CZ20003207A3 - Dynamic vulcanization of polymeric mixtures within reactors arranged one after the other - Google Patents

Abstract

A method of dynamic vulcanization of a polymer blend produced solution polymerization in reactors arranged therewith. The polymer blends are mixed under heat and shear conditions the curing agent is added to at least partially crosslinking the components of the mixture.

Description

Dynamic vulcanization of polymer mixtures in sequential reactors

Technical field

The present invention relates to a process for preparing polymer blends using sequential reactors and a metallocene catalyst. The monomers used in this invention are ethylene, higher alpha-olefins (most preferred is propylene), and optionally unconjugated diene (preferably ethylidennorbornene ENB). More specifically, the present invention relates to the preparation of mixtures of EP (ethylene-propylene) copolymers in which the components of the mixture differ in any of the following properties: 1. composition, 2. molecular weight, and 3. crystallinity. The term copolymer EP is also used for terpolymers containing different amounts of unconjugated diene. Such terpolymers are commonly known as EPDM.

Various advantages speak for the preparation of the above mixtures. For example, EP (ethylene propylene copolymer) and EPDM (ethylene propylene diene terpolymer) polymers are often used as a blend of two or more polymers to obtain optimal polymer properties for a given application. By mixing high-molecular and low-molecular polymers, the molecular weight distribution is expanded and thus obtains better processability than polymers with a narrow molecular weight distribution with the same average molecular weight. The semi-crystalline polymer may be mixed with an amorphous polymer to improve the toughness (green strength-postforming) of the amorphous component at temperatures below the melting point of the semi-crystalline polymer. Polymers with higher green strength have less tendency to cold flow and exhibit better properties in processing methods such as calendering and extrusion.

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BACKGROUND OF THE INVENTION

One way to form the above blends is to mix two different polymers after polymerization to obtain the desired set of properties. However, this process is expensive and it is therefore much more desirable to prepare the compositions by direct polymerization. Direct polymerization compositions are well known in the prior art, such as the preparation of EPDM using Ziegler-Natta soluble vanadium catalysts in sequential reactors and the preparation of polymers with different properties in each reactor. The patents describing the use of vanadium processes in sequential reactors are US Patent No. 3,629,212, US Patent No. 4,016,342, and US Patent No. 4,306,041, which are incorporated by reference for the purposes of US Patent Law.

While blending of polymers with Ziegler-Natta catalysts in in-line reactors can be carried out, there are serious limitations on the amount and properties of polymers that can be produced in both reactors, especially in the second reactor. For economic reasons, in reactor operation, it is most advantageous to place the catalyst only in the first reactor to reduce the consumption of expensive catalyst components. Since the rate of deactivation of the active vanadium components is considerable, the catalyst concentration in the second reactor is very low in the series and would be even lower in others. As a result, it would be very difficult to prepare more than about 35% of the total polymer in the second reactor. A low catalyst concentration can also limit the composition or molecular weight of the polymer. This problem can be solved by adding catalyst activators or other catalysts to the second and subsequent reactors, but this increases production costs. In addition, vanadium catalysts have a limited ability to produce polymers with

an ethylene content of less than 35% by weight, since they more readily polymerize ethylene than propylene or higher alpha olefins. In addition, soluble vanadium catalysts are unable to produce copolymers or terpolymers exhibiting crystallinity due to the presence of long isotactic polypropylene sequences.

SUMMARY OF THE INVENTION

The present invention differs from the prior art descriptions in that it offers a process for producing polymer blends in sequential reactors solving the prior art problems associated with quality deficiencies. Note that the terms multistage reactor and sequential reactors are used interchangeably herein. Using high life metallocene catalysts, polymer blends varying in the number of components, the composition of the components and their molecular weight can be produced in a much broader range than the polymer blends obtainable with prior art vanadium catalysts. In particular, it is an object of the present invention to employ sequential reactors and to produce the following types of blends: a. Blends in which the ethylene content of the polymer produced in the first and second reactors varies by 3 to 75 wt. b. Mixtures in which the molecular weight distribution (MWD) of the mixture is characterized by a ratio Mw / Mn = 2,5 to 20 and MW / MN of the individual components of the mixture is 1,7 to 2,5; and c. and d. of the blend, in which one component contains 0 to 20 wt. 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. mixtures in which one component contains 60 to 85% by weight ethylene are semi-crystalline due to the presence of long ethylene sequences 40-120 ° C and the other component is amorphous.

This polymer blend prepared in sequential reactors is used in dynamic vulcanization to provide improved thermoplastic elastomeric products.

