catalyst system (i.e. either the procatalyst or the procatalyst activator) to substantially all of the cycloolefin and, just prior to the polymerization and molding, mixing in a concentrate of the other part.

Poly(dicyclopentadiene) can be produced via a RIM process, to result in a polymeric product having a desired form. The procatalyst and the procatalyst activator are each mixed with dicyclcopentadiene to form solutions that are placed in separate vessels. These containers provide the source for two separate reactant streams, with each container provided with a solution of the cycloolefin monomer or monomers. The two reactant streams are combined in the RIM machine's mixing head and then injected into a warm mold where they quickly polymerize into a solid, infusible mass. The reaction mixture is preferably allowed to polymerize to a degree of substantial reaction termination while the reaction mixture is within the mold, whereby a molded article is produced, followed by removing the molded article from the mold. Similar methods can be utilized for RIM processes utilizing other metathesis polymerizable olefins.

The method of the invention is not intended to be limited to systems employing two reactant streams, each containing monomer. In fact, in practicing the instant invention it may be preferable, under certain conditions, to add, for example, a cationic initiator as a third reactant stream. In general, the invention is carried out using two to four reactant streams. Preferably, however, only two reactant streams are utilized in the process. The first reactant stream preferably comprises dicyclopentadiene monomer, the metathesis polymerization procatalyst, and the Lewis acid catalyst, while the second stream preferably comprises dicyclopentadiene monomer, the metathesis polymerization procatalyst activator, and the Lewis acid cocatalyst. However, if enough of the delay additive (i.e. moderator, as discussed above) is used, a one-stream system can be used in a RIM process.

The composition of the present invention preferably comprises a low level of residual metathesis polymerizable olefin monomer, regardless of the particular combination of catalysts present in the composition. Preferably the composition has a residual methathesis polymerizable olefin monomer level of from about 0 to 0.25 weight percent, based on the weight of the polyolefin. Still more preferably, the level of residual metathesis polymerizable olefin monomer is from about 0 to 0.15 weight percent, based on the weight of the polyolefin.

If the olefin monomer is dicyclopentadiene, as is preferred, obtaining a low residual dicyclopentadiene monomer level is a major objective of the present invention. A low level of residual dicyclopentadiene monomer enables the production of molded articles comprising polydicyclopentadiene suitable for indoor use, if the odor level from the monomer is reduced to a very low level.

As referred to herein, the "amount" of residual monomer in the composition of the present invention is an amount present immediately upon completion of the polymerization reaction, i.e., immediately upon removing the molded product from the mold.

Various additives can be included to modify the properties of polyolefin. Possible additives include fillers and reinforcing agents, pigments, antioxidants, light stabilizers and polymeric modifiers such as elastomers, among others. U.S. Patent 4,689,380, U.S. Patent No. 4,400,340, and U.S. Patent No. 4,436,858 (each of which is incorporated, in its entirety, by reference thereto), disclose various additives for a variety of different purposes.

Because of the rapid polymerization time, the additives must be incorporated before the polyolefin sets up in the mold. It is often desirable that the additives be combined with one or both of the catalyst system's streams before being injected into the mold. Fillers can also be charged to the mold cavity, prior to charging the reaction streams, if the fillers are such that the reaction stream can readily flow around them to fill the remaining void space in the mold. However, it is essential that the additives do not adversely affect the catalytic activity of the various catalyst components.

Light stabilizers which are useful in the composition of the present invention comprise hindered amines such as 1-octyl-2,2,6,6-tetramethylpiperidine (available from Ciba-Geigy, under the name Tinuvin® 123), as well as carbon black and other pigments which can serve as light stabilizers. Light stabilizers comprising --NH groups therein are not recommended, because at least some of such compounds interfere with the catalyst system.

Reinforcing agents and fillers can increase the polymer's flexural modulus with only a small sacrifice in impact resistance. Such reinforcing agents/fillers include glass, wollastonite, mica, carbon black, talc, and calcium carbonate. It is surprising that in spite of the highly polar nature of their surfaces, these materials can be added without appreciably affecting the polymerization rate. From about 5% to 75% by weight may be incorporated, based on the weight of the final product. The addition of the materials having modified surface properties is particularly advantageous. The exact amount is easily determinable by one skilled in the art and depends on the preferences of the practitioner. The addition of these materials also serves to decrease the mold shrinkage of the product.

Since poly(dicyclopentadiene) contains some unsaturation it may be subject to oxidation. The product can be protected from oxidation by the incorporation of as much as about 5 weight percent of at least one antioxidant selected from the group consisting of phenolic antioxidants and amine antioxidants, and mixtures of these antioxidants. Preferred antioxidants include 2,6-tert-butyl-p-cresol, N,N'-diphenyl-p-phenylenediamine and tetrakis[methylene(3,5-di-t-butyl-4-hydroxycinnamate)]-methane. While the antioxidant can be added to either or both reactant streams, incorporation into the activator/monomer reactant streams is preferred.

The addition of an elastomer can increase the impact strength of the polymer with only a slight decrease in flexural modulus. The elastomer can be dissolved in one or all of the reactant streams. The amount of elastomer used is determined by its molecular weight and by the initial viscosity of the reactant streams to which it is added. Amounts within the range of 1% to 10% by weight and preferably 3% to 10% by weight, based on the weight of the total stream, can be used without causing an excessive increase in solution viscosity. An example of preferred elastomer is styrenebutadiene rubber, made by solution polymerization.

The reactant streams cannot be so viscous that adequate mixing of the reactant streams is not possible. However, increasing the viscosity to between 300 cps and 1,000 cps improves the mold filling characteristics of the combined reactant streams. The elastomer is preferably added to all of the reactant streams so that the viscosities of the two reactant streams are similar. When the reactant streams have similar viscosities, more uniform mixing is obtained when the reactant streams are combined. An increase in viscosity also reduces leakage from the mold and simplifies the use of fillers by decreasing the settling rate of solid filler materials. Useful elastomers can be unsaturated hydrocarbon elastomers such as, e.g., styrene-butadiene rubber, polyisoprene, polybutadiene, natural rubber, styrene-isoprenestyrene triblock rubber, styrene-butadiene-styrene triblock rubber, and ethylene-propylene-diene terpolymers, or saturated elastomers such as polyisobutylene and ethylene-propylene copolymers.

Preparation of Catalysts Utilized in Examples

The invention is illustrated by the Examples reported in Tables 1-5, below. In these Examples, a "standard catalyst" component is prepared by suspending a WCl₆ complex in toluene, reacting it with tert-butyl alcohol (so that WOCl₄ is formed as an intermediate), and thereafter adding nonylphenol (resulting in replacement of one or more chlorines by a nonylphenol group) to solubilize catalyst, followed by adding 2,4-pentanedione (resulting in the replacement of one or more additional chlorines, with 2,4-pentanedione), to result in a desired catalyst complex. This product is then diluted to a 0.5 molar concentration by adding sufficient additional toluene. A 1.0 molar toluene solution of an 85:15:100 mixture of tri-n-octyl aluminum: dioctylaluminum iodide:diglyme is prepared. Diglyme is also known as 2-methoxyethyl ether. For a trial with 5 ml dicyclopentadiene, the standard 0.04 ml of 0.5 molar catalyst in toluene plus one equivalent of dichlorodiphenylmethane per W is 0.045 ml (0.02 mmole W), for a monomer to catalyst molar ratio of 2000 to 1. The standard amount of 1.0 M activator is 0.06 ml (0.06 mmole Al).

A "Bell catalyst" [i.e., WOCl₂ (O-2,6-diisopropylphenyl)₂ ] is made by contacting tungsten oxytetrachloride (i.e., WOCl₄) with two equivalents of 2,6-diisopropylphenol in a hydrocarbon solvent. The WOCl₂ (O-2,6-diisopropylphenyl)₂, a solid, is used as 0.045 ml 0.4 M solution in dicyclopentadiene (0.018 mmole W) with no added dichlorodiphenylmethane. It is activated by 0.015 ml tributyltin hydride in 0.015 ml toluene (0.056 mmole Sn), 0.22 ml 1.0 M ethylaluminum dichloride in hexane (0.22 mmole Al), 0.11 ml 1.0 M di-n-butylzinc in toluene (0.11 mmole Zn), 0.03 ml 1.6 M n-butyllithium in hexane (0.048m mole Li), or 0.15 ml 0.7 M di-n-butylmagnesium in heptane (0.015 mmole Mg), except as indicated otherwise in Tables 1-5, below. Ethylaluminum chloride n-propoxide is used as 0.11 ml of 0.5 M solution in toluene (0.055 mmole Al). Thus, the molar ratio for the standard catalyst system is 3 Al/W and for the Bell catalyst 3.1 Sn/W, 12 Al/W for ethylaluminum dichloride, 3 Al/W for ethylaluminum chloride n-propoxide, 6 Zn/W, 6 Mg/W, and 6 Li/W.

The dicyclopentadiene utilized in the preparation of the catalysts and elsewhere in the Examples is a commercially available dicyclopentadiene having a purity level in excess of 98% by weight.

A general description of how the various runs are performed is provided below, for each of the catalyst types utilized, i.e., for the "standard catalyst" (a tungsten hexachloride-based catalyst) as well as for the "Bell Catalyst" (a tungsten oxychloride-based catalyst).

Standard Polymerization Using Standard Catalyst

5 ml of dicyclopentadiene are charged to a nitrogen-sparged vessel. Then 0.04 ml of the 0.5 M tungsten catalyst component solution is injected and mixed well. [In the event that dichlorodiphenylmethane is used in a 1:1 molar ratio with the tungsten catalyst, the dichlorodiphenylmethane is included in the catalyst solution, of which 0.045 ml is then used, instead of the usual 0.04 ml.]Then 0.06 ml of the standard 1.0 M activator prepared above is added, and the mass mixed well. The vessel is then immersed in a constant temperature bath maintained at 32° C., or at some other temperature, as indicated in the individual examples. The Lewis acid catalyst is then mixed with the tungsten catalyst, before the activator is added. The Lewis acid cocatalyst is then added. Otherwise the order of addition is standard catalyst first, Lewis acid second, activator third, followed by Lewis acid cocatalyst.

The time from addition of the tungsten catalyst component until formation of a non-fluid gel is noted, and recorded as the "gel time". Similarly, the time from addition of the catalyst until the temperature reaches 100° C. (or 160° C., in the case of runs started at 80° C.), is recorded as the "cure time". The difference between the starting temperature and the maximum temperatures is recorded as the " T". The thermocouple used to measure the temperatures is rotated during the polymerization (when above 100° C.) so as to break the seal with the polymer plug, then removed before it becomes "frozen" in place. For the control examples, these values are recorded in Table I. It typically takes three seconds to gel and 30 seconds to reach 100° C., for the higher purity dicyclopentadiene monomer.

Standard Polymerization Using Bell Catalyst

A nitrogen-sparged vessel is charged with 5 ml. of dicyclopentadiene. Then 0.045 ml of a 0.4 M Bell catalyst component solution is injected into the vessel, and mixed well therein. Then 0.03 ml. of the standard 1.86 M tributyltin hydride activator, prepared above, is added to the vessel, and the contents mixed well.

The vessel is immersed in a constant temperature bath maintained at 32° C., or at another temperature, as indicated in the individual examples. The Lewis acid catalyst is mixed with the Bell catalyst before the activator is added. The Lewis acid cocatalyst is then added. Otherwise the order of addition is Bell catalyst first, Lewis acid catalyst second, activator third, followed by addition of the Lewis acid cocatalyst.

