MXPA00008557A - Method for making polymer blends by using series reactors - Google Patents

Abstract

This invention relates to a method of making polymer blends using series reactors and a metallocene catalyst. Monomers used by the invention are ethylene, a higher alpha-olefin (propylene most preferred), and optionally, a non-conjugated diene (ethylidene norbornene, i.e., ENB, most preferred). More specifically, this invention relates to making blends of EP (ethylene-propylene) copolymers in which the blend components differ in any of the following characteristics:1) composition, 2) molecular weight, and 3) crystallinity. We use the terminology EP copolymer to also include terpolymers that contain varying amounts of non-conjugated diene. Such terpolymers are commonly known as EPDM.

Description

METHOD FOR MAKING POLYMERIC PHYSICAL MIXTURES USING SERIAL REACTORS BACKGROUND OF THE INVENTION This invention relates to a method of making polymeric physical blends using series reactors and a metallocene catalyst. The monomers used by the invention are ethylene, a higher alpha-olefin (propylene being the most preferred) and, optionally, a non-conjugated diene, being ethylidene norbornene, ie ENB, most preferred). More specifically, this invention relates to preparing physical blends of EP (ethylene-propylene) copolymers in which the physical blend components differ in any of the following characteristics: 1) composition; 2) molecular weight, and 3) crystallinity. The term "EP copolymer" is used to also include terpolymers containing varying amounts of unconjugated diene. Such terpolymers are commonly known as EPDM. There are several advantages of making the physical mixtures mentioned above. For example, polymers of EP (ethylene propylene copolymer) and EPDM (ethylene propylene diene terpolymer) are often used as physical mixtures of two or more polymers to obtain optimum polymeric properties for a given application. The high molecular weight and low molecular weight polymers are physically mixed, giving an extended molecular weight distribution (MWD) and therefore better processing capacity than a polymer with narrow MWD with the same average molecular weight. A semi-crystalline polymer can be physically mixed with an amorphous polymer to improve the tenacity (green strength) of the amorphous component at temperatures below the melting point of the semi-crystalline polymer. Polymers with superior green strength are less likely to flow cold and give improved handling characteristics in processing operations, such as calendering and extrusion. One method of making the physical mixtures mentioned above is by mixing two different polymers after they have been polymerized to achieve an objective set of properties. Such a method is expensive, which makes it much more desirable to prepare the physical mixtures by means of direct polymerization. Physical mixtures by direct polymerization are well known in the state of the art, such as manufacture of EPDM with vanadium-based Ziegler-Natta catalysts, soluble, using reactors in series and making a polymer with different properties in each reactor. Patents showing operation of series reactors with vanadium are US Pat. Nos. 3,629,212; 4,016,342; and 5,306,041, all of which are incorporated by reference herein for purposes of United States patent practice. Although the polymeric physical blends can be carried out by vanadium-based Ziegler-Natta catalysts in series reactors, there are several limitations on the amount and characteristics of the polymers that can be made in each reactor, especially in the second reactor. Due to economic considerations, the most preferred method of reactor operation is to add catalyst only to the first reactor, to minimize the use of costly catalyst components. Due to the rapid inactivation rate of the vanadium active species, the catalyst concentration is extremely low in the second reactor in the series and would be even lower in successive reactors. As a result, it is extremely difficult to make more than about 35% by weight of total polymer in the second reactor. Also, the low catalyst concentration may impose limits on the composition or molecular weight of the polymer. To cure this problem, catalyst activators or additional catalyst can be added to the second and subsequent reactors; however, this raises manufacturing costs. Furthermore, the vanadium catalysts are limited in their ability to produce polymers containing less than about 35% by weight of ethylene, because they polymerize ethylene much more easily than propylene or higher alpha-olefins. In addition, soluble vanadium catalysts are unable to produce copolymers and terpolymers that contain crystallinity due to the presence of long sequences of isotactic polypropylene. SUMMARY OF THE INVENTION This invention departs from the state of the art by providing a process for producing polymeric physical mixtures in series reactors that solves the problems of the processes of the state of the art associated with the limits of the properties. Note that the terms "multi-stage reactor" and "series reactors" are used interchangeably herein. By using metallocene catalysts, which enjoy a long life as catalysts, polymeric physical mixtures can be made that vary in the amount of the components, the composition of the components, and the molecular weight of the components, in much wider ranges than those susceptible to obtained with vanadium catalysts of the state of the art. In particular, it is the object of this invention to use a series reactor process and produce the following types of physical mixtures: a) physical mixtures in which the ethylene content of the polymer made in the first and second reactors differs in 3 -75% by weight of ethylene, and b) physical mixtures in which the MWD of the physical mixture is characterized by Mw / Mn = 2.5-20 and Mw / Mn for the individual components of the physical mixture is 1.7-2.5, and c) physical mixtures in which both the polymeric composition and the MWD satisfy the criteria of a) and b) above, and d) physical mixtures in which a component contains 0 to 20% by weight of ethylene, is semi-crystalline due to the presence of isotactic propylene sequences in the chain, and has a melting point of 40-160 ° C, and the other component is amorphous, and e) physical mixtures in which a component contains 60-85% by weight of ethylene, is semi-crystalline due to the presence of sec It has long ethylene in the chain, and has a melting point of 40-120 'C, and the other component is amorphous. This polymeric physical mixture of reactors in series is used in the dynamic vulcanization process to provide thermoplastic elastomer products. The polymerization is preferably polymerization in homogeneous solution. The catalyst is a cyclopenta-dienyl metallocene complex having two Cp ring systems for ligands, or monocyclopentadienyl metallocene catalyst. The metallocene complexes are activated with an alumoxane, for example methylalumoxane (MAO) or a non-coordinating anion (NCA), described below further. Optionally, a trialkyl aluminum stripping agent can be added to the reactor feed or feeds to prevent deactivation of the catalyst by poisons. The reactors are preferably liquid filled reactors, continuous flow, stirred tank. The method employs two or more continuous flow, stirred tank reactors, in series with two reactors, as a preferred embodiment. Solvent and monomers are fed to each reactor, and preferably catalyst is fed only to the first reactor. The reactors are cooled by reactor liners or cooling coils, self-cooling, pre-cooled feed or combinations of the above.Cooling of the self-cooled reactor requires the presence of a vapor phase in the reactor. Adiabatic reactors with precooled feeds This results in a temperature difference between the reactors, which is useful for controlling polymer molecular weight.The monomers used in the process are ethylene and an upper alpha-olefin C3-C8. It is most preferred as the higher alpha-olefin.The monomers may also optionally include a non-conjugated diene, in which case ENB (5-ethylidene-2-norbornene) is the most preferred diene.The temperature of the reactor depends on the effect of temperature on the catalyst deactivation rate and the polymer properties, for economic reasons, it is desirable to operate at a temperature as high as possible; however, the temperatures should not exceed the point at which the catalyst concentration in the second reactor is insufficient to make the desired polymer component in the desired amount. Therefore, the temperature will be determined by the details of the catalyst system. In general, the temperature of the first reactor can vary between 0 and 110 ° C, with 10 to 90 ° C being preferred, and most preferred 20 to 70 ° C. The temperature of the second reactor will vary from 40 to 160 ° C, preferably 50 to 140 ° C, and most preferably 60 to 120 ° C. When two reactors are used in series, the composition of the polymer made in the first reactor is 0-85% by weight of ethylene, while the The composition of the polymer made in the second reactor is 0-85% by weight of ethylene The average composition of the polymeric physical mixture is from 6 to 85% by weight of ethylene If the ratio Mw / Mn for the physical mixture is lower of 2.5, then the difference in composition between the polymer produced in the first and second reactors is 3 to 75% ethylene, preferably 5 to 60% ethylene, and most preferably 7 to 50% ethylene. the ratio Mw / Mn for the physical mixture is equal to or greater than 2.5, then the composition of the components of the mixture Physical can be the same or different. In another embodiment, the difference in ethylene content between the two components is such that one is semi-crystalline and the other is amorphous. Semi-crystalline is defined as having a melting point, as measured by DSC, and a heat of fusion of at least 10 J / g, while amorphous is defined as the absence of a melting point by DSC or a heat of fusion of less