The polymerization is preferably carried out as a homogeneous solution polymerization. The catalyst is a cyclopentadienylmetalocene complex with two Cp (cyclopentadiene) cyclic systems for ligands or a monocyclopentadienylmetalocene catalyst.

The metallocene complexes are activated with an alumoxane, for example methylalumoxane (MAO) or a non-coordinating anion (NCA) described below. Optionally, a trialkyl aluminum scavanger may be added to the reactor batch to protect the catalyst from poison deactivation. It is preferred that the reactors are stirred flow reactors filled with liquid. As a preferred embodiment, two or more continuous flow stirred-tank reactors in series with two reactors are used in this process. The solvent and monomers are fed to all reactors and it is preferred that the catalyst is only fed to the first reactor. The reactors are cooled by a cooling jacket or coils, self-cooling, pre-cooling of the batch or a combination of all three methods. A self-cooling reactor requires the presence of a vapor phase in the reactor. Adiabatic reactors with pre-cooled batch are preferred. This allows a temperature difference between the reactors, which helps to control the molecular weight of the polymer. The monomers used in this process are ethylene and the higher alpha-olefins C3C8. As the higher alpha-olefin, propylene is most preferred. If desired, monomers may also include unconjugated diene, in which case the most abundant diene is ENB (55

Ethylidene-2-norborene). The temperature in the reactor depends on the effect of temperature on catalyst deactivation rate and polymer properties. For economic reasons, it is desirable to operate at the highest possible temperatures; however, the temperatures should not exceed the limit at which the catalyst concentration in the second factor is insufficient to prepare the desired polymer component in the desired amount. Therefore, the temperature is determined by the nature of the catalyst system. Generally, the temperature in the first reactor may vary between 0-110 ° C, with temperatures of 10-90 CC and most preferred temperatures of 20-70 ’C being preferred.

The temperatures in the second reactor vary between 40 and 160 ° C, with temperatures of 50-140 ° C being preferred and 60-120 ° C being most preferred.

When two reactors are used in series, the polymer composition produced in the first reactor is 0-85% by weight of ethylene and the polymer composition in the second reactor is 0-85% by weight of ethylene. The average composition of the polymer blend is 6-85% by weight of ethylene.

If the Mw / mn ratio of the mixture is less than 2.5, then the difference in the composition of the polymer produced in the first and second reactors is 3-75% ethylene, preferably 5-60% ethylene and most preferably 7-50% ethylene. If the Mw / Mn ratio of the mixture is 2.5 or greater, then the composition of the components of the mixture may be either the same or different.

In another embodiment, the difference in the ethylene content of the two components is such that one is semi-crystalline and the other is amorphous. Semi-crystalline is defined as having a DSC (differential scanning calorimetry) melting point and a latent heat of fusion of at least 10 J / g, while amorphous is defined as having no DSC melting point of less than 10 J / g. The semicrystalline polymers of the present invention typically have a melting point of about 40-160 ° C depending on the composition of the polymer. DSC measurements are performed as described in •

99 · 9 • 9 · 99

99 · 9 ·

9 9 9

9 9 9

9 9 9 chapter Examples. When using the catalysts of the present invention, ethylene propylene copolymers are generally amorphous and have an ethylene content of between 20 and 60% by weight. If a polymer component with ethylene crystallinity is to be present in the mixture, it must have more than 60% ethylene. On the other hand, if a propylene crystallinity component is desired, it must have less than about 20 wt. ethylene. In addition, a catalyst system capable of polymerizing propylene stereospecificers is required. Most preferred are catalyst systems producing isotactic propylene sequences.

Depending on the degree of crystallinity of the semi-crystalline component and the difference in composition between the components, both components may be immiscible and may form a mixture of phase-separated components upon leaving the reactor. The presence of multiple phases can be well measured by standard polymer characterization methods such as visible light microscopy, electron microscopy or atomic force microscopy (AFM). Two-phase polymer blends often have advantageous properties and it is a particular object of the present invention to prepare such two-phase blends by direct polymerization.

When two reactors are used in a row, the amount of polymer produced in the second reactor is 15-85% of the total polymer produced in both reactors, preferably 30-70% of the total polymer produced in both reactors.

The MWD of polymers produced using metallocene catalysts tends to be narrow (MW / Mn <2.5) and as a result the polymers generally do not have good processing properties. It is a particular object of the present invention that the polymers prepared in the first and second reactors have a sufficiently different molecular weight to expand the MWD. The MW / Mn of the final product should preferably be 2.5-20.0, and most preferably 3.0-10.0.