The time from addition of the Bell catalyst component until formation of a non-fluid gel is noted and recorded as the gel time. Similarly, the time from addition of the catalyst until the temperature reaches 100° C. (or 160° C., in the case of runs started at 80° C.) is noted and recorded as the cure time. The difference between the starting and maximum temperatures is noted and recorded as the T. The thermocouple used to measure temperature is rotated during the polymerization (when above 100° C.) so as to break the seal with the polymer plug, and is then removed before it becomes "frozen" in place. Examples of the metathesis-cationic polymerization of dicyclopentadiene are recorded in Table I, i.e. wherein the catalysts include metathesis polymerization procatalyst, metathesis polymerization procatalyst activator, Lewis acid catalyst, and Lewis acid cocatalyst. The polymerization of high purity dicyclopentadiene typically requires about three seconds to gel, and 30 seconds to reach 100° C.

TABLE 1
  Metathesis - Cationic Polymerization of Dicyclopentadiene Std. activator
  used at 2000 monomer per W, with one dichlorodiphenylmethane per W in
 the catalyst. Bell means WOCl.sub.2 (0-2,6-diisopropylphenyl).sub.2 used
 at the same level. The order of addition to the monomer was from left to
 right across the table. 2X means double the usual amount.      Co-
     Moderator  Catalyst      Glass   Lewis for Lewis  for Lewis Initial
  Maximum % Transition Example Metathesis Acid Acid  Acid Temp. Seconds
 Seconds Temp. Residual Temp. Number Catalyst Weight % Weight % Activator
 Weight % C.° to Gel to 100°
  C. °C. Monomer °C. Notes
   1 std. none none std. none 33 3 29 205 -- -- -- (compara- tive) 2 std.
 none none std. 1 isobutyl 33 1-2 39 204 -- -- -- (compara-     chloride
 tive) 3 std. none none std. 0.5 32 2 32 200 0.55 134 Activator and
 isobutyl chloride combined (compara-     isobutyl       before addition.
 tive)     chloride 4 std. none none std. none 33 3 28 203 1.73 128 No
 dichlorodiphenylmethane. (compara- tive) 5 std. none none std. none 33 3
 28 207 0.46 144 -- (compara- tive) 6 std. none none std. 0.25 tert- 32 3
 29 204 0.53 122 No dichlorodiphenylmethane. (compara-     butyl tive)
  chloride 7 std. none none std. 0.25 tert- 31 7 33 205 0.19 137 --
 (compara-     butyl tive)     chloride 8 std. none none std. none 31 5
 30 205 0.41 -- -- (compara- tive) 9 std. none none std. 0.5 32 6-7 30
 208 -- -- -- (compara-     isobutyl tive)     chloride 10 Bell none 0.2
 tributyltin none 32 instant 17 160 0.83 -- -- (compar-   diglyme hydride
 ative) 11 std. none none std. none 31 3 29 214 0.52 139 -- (compar-
 ative) 12 std. none none std. 0.5 tert- 30 3 30 209 0.16 -- -- (compar-
    butyl ative)     chloride 13 std. none none std. 0.5 29 1 50 191 0.42
 -- A duplicate run contained 0.59 Cp.sub.2. (compar-     isobutyl ative)
     chloride 14 std. none none std. none 31 3 34 194 1.56 -- -- (compar-
 ative) 15 std. none none std. none 32 3 24 214 0.43 132 -- (compar-
 ative) 16 Bell none none ethyl- none 32 5 -- 208 0.56 131 After 5
 minutes heated to 72° C. to get exotherm. (compar-    aluminum
 ative)    chloride-n-     propoxide 17 2X Bell none none 2X none 32 6 --
 211 0.20 117 After 5 minutes heated to 70° C. to get exotherm.
 (compar-    ethyl- ative)    aluminum     chloride-n-     propoxide 18
 Bell none none ethyl- 0.5 tert- 32 30  -- 219 0.58 139 After 5 miinutes
 heated to 72° C. to get exotherm. A (compar-    aluminum butyl
    duplicate run gelled in 5 seconds; 0.82% residual Cp.sub.2 ; ative)
  chloride-n- chloride       Tg 136° C.     propoxide 19 std. none
 none std. none 31 3 33 213 0.71 133 -- (compar- ative) 20 std. 0.5 none
 std. 0.25 31 1 30 194 -- -- --   boron   isobutyl   tri-   chloride
 fluoride   etherate 21 std. 0.5 none std. 0.25 tert- 32 1 30 202 0.10
 140 No dichlorodiphenylmethane.   boron   butyl   tri-   chloride
 fluoride   etherate 22 std. 0.5 none std. 0.25 tert- 32 1 23 200 0.15
 141 --   boron   butyl   tri-   chloride   fluoride   etherate 23 std.
 0.5 none std. none 31 2-3 21 204 0.12 139 No dichlorodiphenylmethane.
 (compar-  boron ative)  tri-   fluoride   etherate 24 std. 0.5 none std.
 none 31 2-3 20 207 0.21 139 -- (compar-  boron ative)  tri-   fluoride
 etherate 25 Bell 1.0 0.1 tributyltin 0.25 32 6 -- 184 -- -- Tert-butyl
 chloride mixed with tributyltin hydride   boron trimethyl hydride
 tert-butyl       before addition. Polymer foam 2.5 times usual size.
 tri- phosphite  chloride   fluoride   etherate 26 Bell none none ethyl-
 none 32 instant 14 -- 1.24 127 -- (compar-    aluminum ative)
 dichloride 27 Bell none 0.2 0.5 ethyl- none 32 3 106  189 2.61  93 --
 (compar-   trimethyl aluminum ative)   phosphite dichloride 28 Bell 0.5
 0.2 tributyltin 0.25 benzyl 31 10  32 205 0.10 153 Foamed plug twice
 normal size.   boron tributyl hydride chloride   tri- phosphite
 fluoride   etherate 29 2X std. 0.5 none 2X std. 0.33 tert- 31 <1  27 200
 0.15 121 --   boron   butyl   tri-   chloride   fluoride-   N,N-
 diethyl-   aniline 30 2X std. 0.5 none 2X std. 0.33 tert- 31 3 75 200
 0.12 123 --   boron   butyl   tri-   chloride   fluoride   tetra-
 hydro-   furan 31 2X std. 1.0 none 2X std. 0.66 tert- 31 <1  26 205 0.18
 121 --   boron   butyl   tri-   chloride   fluoride-   N,N-di-   ethyl-
  aniline 32 std. 0.5 0.25 N,N- std. 0.25 tert- 31 2-3 63 207 0.15 137 --
   boron diethyl-  butyl   tri- aniline  chloride   fluoride   etherate
 33 std. 0.5 none std. 0.5 31 4 49 199 0.12 -- --   boron   isobutyl
 tri-   chloride   fluoride   etherate 34 std. 0.5 none std. 0.25 31 <1
 -- 202 0.11 -- --   boron   isobutyl   tri-   chloride   fluoride
 etherate 35 std. 0.5 none std. 0.5 tert- 31 <1  36 199 0.10 -- Duplicate
 runs 0.08 & 0.12% residual Cp.sub.2.   boron   butyl   tri-   chloride
 fluoride   etherate 36 std. 0.5 0.3 std. 0.5 31 5-6 39 205 0.60 -- --
 boron pyridine  isobutyl   tri-   chloride   fluoride   etherate 37 std.
 0.5 1.6 qui- std. 0.5 31 5 42 207 0.13 -- --   boron nuclidine  isobutyl
   tri-   chloride   fluoride   etherate 38 Bell none 0.6 ethyl- 0.5
 tert- 31 -- -- 214 0.13 -- No reaction in five miutes at 31° C.
 Heating to 60° C. gave (compar-   diglyme aluminum butyl
 the exotherm. ative)    dichloride chloride 39 std. 0.5 1.0 N,N- std.
 0.25 tert- 32 7-8 34 199 0.12 -- --   boron diethyl-  butyl   tri-
 aniline  chloride   fluoride   etherate 40 std. 0.5 0.6 std. 0.25 tert-
 32 7 36 205 0.10 -- --   boron diglyme  butyl   tri-   chloride
 fluoride   etherate 41 std. 0.5 0.25 std. 0.5 tert- 32 instant 19 205
 0.14 -- --   boron maleic  butyl   tri- anhydride  chloride   fluoride
 etherate 42 Bell 0.5 0.25 tri- 0.25 benzyl 31 7 44 201 1.47 140 --
 boron maleic butyltin chloride   tri- anhydride hydride   fluoride 0.2
 etherate tributyl    phosphite 43 Bell none 0.6 0.50 ethyl- 0.5 tert- 31
 120-140 -- 209 0.10 -- No reaction in 5 minutes. Heating to 47°
 C. gave (compar-   butyl- aluminum butyl       exotherm. Monomer mixture
 slightly hazy. ative)   diglyme dichloride chloride 44 Bell 0.5 0.2
 tributyltin 0.5 tert- 32 instant 10 169 0.07 -- --   boron diglyme
 hydride butyl   tri-   chloride   fluoride   etherate 45 Bell none 0.6
 ethyl- 0.5 tert- 75 1- 2 44 225 0.43 -- -- (compar-   diglyme aluminum
 butyl ative)    dichloride chloride 46 std. 0.5 0.6 std. 0.5 tert- 31 7
 128  197 0.07 -- --   boron diglyme  butyl  tri- 0.25  chloride
 fluoride maleic   etherate anhydride 47 std. 0.5 none std. 0.5 tert- 31
 1 15 207 0.28 -- 91% gel, 177% swell. A duplicate run gave 0.07%   boron
   butyl       residual dicyclopentadiene.   tri-   chloride   fluoride
 etherate 48 std. 0.5 0.6 std. 0.25 tert- 32 6 43 206 0.11 -- Duplicate
 runs behaved similarly.   boron diglyme  butyl   tri-   chloride
 fluoride   etherate 49 std. 1.0 0.6 std. 0.5 tert- 32 4 53 205 0.05 --
 --   boron diglyme  butyl   tri-   chloride   fluoride   etherate 50
 std. 0.5 0.6 std. 0.5 31 12 300  189 0.06 129 0.09% vinylbenzyl chloride
 remained.   boron diglyme  vinylbenzyl   tri-   chloride   fluoride
 etherate 51 std. 1.0 0.6 std. 0.5 tert- 31 8 115  203 0.09 127 --
 boron diglyme  butyl   tri-   chloride   fluoride   etherate 52 std. 0.5
 0.6 std. 0.5 benzyl 31 5 21 204 0.08 126 --   boron diglyme  chloride
 tri-   fluoride   etherate 53 std. 0.5 0.6 std. 0.7 1- 31 9 20 202 0.09
 125 --   boron diglyme  bromo-   tri-   decane   fluoride   etherate 54
 std. 0.5 0.6 std. 0.5 2- 30 9 24 200 0.08 125 --   boron diglyme
 ethylhexyl   tri-   bromide   fluoride   etherate 55 std. 0.5 0.6 std.
 0.5 2- 30 10  26 202 0.22 126 --   boron diglyme  ethylhexyl   tri-
 chloride   fluoride   etherate 56 std. 0.5 0.6 std. 0.25 30 7 26 205
 0.34 127 --   boron diglyme  tert-butyl   tri-   acetate   fluoride
 etherate 57 std. 0.5 0.6 std. none 32 7 21 201 0.11 132 -- (compar-
 boron diglyme ative)  tri-   fluoride   etherate 58 2X std. 1.0 tin none
 2X std. 0.5 tert- 32 instant -- 207 0.07 107 Temperature climbed from 32
 to 40°
  C. in 5 minutes.   (IV)   butyl       Heating to 50° C. gave the
 exotherm.   bromide   chloride 59 std. 1.1 tin 0.3 std. 1.0 32 <1  --
 224 0.36 117 After 5 minutes, heated to 82° C. to get exotherm.
 (IV) diglyme  isobutyl   chloride 0.25  chloride    maleic    anhydride
 60 std. 0.5 0.67 std. 0.5 tert- 31 10  105  105 0.63 -- 3 ml run with
 0.8 × 10 cm steel rod in test tube.   boron diglyme  butyl   tri-
  chloride   fluoride   etherate 61 std. 0.5 0.67 std. 0.5 tert- 32 6 184
   184 0.16 -- --   boron diglyme  butyl   tri-   chloride   fluoride
 etherate 62 Bell none 0.85 n- 0.5 ethyl- 0.5 32 26  -- 117 1.75 --
 Contained rod as in Ex. No. 24. Heated to 65° C. to get (compara-
   hexyl aluminum isobutyl       exotherm. tive)   ether dichloride
 chloride 63 2X std. 0.5 0.67 2X std. 0.5 29 3 --  93 0.20 -- Contained
 rod as in Ex. No. 24. Maximum temperature   boron diglyme  isobuty
 reached in 47 seconds.   tri-   chloride   fluoride   etherate 64 std.
 1.0 0.67 std. 0.5 29 1-2 35 121 0.76 -- Contained rod as in Ex. No. 24.
  boron diglyme  isobutyl   tri-   chloride   fluoride   etherate 65 Bell
 none 0.67 0.5 ethyl- 0.5 -- -- -- 124 2.86 -- Contained rod as in Ex.
 No. 24. Heated to 80° C. to get (compara-   diglyme aluminum
 isobutyl       exotherm. tive)    dichloride chloride 66 2X std. 1.0 1.3
 2X std. 1.0 59 --    3.35   117.5 0.20 -- Contained 3.75% EPDM rubber.
 Run on mini RIM   boron diglyme  isobutyl       machine. 100% swell;
 very little odor, possibly trace   tri-   chloride       of odor of
 ethyl ether, 647 kg/cm.sup.2 flexural strength,   fluoride          5.0%
 flexural strain, 18900 kg/cm.sup.2 flexural modulus,   etherate
 6.8-6.9 mm deflection (9.2 kpsi flexural strength, 269             kpsi
 flexural modulus), 9.11 ft lb/inch width in notched             Izod
 impact test at 23° C., 83° C. deflection
 temperature under 264 psi load. 67 2X std. 1.0 0.67 2X std. 1.0 32 7 88
 -- 2.38 -- Contained rod as in Ex. No. 24.   boron diglyme  isobutyl
 tri-   chloride   fluoride   etherate

