POLYMERIZATION PROCESS AND PRODUCTS

Abstract: A tough polymer of relatively high glass transition temperature and low crosslink density comprises the product of a ring-opening polymerization of 5-(3-cyclohexen-1-yl)-2-norbornene in the presence of a hindered-alkylphenoxy substituted tungsten halide and a cocatalyst and in the optional presence of dicyclopentadiene or norbornene-type crosslinking monomers.

Description: DESCRIPTION POLYMERIZATION PROCESS AND PRODUCTS Technical Field The present invention relates to a process for the production of polymeric product derived from certain adducts of vinylcyclohexene and cyclopentadiene and products thereof. More particularly, the invention relates to the ring-opening polymerization process of 5-(3- cyclohexen-1-yl)-2-norbornene and the polymer produced therefrom. Background Art The production of polymers by the ring-opening or metathesis polymerization of cyclic and polycyclic olefins is well known in the art. Numerous patents and literature references, both U.S. and foreign, relate to the ring- opening polymerization of dicyclopentadiene in the presence of a variety of olefin metathesis catalyst systems. One such catalyst system is disclosed by Sjardijn et al, U.S. 4,810,762, wherein substituted phenolic tungsten halides are employed in conjunction with triorganotin hydrides. Bulk polymerization of dicyclopentadiene in the presence of similar catalyst systems is shown by U.S. 4,729,976. The ring-opening polymerization of dicyclo¬ pentadiene produces a solid, hard, infusible thermoset polymer product of established utility. However, the polymerization and resulting polymer suffer from a number of disadvantages. Unless the polymerization is virtually quantitative, there will be unreacted monomer in the polymer product and a molded article formed therefrom will have a most undesirable dicyclopentadiene odor. This odor greatly limits the applications in which the polymer product can be used. It is also known to polymerize polycyclic polyolefin monomers such as cyclopentadiene trimers, tetra ers and higher oligomers, alone or with other cycloolefins. In European Patent Specification 313,838 there is disclosed a process of producing ring-opening polymerization products by polymerizing cycloolefin monomers such as norbornene or tetracyclododecene in the presence of from about 5% to about 45% of resinous cycloolefin formed from dicyclopentadiene trimers and higher oligomers which also contain common olefins such as styrene, propylene, butadiene, vinylcyclohexene and isopentene. The resinous cycloolefins are produced by heating dicyclopentadiene in the presence of more common olefins. In U.S. 5,095,082 a mixture of adducts of 4- vinylcyclohexene and cyclopentadiene Diels-Alder oligomers, optionally in the presence of dicyclopentadiene, undergoes ring-opening polymerization to produce a hard, polymeric produc . It is characteristic of many if not most ring- opening polymerizations that all carbon-carbon double bonds present in the ring or rings of monomeric reactants are involved in ring-opening polymerization. Thus, when one or more of the monomeric reactants contain multiple carbon- carbon double bonds the resulting polymer product is a highly crosslinked thermoset polymer. The thermoset polymers often exhibit useful properties. It would be of advantage, however, to provide a ring-opening poly¬ merization process for a polycyclic polyolefin wherein the product evidences improved mechanical properties with a varying degree of crosslinking and is useful in applications not available to thermoset polymers. Disclosure of the Invention The invention relates to the ring-opening polymerization of 5-(3-cyclohexen-l-yl)-2-norbornene iso ers in the presence of a hindered alkylphenoxy tungsten halide and a cocatalyst which produces polymeric products with low crosslink densities. Best Mode for Carrying; Out the Invention The process of the invention comprises the ring- opening polymerization of certain Diels-Alder adducts of 4- vinylcyclohexene and cyclopentadiene in the presence of a certain tungsten-based catalyst and a cocatalyst system. A mixture of such adducts is produced by heating 4-vinyl¬ cyclohexene and cyclopentadiene (provided as dicyclo¬ pentadiene) at elevated temperatures and separating from the resulting mixture the isomers of 5-(3-cyclohexen-l-yl)- 2-norbornene. These "separated" or purified 5-(3- cyclohexen-1-yl)-2-norbornene mixed isomers in at least a relatively pure form are then subjected to ring-opening polymerization in the presence of a hindered alkylphenoxy substituted