·· · *

The diene content of the polymer may 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 contents of the polymers produced in both reactors may be the same or different. Mixtures of copolymer and terpolymer can be produced by the process of the invention. For example, if diene is added only to the second reactor, an ethylene-propylene copolymer can be produced in the first reactor, while an ethylene, propylene and diene terpolymer can be prepared in the second reactor.

A preferred embodiment of the invention is to operate sequential reactors to produce mixtures in which the proportion of the components of the mixture differs by at least 3% by weight of ethylene, the Mw / Mn of the mixture is equal to or greater than 2.5 and one of the components of the mixture is semi-crystalline. Another preferred feature is that the semi-crystalline polymer comprises isotactic polypropylene exhibiting crystallinity.

In a mixture combining all the above-described features of the invention, given the average ethylene content and the molecular weight of the final product, the properties of the polymer will vary depending on the composition and molecular weight of all components. The process according to the invention is capable of producing mixtures in which: a. Polymer 1 has either an ethylene content and a molecular weight higher than polymer 2; or b. Polymer 1 has a higher ethylene content and a lower molecular weight than polymer 2. they can be prepared either in the first or second reactor.

In the case of terpolymerization, the blends may further vary depending on the diene content of each component. Typically, it is preferred to have a higher diene content in the lower molecular weight component, resulting in optimal product properties in the vulcanized thermosetting compounds.

The present invention can be characterized as a method. * · <

Forming a polymer blend by solution polymerization comprising: a. Feeding a first set of monomers and solvent in predetermined proportions to the first reactor; b. Adding a metallocene catalyst to the first reactor; c. Polymerizing the first set; d. introducing the c. outlet to the second reactor; e. introducing a second set of monomers at predetermined proportions into the second reactor with an optional co-solvent; f. polymerizing the second set of monomers in the first reactor; a second reactor to a second polymer without adding a significant amount of catalyst. Thus, preferably more than 50% by weight of the total amount of catalyst charged to all reactors is added to the first reactor, but preferably more than 75% by weight, and most preferably 100% of the total amount of catalyst added to all reactors is added to the first reactor. The first and second sets of monomers are selected from the group consisting of ethylene, higher alpha-olefins and unconjugated dienes. The preferred higher alpha-olefin is polypropylene and the preferred 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), with ENB being most preferred.

The unconjugated diene may be added to the first set of monomers and / or the second set of monomers in an amount such that the diene content of the polymer blend is preferably from 0 to 15%, more preferably from 2 to 12% and most preferably from 3 to 10%.

The relative proportions of the monomers can be controlled to obtain different blends of polymers with components containing different ethylene contents. For example, the monomer fractions in the first reactor and the second reactor can be controlled so that the ethylene contents of the first and second polymer differ by 39%.

4 444

45 · 4 «

4 4 4

4 4 «

4 4 4

44% by weight. In addition, the monomer fractions in the first and second reactors can be controlled such that the first polymer contains 0-85 wt% ethylene, the second polymer has 0-85 wt% ethylene, and the polymer blend has 6-85 wt% ethylene. Preferably, the mixture of semicrystalline and amorphous polymer is obtained by adjusting the relative quantitative ratio of monomers in the first and second reactors such that the ethylene content of the first and second polymers is different such that either a. The first polymer is semi-crystalline and the second polymer is amorphous; the polymer is amorphous and the second polymer is semi-crystalline.

Preferably, the molecular weight of the components of the mixture is determined to produce a polymer product with a wider MWD than the MWD of the individual components. Specifically, the molecular weight of the first and second polymers or both polymers can be controlled by at least one of the following methods: a. Adding a chain transfer agent to the first or second or both reactors; b. Adiabatic operation of the first and second reactors with temperature differences between the reactors. If enhanced MWD is desired, it is preferred that the molecular weight of the first or second polymer or both polymers be controlled so that the first and second polymers have an Mw / Mn ratio of 1.7 to 2.5, while the polymer blend has a Mw / Mn 2 , 5-20. Most preferably, the molecular weight of the first and second polymers, or both, is controlled so that the first and second polymers have an Mw / Mn of 1.7 to 2.5, and the polymer blend has a Mw / Mn of 3.0 to 10.0. When a narrow MWD product is required for a particular application, the molecular weight of the first and second polymer is controlled so that the polymer blend has an Mw / Mn ratio below 2.5.

When the molecular weight distribution is widened, it is necessary that one component of the mixture has a higher molecular weight than the other component of the mixture. Therefore, it is regulated · · • • • • • • · · · · regul · · · · · · * regul regul regul regul regul regul regul regul regul regul regul regul The molecular weight of the first and second polymers, or both, so that: a. Either the first polymer has a higher molecular weight than the second polymer, b. Or the first polymer has a lower molecular weight than the second polymer. The Mw of each component may 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 mixed polymers from sequential reactors can be further dynamically cured by vulcanizing thermoplastics.