than 10 J / g. The semi-crystalline polymers of this invention generally have melting points of about 40-160 * C, depending on the composition of the polymer. The DSC measurements are made by the procedure described in the examples section. The ethylene and propylene copolymers are generally amorphous at ethylene contents between 20 and 60% by weight with the catalysts of this invention. If a polymeric component with ethylene crystallinity is desired in the physical mixture, it must have more than 60% by weight of ethylene. On the other hand, if a component with propylene crystallinity is desired, it must have less than about 20% by weight of ethylene. Furthermore, in this case, it is necessary to use a catalyst system that is capable of polymerising propylene in a stereo-specific manner. Catalyst systems that produce isotactic propylene sequences are most preferred. Depending on the level of crystallinity of the semi-crystalline component and the difference in composition between the two components, the two components can be immiscible and form a separate mixture in phases following the recovery of the reactor product. The presence of multiple phases can easily be measured by standard techniques of polymer characterization, such as optical microscopy, electron microscopy, or atomic force microscopy (AFM). Two-phase polymeric physical blends often have advantageous properties, and it is a particular object of this invention to produce such physical blends in two phases by direct polymerization. When using two reactors in series, the amount of polymer made in the second reactor is 15-85% by weight of the total polymer made in both reactors, preferably 30-70% by weight of the total polymer made in both reactors. The MWD of polymers made with metallocene catalysts tends to be narrow (Mw / Mn less than 2.5) and, as a result, polymers generally do not have good processing characteristics. It is a particular object of this invention that the polymers made in the first and second reactors are of sufficiently different molecular weight such that the MWD is amplified. The Mw / Mn ratio of the final product is preferably from 2.5 to 20.0, and with the greater preference of 3.0 to 10.0. The diene content in the polymer can vary from 0 to 15% by weight, preferably from 2 to 12% by weight, and most preferably from 3 to 10% by weight. The diene levels in the polymer "made in each reactor can be the same or different." The physical copolymer / terpolymer mixtures can be made by the process of the invention For example, if diene is added only to the second reactor, a copolymer can be made of ethylene and propylene in the first reactor while in the second reactor a terpolymer of ethylene, propylene and diene can be made.A preferred embodiment of the invention is to operate reactors in series to produce physical mixtures in which the composition of the components of physical mixture differs by at least 3% by weight of ethylene, the ratio Mw / Mn for the physical mixture is equal to or greater than 2.5, and one of the components of the physical mixture is semi-crystalline. Semi-crystalline polymer contains isotactic polypropylene crystallinity.

For a physical mixture that combines all aspects of the invention described above, at a given average ethylene content and a given molecular weight for the final product, the polymeric properties will vary depending on the composition and molecular weight of each component. The process of the invention is capable of making physical blends in which either: a) polymer 1 has a higher content of ethylene and a higher molecular weight than polymer 2, or b) polymer 1 has a higher ethylene content and a lower molecular weight than polymer 2. Polymer 1 and polymer 2 can be made in either the first or the second reactor. For terpolymerization, the physical mixtures can be further distinguished by the level of diene in each component. Typically, it is preferred to have a higher diene content in the lower molecular weight component to give optimum properties of the product in vulcanized thermoset compounds. The present invention can be summarized as a method of making a polymeric physical mixture by solution polymerization, comprising: a) feeding a first set of monomers and a solvent in predetermined proportions to a first reactor, b) adding a metallocene catalyst to the first reactor, c) operating the first reactor to polymerize the first set of monomers to produce an effluent containing a first polymer, d) feed the effluent of c) to a second reactor, e) feed a second set of monomers in proportions predetermined to the second reactor with optional additional solvent, f) operating the second reactor to polymerize the second set of monomers to produce a second polymer without introduction of any substantial amount of catalyst. In this way, preferably more than 50% by weight of the total amount of catalyst added to all the reactors is added to the first reactor, more preferably more than 75% by weight, and most preferably 100% by weight of the Total amount of catalyst added to all the reactors is added to the first reactor. The first and second sets of monomers are selected from a group consisting of ethylene, higher alpha-olefin and non-conjugated diene. The preferred higher alpha-olefin is polypropylene and the preferred non-conjugated diene is selected from the group consisting of 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl- 2 -norbornene (VNB), with ENB being the most preferred. A non-conjugated diene can be added to the first set of monomers and / or to the second set of monomers in an amount such that the diene content in the polymeric physical mixture is preferably from 0 to 15% by weight, more preferably 2 to 12% by weight, and most preferably 3 to 10% by weight. Control of Ethylene Content The monomeric proportions can be controlled to yield various polymeric physical mixtures with the physical mixture components having different ethylene content. For example, the proportions of monomers in the first reactor and the second reactor can be controlled so that the ethylene content of the first and second polymers differs by 3 to 75% by weight. Additionally, the monomer proportions in the first reactor and the second reactor can be controlled so that the first polymer has 0 to 85% by weight of ethylene, the second polymer has 0 to 85% by weight of ethylene, and the polymeric physical mixture have 6 to 85% by weight of ethylene. Preferably, a physical mixture of semi-crystalline and amorphous polymer is achieved by controlling the monomer proportions in the first reactor and the second reactor so that the ethylene content of the first and second polymers differs so that either: a) the first polymer is semi-crystalline and the second polymer is amorphous, or b) the first polymer is amorphous and the second polymer is semi-crystalline. Control of the Distribution of Molecular Weights (MWD) Preferably, the molecular weight of the physical mixture components is controlled to produce a polymeric product with a larger MWD than that of the individual components. Specifically, the molecular weight of the first or second polymers or both polymers can be controlled by at least one of: a) adding a chain transfer agent to the first or second reactors or both reactors, b) operating the first and second reactors Adiabatically, with a temperature difference between the reactors. When a larger MWD is desired, preferably the molecular weight of the first or second polymer or both polymers is controlled so that the first and second polymers have an Mw / Mn ratio of 1.7 to 2.5, while the polymeric physical mixture has an Mw / Mn ratio of 2.5 to 20. Most preferably, the molecular weight of the first or second polymer or both polymers is controlled so that the first and second polymers have an Mw / Mn ratio of 1.7 to 2.5, while the Polymeric physical mixture has a Mw / Mn ratio of 3.0 to 10.0. When a product with narrow MWD is desired for a particular application, the molecular weight of the first or second polymer or both polymers is controlled so that the polymeric physical mixture has an Mw / Mn ratio of less than 2.5. When the molecular weight distribution is extended, it is necessary that one component of the physical mixture be of a higher molecular weight than another component of the physical mixture. In this way, the molecular weight of the first or second polymers or both polymers is controlled so that either: a) the first polymer has a higher molecular weight than the second polymer or b) the first polymer has a lower molecular weight than the first polymer. second polymer. The Mw of each component can be in the range of 10,000 to 2,000,000, preferably in the range of 25,000 to 1,000,000, and most preferably in the range of 50,000 to 500,000. These physical mix polymers of series reactors can be dynamically vulcanized additionally to provide thermoplastic vulcanization. Control of both Ethylene Content and MWD It is also possible to jointly control both the ethylene content and the molecular weight. When the molecular weight is controlled to yield a physical mixture where one component is of higher molecular weight than another, it is preferable to control the ethylene content of each component. In this way, the monomer proportions in the first and second reactors can be controlled so that: a) if the first polymer has a higher molecular weight, then the first polymer has a higher ethylene content as compared to the second polymer, or b) if the first polymer has a lower molecular weight, then the first polymer has a lower ethylene content compared to the second polymer. Further, the monomer proportions in the first and second reactors can be controlled so that: a) if the first polymer has a higher molecular weight, then the first polymer has a lower ethylene content as compared to the second polymer, ) if the first polymer has a lower molecular weight, then the first polymer has a higher ethylene content as compared to the second polymer.