tungsten halide and a cocatalyst, preferably an alkylaluminum or a triorganotin cocatalyst, and optionally with a boron promoter. Cycloolefins such as dicyclopentadiene and/or certain crosslinking agents can optionally be present. The monomers of the present process are certain isomers of 1:1 molar adducts of 4-vinylcyclohexene and cyclopentadiene. When 4-vinylcyclohexene and cyclopenta¬ diene are heated at an elevated temperature, a variety of adducts are produced including the 1:1 adducts, 1:2 molar adducts of 4-vinylcyclohexene and cyclopentadiene, 1:3 molar adducts of 4-vinylcyclohexene and cyclopentadiene and a number of cyclopentadiene Diels-Alder oligomers such as trimers, tetramers, pentamers, and higher adducts. Of the 1:1 molar adducts, two adducts are stereoisomers represented by the following formulas (la) (lb) and a third type of 1:1 molar adduct is represented by the formula The isomers represented by the formulas la and lb are isomers of 5-(3-cyclohexen-l-yl)bicyclo[2.2.l]hept-2-ene or, in more common terms, 5-(3-cyclohexen-l-yl)-2- norbornene. The isomer la is termed an "endo" isomer and the isomer lb is termed an "exo" isomer as reflects the steric relationship of the cyclohexene substituent to the non-planar 6-membered ring of the norbornene moiety. As stated, the process of producing the above la, lb and II adducts also produces other adducts and cyclopentadiene oligomers. The 4-vinylcyclohexene is a well known compound illustratively produced by thermal dimerization of butadiene. The dicyclopentadiene source of cyclopentadiene is also well known and is often obtained as a by-product of olefin crackers. Dicyclopentadiene also exists in an endo form and an exo form. Either stereoisomer, or a mixture of the isomers, is suitably employed to produce the vinyl- cyclohexene/cyclopentadiene adducts employed in the process of the invention. Particularly useful are commercially available technical grade of dicyclopentadiene having a purity of about 83% to 95%. The technical grades are easily processed by virtue of being liquid at ambient temperature whereas the pure endo-cyclopentadiene is normally a solid melting at 32°C. The Diels-Alder formation ■ of vinylcyclo- hexene/cyclopentadiene adducts is conducted at temperatures above about 160°C. At these temperatures, the provided dicyclopentadiene de-dimerizes or cracks to produce cyclopentadiene which reacts in situ with the 4-vinyl- cyclohexene. Because of the reactive nature of the monomeric reactants and/or the adduct products it is desirable that adduct production is conducted in an inert reaction environment and traces of reactive materials such as oxygen should be excluded. The inclusion in the reaction mixture of free radical scavengers is also useful. Although the use of a reaction diluent is not precluded for the adduct formation process, the preferred production of adducts is conducted in the substantial absence of reaction diluent. The reaction of 4-vinylcyclohexene and cyclo¬ pentadiene under the influence of heat produces the above 1:1 adduct isomers la, lb and II as well as adducts containing greater proportions of cyclopentadiene and cyclopentadiene oligomers. To obtain the reactants for the polymerization process of the present invention, the mixture of adducts and cyclopentadiene oligomers is separated to provide a material at least substantially enriched in the 5-(3- cyclohexen-l-yl)-2-norbornene isomers (isomers la and lb) i.e., separated 5-(3-cyclohexen-l-yl)-2-norbornene, preferably having a purity of at least 80% by weight, more preferably at least 90% by weight and even more preferably 95% by weight. The recovery of these isomers is effected by conventional physical methods. In one modification, the separation results from application of chromatographic techniques. In an alternate but generally preferred modification the separation/recovery is effected by fractional distillation, generally at a substantially reduced pressure. An initial preliminary separation is conveniently made with the use of a simple distillation column or a wiped film evaporator. More effective separation results from distillation in a multi-tray distillation column. Careful separation typically results in 1:1 adduct mixtures having as much as 90% by weight and preferably as much as 95% by weight of a mixture of la and lb isomers although adduct mixtures having at least 80% by weight of 5-(3-cyclohexen-l-yl)-2-norbornene isomers are useful in the polymerization process of the invention. The remainder of the adduct mixture is typically the isomer of the formula II