It is also possible to simultaneously control the ethylene content and the molecular weight. When controlling the molecular weight to obtain a mixture in which one component has a higher molecular weight than another, it is preferable to control the ethylene content of each component. Then, the ratio of the monomer fractions 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 than the second polymer, or b. then the first polymer has a lower ethylene content compared to the second polymer. In addition, the quantitative ratios of the monomers in the first reactor and the second reactor can be controlled such that: a. If the first polymer has a higher molecular weight, then the first polymer has a lower ethylene content than the second polymer; or b. lower molecular weight, then the first polymer has a higher ethylene content than the second polymer.

As will be apparent from the foregoing descriptions, in the practice of the present invention, polymer blends can be obtained with various combinations of the distribution width of the ingredients, the molecular weight distribution width, or both. If the molecular weight of the polymer blend component is controlled to maintain a final product Mw / Mn ratio of 2.5 or less, it is preferable to control the quantitative ratio of monomers in the first one. and a second reactor such that the ethylene content of the first and second reactors varies by 3 to 7.5% by weight, more preferably 5-60% by weight, and most preferably by 7 to 50% by weight.

The monomer ratio can also be controlled to give a mixture in which one component is semi-crystalline while the other is amorphous. In this way, the ratio of monomers in the first reactor and the second reactor can be controlled so that one of the two polymers contains 0 to 20% ethylene, is semi-crystalline due to the presence of isotactic propylene sequences and has a melting point of 40 to 160 ° C was amorphous. In addition, the weight ratios in the first and second reactors can be controlled such that one of the two polymers contains 60-85% ethylene, is semi-crystalline due to the presence of isotactic propylene sequences, and has a melting point of 40-120 ° C while the other polymer is amorphous. Mixtures of two semi-crystalline polymers, one with 0-20% ethylene and the other with 60-85% ethylene are also within the scope of the present invention. The degree of crystallinity and the difference in the composition of the components can also be chosen so that the components of the mixture do not mix and the final product consists of a two-phase mixture. It is particularly desirable that one of the components of the biphasic mixture exhibit crystallinity as a result of the presence of isotactic propylene sequences. Such biphasic mixtures cannot be prepared using previously patented vanadium catalyst systems.

With regard to the catalyst, it is advantageous for economical reasons that virtually all of the catalyst is added to the first reactor. The catalyst components can be fed to the reactor either separately or premixed. The catalyst described below is based on Group 4, 5 and 6 metallocene and is activated with methylalumoxane MA.0 or a non-coordinating anion of NCA and may optionally contain a scavenger. Preferably, the catalyst is chiral and stereorigid. Preferably, the catalyst is capable of producing stereoregular polypropylene.

With respect to temperatures, it is preferred that the first reactor operates at temperatures between about 0 and 110 ° C and the second reactor between about 40 and 160 C. More preferably, the first reactor operates at temperatures between about 10 and 90 ° C and the second reactor between about 50 and 140 ° C. Most preferably, the first reactor operates at temperatures between about 20 and 70 ° C and the second reactor between about 60 and 120 ° C. It is also preferred that the reactors are cooled at least in part by pre-cooling the batch and when there is a temperature difference between the reactors.

To protect the catalyst from deactivation, a scavenger may be added to at least one of the batches to the reactors prior to polymerization. It is preferred that the trap is a trialkylaluminum.

With respect to the reactors, it is preferred that the first and second reactors are sequentially stirred flow reactors. In addition, it is preferred that the polymerization in the first and second reactors be a homogeneous solution polymerization.

The process of the invention can be carried out in any of the known multistage reactor systems. Two suitable systems are disclosed in U.S. Patent Nos. 4,016,342 and 4,306,041, incorporated herein by reference. In addition, suitable multistage reactor systems disclose copending patent applications 98B009 of March 4, 1998 and 98B011 of March 4, 1998, and are incorporated herein by reference in accordance with US patent law. If desired, more than two reactors may be used in the process of the present invention. The process of the present invention can be used in solution or suspension polymerization, but solution polymerization is preferred and is used herein in this invention.

• The attached examples.