TABLE 2
  Metathesis - Cationic Copolymerization or Alkylation Conventions as in
 Table 1. Cp.sub.2 & Cp.sub.3 inidcate di- and tricyclopentadiene. 2X
 means two times.   Other   Moderator         Glass    Monomer or  Lewis
 for  Cocatalyst Initial   Max. % % Residual Trans. Ex.  Compound to
 Metathesis Acid Lewis Acid  for Lewis Temp. Seconds Seconds Temp.
 ResidualOther Temp. Number Cp.sub.2 & Cp.sub.3 be Alkylated Catalyst
 Weight % Weight % Activator Acid °C. to Gel to 100° C.
 °C. Cp.sub.2 Compound °C. Notes
   68 80 Cp.sub.2 20 m- std. 1 BF.sub.3 none std. 0.5 isobutyl 31 <1  54
 192 -- -- -- Activator and isobutyl   diisopro-  etherate   chloride
    chloride combined before   penylbenzene             addition. 69 80
 Cp.sub.2 20 m- std. 1 BF.sub.3 none Std. 0.5 isobutyl  4 30-50 306  189
 0.01 -- -- Put in 33° C. block after   diisopro-  etherate
 chloride        60 sec. Post-cured 90° C./   penylbenzene
     1 hr. 70 80 Cp.sub.2 20 m- std. 1 BF.sub.3 none std. 0.5 chloro- 31
 2-3 -- 203 -- -- -- Ten minutes to 46° C.,   diisopro-  etherate
  di-phenyl-        then heated to 55° C. to   penylbenzene
 methane        get the strong exotherm. 71 80 Cp.sub.2 20 m- std. 0.5
 BF.sub.3 none std. 0.5 isobutyl 32  1 47 179 0.00- 1.30 m- 107 Activator
 and isobutyl   diisopro-  etherate   chloride     0.02 diiso-  chloride
 combined before   penylbenzene           propenyl-  addition. 6.9%
 higher GC              benzene  peaks present. 72 80 Cp.sub.2 20 m- std.
 0.5 BF.sub.3 none std. 0.25 isobutyl 32 2-3 50 181 0.01- 1.24 m- -- --
 diisopro-  etherate   chloride     0.02 diiso-   penylbenzene
 propenyl-              benzene 73 (com- 60 Cp.sub.2 none std. none none
 std. none  3 -- -- 191 0.57 -- 182 Exotherm after placing parative) 40
 Cp.sub.3              in 33° C. block. 74 60 Cp.sub.2 none std. 1
 BF.sub.3 none std. 0.5 isobutyl  3 2-3 -- 186 0.02 -- none Exotherm
 after placing  40 Cp.sub.3   etherate   chloride       ob- in 33°
 C. block.               served Activator and isobutyl
 chloride combined before                addition. 75 80 Cp.sub.2 20
 α-methyl- std. 1 BF.sub.3 none std. 0.5 isobutyl  3  1 175  170
 0.02- 0.42 α- 69.5 Exotherm after placing   styrene  etherate
 chloride     0.03 methyl-  in 33° C. block,              styrene
 14.7% of α-methyl-styrene                dimer present. 76 80
 Cp.sub.2 20 5- std. 1 BF.sub.3 none std. 0.5 isobutyl  2 -- -- 186 0.04-
 0 5- none Placed in 33° C. block   ethylidene-2-  etherate
 chloride     0.06 ethylidene- ob- after four minutes.   norbornene
     2-nor- served              bornene 77 80 Cp.sub.2 15 α-methyl-
 std. 0.5 BF.sub.3 none std. 0.25 isobutyl  0 300  415 158 0.01- 0.26
 α- none Put in 32° C. block after   styrene  etherate
 chloride     0.02 methyl- ob- five minutes. Post cured   5 m-diisopro-
         styrene, served 90° C./1 hr. 8.1% α-   penylbenzene
           0.10 m-  methylstyrene dimer              diiso-  present.
          propenyl-              benzene 78 80 Cp.sub.2 13 m- std. 0.5
 BF.sub.3 none std. 0.25 isobutyl 32 2-3 -- 176 0.00- 0.43 m- 72.5 --
 diisopro-  etherate   chloride     0.01 diiso-   penylbenzene
 propenyl-   7 naphthalene           benzene              0.62
   naphtha-              lene 79 80 Cp.sub.2 15 β-pinene std. 0.5
 BF.sub.3 none std. 0.25 31  1 57 183 0.16 0 β-pinene 80 2.0%
 unknown GC peaks   5 m-  etherate   isobutyl      0.22 m-  between
 β-pinene and m-   diisopropenyl-     chloride      diiso-  diisoprop
 enylbenzene,   benzene           propenyl-  5.8% higher than m-
     benzene  diisopropenylbenzene. 80 95 Cp.sub.2 5 2,6-di- std. 0.5
 BF.sub.3 none std. 0.25 isobutyl 31  1 42 198 0.04- 5.6 2,6- 111 --
 tert-  etherate   chloride     0.06 di-tert-   butylphenol
 butyl-              phenol 81 90 Cp.sub.2 10 std. 0.5 BF.sub.3 none std.
 0.25 isobutyl 31  1 27 185 0.16- 12.9 70 Plug slightly foamed.
 naphthalene  etherate   chloride     0.23 naphtha-              lene 82
 80 Cp.sub.2 20 std. 0.5 BF.sub.3 none std. 0.25 isobutyl 31  5 66 182
 0.06 -- 110 Rubber, catalyst and   polyisoprene  etherate   chloride
    Lewis acid in half the Cp.sub.2 ;                rubber activator and
 co-                catalyst in the other half. 83 95 Cp.sub.2 5 Bell --
 none 0.5 ethyl- 0.25 tert- 31  1 57 179 0.06- 3.87 101 Poorly mixed.
 diphenylamine    aluminum butyl     0.29 diphenyl-       di-chloride
 chloride      amine 84 48 Cp.sub.2 20 std. 0.5 none std. 0.25 tert- 31
 3 -- 192 0.98 -- none 10 ml run. Rubber,  32 Cp.sub.3 polyisoprene
 boron   butyl       ob- catalyst and Lewis acid in     tri-   chloride
     served half the monomer;     fluoride           activator and
 cocatalyst in     etherate           the other. After 5 minutes
       the temperature was 39° C.                Heating to
 65° C. gave the                exotherm. Post-cured at
     90° C./1 hour. 85 80 Cp.sub.2 20 m- std. 0.5 none std. 0.25
 tert- 30 8-9 94 173 0.11 -- -- --   diisopro-  boron   butyl   penylbenze
 ne  tri-   chloride     fluoride-     N,N-di-     ethyl-     aniline 86
 80 Cp.sub.2 20 m- std. 0.5 none std. 0.25 tert- 31  8 -- 194 -- -- --
 After five minutes at   diisopro-  boron   butyl        31° C.,
 heated to 60° C. to   penylbenzene  tri-   chloride        get
 exotherm.     fluoride     tetra-     hydro-     furan 87 80 Cp.sub.2 20
 5- std. 0.5 none std. 0.5 isobutyl  0 <1  -- 199 0.09 -- --  Placed in
 block at 31° C.   ethylidene-2-  boron   chloride        after 5
 minutes.   norbornene  tri-     fluoride     etherate 88 60 Cp.sub.2
 none std. 1.0 none std. 0.5 tert-  3  3 -- 166 0.22 -- -- Put in
 32° C. block after  40 Cp.sub.3   boron   butyl        5 minutes.
     tri-   chloride     fluoride     etherate89 60 Cp.sub.2 none std.
 0.5 none std. 0.25 tert- 3 4 -- 171 0.44 -- -- Put in 32° C.
 block after  40 Cp.sub.3   boron   butyl        5 minutes.    tri-
 chloride     fluoride     etherate 90 (com- 60 Cp.sub.2 none std. none
 none std. none  3 300  -- 160 1.40 -- -- Put in 32° C. block
 after parative) 40 Cp.sub.3              5 minutes. 91 60 Cp.sub.2 none
 std. 0.5 none std. 0.25 32  1 30 201 0.22 -- -- --  40 Cp.sub.3   boron
  tert-butyl     tri-   chloride     fluoride     etherate 92 42 Cp.sub.2
 15 5- Bell none 0.6 ethyl- 1.0 2- 32 -- -- 202 0.75 -- -- No reaction in
 5 minutes.  28 Cp.sub.3 ethylidene-   diglyme aluminum ethylhexyl
 Heating to 70° C. pro-   2-norbornene    dichloride bromide
  duced the exotherm. A   15             duplicate run had no   polyisopre
 ne             residual Cp.sub.2, Cp.sub.3, or 5-
 ethylidene-2-norbornene                and had Tg 154° C. 93 75
 Cp.sub.2 20 5- Bell none 0.6 ethyl- 0.5 tert- 32 -- -- 218 none no
 5-ethyl -- No reaction in 5 minutes.   ethylidene-   diglyme aluminum
 butyl      idene-2-  Heating to 60° C. induced   2-norbornene
 dichloride chloride      nor-  the exotherm.   5           bornene
 diphenylamine           2.79%              diphenyl-              amine
 94 75 Cp.sub.2 20 5- Bell none 0.6 ethyl- 0.5 32 -- -- 205 none no 5- --
 No reaction in 5 minutes.   ethylidene-2-   diglyme aluminum tert-butyl
     ethylidene-  Heating to 70°
  C. gave   norbornene    dichloride chloride      2-nor-  the exotherm.
  5 2,6-di-           bornene   tert-           2.71% 2,6-   butylphenol
         di-tert-               butyl-                phenol 95 42
 Cp.sub.2 15 5- Bell none 0.6 ethyl- 1.0 2-ethyl- 31 -- -- -- none no
 Cp.sub.3 154 No reaction in 5 minutes.  28 Cp.sub.3 ethylidene-
 diglyme aluminum hexyl      no 5-  Heated 90° C./1 hour.
 2-norbornene    dichloride bromide      ethylidene-  Extraction of a
 duplicate   15           2-nor-  run with methylene   polyisoprene
     bornene  chloride removed 8.4%,                compared to 0.5% for
 a                control run with                monomer ratios,
 51:34:15:0. 96 95 Cp.sub.2 5 p-diisopro- Bell none 0.6 ethyl- 0.5 31 --
 --  170 0.16 0.49 p- 100 Mixed at 31° C., then   penylbenzene
 diglyme aluminum tert-butyl      diiso-  heated immediately to
 dichloride chloride      propenyl-  73° C.              benzene
 97 90 CP.sub.2 10 p- Bell none 0.6 ethyl-. 0.5 32 -- -- -- 0.10 0.54 p-
 94 Mixed at 31°
  C., then   diisopro-   diglyme aluminum tert-butyl      diiso-  heated
 immediately to   penylbenzene    dichloride chloride      propenyl-
 73° C.              benzene 98 54 Cp.sub.2 5 naphthalene std. 1.0
 0.6 std. 0.5 tert- 31  4 84 179 0.17 4.58 125 --  36 Cp.sub.3 5 diiso-
 boron diglyme  butyl      naphtha-   butylene  tri-   chloride      lene
     fluoride         3.15     etherate         diiso-
 butylene 99 80 Cp.sub.2 20 polyindane std. 0.5 0.6 std. 0.5 31 12 148
 169 0.12 -- 126 Polyindane made by treat-     boron diglyme  tert-butyl
       ment of m-diisopropenyl-     trifluor   chloride        benzene
 with acid.     ide     etherate 100 95 Cp.sub.2 5 poly std. 0.5 0.6 std.
 0.5 tert- 32  2 45 181 0.20 -- 135 --   (vinylbenzyl  boron diglyme
 butyl   chloride)  trifluo-   chloride     ride     etherate 101 (com-
 80 Cp.sub.2 20 acenaph- std. none 0.6 std. 0.25 31 12 -- 200 0.14 6.1
 109 After 5 minutes at 31° C., parative)  thylene   diglyme
 tert-butyl      acenaph-  heated to 55° C. to        chloride
  thylene  get exotherm. 102 (com- 90 Cp.sub.2 10 5,5'- std. none 0.6
 std. 0.25 31 200
   -- 203 0.95 0.36 5,5'- 164 After 5 minutes at 31° C., parative)
  sulfonyl-   diglyme  tert-butyl      sulfonyl-  heated to 63° C.
 to   bis(2-     chloride      bis(2-  get exotherm.   norbornene)
    norbor-              nene) 103 (com- 90 Cp.sub.2 10 5,5'- std. none
 none std. none 31 14 40 199 0.90 -- 142 -- parative)  sulfonyl-   bis(2-
   norbornene) 104 (com- 48 Cp.sub.2 10 Bell none 0.6 ethyl- 0.5 31 -- --
 200 0.62 0.08 Cp.sub.3 178 Heated to 73° C. to get parative) 32
 Cp.sub.3 polyisoprene   diglyme aluminum tert-butyl      0.12 --
 exotherm.   10    dichloride chloride      diester   hexamethy-
 lene-bis(5-   norbornene-2-   carboxylate) 105 (com- same same 2X std.
 none none 2X std. none 31 26 56 169 0.30 -- 158 -- parative) 106 90
 Cp.sub.2 10 1,4,5,8- std. 0.5 0.6 std. 0.25 31  6 22 205 0.08 0 di- 177
 --   dimethano-  boron diglyme  tert-butyl      methanohex   1,4,4a,5,8,8
 a-  tri-   chloride      ahydro-   hexahydro-  fluoride         naphtha-
   naphthalene           lene 107 (com- 90 Cp.sub.2 10 1,4,5,8- std. none
 none std. none 32  2 27 212 0.97 -- 168 -- parative)  dimethano-
 1,4,4a,5,8,8a-   hexahydro-   naphthalene 108 (com- 73 Cp.sub.2 18 Bell
 none 0.6 ethyl- 0.5 tert- -- -- -- 179 0.06 9.1  96 The exotherm
 occurred on parative)  polyisoprene   diglyme aluminum butyl
 diamine  heating to 100°  C.   9 N,N'-    dichloride chloride
 diphenyl-p-   phenylene-   diamine 109 80 Cp.sub.2 13 5- Bell none 0.6
 ethyl- 0.5 -- -- -- 197 0.14 0 5-  76 Heated to 63° C. to get
 ethylidene-2-   diglyme aluminum tert-butyl      ethylidene-  exotherm.
  norbornene    dichloride chloride      2-norbor-   7 naphthalene
    nene 6.4              naphtha-              lene 110 70 Cp.sub.2 20
 5- std. 1.0 0.6 std. 0.5 31  9 38 201 0 0 5-  92 --   ethylidene-2-
 boron diglyme  tert-butyl      ethylidene-   norbornene  tri-   chloride
      2-norbor-   10 1,5-  fluoride         nene   cycloocta-
 5.3 1,5-   diene           cycloocta-              diene 111 70 Cp.sub.2
 20 5- std. 1.0 0.6 std. 0.5 31  9 37 197 0 0 5-  97 --   ethylidene-2-
 boron diglyme  tert-butyl      ethylidene-   norbornene  trifluor
 chloride      2-norbor-   10 1,5,9-  ide         nene   cyclododeca-
       7.4 1,5,9-   triene           cyclodo-              decatriene 112
 80 Cp.sub.2 13 poly- Bell none 0.6 ethyl- 0.5 -- -- -- 181 -- -- 102
 Heated to 75° C. to get   isoprene   diglyme aluminum tert-butyl
       exotherm. Some foaming.   7 naphthalene    dichloride chloride 113
 54 Cp.sub.2 10 std. 0.5 0.6 std. 0.5 31 instant -- 134 5.95 2.46
 Cp.sub.3  82 Activator, tert-butyl  36 Cp.sub.3 hexamethyl-  boron
 diglyme  tert-butyl      1.94  chloride and diglyme   cyclo-  tri-
 chloride      hexamethyl  mixed with monomers   trisiloxane  fluoride
      cyclotri-  before adding catalyst and     etherate         siloxane
  boron trifluoride etherate.                Poor mixing. 114 42 Cp.sub.2
 15 5- 2X Bell 1.0 0.6 2X ethyl- 0.5 isobutyl -- -- -- 184 -- -- 146
 Heated to 75° C. to get the  28 Cp.sub.3 ethylidene-2-  boron
 diglyme aluminum chloride        exotherm.   norbornene  trifluor
 di-chloride   15  ide   polyisoprene  etherate 115 42 Cp.sub.2 15 5- 2X
 std. 1.0 none 2X std. 0.5 isobutyl 31 10 56 169 -- -- 150 See Ex. No.
 136 for  28 Cp.sub.3 ethylidiene-  boron   chloride        extraction of
 the rubber.   2-norbornene  trifluor   15  ide   polyisoprene 116 95
 Cp.sub.2 5 p-diisopro- 2X std. 1.0 Tin none 2X std. 0.5 isobutyl -- --
 -- 207 -- --  79 Heated to 63° C. to get   penylbenzene  (IV)
 chloride        exotherm.     bromide 117 90 Cp.sub.2 10 m- 2X std. 1.0
 Tin none 2X std. 0.5 isobutyl -- -- -- 187 -- --
  54 Heated to 63° C. to get   diisopro-  (IV)   chloride
 exotherm.   penylbenzene  bromide 118 90 Cp.sub.2 10 2X std. 0.7 Tin
 none 2X std. 0.5 isobutyl -- -- -- 203 0.13 -- 132 Heated to 57°
 C. to get   polyisoprene  (IV)   chloride        exotherm.     bromide
 119 48 Cp.sub.2 10 Bell none 0.85 n- 0.5 ethyl- 0.5 -- -- -- 211 0.21
 0.01 Cp.sub.3 none Heated to 80°
  C. to get  32 Cp.sub.3 polyisoprene   hexyl aluminum tert-butyl
 <0.11 ob- exotherm.   10   ether di-chloride chloride      diester
 served   hexamethylene-   bis(2-nor-   bornene-5   carboxylate) 120 48
 Cp.sub.2 10 Bell none 0.6 butyl diethyl- 0.5 -- -- -- 182 0.59 0.34
 Cp.sub.3 153 Heated to 75° C. to get  32 Cp.sub.3 polyisoprene
 diglyme aluminum tert-butyl      <0.11  exotherm.   10    chloride 6
 chloride      diester   hexamethylene    Al/W   bis(2-   norborene-5-
 carboxylate) 121 80 Cp.sub.2 20 5- std. 0.5 0.67 std. 0.5 isobutyl --  1
 -- -- 0.47 -- -- 3 ml. run with 0.8 ×  10   ethylidiene-  boron
 diglyme  chloride        cm steel rod in test tube.   2-norbornene  tri-
     fluoride     etherate 122 80 Cp.sub.2 20 5- 2X std. 1.0 1.3 2X std.
 1.0 isobutyl 32
  5 13 -- 0.11 -- -- Contained steel rod as in   ethylidene-2-  boron
 diglyme  chloride        Ex. No. 121   norbornene  tri-     fluoride
 etherate 123 80 Cp.sub.2 20 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 51
 -- instant 98.5 0.40 -- -- Contained EPDM rubber.   ethylidene-2-  boron
 diglyme  chloride        Odor not of dicylco-   norbornene  tri-
   pentadiene, possibly of 5-     fluoride           ethylidene-2-norborne
 ne;     etherate           280% swell; 624 kg/cm.sup. 2
 (8.9 kpsi) flexural strength,                5.00% flexural strain,
           18500 kg/cm.sup.2 (263 kpsi)                flexural modulus,
 6.77-6.90                mm deflection; 7.28 ft lb/                inch
 width in notched Izod                impact test at 23° C.;
          79° C. deflection tempera-                ture under 264
 psi load. 124 80 Cp.sub.2 20 5- Bell none none ethyl- 0.5 32 2-3 -- 224
 0.06 -- 124 After 5 minutes heated to   ethylidene-2-    aluminum
 tert-butyl        72° C. to get exotherm.   norbornene
 chloride-n- chloride       propoxide 125 80 Cp.sub.2 20 4- Bell none
 none ethyl- 0.5 tert- 32 400 -- 184 0.53 --  48 After 5 minutes heated
 to   methylstyrene    aluminum butyl        72° C. to get
 exotherm.       chloride-n- chloride       propoxide 126 75 Cp.sub.2 15
 5- std. 0.5 0.6 std. 0.25 isobutyl 30  5 23 226 0.07 -- 175 --
 ethylidene-2-  boron diglyme  chloride   norbornene  tri-   10 dimethano-
   fluoride   hexahydro-  etherate   naphthalene 127 same same 2X std.
 1.0 1.25 2X std. 1.0 isobutyl 31 -- -- -- 0.26 -- none Contained steel
 rod as     boron diglyme  chloride       ob- in Ex. No. 121     tri-
      served     fluoride     etherate 128 45 Cp.sub.2 same std. 0.5 0.6
 std. 0.25 isobutyl 31  5 21 229 0.08 -- none  30 Cp.sub.3   boron
 diglyme  chloride       ob-     tri-          served     fluoride
 etherate 129 same same 2X std. 1.0 1.25 2X std. 1.0 isobutyl  3 -- -- --
 0.21 -- none Contained steel rod as in     boron diglyme  chloride
 ob- Ex. No. 121     tri-          served     fluoride     etherate 130
 70 Cp.sub.2 15 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 31  7 21 178 0.09
 -- 114 Extraction overnight twice   ethylidene-2-  boron diglyme
 chloride        with methylene chloride   norbornene  tri-
 removed 20.5%.   15 polyindane  fluoride     etherate 131 (com- 42
 Cp.sub.2 15 5- std. none none std. none 31  3 -- 207 0.64 -- 166 After 5
 minutes heated to parative) 28 Cp.sub.3 ethylidene-2-
 90° C. to get exotherm.   norbornene   15   polyisoprene 132
 (com- same same 2X std. none none 2X std. none 31  3 79 158 0.54 -- 145
 parative) 133 70 Cp.sub.2 15 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 28
 1-2 17 165 0.06 -- 127 Polydicyclopentadiene made   ethylidene-2-  boron
 diglyme  chloride        with aluminum chloride.   norbornene  tri-
      Extraction with methylene   15 poly-  fluoride           chloride
 overnight twice   (dicyclo-  etherate           removed 11.7%   pentadien
 e) 134 54 Cp.sub.2 10 std. 0.5 0.6 std. 0.5 isobutyl 31  5 -- 197 0.02-
 0.05 Cp.sub.3, 159 Went from 31° C. to 40° C.  36 Cp.sub.3
 hexamethyl-  boron diglyme  chloride     0.04 3.3  in 5 minutes. Heated
 to   cyclotri-  tri-         siloxane  47° C. to get exotherm.
 siloxane  fluoride     etherate 135 54 Cp.sub.2 10 std. none none std.
 0.5 isobutyl 32  3 26 208 -- -- -- --  36 Cp.sub.3 hexamethyl-
 chloride   cyclotri-   siloxane 136 42 Cp.sub.2 15 5- 2X std. 1.0 none
 2X std. 0.5 isobutyl 31  8 76 174 -- -- -- A duplicate of Ex. No.  28
 Cp.sub.3 ethylidene-2-  boron   chloride        115. Extraction overnight
    norbornene  tri-           twice with methylene   15 fluoride
   chloride removed 12%.   polyisoprene  etherate 137 95 Cp.sub.2
 5-p-diisopro- 2X std. 1.0 tin none 2X std. 0.5 isobutyl 31 30 -- 195 --
 -- -- A duplicate of Ex. No.   penylbenzene  (IV)   chloride        116.
 Went from 31° C. to     bromide           34° C. in 5
 minutes.                Heated to 63° C. to get the
  exotherm. Two overnight                extractions with methylene
          chloride removed 13%.