As shown by the foregoing disclosure, by practicing the process of this invention, polymeric physical mixtures can be obtained with various combinations of compositional distribution amplitude, molecular weight distribution amplitude, or both together. If the molecular weight of the component of the polymer mixture is controlled to maintain the Mw / Mn ratio for the final product at 2.5 or less, it is preferred that the monomer proportions in the first reactor and the second reactor be controlled so that the content of The ethylene of the first and second polymers differs by 3 to 75% by weight, more preferably 5 to 60% by weight, most preferably 7 to 50% by weight. Making a Semi-Crystalline / Amorphous Physical Mixture Monomeric proportions can also be controlled to yield a physical mixture where one component is semi-crystalline while the other is amorphous. In this way, the monomer proportions in the first reactor and the second reactor can be controlled so that one of the polymers chosen from the first or second polymers contains 0 to 20% by weight of ethylene, be semi-crystalline due to the presence of sequences of isotactic propylene, and tanga a melting point of 40 to 160 ° C, while the other polymer is amorphous.Further, the monomer proportions in the first reactor and the second reactor can be controlled so that one of the selected polymers of the first or second polymers contain 60 to 85% by weight of ethylene, be semi-crystalline due to the presence of long ethylene sequences, and have a melting point of 40 to 120 * C, while the other polymer is amorphous Physical mixtures of two semi-crystalline polymers, one with 0 to 20% ethylene and the other with 60 to 85% ethylene, are also within the scope of this invention. The composition of the components can also be selected so that the physical mixture components are immiscible and the final product consists of a mixture of two phases. It is particularly desirable that one of the components of the two phase mixture contains crystallinity due to the presence of isotactic propylene sequences. Such physical mixtures of two phases can not be produced by the vanadium catalyst systems of the state of the art. lafcalizadar v Reactor Operation Preferably, the catalyst is chiral and stereo-rigid. Preferably, the catalyst is capable of producing stereo-regular polypropylene. As regards reactor temperatures, it is preferred that the first reactor operates at temperatures between about 0 and 110 ° C, and the second reactor operates between about 40 and 160 ° C. Preferably, the first reactor operates at temperatures between about 10 and 90 ° C, and the second reactor operates between about 50 and 140 * C. Most preferably, the first reactor operates at temperatures between about 20 and 70 * C, and the second reactor operates between about 60 and 120 ° C. Preferably, the reactors are cooled at least in part by pre-cooling the feed and there is a temperature difference between the reactors. To protect against deactivation of the catalyst, a stripping agent can be added to at least one of the sets of reactor feeds before their respective polymerizations. Preferably, the stripping agent is trialkyl aluminum. As far as the reactors are concerned, it is preferred that the first and second reactors are series reactors, stirred tank, continuous flow. Additionally, it is preferred that the polymerization in the first and second reactors be homogeneous solution polymerization. Detailed Description of the Invention The process of the present invention can be performed by any of the well-known multi-stage reactor systems. Two convenient systems are described in United States Patent No. 4, 016,342 and U.S. Patent No. 4,306,041 which are incorporated by reference for the practice of patents in the United States. Additionally, the pending patent applications of the United States with Serial No. 60 / 076,713, filed March 4, 1998 (published as WO 99/45062) and Serial No. 60 / 076,712, filed March 4, 1998. of 1998 (published as WO 99/45049), describe convenient multi-stage reactor systems and are incorporated by reference for the practice of patents in the United States. If desired, more than two reactors can be used in the process of this invention. The process of the present invention is applicable for slurry or solution polymerization but solution polymerization is preferred and exemplified herein. The choice of reactor temperature depends on the effect of temperature on the rate of deactivation of catalyst and the properties of the polymer, mainly the molecular weight of the polymer. The temperatures should not exceed the point at which the concentration of catalyst in the second reactor is insufficient to make the desired polymer component in the desired amount. This temperature will be a function of the details of the catalyst system. In general, the temperature of the first reactor will vary between 0 and 110 * C, with 10 to 90 * C being preferred, and most preferably 20 to 70 'C. The temperatures of the second reactor will vary from 40 to 160 ° C, with 50 to 140 ° C being preferred and most preferred from 60 to 120 * C. The reactor can be cooled by reactor liners, cooling coils, self-cooling, precooled feeds, or combinations thereof. Adiabatic reactors with pre-cooled feeds are preferred. This results in a temperature difference between the reactors which is useful for controlling the polymer molecular weight. The residence time is the same or different in each reactor stage as it is set by the reactor volumes and the flow rates. Residence time is defined as the average length of the reagents of time spent within a process vessel. The total residence time, ie the total time elapsed in all the reactors is preferably 2 to 80 minutes and more preferably 5 to 40 minutes. The polymer composition is controlled by the amount of monomers fed to each train reactor. In a series of two reactors, the unreacted monomers of the first reactor flow into the second reactor and thus the monomers added to the second reactor are just enough to adjust the composition of the feed to the desired level, taking into account the carry-over of monomers. Depending on the reaction conditions in the first reactor (catalyst concentration, temperature, monomer feed rates, etc.) a monomer may have an excess at the reactor outlet relative to the amount required to make a certain composition in the second reactor. Since it is not economically feasible to remove a monomer from the reaction mixture, situations like this should be avoided by adjusting the reaction conditions. The amount of polymer made in each reactor depends on numerous operating conditions of the reactor, such as residence time, temperature, catalyst concentration and monomer concentration, but it depends more preponderantly on the concentration of monomers. In this way, the amount and composition of the polymer made in the second reactor are interdependent to some extent. The molecular weight of the polymer is controlled by the temperature of the reactor, the concentration of the monomer, and by the addition of chain transfer agents such as hydrogen. With metallocene catalysts, the molecular weight of the polymer usually declines as the temperature of the reaction increases and according to the content Ethylene content of the polymer decreases. The operation of the adiabatic reactor in a series of two reactors produces a higher temperature in the second reactor than in the first one making it easier to make the low molecular weight component in the second reactor. The molecular weight in the second reactor can be further reduced and the molecular weight distribution expanded by adding hydrogen to the second reactor. The hydrogen can also be added to the first reactor but because the unreacted hydrogen will carry the second reactor the molecular weight of both components of the polymer will decrease in this situation and the effect of hydrogen on the molecular weight distribution will be much less. The polymer composition can affect the molecular weight of the polymer, other things being equal, due to the chain transfer processes involving the alpha-olefin co-monomer. In general, it is often observed that the molecular weight is reduced by raising the alpha-olefin content of the polymer. In the context of molecular weight control, the alpha-olefin comonomer can be viewed as a chain transfer agent and can be used to affect the molecular weight of one of the physical blend components. In a series of two reactors, the diene can be added to either or both reactors. The diene is added only to the second reactor to produce a physical copolymer / terpolymer mixture. The polymer product can be recovered from a solution upon completion of the polymerization by any of the techniques well known in the art, such as steam stripping followed by extrusion drying or by devolatilizing extrusion. Higher Alpha-Olefins Although the most preferred alpha-olefin is propylene for use with this invention, other higher alpha-olefins may be used as noted below. Suitable higher alphaolefins for use can