with less than about 5% by weight and preferably less than about 1% by weight of unreacted vinylcyclohexene and dicyclopentadiene, higher adducts and possibly cyclopentadiene oligomers, particularly cyclopentadiene trimers, also being present. Themixture of 5-(3-cyclohexen-l-yl)-2-norbornene isomers is then subjected, according to the invention, to ring-opening polymerization in the presence of a hindered alkylphenoxy-substituted tungsten halide olefin metathesis catalyst system. The preferred olefin metathesis catalyst system comprise a hexavalent tungsten halide with from 0 to 1 oxygen substituents and at least one hindered alkylphenoxy substituent having at least one bulky alkyl group attached at the ortho position, employed with an alkylaluminum compound or a triorganotin compound, and optionally, with a boron halide promoter. One class of such tungsten halides is represent (X (III) where R independently is a branched alkyl of up to 10 carbon atoms inclusive, preferably from 3 to 8 carbon atoms inclusive and branched on the alpha carbon atom, R* independently is hydrogen or R and R' ' is hydrogen or alkyl of up to 10 carbon atoms. The X moiety independently is halo, i.e., fluoro, chloro, bromo or iodo, but preferably is middle halo, chloro or bromo, x is a number from 1 to 4, z is a number from 1 to 4, and y is 0 or 1 with the sum of x + 2y + z being 6. In the above formula III R is suitably isopropyl, sec-butyl, t-butyl, t-amyl, neo-pentyl, 2-methyl-2-hexyl or 3-ethyl-3-hexyl, but is preferably isopropyl. R 1 is suitably hydrogen but is preferably R. The R' ' group is suitably alkyl but is preferably hydrogen. Illustrative of the alkylphenoxy groups of the above formula III are 2,6- di-sec-butylphenoxy, 2,6-di-t-butyl-4-methylphenoxy, 2- isopropyl-4-ethylphenoxy and 2-t-butyl-4-hexylphenoxy. The preferred alkylphenoxy substituent of the above formula III is 2,6-diisopropylphenoxy. The tungsten-containing catalyst system component will be a halide or an oxyhalide. Such components are hindered phenoxy-substituted tungsten halides or oxyhalides. Particularly preferred catalyst system components are di(hindered alkyl phenoxy)-substituted tungsten oxydichlorides. The alkylaluminum compounds are usefully employed with the tungsten catalyst are of the formula R' ' ' A1Z wherein R' ' ' is alkyl of from 1 to 20 carbon atoms inclusive, preferably from 2 to 8 carbon atoms inclusive, Z is higher halo, preferably chloro, bromo or iodo, r is at least 1 but not more than 3 and r + s equal 3. Illustrative of such alkylaluminum compounds are ethylaluminu dichloride, diethylaluminum chloride, triethylaluminum, diisobutyl-aluminum chloride, dioctylaluminum chloride, diethyl-aluminum iodide, ethylaluminum dibromide, tripropyl-aluminum, triisobut laluminum and trihexylaluminum, and mixtures thereof. When an alkylaluminum compound is employed in the catalyst system, molar ratios of aluminum compound to the tungsten halide from about 1:1 to about 10:1 are useful and molar ratios from about 2:1 to about 6:1 are preferred. The preferred material for use in the catalyst system with the tungsten halide, however, is a triorganotin compound, particularly a triorganotin hydride such as a trialkyltin hydride or triaryltin hydride wherein each alkyl or aryl (or alkyaryl) independently has up to 10 carbon atoms. Illustrative of such tin hydrides are triethyltin hydride, triisopropyltin hydride, tributyltin hydride, trioctyltin hydride, dimethylhexyltin hydride, ethylpropyloctyltin hydride, triphen ltin hydride and tritolyltin hydride. Trialkyltin hydrides wherein each alkyl is straight-chain lower alkyl of from 3 to 8 carbon atoms inclusive are preferred, and particularly preferred as the trialkyltin hydride is tri-n-butyltin hydride. The hindered alkyl phenoxy-substituted tungsten halide and the trialkyltin hydride are suitably employed in molar ratios from about 1:1 to about 1:15 but molar ratios from about 1:2 to about 1:8 are preferred. The tungsten/tin catalyst system is provided to the polymerization mixture in a catalytic quantity. Quantities of the catalyst system sufficient to provide from about 0.001 mole percent to about 5 mole percent of tungsten based on the adduct mixture are suitable. Quantities of the catalyst system sufficient to provide from about 0.01 mole percent to about 0.1 mole percent of tungsten on the same basis are preferred. It is, on occasion, useful to provide to the catalyst system a boron halide promoter, including boron trihalides, boron trihalide complexes and tetrahaloborates. Suitable boron halides are illustrated