The choice of temperature used in the reactors depends on the effect of temperature on the catalyst deactivation rate and on the polymer properties, especially the molecular weight of the polymer. The temperatures should not exceed the point at which the concentration of catalyst in the second reactor is not sufficient to form the desired polymer component in the required amount. This temperature is a function of the detailed characteristics of the catalyst system. In general, the temperature in the first reactor may be between 0 and 110 ° C, with a temperature of 10 to 90 ° C being preferred and most preferably 20 to 70 ° C. The temperatures in the second reactor range from 40 to 160 ° C, with temperatures between 50 and 140 ° C being more preferred and between 60 and 120 ° C being most preferred. The reactor may be cooled by a cooling jacket, cooling coils, spontaneous cooling, pre-cooled batch, and combinations of these methods. Pre-cooled adiabatic reactors are preferred. This creates a temperature difference between the reactors, which assists in controlling the molecular weight of the polymer.

In all reactor stages, the residence time is the same or different and is determined by the reactor volumes and flow rates.

The residence time is defined as the average residence time of the reactants in the reactor space. The total residence time, i.e. the total time spent in all 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 reactor of the assembly. In two-row rows, unreacted monomers from the first reactor flow into the second reactor and therefore the monomers added to the second reactor serve to adjust the composition of the reactants to the desired level, taking into account the monomer transfer from the first reactor. Depending on the reaction conditions in the first reactor (catalyst concentration, temperature, monomer feed rate and so on), it may be that the amount of monomer in the reactor outlet is in proportion to the amount required to achieve the desired composition in the second reactor. Since it is not economically feasible to remove the monomer from the reaction mixture, this situation should be avoided by adjusting the reaction conditions. The amount of polymer produced in each reactor depends on numerous reactor operating conditions such as residence time, temperature, catalyst concentration and monomer concentration, but most depends on monomer concentration. Therefore, the amount and composition of the polymer formed in the second reactor is largely independent.

The molecular weight of the polymer is controlled by reactor temperature, monomer concentration and addition of a chain transfer agent such as hydrogen. In the case of metallocene catalysts, the molecular weight of the polymers generally decreases as the reaction temperature rises and the ethylene content of the polymer decreases. When working in a two-reactor assembly with adiabatic reactors, the temperature in the second reactor is higher than in the first, thereby facilitating the formation of a lower molecular weight component in the second reactor. The molecular weight in the second reactor can be further reduced and the MWD expanded by adding hydrogen to the second reactor. Hydrogen can also be added to the first reactor, but since unreacted hydrogen is transferred to the second reactor, the molecular weight of the two polymer components in this case will decrease and the effect of hydrogen on the MWD will be much less. A high monomer concentration generally increases the molecular weight of the polymer.

The composition of the polymer may affect the molecular weight of the polymer under otherwise identical conditions due to chain transfer processes including alpha-olefin comonomers. It is often observed that the molecular weight decreases as the alpha-olefin content in the polymer increases. In connection with molecular weight control

** alpha-olefin comonomer can be considered as a chain transfer agent and can be used to influence the molecular weight of one of the components of the composition.

In the case of two reactors in series, the diene may be added to one or the other or both. In the preparation of the copolymer / terpolymer mixture, the diene is added only to the second reactor.

The polymer product, upon completion of polymerization, is recovered from solution by any of the techniques well known in the art such as steam stripping, extrusion drying, and volatile withdrawal extrusion.

While propylene is the most preferred alpha-olefin for use in the present invention, other higher alpha-olefins may be used as shown below. Higher alpha-olefins suitable for this application may be branched or straight chain, cyclic, aromatic substituted or unsubstituted, and C3-C18 alpha olefins are most preferred. By way of illustration, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-dodecene may be exemplified to illustrate suitable higher alpha-olefins. Mixed alpha-olefins may also be used as a mixture of alpha and (non) alpha-olefins (eg, butene mixtures), provided that any non-polymerizable olefins in the mixture act inert to the catalysts. Examples of such substituted higher alpha-olefins include compounds of the formula H ₂ C = CH-C _n H ₂ -n, wherein n is an integer indicating from 1 to 30 carbon atoms (preferably up to 10 atoms) and X preferably represents CH 3, but may also be aryl, alkaryl or cycloalkyl substituents. Also useful are higher alpha-olefins substituted by one or more such X-substituents, wherein the substituent or substituents are bonded to a non-terminal carbon and which is preferably 2 to 30 ° C from the terminal carbon atom, provided that such substituted 4 »·

W · · · * * t t t t t

B, the carbon atom is preferably not in the 1 or 2 position of the olefin. If the alpha- olefins substituted, it is preferred that they are not substituted by aromatic cycles or other bulky groups at the C2 position, since the aromatic or bulky groups interfere with the subsequent desired polymerization.