be branched or straight chain, cyclic, and substituted or unsubstituted aromatics, and are preferably alpha-olefins with from 3 to 18 carbon atoms. Illustrative non-limiting examples of the preferred higher alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-dodecene. Mixed alpha-olefins as well as mixed alpha and non-alpha olefins (eg, mixed butenes) can also be used as long as no non-polymerizable olefins in the mixture act as inerts towards the catalyst. Illustrative of these substituted higher alpha-olefins are compounds of the formula H2C = CH-CnH2n-X where n is an integer of 1 to 30 carbon atoms (preferably up to 10 carbon atoms) and X preferably comprises CH3 but may comprise aryl, alkaryl, or cycloalkyl substituents. Also useful are higher alpha-olefins substituted by one or more of these substituents X where the substituent (s) is bonded to a non-terminal carbon atom (s), more preferably being bonded to a non-terminal carbon atom which preferably is from 2 to 30. carbon atoms removed from the terminal carbon atom, with the proviso that the thus substituted carbon atom is preferably not in the carbon 1 or 2 position in the olefin. The higher alpha-olefins, when substituted, are preferably unsubstituted with aromatics or other groups by volume of the carbon 2 position since the aromatic and bulky groups interfere with the subsequent desired polymerization. Diene Although ENB is the most preferred non-conjugated diene to be used in the invention, other non-conjugated dienes are useful as presented below. The non-conjugated dienes useful as co-monomers are preferably straight-chain substituted hydrocarbon or alkene cycloalkenyl diolefins having from about 6 to about 15 carbon atoms, for example: (a) straight chain acyclic dienes, such as 1, 4-hexadiene and 1,6-octadiene; (b) branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene; 3, 7-dimethyl-l, 6-octadiene; and 3,7-dimethyl-l, 7-octadiene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1, 5-cyclo-octadiene and 1,7-cyclododecadiene; (d) bridged ring dienes and fused alicyclic multi-ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroin-deno; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2, 5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, norbornodiene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); (e) alkenes substituted by cycloalkenyl, such as vinyl cyclohexane, allyl cyclohexane, vinyl cyclo-octane, 4-vinyl cyclohexa-no, allylcyclodecene, and vinylcyclododecene. Of the non-conjugated dienes typically used, the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and tetracycle (γ-1, 12) 5,8 dodecene. Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, norbornodiene, dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB). Note that throughout this application the terms "non-conjugated diene" and "diene" are used interchangeably. Solvent Although hexane is the most preferred solvent for use in the invention, other solvents that may be used are hydrocarbons such as aliphatics, cycloaliphatics, and aromatic hydrocarbons. Preferred solvents are branched chain or straight chain saturated hydrocarbons with 12 carbon atoms or less, and aromatic or alicyclic hydrocarbons saturated with 5 to 9 carbon atoms. Examples of these solvents of the reaction medium are hexane, butane, pentane, heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane, iso-octane, benzene, toluene, xylene and mixtures thereof. In addition, one or more olefins, either alone or mixed with other media, can serve as the reaction medium, at selected concentrations of these olefins. Metallocene Catalyst Precursors The term "metallocene" and "metallocene catalyst precursor" as used herein will be understood to refer to compounds possessing a transition metal M, with cyclopentadienyl ligands (Cp), at least one ligand derived not from cyclopentadienyl X, and zero or a ligand containing the heteroatom Y, using the ligands coordinated with M and the number corresponding to the valence thereof. Metallocene catalyst precursors are generally neutral complexes but when activated with a convenient co-catalyst they produce an active metallocene catalyst which is generally referred to as an organometallic complex with a vacant coordination site that can coordinate, insert and polymerize olefins . Precursors of metallocene catalysts are preferably one of, or a mixture of metallocene compounds of either or both of the following types: 1) Cyclopentadienyl (Cp) complexes having two Cp ring systems for ligands. The Cp ligands form a sandwich complex with the metal and can be released to rotate (without bridging) or close in a rigid configuration through a bridging group. The ligands of the Cp ring can be the same or unequal, unsubstituted, substituted or a derivative thereof such as a heterocyclic ring system that can be substituted, and the substitutions can be fused to form other saturated or unsaturated ring systems such as tetrahydroindenyl, indenyl, or fluorenyl ring systems. These cyclopentadie-nyl complexes have the general formula (Cp ^ R ^ ÍCp'R ^ Xg where Cp1 of the ligand (Cp ^ and Cp2 of the ligand (Cp2R2p) are identical or different cyclopentadienyl rings, R1 and R2 each is, independently, a halogen or a hydrocarbyl, halocarbyl, organometallo substituted by hydrocarbyl or an organometaloid group substituted by halocarbyl containing up to about 20 carbon atoms, m is from 0 to 5, p is from 0 to 5, and two substituents R1 and / or R2 on adjacent carbon atoms of the cyclopentadienyl ring associated therewith can be linked together to form a ring containing from 4 to about 20 carbon atoms, R3 is a bridging group, is the number of atoms in a direct chain between two ligands and is from 0 to 8, preferably from 0 to 3, M is a transition metal having a valence of from 3 to 6, preferably of group 4, 5, or 6 of the periodic table of the elements and preferably is in its highest oxidation state, each X is a non-cyclopentadienyl ligand and, independently is a halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, organometaloid substituted by hydrocarbyl, organometalloid substituted by oxyhydrocarbyl or an organometaloid group substituted by halocarbyl containing up to about 20 carbon atoms, q equals the valence of M minus 2. 2) monocyclopentadienyl complexes which have only one ring system Cp as a ligand Ligand Cp forms a complex of medium sandwich with the metal and can be released to rotate (without bridging) or close in a rigid configuration through a bridging group to a ligand containing heteroatom. The ring ligand Cp may be unsubstituted, substituted, or a derivative thereof such as a heterocyclic ring system which may be substituted, and the substitutions may be fused to form other saturated or unsaturated ring systems such as systems of tetrahydroindenyl, indenyl, or fluorenyl rings. The heteroatom-containing ligand binds both the metal and optionally the Cp ligand through the linking group. The same hetero atom is an atom with a coordination number of three from the group VA or VIA of the periodic table of the elements. These monocyclopentadienyl complexes have the general formula (Cp1R1ra) R3n (YrR2) MXs where R1 is, each independently, a halogen or a hydrocarbyl, halocarbyl, organometaloid group substituted by hydrocarbyl or organometaloid group substituted by halocarbyl containing up to about 20 carbon atoms. carbon, "m" is from 0 to 5, and two substituents R1 on adjacent carbon atoms of the cyclopentadienyl ring associated therewith can be linked together to form a ring containing from 4 to about 20 carbon atoms, R3 is a bridging group, "n" is from 0 to 3, M is a transition metal having a valence of 3 to 6, preferably of group 4, 5, or 6 of the periodic table of the elements and is preferably in its highest oxidation state, Y is a group that contains heteroatom in which the heteroatom is an element with a coordination number of three of the VA group or a coordination number of and two of the group VIA preferably nitrogen, phosphorus, oxygen, or sulfur, R2 is a radical selected from a group consisting of hydrocarbon radicals with from 1 to 20 substituted carbon atoms, wherein one more of the hydrogen atoms is replaced with halogen atom, and where Y is 3 coordinates and not bridged there may be two groups R2 in about Y each independently a radical selected from a group consisting of hydrocarbon radicals of 1 to 20 carbon atoms, hydrocarbon radicals substituted with 1 to 20 carbon atoms, wherein one or more hydrogen atoms are replaced with a halogen atom, and each X is a non-cyclopentadienyl ligand and is independently a halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, substituted organometalloid by hydrocarbyl, organometalloid substituted by oxyhydrocarbyl or an organometaloid group substituted by halocarbyl containing up to about 20 carbon atoms rbono, "s" is equal to the valence of M minus 2. Examples of suitable biscyclopentadienyl metallocenes of the type described in group 1 above for the invention are described in U.S. Patent Nos. 5,324,800; 5,198,401; 5,278,119; 5,387,568; 