by boron tri- fluoride, boron tribromide, boron trifluoride diethyl ether complex, boron trifluoride dibutyl ether complex, tetra- fluoroboric acid, methylboron difluoride, phenylbor.on dichloride, ammonium tetrafluoroborate, boron dichloride di ethylsulfide complex and boron trifluoride alcohol complexes. The use of boron halide promoter is optional and the promoter can be present in amounts up to about 10 moles per mole of tungsten compound. When employed, amounts of boron halide promoter from about 0.01 mole to about 2 moles per mole of tungsten compound are preferred. Particularly useful are boron trifluoride and its diethyl ether and dibutyl ether complexes. The ring-opening polymerization of the invention is conducted by contacting the 5-(3-cyclohexen-l-yl)-2- norbornene isomers and the olefin metathesis catalyst system. It is on some occasions useful to provide an inert reaction diluent in order to solubilize the catalyst system components. In such an embodiment, one catalyst system component would be provided with each of two portions of the reaction diluent. The adduct monomer mixture to be polymerized is suitably provided separately or with either portion. In the preferred modification, however, no added reaction diluent is employed and the monomeric mixture and the catalyst components are mixed directly. To effect polymerization, the 5-(3-cyclohexen-l-yl)-2-norbornene isomers and the catalyst system are contacted under polymerization conditions. Typical polymerization conditions include a polymerization temperature from about 25°C to about 200°C with polymerization temperatures from about 75°C to about 140°C being preferred. The polymerization pressure is that pressure required to maintain the polymerization mixture in a non-gaseous state. Such pressures will vary with the reaction temperature but pressures up to 5 atmospheres are typical and frequently ambient pressure is suitable and is preferred. The polymerization is preferably conducted in an inert environment with reactive materials such as water or oxygen being excluded. However, the catalyst system employed in this invention is relatively insensitive to oxygen- containing organic impurities which can be present in the mixture of 5-(3-cyclohexen-l-yl)-2-norbornene isomers. The polymeric products obtained from the process of this invention have a very low crosslink density, which can be measured by toluene swell of greater than 200%, preferably greater than 300%. For example, swell is measured by placing approximately .7-1 g of a sample optionally divided in up to three pieces in 20 ml of toluene at room temperature for 24 hours. Percent swell is calculated as W— Wo X 100 where W is the final weight of the Wo sample and Wo is initial weight of the sample before immersion in toluene. If the polymer samples swell extensively to a point where they have become gel-like and are no longer removable from the toluene solution, the swell is then estimated to be greater than 1000% The polymer products also have a relatively high glass transition temperature. In Japanese patent specification 63-92640, a polymeric product obtained by polymerizing 2-(cyclohexene- 3-yl)-bicyclo[2.2.1]heptene-5 ("CHB") with a catalyst prepared from tungsten hexachloride and nonylphenol is disclosed. However, the polymeric product obtained from such process has a relatively high crosslink density with a correspondingly low toluene swell of 181% (calculated from the reported toluene swell ratio of 2.81). Themixture of 5-(3-cyclohexen-l-yl)-2-norbornene isomers is polymerized in the optional presence of other cyclic polyolefins. In one embodiment, dicyclopentadiene is provided to modify the properties of the resulting polymeric product. The amount of dicyclopentadiene to be employed, when dicyclopentadiene is to be provided, is relatively small and dicyclopentadiene should not constitute more than about 20% by weight- of the mixture to be polymerized. For most purposes, however, added dicyclopentadiene is not provided. In a second embodiment, the mixture to be polymerized contains added crosslinking agent in order to produce a more extensively crosslinked polymer product. Suitable crosslinking agents are polycyclic olefin monomers characterized by strained unsaturated ring systems such as are found in norbornene- type compounds. To be an effective crosslinking agent for the polymers of the present invention, a compound must contain at least two of the strained unsaturated ring systems of the norbornene type, i.e. having the norbornene structure. Illustrative of suitable crosslinking