Although the most preferred unconjugated diene useful in the present invention is ENB, other unconjugated dienes may be used, as will be apparent from the following. Unconjugated pulps useful as comonomers are preferably straight chain hydrocarbons, diolefins or alkenyl substituted cycloalkenyls of 6 to about 15 carbon atoms such as: 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-1,6-octadiene and 3,7-dimethyl-1,7-octadiene; c. single cycle alicyclic dienes such as 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,7-cyclododecadiene; d. fused and bridged ring-fused polycyclic alicyclic dienes such as tetrahydroindene; norbornadien; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo (2,2,1) -hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidennorbornenes such as 5-methylene-2-norbornene (MNB); 5-Propenyl-2-norbornene; 5-Isopropylidene-2-norbornene; 5- (4-cyclopentenyl) -2-norbornene; 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene (VNB); e. cycloalkenylalkenes such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene and vinylcyclododecene. Among the unconjugated dienes that are typically used, preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and tetracycllo (Δ-11,12) 5,8-dodecene. Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1,417, 917, and 9,9. Hexadiene, dicyclopentadiene (DCPD), norbornadiene and 5-vinyl-2-norbornene (VNB). It is worth noting that in this application the terms unconjugated diene and diene are used interchangeably.

While hexane is the most suitable solvent for use in the patent, other useful solvents are hydrocarbons, such as aliphatic, cycloaliphatic and aromatic hydrocarbons, provided that the solvent is inert to the catalyst. Preferred solvents are C12 or lower branched or unbranched saturated hydrocarbons and saturated alicyclic or C5-C9 aromatic hydrocarbons. Examples of such solvents or reaction media are hexane, butane, pentane, heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene and xylene. In addition, one or more olefins, either alone or mixed with other media, can serve at selected concentrations of such olefins as media for the reaction.

The term metallocene or metallocene catalyst precursor used in this application refers to compounds containing a transition group metal M with cyclopentadienyl ligands (Cp), at least one X ligand not derived from cyclopentadienyl and a Y ligand containing no or one heteroatom, wherein the ligands are in coordination bond to M and its number correspond to its valency. The metallocene catalyst precursors are generally? neutral complexes which, upon activation with suitable co-catalysts, provide an active metallocene catalyst which is an organometallic complex with an unoccupied coordination site that can coordinate, bind or polymerize olefins. The metallocene catalyst precursors are preferably a metallocene compound or a mixture of metallocene compounds of one or both of the following types.

Cyclopentadienyl (Cp) complexes with two Cp cyclic systems as ligands. The Cp ligands form sandwich complexes with the metals and may be free and capable of rotation, or are closed by a bridging group in a rigid configuration. The Cp cyclic ligands may be the same or different, substituted or unsubstituted, or may be derived as a heterocyclic ring system which may be substituted and the substituents may be condensed to form other saturated or unsaturated cyclic systems such as tetrahydroindenyl, indenyl or fluorenyl cyclic systems. These cyclopentadienyl complexes have the general formula (Cp 2 J ¹ R ¹ C ¹ P ¹ M X g wherein the Cp ¹ ligand (CP ¹ R ¹ ) and Cp ² ligand (Cp ² R ² p) are the same or different cyclopentadienyl cycles, R ¹ and R ² are independently halogen, hydrocarbyl, halocarbyl, hydrocarbyl substituted organometaloid or halocarbyl substituted organometaloid group containing up to about 20 carbon atoms, m is 0 to 5, p is 0 to 5, and two R ¹ and / or R ² substituents on adjacent carbons of the cyclopentadienyl ring attached herein may be joined together to form a cycle containing from 4 to about 20 carbon atoms, R ³ is a bridging group, n is the number of atoms in a straight chain between two ligands and is 0 to 8, preferably 0 to 3, M is a transition metal of valency 3 to 6 , preferably from groups 4, 5 or 6 of the Periodic Table of the Elements and should be in its highest oxidation state, each X being a non-cyclopentadienyl ligand and is independently halogen or hydrocarbyl; xyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometaloid, oxyhydrocarbyl-substituted organometaloid or halocarbyl-substituted organometaloid group containing up to about 20 carbon atoms, q corresponds to a valency of M / wws 2.