                                  TABLE 3                                 
__________________________________________________________________________
Metathesis - Anionic Polymerization of Dicyclopentadiene                  
__________________________________________________________________________
                              Procatalyst                                 
Example    Other  Metathesis  Activator/                                  
                                     Initial                              
                                          Seconds                         
                                               Seconds                    
Number                                                                    
     Cp.sub.2 & Cp.sub.3                                                  
           Monomer                                                        
                  Catalyst                                                
                        Moderator                                         
                              Anionic                                     
                                     Temp °C.                      
                                          to Gel                          
                                               to 100° C.          
__________________________________________________________________________
138  100 Cp.sub.2                                                         
           none   Bell  none  n-     31   1    194                        
                              butyllithium                                
139  100 Cp.sub.2                                                         
           none   Bell  none  dibutylzine                                 
                                     32   3    36                         
140  48 Cp.sub.2                                                          
           20     Bell  none  dibutylzinc                                 
                                     31   11                              
     32 Cp.sub.3                                                          
           caprolactone                                                   
141  same  same   2X std.                                                 
                        none  2X std.                                     
                                     31   --   --                         
142  60 Cp.sub.2                                                          
           none   2X std.                                                 
                        none  2X std.                                     
                                     31   3    24                         
     40 Cp.sub.3                                                          
143  48 Cp.sub.2                                                          
           20     std.  none  dibutylzinc                                 
                                     31   --   --                         
     32 Cp.sub.3                                                          
           caprolactone                                                   
144  54 Cp.sub.2                                                          
           10     Bell  none  dibutylzinc                                 
                                     30   5    38                         
     36 Cp.sub.3                                                          
           hexamethyl-                                                    
           cyclotri-                                                      
           siloxane                                                       
__________________________________________________________________________
                          % Residual                                      
                                Glass                                     
         Example                                                          
              Maximum                                                     
                    % Residual                                            
                          Other Trans.                                    
         Number                                                           
              Temp °C.                                             
                    Cp.sub.2                                              
                          Monomer                                         
                                Temp °C.                           
                                     Notes                                
__________________________________________________________________________
         138  139   --    --    113  Poor mixing. Post-cured 90°   
                                     C./1                                 
                                     hour.                                
         139  195   3.58  --    152  Temperature rose to 40° C. in 
                                     5                                    
                                     minutes.                             
         140  181   1.12-1.25                                             
                          0.71 Cp.sub.3 -                                 
                                --   Heating to 72° C. gave the    
                                     strong                               
                          caprolacton                                     
                                     exotherm. 10% weight loss by         
                                     370° C. (under nitrogen, at   
                                     20° C./minute).               
         141  --    0.54        151  Exotherm sometime after 5            
                                     minutes. 7% weight loss by           
                                     370° C.                       
         142  203   --    --    --   Control for Ex. No. 141. 3.5%        
                                     weight loss by 370° C.        
         143  164   3.12  --    135  Went from 31° C. to           
                                     61° C. in 5                   
                                     minutes.                             
                                     Heating to 75° C. gave the    
                                     exotherm.                            
         144  187   0.38  --    147  --                                   
__________________________________________________________________________