agents are reactive monomers such as norbornadiene, which is considered a superimposition of two norbornene structures, a number of isomeric norbornadiene dimers illustrated by dimers of the formula and certain cyclopentadiene trimers, tetramers, and pentamers. Such monomers are well known compounds. The presence of crosslinking agent in the polymerization mixture of the invention is optional and no crosslinking agent is required. Quantities of crosslinking agent up to about 10% by weight of the total polymerization mixture are suitable and when present, quantities of crosslinking agent from about 0.1% by weight to about 8% by weight of the total polymerization mixture are preferred. In an illustrative polymerization, the monomeric adducts, the catalyst system and any added dicyclo¬ pentadiene or crosslinking agent are mixed at a relatively low temperature at which polymerization at a rapid rate does not occur. This relatively slow initial reaction rate permits efficient mixing or other processing of the polymerization mixture as well as the incorporation of fillers, reinforcements, antioxidants, stabilizers, pigments, elastomers, or other materials in order to influence the properties of the polymerization product. The polymerization mixture is then raised to polymerization temperature and the polymerization is rapidly complete. A particularly contemplated embodiment of the polymerization process is in a reaction injection molding (RIM) process. Because of the initial relatively low viscosity of the polymerization mixture and the low reaction rate of ambient conditions, the monomers and catalyst system are mixed and transferred to a suitable mold including those molds for large castings of complex shapes. In a typical RIM-type process of the invention, the mixing/transfer time is no more than about 2 minutes and frequently is considerably less and the time for polymerization when in a mold is from about 10 seconds to about 1 minute, depending in part upon the polymerization temperature and catalyst system employed. The polymer product is of variable character depending in part upon the purity of the 5-(3-cyclohexen-l- yl)-2-norbornene isomers used in the polymerization, the presence or absence of boron halide catalyst system promoter and the presence or absence of added crosslinking agent. When crosslinking agent is provided to the polymerization mixture, the product will be at least partly thermoset in character and will demonstrate properties characteristic of thermoset polymers, e.g., hardness and insolubility. The use of a boron promoter, while enabling reaction under milder polymerization conditions, also promotes a somewhat greater degree of crosslinking and more thermoset polymer properties in the polymer product. The degree of crosslinking is also enhanced by a relatively impure 5-(3-cyclohexen-l-yl)-2-norbornene isomer mixture, particularly if that mixture contains amounts of 1:2 and higher molar adducts of 4-vinylcyclohexene and cyclo¬ pentadiene or cyclopentadiene oligomers, particularly the cyclopentadiene trimer. The thermoset-like polymer products have properties typical of conventional thermoset polymers but exhibit elasticity which most thermoset polymers do not have. They are processed by methods conventional for thermoset polymers and find utility in applications such as circuit boards for electrical and electronic applications and as encapsulating material where properties of toughness and strength are important. Conversely, in the absence of crosslinking agent and when relatively pure 5-(3-cyclohexen-1-yl)-2-norbornene isomer mixtures are employed in the polymerization, the polymer product is more thermoplastic in character. Such polymers have toughness and strength as well as elasticity and are processed by methods typical for conventional thermoplastics, e.g. , extrusion or injection molding. The thermoplastic products are at least partially soluble in conventional solvents such as xylene and flexible films can be cast from the resulting solutions. Among other applications for the thermoplastic polymer products are the production of parts and housings for automotive applications. The process of the invention provides polymer products of wider application than when dicyclopentadiene is polymerized because of improved physical properties such as better toughness as determined by elongation to break, better heat welding and post-polymerization forming, but also because of the lower exotherm which results when the reactants and catalyst system are mixed. In bulk or adiabatic polymerization, dicyclopentadiene