5,120,867; ,017,714; 4,871,705; 4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243,001; 5,278,264; 5,296,434; and 5,304,614, all of which are incorporated by reference herein. Illustrative but not limiting examples of preferred biscyclopentadienyl metallocenes of the type described in group 1 above of the invention are the racemic isomers of: μ- (CH 3) 2 Si (indenyl) 2M (Cl) 2 μ- (CH 3) 2 Si (indenyl ) 2M (CH3) 2μ- (CH3) 2Si (tetrahydroindenyl) 2M (Cl) 2μ- (CH3) 2Si (tetrahydroindenyl) 2M (CH3) 2μ- (CH3) 2Si (indenyl) 2M (CH2CH3) 2μ- (C6H5) 2C (indenyl) 2M (CH3) 2 where M is selected from a group consisting of Zr and Hf. Examples of suitable non-symmetrical cyclopentadienyl metallocenes of the type described in group 1 above for the invention are described in U.S. Patent Nos. 4,892,851; 5,334,677; 5,416,228; and 5,449,651; and are described in J. Am. Chem. Soc. 1988, 110, 6255, all of which are incorporated by reference herein. Illustrative but not limiting examples of preferred non-symmetrical cyclopentadienyl metallocenes of the type described in group 1 above for the invention are: μ- (C6HS) 2C (cyclopentadienyl) (fluorenyl) M (R) 2μ- (C6HS) 2C (3 -methylcyclopentadienyl) (fluorenyl) M (R) 2μ- (CH3) 2C (cyclopentadienyl) (fluorenyl) M (R) 2μ- (C6H5) 2C (cyclopentadienyl) (2-methylindenyl) M (CH3) 2μ- ( C6HS) 2C (3-methylcyclopentadienyl) (2-methylindenyl) M (Cl) 2μ- (C6H5) 2C (cyclopentadienyl) (2,7-dimethylfluorenyl) M (R) 2μ- (CH3) 2C (cyclopentadienyl) (2 , 7-dimethylfluorenyl) M (R) 2 wherein M is selected from a group consisting of Zr and Hf, and R is selected from a group consisting of Cl and CH3. Examples of suitable monocyclopentadienyl metallocenes of the type described in group 2 above of the invention are described in U.S. Pat. Nos. 5,026,798; 5,057,475; 5,350,723; 5,264,405; 5,055,438 and are described in WO 96/002244, all of which are incorporated by reference herein. Illustrative but not limiting examples of the preferred monocyclopentadienyl metallocenes of the type described in group 2 above for the invention are: μ- (CH 3) 2 Si (cyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH 3) 2 Si (3-butylcyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH2 (tetramethylcyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH3) 2Si (tetramethylcyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH 3) 2 C (tetramethylcyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH 3) 2 Si (tetramethylcyclopentadienyl) (1-erbutylamido) M (R) 2 μ- (CH 3) 2 Si (fluorenyl) (1 - erbutylamido) M (R) 2 μ- (CH 3) 2 Si (tetramethylcyclopentadienyl) (1-cyclododecylamido) M (R) 2 μ- (C6HS) 2C (tetramethylcyclopentadienyl) (1-cyclododecylamido) M (R) 2 where M is selected of a group consisting of Ti, Zr, and Hf and where R is selected from Cl and CH3 Another class of organometallic complexes which are useful catalysts for the process described herein are those with di-imido ligand systems such as those described in WO 96/23010, assigned to Du Pont. These catalytic polymerization compounds are incorporated herein by reference. Non-Coordinating Anions The term "non-coordinating anion" (NCA) means an anion that does not coordinate with the transition metal cation or that only weakly coordinates with said cation whereby it is sufficiently labile to be displaced by a neutral Lewis base. The "compatible" noncoordinating anions are those that are not degraded to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer an anionic substituent or cation fragment to cause it to form a four-coordinate neutral metallocene compound and a neutral by-product from the anion. The non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in the A + 1 state, while retaining sufficient ability to allow displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. Additionally, the anions useful in this invention will be large or bulky in the sense of sufficient molecular size to largely prevent the neutralization of the metallocene cation by Lewis bases other than the polymerizable monomers that may be present in the polymerization process. Typically the anion will have a molecular size greater than or equal to about 4 angstroms. Descriptions of ionic catalysts for coordination polymerization composed of metallocene cations activated by non-coordinating anions appear in the earlier work in EP-A-0 277 003, EP-A-0 277, U.S. Patent Nos. 5,198,401 and 5,278,119, and WO92 / 00333. These show a preferred method of preparation wherein the metallocenes (bisCp and monoCp) are protonated by an anionic precursor so that an alkyl / hydride group is abstracted from a transition metal to make it both cationic and balanced in charge by the non-coordinating anion . The use of ionizing ionic compounds that do not contain an active proton but capable of producing both the active metallocene cation and a non-coordinating anion is also known. See, EP-A-0 573 403 and U.S. Patent No. 5,387,568. Reactive cations other than Bronsted acids capable of ionizing the metallocene compounds include ferrocenium triphenylcarbonium cations and triethylsililinium cations. Any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Bronsted or Lewis acids) can be used or contained in the anion of the second activating compound. Suitable metals include, but are not limited to, aluminum, gold, platinum and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon, and the like. The description of non-coordinating anions and precursors to them from these documents are incorporated by reference for purposes of patent practice in the United States. An additional method of making the ionic catalysts uses ionizing anionic precursors which are initially neutral Lewis acids but form the cation and the anion after the ionization reaction with the metallocene compounds, for example, tris (pentafluorophenyl) boron acts to abstract an alkyl, hydride or silyl ligand to produce a metallocene cation and a non-coordinating stabilization anion, see EP-A-0 427 697 and EP-A-0 520 732. Ionic catalysts for addition polymerization can also be prepared by oxidizing the metal centers of transition metal compounds by anionic precursors containing metal oxidizing groups together with the anion groups, see EP-A-0 495 375. The description of non-coordinating anions and precursors thereto these documents are similarly incorporated by reference for purposes of United States patent practice. Examples of suitable activators capable of the ionic cationization of the metallocene compounds of the invention, and the consequent stabilization with a resulting non-coordinating anion include: trialkyl substituted ammonium salts such as: triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tetraphenylborate tri (n-butyl) ammonium, tetrakis (p-tolyl) borate trimethylammonium, tetrakis (o-tolyl) orate trimethylammonium, tetrakis (pentafluorophenyl) borate tributylammonium, tetrakis (o, p-dimethylphenyl) borate tripropylammonium, tetrakis (m , tributylammonium m-dimethylphenyl), tributylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate and the like; N, N-dialkylanilinium salts such as: N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (heptafluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoro-4-biphenyl) borate, N, N-dimethylanilinium tetraphenyl borate, N, N-diethylanilinium tetraphenyl borate, N, N-2,4,6-pentamethylanilinium tetraphenyl borate and the like; dialkylammonium salts such as: di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like; and triarylphosphonium salts such as: triphenylphosphonium tetraphenyl borate, tri (methylphenyl) phosphonium tetraphenylborate, tri (dimethylphenyl) phosphonium tetraphenylborate and the like. Other examples of suitable anionic precursors include those comprising a stable carbonium ion, and a compatible non-coordinating anion. These include: tetracyl (pentafluorophenyl) borate of tropilium, tetrakis (pentafluorophenyl) borate of triphenylmethylium, tetrakis (pentafluorophenyl) borate of benzene (diazonium), phenyltris (pentafluorophenyl) borate of tropilium, phenyl- (trispentafluorophenyl) borate of triphenylmethylium, phenyltris (pentafluorophenyl) benzene borate (diazonium), tetrakis (2, 3, 5, 6, 6-tetrafluorophenyl) borate of tropilium, tetrakis (2, 3, 5, 6-tetrafluorophenyl) borate of triphenylmethylium, tetrakis (3, 4, 5- trifluorophenyl) benzene borate (diazonium), tetrakis (3, 4, 5-trifluorophenyl) borate of tropylium, tetrakis (3,4,5-trifluorophenyl) borate of benzene (diazonium), tetrakis (3,4,5-trifluorophenyl) tropilium aluminate, triphenyl (3, 4, 5-trifluorophenyl) aluminate of triphenylmethyl, tetrakis (3,4,5-trifluorophenyl) aluminate of benzene (diazonium), tetrakis (1,2,2-trifluoroethenyl) borate of tropilin, tetrakis (1, 2, 2-trifluoroethenyl) borate triphenylmethylium, tetrakis (1, 2, 2-trif) luoroethenyl) benzene (diazonium) borate, tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate of tropilium, tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate of triphenylmethylium, tetrakis (2, 3, 4, 5 -tetrafluorophenyl) benzene (diazonium) borate, and the