                                  TABLE 4                                 
__________________________________________________________________________
Metathesis - Free Radical Copolymerization                                
Conventions as in Tables 1, 2 and 3. Azobis means 2,2'-azobis(2-methylprop
ionitrile). Solids were put in the tube first.                            
The free radical sources were dissolved in the monomers                   
__________________________________________________________________________
first.                                                                    
Ex.                  Metathesis                                           
                           Methasis                                       
                                Free Radical Source,                      
                                           Initial                        
                                                 Seconds                  
Number                                                                    
     Cp.sub.2 & Cp.sub.3                                                  
           Other Monomer                                                  
                     Catalyst                                             
                           Activator                                      
                                Weight %   Temp. °C.               
                                                 to Gel                   
__________________________________________________________________________
145  100 Cp.sub.2                                                         
           none      std. + 1                                             
                           std. 0.5 azobis 31    3                        
                     diglyme/W  0.5 dicumyl peroxide                      
146  100 Cp.sub.2                                                         
           none      std. + 1                                             
                           std. 0.5 azobis 32    2-3                      
                     diglyme/W  0.5 2,5-dimethyl-2,5-                     
                                di-tert-butylperoxy                       
                                hexane                                    
147  100 Cp.sub.2                                                         
           none      std. + 1                                             
                           std. 0.5 2,2'-azobis(2-                        
                                           32    2-3                      
                     diglyme/W  methylbutyronitrile)                      
                                0.5 dicumyl peroxide                      
148  100 Cp.sub.2                                                         
           none      2X std.                                              
                           2X std.                                        
                                0.5 tert-  32    10                       
                                butylperoxyoctoate                        
                                0.5 dicumyl peroxide                      
149  100 Cp.sub.2                                                         
           none      std.  std. 0.5 1,1'-azobis                           
                                           32    6                        
                                (cyclohexanecarbo-                        
                                nitrile)                                  
                                0.5 dicumyl peroxide                      
150  100 Cp.sub.2                                                         
           none      std. + 1                                             
                           std. 0.5 2,2'-azobis(2-                        
                                           31    4                        
                     diglyme/W  methylbutyronitrile)                      
                                0.5 tert-butyl-peroxide                   
151  100 Cp.sub.2                                                         
           none      std.  std. 1.25 1,1-bis(tert-                        
                                           30    5                        
                                butylperoxy)-                             
                                3,3,5-                                    
                                trimethylcyclohexane                      
                                (40% on CaCO.sub.3)                       
                                1.0 dicumyl peroxide                      
152  100 Cp.sub.2                                                         
           none      2X std.                                              
                           2X std.                                        
                                0.5 tert-butyl                            
                                           32    5                        
                                peroctoate                                
                                0.5 2,5-dimethyl-2,5-                     
                                di-tert-                                  
                                butylperoxyhexane                         
153  100 Cp.sub.2                                                         
           none      std.  std. 0.5 2,2'-azobis(2-                        
                                           27    3                        
                                methylbutyronitrile)                      
                                0.5 azo-tert-butane                       
154  90 Cp.sub.2                                                          
           7.5 isobornyl                                                  
                     2X std.                                              
                           2X std.                                        
                                0.5 2,2'-azobis(2-                        
                                           32    5                        
           methacrylate         methyl-butyronitrile)                     
           2.5                  0.5 dicumyl peroxide                      
           trimethylolpropane-                                            
           trimethacrylate                                                
155  same  same      2X std.                                              
                           2X std.                                        
                                0.5 tert-butyl                            
                                           32    6                        
                                peroctoate                                
                                0.5 dicumyl peroxide                      
156  80 Cp.sub.2                                                          
           15 4-methylstyrene                                             
                     2X std.                                              
                           2X std.                                        
                                same       32    12                       
           5 divinylbenzene                                               
157  80 Cp.sub.2                                                          
           15 isobornyl                                                   
                     2X std.                                              
                           2X std.                                        
                                0.5 dicumyl peroxide                      
                                           32    7                        
           methacrylate                                                   
           5                                                              
           trimethylolpropane-                                            
           trimethacrylate                                                
158  80 Cp.sub.2                                                          
           15 4-methylstyrene                                             
                     2X std.                                              
                           2X std.                                        
                                0.5 dicumyl peroxide                      
                                           32    12                       
           divinylbenzene                                                 
159  90 Cp.sub.2                                                          
           10 dimethanohexa-                                              
                     std.  std. 0.5 tert-butyl                            
                                           31    9                        
           hydronaphthalene     peroctoate                                
                                0.5 dicumyl peroxide                      
160  80 Cp.sub.2                                                          
           10 dimethanohexa-                                              
                     std.  std. same       31    17                       
           hydronaphthalene                                               
           10 divinylbenzene                                              
161  90 Cp.sub.2                                                          
           10        std.  std. same       31    7                        
           trimethylolpropane-                                            
           trimethacrylate                                                
162  90 Cp.sub.2                                                          
           7 4-methylstyrene                                              
                     2X std.                                              
                           2X std.                                        
                                0.5 tert-butyl                            
                                           31    26                       
           3 divinylbenzene     peroctoate                                
                                0.5 dicumyl peroxide                      
                                0.5 N,N-diethylaniline                    
163  80 Cp.sub.2                                                          
           15 4-methylstyrene                                             
                     2X std.                                              
                           2X std.                                        
                                0.5 tert-butyl                            
                                           30    60                       
           5 divinylbenzene     peroctoate                                
                                0.5 dicumyl peroxide                      
164  same  same      Bell  tributyl-                                      
                                0.5 2,2'-azobis(2-                        
                                           30    6                        
                           tin  methyl-butyronitrile)                     
                           hydride                                        
                                0.5 dicumyl peroxide                      
165  100 Cp.sub.2                                                         
           none      Bell  tributyl-                                      
                                same       28    1-2                      
                           tin                                            
                           hydride                                        
166  90 Cp.sub.2                                                          
           10 dimethanohexa-                                              
                     Bell  tributyl-                                      
                                same       28    1-2                      
           hydronaphthalene                                               
                           tin                                            
                           hydride                                        
167  90 Cp.sub.2                                                          
           10 isobornyl                                                   
                     Bell  tributyl-                                      
                                same       26    1-2                      
           methacrylate    tin                                            
                           hydride                                        
168  90 Cp.sub.2                                                          
           7.5 4-    std.  std. 0.5 2,2'-azobis(2-                        
                                           29    3                        
           methylstyrene        methyl-butyronitrile)                     
           2.5 divinylbenzene   0.5 azo-tert-butane                       
169  87.6 Cp.sub.2                                                        
           10 isobornyl                                                   
                     2X std.                                              
                           2X std.                                        
                                0.6 dicumyl peroxide                      
                                           1.4   10                       
           methacrylate         0.6 2,2'-azobis(2-                        
           2.4                  methyl-butyronitrile)                     
           trimethylolpropane-                                            
           trimethacrylate                                                
__________________________________________________________________________
                             %                                            
                       %     Residual                                     
                                   Glass                                  
       Ex.  Seconds                                                       
                  Maximum                                                 
                       Residual                                           
                             Other Transition                             
       Number                                                             
            to 100° C.                                             
                  Temp. ° C.                                       
                       Cp.sub.2                                           
                             Monomer                                      
                                   Temp. °C.                       
                                         Notes                            
__________________________________________________________________________
       145  26    207  2.51  --    108   --                               
       146  27    210  2.98  --    104   --                               
       147  28    214  2.28  --    113   --                               
       148  34    210  0.46  --    115   --                               
       149  24    213  1.84  --    123   --                               
       150  22    205  2.56  --    114   --                               
       151  33    202  6.87  --    --    duplicate run had Tg             
                                         85° C.                    
       152  27    214  0.43  --    112   --                               
       153  23    214  0.62  --    130   --                               
       154  32    184  7.40  --    73    --                               
       155  97    184  4.48  --    76    --                               
       156  30    207  0.63  --    46    --                               
       157  140   159  9.97  --    53    --                               
       158  28    220  1.08  --    51    --                               
       159  50    225  0.99  --    138   --                               
       160  66    228  1.32  --    108   --                               
       161  --    185  8.91  --    73    Temperature to 37° C. in  
                                         5                                
                                         minutes, then heated to          
                                         72°  C. to get exotherm.  
       162  127   202  1.50  2.37 4-                                      
                                   59    Metathesis activator and         
                             methyl-     N,N-diethylaniline               
                             styrene     combined before addition.        
       163  274   179  2.66  0.66  none ob-                               
                                         --                               
                             divinyl-                                     
                                   served                                 
                             benzene                                      
       164  63    164  0.20  --    90.7  25% larger than original         
                                         volume.                          
       165  62    200  0.86  --    137   --                               
       166  65    217  0.75  --    177   --                               
       167  113   178  1.72  --    136   --                               
       168  24    189  0.42  --    91    --                               
       169  110   149  2.64  0,52  --    --                               
                             isobornyl                                    
                             methacry-                                    
                             late 0.07                                    
                             trimethyl                                    
                             propane                                      
                             tri-                                         
                             acrylate                                     
__________________________________________________________________________