exotherms to about 180°C to 210°C whereas in the present process the monomer mixture exhibits a reaction exotherm of from about 140°C to 160°C. In the case of dicyclopentadiene polymerization, the heat transfer from relatively thick portions of an article being molded is often inadequate during the exotherm and often the process causes the monomer to "boil" and form bubbles which weaken the part. If a lower polymerization temperature is used, the thin portions of the article are under-polymerized. The present process with a lower exotherm allows thicker articles to be molded as well as articles having greater variation in cross-section. Also, the product has no detectable characteristic dicyclopentadiene odor. The invention is further illustrated by the following Illustrative Embodiments which should not be regarded as limitations. Illustrative Embodiment I Dicyclopentadiene and 4-vinylcyclohexene in equimolar mixture were heated in an autoclave at 240°C for 4-4.5 hours. The reaction product was diluted with cyclohexane and passed through a packed bed of alumina in order to remove the t-butylcatechol inhibitor introduced with the reactants. The resulting product mixture as distilled in a wiped film evaporator at 3 mm Hg pressure at 90°C to afford a light fraction containing unreacted vinylcyclohexene and dicyclopentadiene and the mono-adducts of 4-vinylcyclohexene and cyclopentadiene. A 150 g sample of this distillate was vacuum distilled using a 10-tray Oldershaw column to give four fractions. The fourth fraction, 65 g, was shown by gas chromatographic analysis to consist of 0.15% dicyclopentadiene, 88.3% endo-5-(3- cyclohexen-1-yl)-2-norbornene, 6.1% exo-5-(3-cyclohexen-l- yl)-2-norbornene and two additional components present in an amount of 1.9% and 2.4% which are believed to be iso eric adduct of the formula several additional components totalling about 0.4%, 0.4% tricyclopentadiene and about 0.4% unidentified components. Analysis of the fraction by nuclear magnetic resonance indicated about 87 mole percent of the above endo adduct, about 9 mole percent of the above exo adduct and about 5% of the isomeric adducts of the above formula. Illustrative Embodiment II In a glove box under a nitrogen atmosphere, a 1.5 g portion of the fourth fraction of Illustrative Embodiment I, dried by molecular sieves, was mixed with 0.0035 g (0.0056 mmol) of bis(2,6-diisopropylphenoxy)tungsten oxydichloride and to the resulting mixture was added 0.0065 g (0.0223 mmol) of tributyltin hydride. The mixture was transferred to an aluminum mold which was then quickly heated to 100°C, held at that temperature for about 15 minutes and then cooled to ambient temperature. The polymeric product contained in the mold was a hard polymeric product having a glass transition temperature of 120°C (as determined by dynamic mechanical thermal analysis) . The structure of the polymer is difficult to determine precisely but is believed to have at least 80% of the repeating units of the structure An attempt to determine the swel όl of the polymer in toluene gave a viscous, jelly-like mass which was further diluted with toluene to afford a clear solution with little or no obvious gel present. This solution was used to cast transparent, flexible films of the polymer. Illustrative Embodiment III Samples of mono-adduct (MA) mixture similar to that produced in Illustrative Embodiment I were polymerized with a norbornadiene (NB) or norbornadiene dimer (NBD) crosslinking agent present in order to produce a more extensively crosslinked polymer. In each case the catalyst system comprised 0.023 g of bis(2,6-diisopropylphenoxy) tungsten oxydichloride and 0.093 g of tributyltin hydride and 0.0017 g of boron trifluoride dibutyl ether complex was also present. For each polymer product, the glass transition temperature was determined (by dynamic mechanical thermal analysis) as was the swell in toluene and the weight percent extracted by toluene. The results are shown in Table I. TABLE I Swell Extractables MA, g Crosslinker, g Tg, °C % % 15.92 NBD, 0.08 15.82 NBD, 0.16 15.68 NBD, 0.32 15.92 NB, 0.08 15.84 NB, 0.16 15.68 NB, 0.32 15.2 NB, 0.8 Illustrative Embodiment IV A 50 g quantity of a mono-adduct mixture similar to that produced in Illustrative Embodiment I was polymerized in a RIM-type polymerization using a catalyst system which comprised 0.116 g of bis(2,6-diisopropyl- phenoxy)tungsten oxydichloride and 0.215 g of tributyltin hydride. The polymerization took place in a mold heated to 120°C and the reaction exotherm was 4°C. The resulting polymeric product has a