• • • •

* ·

Monocyclopentadienyl complexes with only one Cp cyclic system as ligand. The Cp ligand forms a half-sand complex and may be free (not bridged) and capable of rotation, or is closed in a rigid configuration by bridging the bridging group to the heteroatom ligand. The Cp cyclic ligand may be substituted or unsubstituted or derived (derived) as a heterocyclic ring system which may be substituted and the substituents may be condensed to form other saturated or unsaturated cyclic systems such as tetrahydroindenyl, indenyl or fluorenyl ring systems. The heterbatom-containing ligand is bound to the metal and optionally to the Cp ligand bridging group. The heteroatom itself is an atom with a coordination number three of the VA or VIA group of the Periodic Table of the Elements. The monocyclopentadienyl complexes have the general formula (Cp) R ³ n (Y _r R ²⁾ MX _s wherein R ¹ is independently halo, hydrocarbyl, halocarbyl, hydrocarbyl substituted organometaloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, m is 0 to 5 and the two R ¹ substituents on the adjacent carbon of the cyclopentadienyl ring attached herein may be linked together to form a cycle containing from 4 to about 20 carbon atoms, R ³ is a bridging group, n is 0 to 3, preferably 0 to 3, M is transient a valence metal of 3 to 6, preferably from groups 4, 5 or 6 of the Periodic Table of the Elements and is to be in its highest oxidation state, Y is a heteroatom-containing group in which the heteroatom is an element with coordination number three of VA or with coordination number two of group VIA preferably nitrogen, phosphorus, oxygen or sulfur, R ² is a radical selected from the group consisting of C ¹ to C ²⁰ hydrocarbon radicals substituted by C 1 to C 20 hydrocarbon radicals, wherein one or more of the hydrogen atoms is replaced by a halogen atom, and when Y has a coordination number of 3 and is bridged, on Y there may be independently two R ² radicals selected from the group consisting of hydrocarbon radicals Ci to C 20, wherein one or more 4

4 4 4 4 4 4 4 4 4

4 4 4

The hydrogen atoms are replaced by a halogen atom and each X is a non-cyclopentadienyl ligand and is independently halogen or hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl substituted organometaloid, oxyhydrocarbyl substituted organometaloid or halocarbyl substituted organometaloid moiety containing up to about 20 carbon atoms. / nus 2 <

Examples of suitable biscyclopentadienyl metallocenes for the present invention are described in US Patents 5,324,800,

5,198.401, 5,278.119, 5,387,568, 5,120. 867, 5,017.714, 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, that are here

incorporated by reference.

Illustrative examples of biscyclopentadienyl metallocenes suitable for the present invention, of the type described in paragraph 1 above, but which are not exhaustive, are the racemic isomers of the compounds:

μ- (CH ₃ ) ₂ Si (indenyl) ₂ M (Cl) ₂ μ- (CH ₃ ) ₂ Si (indenyl) ₂ M (CH ₃ ) ₂ μ- (CH ₃ ) ₂ Si (tetrahydroindenyl) ₂ M (Cl ) ₂ μ- (CH ₃ ) ₂ Si (tetrahydroindenyl) ₂ M (CH ₃ ) ₂ μ- (CH ₃ ) ₂ Si (indenyl) ₂ M (CH ₂ CH ₃ ) ₂ μ- (C ₆ H ₅ ) ₂ C (indenyl) ₂ M (CH ₃ ) ₂ , wherein M is selected from the group consisting of Zr and Hf.

Examples of the present invention of suitable unsymmetrical cyclopentadienyl metallocenes of the type described in paragraph 1 above are described in U.S. Patents 4,892,851, 5,334,677, 5,416,228 and 5,449,651 and are also described in J. Am.

1988, vol. 110, p. 6255, which are incorporated herein by reference.

Illustrative examples of unsymmetrical cyclopentadienyl metallocenes suitable for this invention of the type described in paragraph 1 above, but are not exhaustive, are: μ- (C ₆ H ₅ ) ₂ C (cyclopentadienyl) (fluorenyl) M (R) ₂ μ- (C ₆ H ₅ ) ₂ C (3-methylcyclopentadienyl) (fluorenyl) M (R) ₂ μ- (CH ₃ ) ₂ C (cyclopentadienyl) (fluorenyl) M (R) ₂

μ- (C ₆ H ₅ ) ₂ C (cyclopentadienyl) (2-methylindenyl) M (CH ₃ ) 2 μ- (C ₆ H ₅ ) ₂ C (3-methylcyclopentadienyl) (2-methylindenyl) M (Cl) ₂ μ - (C ₆ H ₅ ) ₂ C (cyclopentadienyl) (2,7-dimethylfluorenyl) M (R) ₂ μ- (CH ₃ ) ₂ C (cyclopentadienyl) (2,7-dimethylfluorenyl) M (R) ₂ , where M is selected from the group consisting of Zr and Hf, and R is selected from the group consisting of Cl and CH _third

Examples of the present invention of suitable monocyclopentadienyl metallocenes of the type described in paragraph 2 above are described in U.S. Patents 5,026,798, 5,057,475, 5,350.723, 5,264.405 and 5,055,438, and are also. described in WO 96/002244, which are incorporated herein by reference.