                                  TABLE 5                                 
__________________________________________________________________________
Metathesis - Hydrosilation                                                
The catalyst for a 5 ml polymerization was 0.06 ml containing 0.045 ml    
standard catalyst (0.02 mmole W), containing one                          
diphenyldichloromethane per W and 0.0165 ml platinum/siloxane complex in  
silicon fluid (3% Pt).                                                    
Other convention as in Tables 1 & 2.                                      
__________________________________________________________________________
                    Metathesis +                                          
Example             Hydrosil.          Initial                            
                                            Seconds                       
                                                 Seconds                  
Number                                                                    
     Cp.sub.2 & Cp.sub.3                                                  
           Other Monomer                                                  
                    Catalyst                                              
                           Moderator                                      
                                  Activator                               
                                       Temp °C.                    
                                            to Gel                        
                                                 to 100° C.        
__________________________________________________________________________
170  90 Cp.sub.2                                                          
           10       std. + Pt                                             
                           0.25%  std. 31   20   --                       
           methylhydrocy   maleic                                         
           cio-siloxanes   anhydride                                      
171  90 Cp.sub.2                                                          
           10 methyl-                                                     
                    2X (std. +                                            
                           0.25%  2X std.                                 
                                       31   12   --                       
           hydrocyclo-                                                    
                    Pt)    maleic                                         
           siloxanes       anhydride                                      
172  80 Cp.sub.2                                                          
           20 methyl-                                                     
                    std. + Pt.                                            
                           0.25%  std. 32   19   --                       
           hydrocyclo-     maleic                                         
           siloxanes       anhydride                                      
173  80 Cp.sub.2                                                          
           20 methyl-                                                     
                    2X (std. +                                            
                           0.25%  2X std.                                 
                                       31   15   315                      
           hydrocyclo-                                                    
                    Pt.)   maleic                                         
           siloxanes       anhydride                                      
174  90 Cp.sub.2                                                          
           10(15-   std. + Pt.                                            
                           1.0% maleic                                    
                                  std. 32    9   70                       
           18%)methyl-     anhydride                                      
           hydro(82-                                                      
           85%)di-                                                        
           methyl-                                                        
           siloxane                                                       
           copolymer                                                      
175  90 Cp.sub.2                                                          
           10(3-    std. + Pt.                                            
                           1.0% maleic                                    
                                  std. 32   8-9  99                       
           4%)methyl-      anhydride                                      
           hydro-(96-                                                     
           97%)dimethyl-                                                  
           siloxane                                                       
           copolymer                                                      
176  100 Cp.sub.2                                                         
           none     std. + Pt                                             
                           1.0% maleic                                    
                                  std. 32    8   --                       
                           anhydride                                      
177  100 Cp.sub.2                                                         
           none     std. + Pt                                             
                           none   std. 32    3   81                       
__________________________________________________________________________
                           % Residual                                     
                                 Glass                                    
         Example                                                          
               Maximum                                                    
                     % Residual                                           
                           Other Trans.                                   
         Number                                                           
               Temp °C.                                            
                     Cp.sub.2                                             
                           Monomer                                        
                                 Temp °C.                          
                                      Notes                               
__________________________________________________________________________
         170   214   0.20  --    86   After 5 minutes, heated to          
                                      45° C.                       
                                      to get exotherm. Hydrosilation      
                                      33% complete by solid state .sup.29 
                                      Si                                  
                                      NMR.                                
         171   221   0.05-0.07                                            
                           0.30 silane                                    
                                 85   37°  C. after 5 minutes,     
                                      then                                
                                      heated to 40° C. to get      
                                      exotherm.                           
                                      Hydrosilation 45% complete by       
                                      solid state .sup.29 Si NMR.         
         172   214   0.29  --    76   Heated to 50° C. after 5     
                                      minutes                             
                                      to get exotherm. Hydrosilation      
                                      36% complete by solid state .sup.29 
                                      Si                                  
                                      NMR.                                
         173   189   0.15  --    82   Hydrosilation 42% complete by       
                                      solid state .sup.29 Si NMR.         
         174   190   0.20  --    144  Two extractions overnight with      
                                      methylene chloride removed 9.5%.    
         175   187   0.34  --    152  Two extractions overnight with      
                                      methylene chloride removed          
                                      10.8%.                              
         176   205   0.23  --    141  Went from 32° C. to          
                                      41° C. in 5                  
                                      minutes.                            
                                      Heating to 50° C. gave the   
                                      exotherm.                           
                                      Two extractions overnight with      
                                      methylene chloride removed 1.2%.    
         177   207   0.33  --    136                                      
__________________________________________________________________________

Table 1 provides data for Examples 1 through 67. The combination of metathesis polymerization procatalyst, metathesis polymerization procatalyst activator, Lewis Acid catalyst, and Lewis Acid cocatalyst are well-represented by Examples 28, 34, 35, 37, 39, 40, 43, 44, 46, 51-58. and 66. The results given in Table 1 indicate that the use of a Lewis acid together with a Lewis acid cocatalyst can produce a level of residual dicyclopentadiene of less than 0.25 weight percent. The low residual dicyclopentadiene monomer is also obtained with a variety of metathesis polymerization procatalysts, as well as a variety of metathesis polymerization procatalyst activators. A variety of Lewis acid catalysts and cocatalysts can also be used. A variety of moderators can be used to control the rate of the polymerization. The polymerization can also be run in a molding machine to give a low-odor polymer with good physical properties. Various levels of the catalyst components can also be used.

Table 2 provides data for Examples 68 through 137, involving a copolymerization utilizing, in combination, a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, a Lewis acid catalyst, and a Lewis acid cocatalyst. Copolymerization and/or alkylation using the combination of a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, a Lewis Acid catalyst, and a Lewis Acid cocatalyst, is well-represented by Examples 71, 75, 76, 77-82, 85-97, 101, 106-108, 112-113, 118, 122, 124, 126, 128, 131, and 134. Most of the Examples provided in Table 2 utilize dicyclopentadiene as the principal monomer, together with an additional monomer or alkylation compound. The results provided in Table 2 indicate that copolymerization and alkylation are possible. A variety of comonomers and materials to be alkylated can be used. Various catalyst systems at various levels are possible. Very low levels of residual monomers can be obtained, as low as zero for the combination of dicyclopentadiene and 5-ethylidene-2-norbornene. The rate of polymerization can be controlled by the starting temperature and the ligand on the Lewis acid. The method is also applicable to mixtures of dicyclopentadiene and tricyclopentadiene. Antioxidants can be alkylated, and various levels of antioxidants can be used. Antioxidants can be partially linked to the polymer to reduce losses by evaporation or extrusion from a finished object.

Table 3 provides various data for Examples 138 through 144, each of which utilizes a combination of metathesis polymerization and anionic polymerization of dicyclopentadiene, either alone or in combination with caprolactone or hexamethylcyclotrisiloxane. The combination of a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and anionic polymerization catalyst are well-represented by Examples 140, 141, and 144. The results given in Table 3 indicate that anionic polymerization and metathesis polymerization can be carried out in a manner so that they are compatible with one another. More than one catalyst system can be used. More than one comonomer can be used. It is possible to prepare "soft" polymers within "hard" polymers, which should improve the impact strength, compared with the "hard" polymer alone.

Table 4 relates to metathesis-free radical copolymerization, and provides data for Examples 145 through 169. The combination of metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and a free radical polymerization initiator is well-represented by Examples 147, 152, 162, and 169. The results given in Table 4 indicate that metathesis and free radical polymerizations can be carried out in a manner compatible with one another. A variety of free radical initiators can be used. More than one type of comonomer can be used.