glass transition temperature (as determined by dynamic mechanical thermal analysis) of 126°C, a flexural modulus of 250,000 psi, a flexural strength of 9500 psi and an Izod impact of 0.52 ft-lb/in. Illustrative Embodiment V Samples of the polymer product of the invention were produced and the properties of these samples were compared to a sample of polydicyclopentadiene aged in air for a period of days. In each case, the monomer mixture was mixed with the catalyst system and placed in a mold approximately 1/32-inch thick heated to 120°C. Comparative sample A was produced by polymerizing 50 g of dicyclopentadiene in the presence of 0.079 g of bis(2,6- diisopropylphenoxy)tungsten oxydichloride, 0.15 g of tributyltin hydride and 0.0062 g of boron trifluoride dibutyl ether complex. Sample B was produced by polymerizing 70 g of a mono-adduct mixture similar to that of Illustrative Embodiment I in the presence of 0.165 g of bis(2,6-diisopropylphenoxy)tungsten oxydichloride and 0.308 g of tributyltin hydride. Sample C was prepared in a similar manner except that 0.35 g of a norbornadiene di er replaced an equivalent weight of the mono-adduct mixture. The results of the property comparison are shown in Table II. The elongation to break data demonstrate that the toughness of Samples B and C is comparable to other tough thermoplastic polymers and is observed over longer aging times than are observed with polydicyclopentadiene. Swell in toluene (room temperature, 24 hours) showed 1130% swell for Sample B when measured 1-2 days after molding. The polymer product of the invention has a very low crosslink density as seen from the very high swell value. In a dry nitrogen glove box, a 30 ml dried, silanized serum bottle with a magnetic stirrer was charged with 0.527 g of a 7% solution of the bis(2,6-diisopropyl- phenoxy)tungsten oxydichloride catalyst (0.059 mmol) in dry mono-adduct monomer and 15.51 g dry, degassed mono-adduct mixture similar to that of Illustrative Embodiment I, and the bottle was sealed and removed from the nitrogen box. In the hood, the bottle was placed under an argon purge via syringe needles, a 1/16" x 3" thermocouple protection tube was positioned near the center of solution, and 0.197 ml of a 1.8M solution of ethylaluminum dichloride (0.355 mmol) in toluene was added via syringe, whereupon the reaction mixture gelled. The mixture was then placed in a 90°C oil bath, a K thermocouple was insert into the protection tube, and the mixture's temperature was monitored. Within approximately 0.1 minute after beginning monitoring, the polymerization mixture had reached a maximum exotherm temperature of 151°C and the internal temperature slowly declined over the next 10 minutes. The product was a hard polymer. Swell and extraction in toluene (room temperature, 24 hours) showed 929% swell and 0.6% extractable monomer by gas chromatography (nonane internal standard) . Illustrative Embodiment VII The procedure of Illustrative Embodiment VI was followed using 0.205 g of the tungsten catalyst solution (0.020 mmol), 35 μl of a 1% solution of boron trifluoride dibutyl ether complex (0.0017 mmol) in mono-adduct, 15.78 g of dry, degassed mono-adduct mixture similar to that of Illustrative Embodiment I, and tributytin hydride (0.027 g, 0.093 mmol) cocatalyst in place of ethylaluminum chloride. Within about 2.2 minutes after beginning monitoring of the reaction temperature, the polymerization mixture had reached a maximum exotherm temperature of 167°C. The product was a hard polymer. In attempting to measure the swell, the resulting polymer product was placed in toluene, but the product formed a gel-like material which was unremovable for swell measurements and the swell was estimated to be greater than 1000%. The glass transition temperature ("Tg") , sometimes referred to in the art as the "softening point" (when measured by TMA) of the polymer product sample was measured by thermal mechanical analysis ("TMA") by heating the sample from room temperature at 10°C/min in a stream of nitrogen to a final temperature of about 280°C. The heating cycle was repeated two additional times. The glass transition temperatures were 120°C, 131°C, and 131°C for the first, second and third cycles, respectively. To summarize, the polymer products obtained without any added crosslinking agents according to the invention have a swell value greater than about 500%. Even with added crosslinking agent, the crosslink densities of the products are low as can be seen from the relatively high percent toluene swell values of between 230% and 605% (Table I) .