like. When the metal ligands include halide fractions for example, (methyl-phenyl) silylene (tetra-methyl-cyclopentadienyl) (tert-butyl-amido) zirconium dichloride) which is not capable of ionization abstraction under standard conditions, it can convert via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, and so on. See EP-A-0 500 944, EP-A1-0 570 982 and EP-A1-0 612 768 for processes that describe the reaction of alkylaluminum compounds with metallocene compounds substituted by dihalide before or with the addition of anionic compounds of activation. For example an alkylaluminum compound can be mixed with the metallocene before its introduction into the reaction vessel. Since alkylaluminum is also convenient as a dissociator its use in excess of that normally required stoichiometrically for the alkylation of the metallocene will allow its addition to the solvent of the reaction with the metallocene compound. Normally alumoxane would not be added with the metallocene to prevent premature activation, but it can be added directly to the reaction vessel in the presence of polymerizable monomers when it serves as both a dissociator and an alkylation activator. The known alkylalumoxanes are additionally suitable as catalyst activators, particularly for those metallocenes comprising halide ligands. The alumoxane component useful as a catalyst activator is typically an oligomeric aluminum compound represented by the general formula (R-Al-0) p, which is a cyclic compound, or R (R-Al-O) J-A1R2, which is a linear compound. In the general alumoxane formula R is an alkyl radical with 1 to 5 carbon atoms, for example, methyl, ethyl, propyl, butyl or pentyl and "n" is an integer from 1 to about 50. More preferably, R is methyl and "n" is at least 4, ie methylalumoxane (MAO). The alumoxanes can be prepared by various methods known in the art. For example, an aluminum alkyl can be treated with water dissolved in an inert organic solvent, or can be contacted with a hydrated salt, such as hydrated copper sulfate suspended in the inert organic solvent, to produce an alumoxane. Generally, however prepared, the reaction of the alkylaluminium with a limited amount of water produces a mixture of the linear and cyclic species of the alumoxane. Although trialkylaluminum is the most preferred dissociator for use in the invention, other dissociators may also be used as discussed below. The term "dissociating compounds" is used in this application and in the claims to mean that they include those compounds effective to remove polar impurities from the reaction solvent. These impurities can be inadvertently introduced with any of the components of the polymerization reaction, particularly with the solvent, monomer and co-monomer feed, and adversely affect the activity and stability of the catalyst. It can result in a decrease or even the elimination of the catalytic activity, particularly when a pair of non-coordinating anion metallocene cation is the catalyst system. Polar impurities, or catalyst poisons include water, oxygen, oxygenated hydrocarbons, metal impurities, and so on. The steps are preferably taken before the provision of these in the reaction vessel, for example by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components, but some small amounts of dissociating compound will normally be required in the polymerization process itself. Typically the dissociating compound will be an organometallic compound such as Group-13 organometallic compounds of 5,153,157, 5,241,025, EP-A-638 and WO-A-91/09882 and WO-A-94/03506, noted above, and that of WO -A-93/14132. Exemplary compounds include triethylaluminum, triethylborane, tri-isobutylaluminum, isobutylalumino-oxane, those having bulky substituents covalently bonded to the metal or metalloid center are preferred to minimize adverse interaction with the active catalyst. When alumoxane is used as an activator, additional dissociating compounds are not necessary. The amount of dissociating agent to be used with non-coordinating metallocene-anion cation pairs is minimized during polymerization reactions to the effective amount to increase the activity. Dynamic Vulcanization The amorphous components of the physical mixture of series reactors are generally present as small particles, that is to say micro-size, within a continuous semi-crystalline plastic matrix, although a co-continuous morphology or reversal is also possible. phases, depending on the amount of amorphous in relation to semi-crystalline plastic. The amorphous component is desirably at least partially crosslinked, and preferably is completely or fully crosslinked. It is preferred that the amorphous component be crosslinked by means of the dynamic vulcanization process. As used in the description and claims, the term "dynamic vulcanization" means a vulcanization or curing process for an amorphous component physically mixed with a semi-crystalline plastic, where the amorphous component is vulcanized under shear conditions at a temperature to which the mixture will flow. The amorphous component is in this way simultaneously crosslinked and dispersed as fine particles within the semi-crystalline plastic matrix, although as noted above, other morphologies may exist. Dynamic vulcanization is carried out by mixing the components at elevated temperatures in conventional mixing equipment such as roller mills, Banbury mixers, Brabender mixers, continuous mixers, mixing extruders, and the like. The unique feature of the dynamically cured compositions is that, notwithstanding the fact that the amorphous component is partially or fully cured, the compositions can be processed and re-processed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Waste or runoff can be recovered and re-processed. The terms "fully vulcanized" and "fully cured" or "fully crosslinked", as used in the description and claims, mean that the amorphous component to be vulcanized has been cured or crosslinked to a state in which the elastomeric properties of the component amorphous crosslinked are similar to those of the amorphous component in its conventional vulcanized state, apart from the physically mixed, cured composition of serial reactors. The degree of curing can be described in terms of gel content or, conversely, extractable components. The amorphous component can be described as fully cured when less than about 5%, and preferably less than 3%, of the amorphous component that is capable of being cured by hydrosilation is extractable from the product by a solvent for that amorphous component. Alternatively, the degree of cure can be expressed in terms of crosslink density. All of these descriptions are well known in the art, for example, U.S. Patent Nos. 5,100,947 and 5,157,081, both of which are hereby incorporated by reference for purposes of United States patent practice. The compositions can be processed and re-processed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Those skilled in the art will appreciate the appropriate amounts, the types of curing systems and the vulcanization conditions required to carry out the vulcanization of the amorphous component. The amorphous component can be vulcanized using varying amounts of curing agent, variable temperature, and variable cure time in order to obtain the desired optimum crosslinking. Any known curing system for the amorphous component can be used, as long as it is suitable under vulcanization conditions with the specific amorphous olefinic component or combination of amorphous components that are used with the polyolefin. These curing agents include sulfur, sulfur donors, metal oxides, resin systems, peroxide-based systems, hydrosilation with platinum or peroxide, or both, both with and without accelerators and co-agents. Examples The polymerizations were carried out in two reactors with one liter agitation in series with continuous flow of feeds to the system and continuous withdrawal of products. The first reactor could be operated as a single reactor. The solvent, including but not limited to hexane, and monomers including but not limited to ethylene, propylene, and ENB (5-ethylidene-2-norbornene) were purified on aluminum oxide beds and molar sieves. Toluene to prepare catalyst solutions was also purified by the same technique. All feeds were pumped into the reactors by metering pumps except for ethylene that flowed as gas under its own pressure through a mass flow meter / controller. The temperature of the reactor was controlled by circulating water through the cooling jacket of the reactor. The reactors were maintained at a pressure in excess of the vapor pressure of the reaction mixture to maintain the reactants in the liquid phase. The reactors were operated filled with liquid. The ethylene and propylene feeds were combined in one stream and then mixed in a stream of pre-cooled hexane that had been cooled to at least 0 ° C. If ENB was used, this was also fed into the hexane stream upstream of the other monomers. A solution of tri-isobutylaluminum dissociator hexane was added to the combined solvent and to the