Table 5 relates to a combination of metathesis polymerization and hydrosilation polymerization, and provides data for Examples 170 through 177. The combination of a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and a free radical polymerization initiator is well-represented by Examples 170-173, and 176-177. The results given in Table 5 indicate that metathesis and hydrosilation polymerization can be carried out in a manner in which they are compatible with one another. Furthermore, the combination of metathesis polymerization and hydrosilation polymerization can be used to produce a polymeric product having a low level of residual dicyclopentadiene monomer.

Finally, although the invention has been described with reference to particular means, materials and embodiments, it should be noted that the invention is not limited to the particulars disclosed, and extends to all equivalents within the scope of the claims.

Claims (33)

What is claimed is:

1. A polymer comprising the reaction product of:

A. a polyolefin comprising repeating units of a metathesis polymerizable olefin;

B. a metathesis polymerization procatalyst and a metathesis polymerization procatalyst activator; and

C. at least one member selected from the group consisting of:

i. a Lewis acid catalyst, and a Lewis acid cocatalyst, effective to obtain a residual metathesis polymerizable olefin monomer level of from about 0 to 0.25 weight percent, based on the weight of the polyolefin;

ii. an anionic polymerization catalyst;

iii. a free radical polymerization initiator; and

iv. a hydrosilation polymerization catalyst and a monomer comprising a hydrosilane group.

2. The polymer as described in claim 1, wherein the polymer has a residual metathesis polymerizable olefin monomer level of from 0 to 0.25 weight percent, based on the weight of the polyolefin.

3. The polymer as described in claim 2, wherein:

(a) the Lewis acid catalyst comprises at least one member selected from the group consisting of a boron halide, a tin halide, an aluminum halide, a titanium halide, an antimony halide, a bismuth halide, an iron halide, a zinc halide, a zirconium halide, boron trifluoride etherate, boron trifluoride-N,N-diethylaniline, boron trifluoride-tetrahydrofuran, tin (IV) chloride, tin(IV) bromide, boron trifluoride quinuclidine, a polymeric Lewis acid, a protonic acid, a cation generator, and ionizing radiation; and

(b) the Lewis acid cocatalyst comprises at least one member selected from the group consisting of alkyl halide, aryl halide, isobutyl chloride, tert-butyl chloride, benzyl chloride, vinylbenzyl chloride, 1-bromodecane, 2-ethylhexyl chloride, 2-ethylhexyl bromide, t-butyl acetate, chlorodiphenylmethane, and a polymeric chloride.

4. The polymer as described in claim 3, the polyolefin comprising dicyclopentadiene.

5. The polymer as described in claim 4, prepared using the Lewis acid catalyst and the Lewis acid cocatalyst.

6. The polymer as described in claim 5, wherein the polymer is prepared with a polymerization reaction rate moderator.

7. The polymer as described in claim 6, the reaction rate moderator comprising at least one member selected from the group consisting of butyl ether, di-n-butyl ether, n-hexyl ether, dimethyl ether of diethylene glycol (diglyme), butyl diglyme, ethyl benzoate, maleic anhydride, alkylzinc compounds, aniline, dialkylaniline, alkylaniline, N-alkylaniline, N-ethylaniline, N,N-di-ethylaniline, alkyl arylamines, triethylanime, hexamethylene tetramine, indoline, ethylpiperidine, methylpiperidine, pyridine, 2,4,6-trimethylpyridine, borontrifluoride pyridine, borontrifluoride-2,6-dimethylpyridine, 2-,3-,4-disubstituted pyridines, 3,4-disubstitutedpyridines, 2-,2,3,-di-substituted pyrazines, 2,5-di-substituted pyrazines, quinoline, isoquinoline, quinoxaline, quinuclidine, phenanthridine, pyrimidine, tributylphosphine, triphenylphosphosphine, 1,4-diazabicyclo[2.2.2]octane, trialkyl phosphites, trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite, triisobutylphosphite, tripentyl phosphite, trihexylphosphite, triheptylphosphite, triisooctyl phosphite, trineodecyl phosphite, norbornene phosphites, tris(5-norbornenyl-2-methyl) phosphite, isooctyldiphenyl phosphite, diethyl ethylenepyrophosphite, tetraethyl pyrophosphite, di isodecylpentaerythritol diphosphite, tris(2-chloroethyl)phosphite, diethyl chlorophosphite, ethyl dichlorophosphite, ethylene chlorophosphite, tridodecyl trithiophosphite, 1,2-phenylenephosphorochloridite, diisopropyl phenylphosphonite, diethylphenyl phosphonite, ethyl diphenylphosphonite, trialkyl phosphates, triethyl phosphate, tributyl phosphate, tricresylphosphate, norbornene phosphates, tris(5-norbornenyl-2-methyl) phosphate, triaryl phosphates, triphenylphosphate, and butylated triphenyl phosphate.

8. The polymer as described in claim 5, comprising a residual metathesis polymerizable olefin monomer level of from about 0 to 0.15 weight percent, based on the weight of the polyolefin.

9. The polymer as described in claim 8, wherein the monomer in addition to dicyclopentadiene comprises at least one member selected from the group consisting of: tricyclopentadiene, norbornene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, α-methylstyrene, pinene, 5-ethylidene-2-norbornene, β-pinene, polyisoprene, diisobutylene, polyindane, acenaphthylene, 5,5'-sulfonyl-bis(2-norbornene), hexamethylene-bis(5-norbornene-2-carboxylate), 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, hexamethylcyclotrisiloxane, 4-methylstyrene, and poly(vinylbenzyl chloride).

10. The polymer as described in claim 8, wherein the composition is prepared from:

i.

(a) a Lewis acid catalyst comprising at least one member selected from the group consisting of boron trifluoride etherate, boron trifluoride-N,N-diethylaniline, and boron trifluoride-tetrahydrofuran; and

(b) a Lewis acid cocatalyst comprising at least one member selected from the group consisting of isobutyl chloride, tert-butyl chloride, benzyl chloride, vinylbenzyl chloride, 1-bromodecane, 2-ethylhexyl bromide, and 2-ethylhexyl chloride;

ii.

(a) an additional monomer or compound comprising at least one member selected from the group consisting of m-diisopropenylbenzene, p-diisopropenylbenzene, α-methylstyrene, 5-ethylidene-2-norbornene, naphthalene, β-pinene, 2,6-di-tert-butylphenol, polyisoprene, diphenylamine, diisobutylene, polyindane, poly(vinylbenzylchloride), acenaphthylene, 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, N,N'-diphenyl-p-phenylenediamine, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, hexamethylene-bis(5-norbornene-2-carboxylate), dimethanohexahydronaphthalene, poly(dicyclopentadiene), and hexamethylcyclo-trisiloxane; and

(b) a Lewis acid cocatalyst comprising at least one member selected from the group consisting of isobutyl chloride, tert-butyl chloride, 2-ethylhexyl chloride, and 2-ethylhexyl bromide;

iii. a free radical polymerization initiator comprising a mixture of 2,2'-azobis(2-methyl-butyronitrile) and dicumyl peroxide; and

iv. a hydrosilation polymerization catalyst together with at least one member selected from methylhydrocyclosiloxanes and a methylhydrodimethylsiloxane copolymer.

11. The polymer as described in claim 5, comprising the reaction product prepared with the following:

repeating units of dicyclopentadiene in an amount of from about 1 to 99 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst in a molar ratio of metathesis polymerization procatalyst:metathesis polymerizable olefin of from about 1:500 tp 1:15,000;

the metathesis polymerization procatalyst activator in an amount within the group selected from: a molar ratio of Sn:W of from about 1.5:1 to 1:1, and a molar ratio of Al:W of from about 2:1 to 4:1;

the Lewis acid catalyst in an amount of from about 0.1 to 5 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst; and

the Lewis acid cocatalyst in an amount of from about 0.05 to 5 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst.

12. The polymer as described in claim 11, comprising the reaction product prepared with the following:

the repeating units of dicyclopentadiene in an amount of from about 10 to 95 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst in a molar ratio of metathesis polymerization procatalyst:metathes is polymerizable olefin of from about 1:1000 to 1:3000;

the metathesis polymerization procatalyst activator in an amount within the group selected from: a molar ratio of Sn:W of from about 2:1 to 6:1, and a molar ratio of Al:W of from about 2.5:1 to 3.5:1;

the Lewis acid catalyst in an amount of from about 0.25 to 2 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst; and

the Lewis acid cocatalyst in an amount of from about 0.2 to 2 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst.

13. The polymer as described in claim 12, comprising the reaction product prepared with the following:

repeating units of dicyclopentadiene in an amount of from about 75 to 90 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst in the composition in a molar ratio of metathesis polymerization procatalyst:metathesis polymerizable olefin of from about 1:1500 to 1:3000;

the metathesis polymerization procatalyst activator in an amount within the group selected from: a molar ratio of Sn:W of from about 2:1 to 3:1, and a molar ratio of Al:W of from about 2.75:1 to 3.25:1;

the Lewis acid catalyst in an amount of from about 0.5 to 1 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst; and

the Lewis acid cocatalyst in an amount of from about 0.25 to 0.5 weight percent, based on weight of monomer polymerizable with a Lewis acid catalyst.

14. The polymer as described in claim 11, wherein:

the metathesis polymerization procatalyst comprises at least one member selected from the group consisting of tungsten halide, tungsten oxyhalide, molybdenum halide, molybdenum oxyhalide, rhenium halide, rhenium oxyhalide, tantalum halide, tantalum oxyhalide, niobium halide, and niobium oxyhalide; and

the metathesis polymerization procatalyst activator comprises at least one member selected from the group consisting of an alkylaluminum compound, an alkylzinc compound an alkyltin compound, an alkylmagnesium compound, an alkyllithium compound, and a tin hydride.

15. The polymer as described in claim 14, wherein:

the metathesis polymerization procatalyst comprises at least one member selected from the group consisting of a tungsten halide, a tungsten oxyhalide, a molybdenum halide, and a molybdenum oxyhalide, and a tungsten catalyst complex having the formula: ##STR12## wherein: X comprises at least one member selected from the group consisting of Cl and Br;

n comprises at least one member selected from the group consisting of 2 and 3;

R¹ comprises at least one member selected from the group consisting of H, Cl, an alkyl group having 1-10 carbons, an alkoxy group having 1 to 8 carbons, and a phenyl group;

R² comprises at least one member selected from the group consisting of H, a halogen, and an alkyl group having 1 to 9 carbon atoms; and

R³ comprises at least one member selected from the group consisting of H, an alkyl group having 1 to 10 carbon atoms, a tin activator compound having the formula R₃ SnH, where R is an alkyl group having 1 to 10 carbon atoms, and a phenyl group; and

the metathesis polymerization procatalyst activator comprises at least one member selected from the group consisting of a trialkylaluminum compounds, a dialkylaluminum halide, an alkylaluminum dihalide wherein the alkyl groups contain from 1 to 12 carbon atoms, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum chloride n-propoxide, a mixture of tri-n-octylaluminum:dioctyl-aluminum iodide:diglyme, tributyltin hydride, tetrabutyl tin, and t-butyl chloride.

16. A method for making a polyolefin, comprising:

A. combining a metathesis polymerizable olefin monomer with a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and at least one member selected from the group consisting of:

i. a Lewis acid catalyst, and a Lewis acid cocatalyst, efffective to obtain a residual metathesis polymerizable olefin monomer level of from 0 to 0.25 weight percent, based on the weight of the polyolefin;

ii. an anionic polymerization catalyst;

iii. a free radical polymerization initiator; and

iv. a hydrosilation polymerization catalyst and a monomer comprising a hydrosilane group;

B. polymerizing the metathesis polymerizable olefin.

17. The method as described in claim 16, wherein the polyolefin comprises a residual metathesis polymerizable olefin monomer level of from 0 to 0.25 weight percent, based on the weight of the polyolefin.