Claims: CLAIMS 1. A process for the production of tough polymer product by contacting separated 5-(3-cyclohexen-l- yl)-2-norbornene, in the optional presence of up to 10% by weight based on total polymerization mixture of dicyclopentadiene or a crosslinking monomer containing at least two strained unsaturated ring systems of norbornene under polymerization conditions with a catalytic quantity of an olefin metathesis catalyst system comprising a hexavalent tungsten halide having from 0 to 1 oxygen substituent and at least one hindered alkylphenoxy substituent and an alkylaluminum compound or a triorganotin compound, in the optional presence of a boron halide. 2. The process of claim 1 wherein the material contacted is a mixture of 5-(3-cyclohexen-l-yl)-2- norbornene isomers provided as a mixture of Diels-Alder adducts of 4-vinylcyclohexene and cyclopentadiene containing at least 80% by weight of isomers of 5-(3- cyclohexen-1-yl)-2-norbornene. 3. The process of claim 3 wherein the catalyst system is provided in an amount from about 0.001 mole percent to about 5 mole percent based on total Diels-Alder adducts. 4. The process of claim 3 wherein the hindered alkylphenoxy substituent is an alkylphenoxy having at least one bulky alkyl group attached at the ortho position. 5. The process of claim 4 wherein the tungsten halide is represented by the formula * where R independently is alkyl of up to 10 carbon atoms inclusive, R 1 independently is hydrogen or R, R' ' independently is hydrogen or alkyl of up to 10 carbon atoms, X is a halo, x is a number from 1 to 4, z is a number from 1 to 4, and y is 0 or 1 with the sum of x + 2y + z being 6. 6. The process of claim 5 wherein the catalyst system is the tungsten halide and an alkylaluminum compound of the formula R 1 ' 'rA1Zs wherein R' * ' is alkyl of up to 20 carbon atoms inclusive, Z is higher halogen, r is at least 1 and r + s equals 3. 7. The process of claim 5 wherein the catalyst system is tungsten halide and a triorganotin compound wherein the triorganotin compound is a trialkyltin hydride or a triaryltin hydride wherein each alkyl or aryl independently has up to 10 carbon atoms inclusive. 8. The process of claim 7 wherein the triorganotin hydride is a trialkyltin hydride. 9. The process of claim 8 wherein X is chloro. 10. The process of claim 9 wherein each alkyl of the trialkyltin hydride is straight-chain alkyl of from 3 to 8 carbon atoms inclusive. 11. The process of claim 5 wherein R is alkyl from 3 to 8 carbon atoms branched on the alpha carbon atom. 12. The process of claim 11 wherein X is chloro. 13. The process of claim 11 wherein the catalyst system is the tungsten halide and a triorganotin compound. 14. The process of claim 13 wherein the tungsten halide is bis (2 , 6-diisopropylphenoxy) tungsten oxydichloride. 15. The process of claim 5 wherein the reaction mixture contains from about 0.1% by weight to about 8% by weight, based on total reaction mixture, of a polycyclic olefin containing at least two strained ring systems of norbornene. 16. The process of claim 15 wherein the polycyclic olefin is norbornadiene, norbornene dimer, cyclopentadiene tri er, cyclopentadiene tetramer or cyclopentadiene pentamer. 17. The process of claim 1 wherein the boron halide is boron trifluoride or diethyl ether complexes of boron trifluoride or dibutyl ether complexes of boron trifluoride. 18. The process of claim 17 wherein the mole ratio of boron halide to tungsten halide ranges from 0.01 to 2. 19. The polymer product produced by the process of claim 1. 20. The polymer product having a toluene swell greater than 200% produced by the process of claim 5. 21. The polymer product having a toluene swell greater than 200% produced by the process of claim 15. 22. The product of claim 20 having a toluene swell greater than 300%. 23. The product of claim 21 having a toluene swell greater than 300%. 24. The polymer product produced by the process of claim 15. 25. A ring-opened polymer having a toluene swell greater than 300% produced by metathesis polymerization of 5-(3-cyclohexen-l-yl)-2-norbornene having at least about 80% of the repeating units of the structure

Inventors: ELLISON ROBERT HARDY, HANDLIN DALE LEE JR, KELSEY DONALD ROSS, ELLISON, ROBERT, HARDY, HANDLIN, DALE, LEE, JR., KELSEY, DONALD, ROSS
Applicants: SHELL OIL CO, SHELL OIL COMPANY
Application year: 1992
Main classification: C08G61
IPC codes: C08G61