monomer stream just before it entered the reactor to further reduce the concentration of any catalyst poison. A mixture of the catalyst components in toluene was pumped separately into the reactor and entered through a separate port. The solution of the polymer solvent, the unconverted monomers, and the catalyst leaving the first reactor entered the second reactor. An additional hexane solution of the monomers was fed into the second reactor through a separate port. The product from the second reactor came out through a pressure control valve that reduced the pressure to atmospheric. This caused the monomers not converted to the solution to vaporize in the vapor phase which was vented from the top of a liquid vapor separator. The liquid phase, comprising mainly polymer and solvent, flowed out of the bottom of the separator and was collected for polymer recovery. The polymer was recovered from the solution either by vapor division followed by drying, or by evaporation of solvent under heat and vacuum. The polymer of the first and second reactors was characterized by the Mooney viscosity (by Mooney Viscometer, ASTM D1648), the ethylene content (by FTIR, ASTM D3900), the ENB content (by FTIR, ASTM D6047), the temperature of fusion and / or glass transition temperature (by differential scanning calorimetry (DSC), described herein), molecular weight (by gel permeation chromatography (GPC), described herein). The analysis of the second reactor polymer represents the properties of the overall polymer mixture. The gel permeation chromatography (GPC) techniques that were used to characterize these products of this invention have been described in several publications especially in U.S. Patent No. 4,989,436 which is incorporated for the purposes of patent practice. the United States. Molecular weight and compositional measurements are described in G. See Strate, C. Cozewith, S. Ju, Macro o-lecules, 21, 3360 (1988) which is incorporated by reference for the purposes of patent practice. U.S. Differential scanning calorimetry (DSC) was used to characterize the products of this invention has a standard protocol of charging a calorimeter at 20 ° C with a specimen free of molding stress, annealing at room temperature for 40 hours, cooling the sample to -75 ° C, scan at 180 ° C at 10 ° C / minute, cool to -75 ° C, and re-scan. The glass transition temperature Tg, and the melting temperature Tm, and the heat of fusion were evaluated. In some cases, the low melting crystallinity was not seen on a second scan since it takes many hours to develop it even at low temperatures. Atomic force microscopy (AFM) was used to determine the number of polymer phases present in the final product after recovery of the reactor solution. AFM analyzes were carried out using a Digital Instruments Dimension 3000 instrument operated under ambient conditions. The instrument was operated in height, amplitude and phase shift mode. The height analysis yielded the overall topography of the sample. The amplitude analysis provides differential height images, which are sensitive to height changes but not to absolute height. Phase shift images provide module / chemical maps of the surface. Cantilever Bar Si (225 μm in length and 30 μm in width) with force constants between 0.4 and 5 N / m were used for these analyzes. While air was applied, the cantilever was oscillated at a frequency slightly lower than its resonance frequency with an rms amplitude between 3.5 and 4.0 volts (measured at the position sensitive detector). During the analysis of samples, the rms amplitude fixed point was adjusted to approximately 30% of the rms amplitude of the cantilever oscillating in air. Prior to analysis, the elastomer samples were cryogenically sliced at -150 ° C using an ultra-microtome, the samples were allowed to warm to room temperature in a nitrogen-filled dissector, and then analyzed at room temperature. polymer solution of the first and second reactors were analyzed for polymer concentration.For this measurement and reactor feed rates, the polymerization rates in both reactors could be determined by material balances.Monomer conversions when calculated from the velocity of polymerization and the polymer composition data for the first reactor only and for the total of both reactors put together In order to calculate the polymerization rate and the polymer composition in the second reactor alone, the following equations of balance were used of material: PR2 = PRt - PR1 Eq. 1 F-. = PR1 / PRt Eq. 2 E2 = (Et - (F-. X E J / tFj. - - i) Eq. 3 D2 =. { Dt - (F, X O1)} / (F1 - - i) Eq. 4 MN, (1 - F / U / MNt - F-./MN-.) Eq. 5 MW2 = (MWt-F1 * MW1) / (1-F Eq. 6 where: PR-L = polymerization rate of the first reactor PR2 = polymerization rate of the second reactor PRt = total polymerization rate E, ethylene content of the polymer of the first reactor E2 = ethylene content of the polymer of the second reactor Et = ethylene content of the polymer of the total reactor Dj_ = diene content of the polymer of the first reactor D2 = diene content of the polymer of the second reactor Dt = diene content of the polymer of the total reactor F? - fraction of the total polymer made in the first reactor M-L = number average molecular weight of the polymer of the first reactor MN2 = number average molecular weight of the polymer of the second reactor MNt = number average molecular weight of the total reactor polymer MW-L = weight average molecular weight of the polymer of the first reactor MW2 = weight average molecular weight of the polymer of the second reactor MWt = weight average molecular weight of the total reactor polymer A series of polymerizations was carried out to demonstrate the process and the products of this invention. All reactor conditions, polymer analysis and polymerization results are given in Table 1. The entries in the table shown for reactor 1 (Rl) and the total product are based on actual measurements for reactor polymer 1 and the polymer mixture leaving reactor 2. The results to reactor 2 (R-2) were only calculated from these data by means of the formulas given above. Example 1 (121C) Polymerization in series reactors was carried out with dimethylsilyne bisindenyl hafnium dichloride catalyst (cat A) mixed with N, N-dimethylaniline tetrakis (penta-fluorophenyl) boron (DMPFB) as activator. The catalyst components were dissolved in toluene in a 1/1 molar ratio. The reactor conditions and the feed rate are shown in Table 1. The catalyst feed rate shown is the feed of catalyst A only and the efficiency of the catalyst is calculated by dividing the polymerization rate by the feed rate of catalyst A A mixture of ethylene and propylene was fed to the first reactor, but only ethylene was fed to the second reactor. The polymer produced in the first reactor had an ethylene content of 15.5% and the polymer of the second reactor had an ethylene content of 55%. The molecular weight of the polymer produced in each reactor was similar so that the physical mixture of the product did not expand in MWD. The polymer of reactor 1 was semi-crystalline due to the crystallinity of the propylene, but the polymer made in reactor 2 was amorphous. Example 2 (125A) A polymerization was carried out with catalyst A at conditions similar to Example 1, except that diene (ENB) was fed to the second reactor to produce a terpolymer. The polymer of the first reactor was a semi-crystalline copolymer with 17% by weight of ethylene that melted in a range of 29.6 to 99 'C. The polymer of the second reactor was an amorphous terpolymer with 50.6% by weight of ethylene and 3.29% by weight of ENB. The reactor conditions and the polymerization results are shown in Table 1. Example 3 (127A, B, C) A series of polymerizations were carried out with catalyst A, at conditions similar to those used in Example 1, except that Increasing amounts of ethylene were fed to the second reactor in runs A to C. The reactor conditions and the polymerization results are shown in Table 1. As a result of raising the ethylene feed to the second reactor, the total polymer fraction made in the first reactor decreased from 36 to 20% and the ethylene content of the polymer of the second reactor was increased from 47.4 to 61% by weight. In this way, by adjusting the feed rates of the second reactor, the composition and the amount of the second component in the physical mixture can be easily varied. The same control magnitude is not possible when using vanadium catalysts of the prior art, due to the low concentration of active catalyst in the second reactor. Example 4 (131C) A polymerization was carried out with the same catalyst and procedures used in Example 1, to produce a physical mixture of terpolymer. The reactor conditions and the polymerization results are shown in Table 1. In this polymerization, ENB was fed to both reactors in addition to the other monomers. The polymer produced in the first reactor had 18.8% by weight of ethylene and 3.25% by weight of ENB, while the polymer produced in the second reactor had 47.8% by weight of ethylene and 8.53% by weight of ENB.