18. The method as described in claim 17, wherein:

(a) the Lewis acid catalyst comprises at least one member selected from the group consisting of a boron halide, a tin halide, an aluminum halide, a titanium halide, an antimony halide, a bismuth halide, an iron halide, a zinc halide, a zirconium halide, boron trifluoride etherate, boron trifluoride-N,N-diethylaniline, boron trifluoride-tetrahydrofuran, tin (IV) chloride, tin(IV) bromide, boron trifluoride quinuclidine, a polymeric Lewis acid, a protonic acid, a cation generator, and ionizing radiation; and

(b) the Lewis acid cocatalyst comprises at least one member selected from the group consisting of alkyl halide, aryl halide, isobutyl chloride, tertbutyl chloride, benzyl chloride, vinylbenzyl chloride, 1-bromodecane, 2-ethylhexyl chloride, 2-ethylhexyl bromide, t-butyl acetate, chlorodiphenylmethane, and a polymeric chloride.

19. The method as described in claim 18, wherein the polyolefin comprises dicyclopentadiene.

20. The method as described in claim 19, comprising a residual metathesis polymerizable olefin monomer level of from about 0 to 0.15 weight percent, based on the weight of the polyolefin.

21. The method as described in claim 20, wherein a monomer in addition to dicyclopentadiene is present and comprises at least one member selected from the group consisting of: tricyclopentadiene, norbornene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, α-methylstyrene, pinene, 5-ethylidene-2-norbornene, β-pinene, polyisoprene, diisobutylene, polyindane, acenaphthylene, 5,5'-sulfonyl-bis(2-norbornene), hexamethylene-bis(5-norbornene-2-carboxylate), 1,4,5,8-dimethyano-1,4,4a,5,8,8a-hexahydronaphthalene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, hexamethylcyclo-trisiloxane, 4-methylstyrene, and poly(vinylbenzyl chloride).

22. The method as described in claim 20, wherein at least one member selected from the group consisting of:

i.

(a) a Lewis acid catalyst comprising at least one member selected from the group consisting of boron trifluoride etherate, boron trifluoride-N,N-diethylaniline, and boron trifluoride-tetahydrofuran; and

(b) a Lewis acid cocatalyst comprising at least one member selected from the group consisting of isobutyl chloride, tert-butyl chloride, benzyl chloride, vinylbenzyl chloride, 1-bromodecane, 2-ethylhexyl bromide, and 2-ethylhexyl chloride;

ii.

(a) an additional monomer or compound comprising at least one member selected from the group consisting of m-diisopropenylbenzene, p-diisopropenylbenzene, α-methylstyrene, 5-ethylidene-2-norbornene, naphthalene, β-pinene, 2,6-di-tert-butylphenol, polyisoprene, diphenylamine, diisobutylene, polyindane, poly(vinylbenzylchloride), acenaphthylene, 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, N,N'-diphenyl-p-phenylenediamine, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, hexamethylene-bis(5-norbornene-2-carboxylate), dimethanohexahydronaphthalene, poly(dicyclopentadiene), and hexamethylcyclo-trisiloxane; and

(b) a Lewis Acid cocatalyst comprising at least one member selected from the group consisting of isobutyl chloride, tert-butyl chloride, 2-ethylhexyl chloride, and 2-ethylhexyl bromide;

iii. a free radical polymerization initiator comprising a mixture of 2,2'-azobis(2-methyl-butyronitrile) and dicumyl peroxide; and

iv. a hydrosilation polymerization catalyst together with at least one member selected from methylhydrocyclosiloxanes and a methylhydrodimethylsiloxane copolymer;

is combined with the metathesis polymerizable olefin, the metathesis polymerization procatalyst, and the metathesis polymerization procatalyst activator.

23. The method as described in claim 19, further comprising:

A. providing a plurality of reactant streams, wherein a first reactant stream comprises the metathesis polymerization procatalyst activator and a portion of the metathesis polymerizable olefin, and a second reactant stream comprises the metathesis polymerization procatalyst and a portion of the the metathesis polymerizable olefin, wherein at least one reactant stream further comprises at least one member selected from the group consisting of:

i. a Lewis acid catalyst and a Lewis acid cocatalyst, present in separate reactant streams;

ii. an anionic polymerization catalyst;

iii. a free radical polymerization initiator;

iv. a hydrosilation polymerization catalyst; and

B. mixing the reactant streams together whereby a reaction mixture is formed;

C. forming the reaction mixture into a desired shape before the polymerization of the metathesis polymerizable olefin.

24. The process as described in claim 23, wherein the step of forming the reaction mixture into a desired shape is carried out by injecting the reaction mixture into a mold cavity, and wherein the reaction mixture is allowed to polymerize to a degree of substantial reaction termination while the reaction mixture is within the mold, whereby a molded article is produced, followed by removing the molded article from the mold.

25. The process as described in claim 24, wherein the number of reactant streams is from two to four.

26. The method as described in claim 19, wherein the Lewis acid catalyst and the Lewis acid cocatalyst are combined with the metathesis polymerizable olefin, the metathesis polymerization procatalyst, and the metathesis polymerization procatalyst activator.

27. The method as described in claim 26, wherein a polymerization reaction rate moderator is combined with the metathesis polymerizable olefin, the metathesis polymerization procatalyst, the metathesis polymerization procatalyst activator, the Lewis acid catalyst, and the Lewis acid cocatalyst.

28. The method as described in claim 27, the polymerization reaction rate moderator comprising at least one member selected from the group consisting of butyl ether, di-n-butyl ether, n-hexyl ether, dimethyl ether of diethylene glycol (diglyme), butyl diglyme, ethyl benzoate, maleic anhydride, alkylzinc compounds, aniline, dialkylaniline, alkylaniline, N-alkylaniline, N-ethylaniline, N,N-diethylaniline,

alkyl arylamines, triethylanime, hexamethylene tetramine, indoline, ethylpiperidine, methylpiperdine, pyridine, 2,4,6-trimethylpyridine, borontrifluoride pyridine, borontrifluoride-2,6-dimethylpyridine, 2-,3-,4-disubstituted pyridines, 3,4-disubstituted pyridines, 2-,2,3,-di-substituted pyrazines, 2,5-di-substituted pyrazines, quinoline, isoquinoline, quinoxaline, quinuclidine, phenanthridine, pyrimidine, tributylphosphine, triphenylphosphosphine, 1,4-dizabicyclo[2.2.2]octane, trialkyl phosphites, trimethylphosphite, triethylphosphite, triisopyropylphosphite, tributylphosphite, triisobutylphosphite, tripentyl phosphite, trihexylphosphite, trikeptylphosphite, triisooctyl phosphite, trineodecyl phosphite, norbornene phosphites, tris(5-norbornenyl-2-methyl)phosphite, isooctyldiphenyl phosphite, diethyl ethylenepyrophosphite, tetraethyl pyrophosphite, diisodecylpentaerythritol diphosphite, tris(2-chloroethyl)phosphite, diethyl chlorophosphite, ethyl dichlorophosphite, ethylene chlorophosphite, tridodecyl trithiophosphite, 1,2-phenylenephosphorochloridite, diisopropyl phenylphosphonite, diethylphenyl phosphonite, ethyl diphenylphosphonite, trialkyl phosphates, triethyl phosphate, tributyl phosphate, tricresylphosphate, norbornene phosphates, tris(5-norbornenyl-2-methyl)phosphate, triaryl phosphates, triphenylphosphate, and butylated triphenyl phosphate.

29. The method as described in claim 26, wherein:

repeating units of dicyclopentadiene are present in an amount of from about 1 to 100 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst is present in a molar ratio of metathesis polymerization procatalyst:metathesis polymerizable olefin of from about 1:500 to 1:15,000;

the metathesis polymerization procatalyst activator is present in an amount within the group selected from: a molar ratio of Sn:W of from about 1.5:1 to 9:1, and a molar ratio of Al:W of from about 2:1 to 4:1;

the Lewis acid catalyst is present in an amount of from about 0.1 to 5 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst; and

the Lewis acid cocatalyst is present in an amount of from about 0.05 to 5 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst.

30. The method as described in claim 29, wherein:

repeating units of dicyclopentadiene are present in an amount of from about 10 to 100 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst is present in a molar ratio of metathesis polymerization procatalyst:metathesis polymerizable olefin of from about 1:1000 to 1:3000;

the metathesis polymerization procatalyst activator is present in an amount within the group selected from: a molar ratio of Sn:W of from about 2:1 to 6:1, and a molar ratio of Al:W of from about 2.5:1 to 3.5:1;

the Lewis acid catalyst is present in an amount of from about 0.25 to 2 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst; and

the Lewis acid cocatalyst is present in an amount of from about 0.2 to 2 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst.

31. The method as described in claim 30, wherein:

repeating units of dicyclopentadiene are present in an amount of from about 75 to 100 weight percent, based on the weight of the polyolefin;

the metathesis polymerization procatalyst is present in the composition in a molar ratio of metathesis polymerization procatalyst:metathesis polymerizable olefin of from about 1:1500 to 1:3000;

the metathesis polymerization procatalyst activator is present in an amount within the group selected from: a molar ratio of Sn:W of from about 2:1 to 3:1, and a molar ratio of Al:W of from about 2.75:1 to 3.25:1;

the Lewis acid catalyst is present in an amount of from about 0.5 to 1 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst; and

the Lewis acid cocatalyst is present in an amount of from about 0.25 to 0.5 weight percent, based on weight of monomer polymerizable with the Lewis acid catalyst.

32. The method as described in claim 29, wherein:

the metathesis polymerization procatalyst comprises at least one member selected from the group consisting of tungsten halide, tungsten oxyhalide, molybdenum halide, molybdenum oxyhalide, rhenium halide, rhenium oxyhalide, tantalum halide, tantalum oxyhalide, niobium halide, and niobium oxyhalide; and

the metathesis polymerization procatalyst activator comprises at least one member selected from the group consisting of an alkylaluminum compound, an alkylzinc compound an alkyltin compound, an alkylmagnesium compound, an alkyllithium compound, and a tin hydride.

33. The method as described in claim 32, the metathesis polymerization procatalyst comprising at least one member selected from the group consisting of a tungsten halide, a tungsten oxyhalide, a molybdenum halide, and a molybdenum oxyhalide, and a tungsten catalyst complex having the formula: ##STR13## wherein: X comprising at least one member selected from the group consisting of Cl and Br;

n comprises at least one member selected from the group consisting of 2 and 3;

R¹ comprises at least one member selected from the group consisting of H, Cl, an alkyl group having 1-10 carbons, an alkoxy group having 1 to 8 carbons, and a phenyl group;

R² comprises at least one member selected from the group consisting of H, a halogen, and an alkyl group having 1 to 9 carbon atoms; and

R³ comprises at least one member selected from the group consisting of H, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a tin activator compound having the formula R₃ SnH, where R is an alkyl group having 1 to 10 carbon atoms, and a phenyl group; and

the metathesis polymerization procatalyst activator comprising at least one member selected from the group consisting of trialkylaluminum compounds, a dialkylaluminum halide, an alkylaluminum dihalide wherein the alkyl groups contain from 1 to 12 carbon atoms, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum chloride n-propoxide, a mixture of tri-n-octylaluminum:dioctylaluminum iodide:diglyme, tributyltin hydride, tetrabutyl tin, and t-butyl chloride.