Example 5 (173A) A polymerization was carried out with the same catalyst and procedures used in Example 4, to produce a physical mixture of terpolymer. However, the reactor temperatures are higher than in the previous examples, and the second reactor is at 65 * compared to 40 * C. The reactor conditions and the polymerization results are shown in Table 1. In this example, the polymers produced in each reactor were amorphous, and the polymer produced in the first reactor had 30.3% by weight of ethylene while the polymer produced in the second reactor had 53.1% by weight of ethylene. The MWD of the final product was enlarged due to the polymer of different molecular weight being produced in each reactor. The Mw / Mn ratio was 2.84. Example 6 (272A) A polymerization was carried out by the procedure used in Example 1, except that the catalyst was dimethylsilyltetracyclopentadienylated dichloride / mantylamido titanium (cat B). As in Example 1, the reactor was fed in a 1/1 molar ratio with DMPFB dissolved in toluene. The copolymerization was carried out at reactor temperatures of 30 and 75 ° C. The reactor conditions and the polymerization results are shown in Table 1. An amorphous copolymer with 32.9% by weight of ethylene was made in the first reactor, while a semi-crystalline copolymer with 79.5% by weight of ethylene was made in the second reactor. 64% by weight of the product was made in the first reactor. The MWD of the final product was narrow, with the Mw / Mn ratio equal to 1.94. Example 7 (293A, B, C, D) A series of polymerizations were carried out with catalyst B using the procedure of Example 6, to prepare physical mixtures of copolymer and terpolymer with extended MWD. In this example, the reactor system was allowed to reach steady state in the initial conditions (run A). After a sample of the product was collected, diene was added to both reactors to prepare a physical mixture of terpolymer and the reactor was again allowed to reach steady state before obtaining a second sample (run B). This procedure was continued for runs C and D. The reactor conditions and the polymerization results are shown in Table 1. In runs A and B, the physical mixture component with high ethylene content was made in the second reactor . In Runs C and D, the compositions were inverted and the component with high ethylene content was made in the first reactor. Likewise, hydrogen was added to the first reactor as a chain transfer agent to produce a low molecular weight product in runs C and D. The polymers made in Runs A, B and C had a broad MWD, as indicated by values Mw / Mn from 4.5 to 9.8. Example 8 (3193.0) This run was made with catalyst B using the procedure of Example 1 to demonstrate the benefits of the operation of reactors in series with monomer feed to both reactors In run B, the series reactors were used without additional monomer feed to the second reactor The reactor conditions and the polymerization results are shown in Table 1. The polymerization rate was low in the second reactor due to the low concentration of monomers and the polymer composition was approximately the same for The polymer made in both reactors In run C, the reactor conditions were kept the same, except that monomers were now added to the second reactor.In comparison with the initial run B, the polymerization rate and catalyst efficiency were improved and produced a polymeric physical mixture with a component containing 76.2% by weight of ethylene and the other containing 3 9.3% by weight of ethylene. Example 9 (268B, 272A, 307C, 318A, 320C, 293A) A series of polymerizations was carried out using the procedure of Example 1, to make polymeric physical blends in which the two components are largely immiscible and the final product, after recovery from solution was a mixture in two phases. The reactor conditions and the polymerization results are shown in Table 2. The products produced in runs 268A and 293A are physical mixtures of two essentially amorphous polymers made with catalysts A and B. The products made in runs 272A and 320C are physical mixtures of an amorphous component and a component having a high ethylene content and containing ethylene crystallinity. The polymers in runs 307C and 318C were made with catalyst A and contain a component with propylene crystallinity and a component with higher ethylene content that does not contain propylene crystallinity. All polymers were analyzed by atomic forces microscopy (AFM) to determine the number of phases present. As shown by the result for polymer 318C in Figure 1, the polymer product consisted of a two phase mixture. All the other products in this example gave similar results. Example 10 A series of physical reactor mixtures is dynamically vulcanized in a Brabender mixer by mixing the physical mixtures until the plastic phase melts and the torsion has equilibrated. At that time, the curing system is added and mixing is continued for 4 minutes. The material is mixed at 180 ° C and 100 rpm and the temperature rises during curing to around 200 ° C. The products are then removed from the Brabender mixer and compression molded and evaluated for physical properties. Table 3 shows the properties and the corresponding compositions.

TABLE 1 CONDITIONS OF OPERATION OF THE REACTOR n TABLE 2 CONDITIONS OF THE REACTOR FOR EXAMPLE 9 01 Table 3 Composition of Physical Mixture of Reactors in Series Polymer Compo- Div.% Weight% weight DSC! Tm DSC / Hf Nentes Poli C2 ENB C C) J / G Mixture 45.68 3.35 127 30 physics A -iPP Reac. 1 46.5 0 0 133 74 m-EPDM Reac. 2 53.5 85.4 6.27 Mix 46.09 4.33 128 25 physics B 134 73 m-iPP Reac. 1 38.76 0 0 m-EPDM Reac. 2 61.24 75.3 7.07 Table 4 Dynamic Vulcanized Properties State of the Art Profax 6723 60 60 Epsyn 70A 100 100 363A i-PP 86.9 86.9 EPDM 100 100 363B i-PP 63.4 63.4 EPDM 100 100 Zinc Oxide - 2 - 2 _ 2 SnC12 H20 - 1.8 - 1.8 - - SP-1045 - 7.0 - 7.0 - SP-1056 Hardness, Shore 37 44D 45D 44D 36D 42D UTS, psi 1812 4601 4061 4371 1560 3463 Elong. ,% 600 551 525 506 300 310 M100, psi 1059 1142 1151 1147 866 1433 Profax 6723 by Montell - PP isotactic of 0.8 MFR Epsyn 70A, EPDM by DSM Copolymer

Claims (16)

1. CLAIMS 1. A method of making a polymeric physical mixture by continuous solution polymerization, comprising: a) feeding a first set of monomers and a solvent in predetermined proportions to a first reactor, b) adding a metallocene catalyst to the first reactor, said metallocene catalyst system comprising two cyclopentadienyl ring systems closed in a rigid configuration through a bypass group, c) operating the first reactor to polymerize the first set of monomers to produce an effluent containing a first polymer, d) feeding the effluent of c) to a second reactor, e) feeding a second set of monomers in predetermined proportions to the second reactor and, optionally, adding solvent, f) operating the second reactor to polymerize the second set of monomers to produce a second polymer , where the first and second sets of monomers comprise, each, ethylene, propylene and, optionally, a non-conjugated diene monomer, and the monomer proportions and said first and second reactors are controlled such that said first and second polymers contain from 20 to 85% by weight of units derived from ethylene and from 0 to 15% by weight. weight of units derived from diene monomer, and the ethylene content of the first and second polymers differs by 3 to 75% by weight; and where 50-100% by weight of the total amount of catalyst added to all the reactors is added to the first reactor.
2. 2. The method of claim 1, wherein at least 35% by weight of the total polymer is made in the second reactor. The method of claim 1, wherein the monomer proportions in the first reactor and the second reactor are controlled so that the ethylene content of the first and second polymers differs so that either: a) the first polymer is semi -crystalline and the second polymer is amorphous, or b) the first polymer is amorphous and the second polymer is semi-crystalline. The method of claim 1, wherein the molecular weight of the first or second polymer or both polymers is controlled by at least one of: a) adding a chain transfer agent to the first or second reactor or both reactors, b ) operate the first or second reactors with a temperature difference between the reactors. The method of claim 4, wherein the molecular weight of the first or second polymer or both polymers is controlled so that the first and second polymers have an Mw / Mn ratio of 1.7 to 2.5 while the polymeric physical mixture has an Mw ratio. / Mn from 2.5 to 20.0, preferably 3.0 to 10.0. 6 The method of claim 1, wherein the components of the first and second polymers have a weight average molecular weight of 10,000 to 2,000,000. The method of claim 4, wherein the average molecular weight of the first or second polymer or both polymers is controlled such that the polymeric physical mixture has a Mw / Mn ratio of less than 2.5. The method of claim 7, wherein the monomer proportions in the first reactor and the second reactor are controlled so that the ethylene content of the first and second polymers differs by 3 to 75% by weight. 9. The method of claim 4, wherein the molecular weight of the first or second polymer or both polymers is controlled so that either: a) the first polymer has a higher molecular weight than the second polymer, or b) the first polymer has a weight lower molecular weight than the second polymer. The method of claim 9, wherein the monomer proportions in the first reactor and the second reactor are controlled so that the first polymer has an ethylene content different from the second polymer. The method of claim 1, wherein the monomer proportions in the first reactor and the second reactor are controlled so that either the first polymer or the second polymer contains 60 to 85% by weight of ethylene, it is semi-crystalline due in the presence of ethylene sequences, Ól-y has a melting point of 40 to 100 ° C, while the other polymer is amorphous. The method of claim 1, wherein the unconjugated diene is selected from the group consisting of 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene and 5-vinyl-2-norbornene (VNB), and mixtures thereof. The method of claim 1, wherein the reactors are liquid-filled, continuous-flow, stirred tank reactors. The method of claim 1, wherein the metallocene catalyst is a metallocene catalyst of group 4, 5 or 6, activated by methylalumoxane or a noncoordinating anion. 15. The method of claim 2, wherein the metallocene catalyst is μ- (CH3) 2Si (indenyl) 2Hf (CH3) 2, μ- (CH3) 2 Si [tetramethylcyclopentadienyl] [adamatylamido] Ti (CH3) 2, or μ- (C6H5) 2 Si [cyclopentadienyl] [fluorenyl] Hf (CH3) 2. 16. The method of claim 1, wherein the first reactor operates at temperatures from 0 to 100 * C, preferably 10 to 90 ° C, more preferably 20 to 70 'C, and the second reactor operates at temperatures of 40 to 140 * C, preferably 50 to 120' C, more preferably 60 to 110"C.