Illustrative examples of preferred monocyclopentadienyl metallocenes suitable for this invention of the type described in paragraph 2 above, but are not exhaustive, are: μ- (CH ₃ ) ₂ Si (cyclopentadienyl) (1-adamantylamido) M (R) 2 μ- (CH ₃₎ ) ₂ Si (3-tert-butylcyclopentadienyl) (1-adamantylamido) M (R) ₂ μ- (CH ₂ (tetramethylcyclopentadienyl) (1-adamantylamido) M (R) ₂ μ- (CH ₃ ) ₂ Si (tetramethylcyclopentadienyl) ( 1-adamantylamido) M (R) 2 µ- (CH ₃ ) 2 C (tetramethylcyclopentadienyl) (1-adamantylamido) M (R) ₂ µ- (CH ₃ ) ₂ Si (tetramethylcyclopentadienyl) (1-tert-butylamido) M (R) ) 2 μ- (CH ₃ ) ₂ Si (fluorenyl) (1-tert-butylamido) M (R) ₂ μ- (CH ₃ ) 2 Si (tetramethylcyclopentadienyl) (1-cyclododecylamido) M (R) ₂ μ- (C ₆ H _{5 12} C (tetramethylcyclopentadienyl) (1cyclododecylamido) M (R) ₂ , wherein M is selected from the group consisting of Ti, Zr and Hf and wherein R is selected from Cl and CH ₃ .

Another class of organometallic complexes useful as catalysts for the methods described herein are diimide-based ligands such as those of Du Pont described in WO 96/23010. These compounds for catalytic polymerization are incorporated herein by reference.

The term non-coordinating anion (NCA) refers to an anion that either does not have a coordination bond to said transition metal cation or is only weakly coordinated to it and therefore remains labile enough to be removed by a neutral Lewis base. Compatible non-coordinating anions are anions that do not degrade to a neutral compound due to decomposition of the primary complex formed. In addition, the anion does not transfer an anionic substituent or fragment to a cation to form a neutral metallocene compound with four coordination bonds and a neutral by-product from the anion. The non-coordinating anions useful in the present invention are those that are compatible, stabilizing the metallocene cation by stabilizing its +1 charge while maintaining the necessary lability to allow ethylene (double bond) or acetylenic (triple bond) removal during polymerization ) unsaturated monomer. In addition, the anions useful in the present invention are large or bulky in terms of sufficient molecule size to significantly inhibit or prevent cation neutralization by Lewis bases other than by the polymerizable monomers that may be present in the polymerization process. Typically, the anion has a molecule size greater than about 4 Angstroms or greater.

Descriptions of ion coordination polymerization catalysts containing non-coordinating anion activated metallocene cations are found in earlier applications in EP-A-0,277.003, EP-A-0,277.004, US Patents 5,198,401, 5,278.119 and WO 92/00333. They disclose a preferred preparation process in which the metallocenes (bisCp and monoCp) are protonated by anionic precursors by cleaving the alkyl or hydride group from the transition metal and thereby both making it cation and neutralizing it (by equalizing its charge) by the non-coordinating anion. The use of an ionizing ionic compound which does not carry an active proton but is capable of producing both an active metallocene cation and a non-coordinating anion is also known, see EP-A-0,426,637, EP-A-0,573.403 and US Patent 5,387.568. Reactive cations other than Bronsted acids capable of ionizing metallocene compounds are ferrocenium triphenyl carbonium and triethylsilylinium. In the anion of the second activator compound is

it may use any metal or metalloid capable of forming a coordination complex resistant to or degraded by the degradation effect of water (or other Bronsted or Lewis acids). Suitable metals are aluminum, gold, platinum and the like without exhaustion. Suitable metalloids include boron, phosphorus, silicon and the like without being exhausted. Descriptions of non-coordinating anions and their precursors in said patents are incorporated herein by reference in US patent law.

Another method for preparing ionic catalysts uses ionizing anionic precursors that are originally neutral Lewis acids, but upon ionization reaction with metallocene compounds form a cation and anion, for example, tris (pentafluorophenyl) boron acts to tear off an alkyl, hydride or silyl ligand to form a metallocene cation and a stabilizing non-coordinating anion, see EP-AO, 427,697 and EP-A-0,520,732. Ion addition catalyst polymerization catalysts can also be prepared by oxidizing metal centers in transition metal compounds by the action of anionic precursors containing metal oxidizing groups together with anionic groups, see EP-A-0,495,375. Descriptions of the coordinating anions and their precursors in these publications are hereby incorporated by reference herein in their entirety.

Examples of suitable activators capable of ionic cationization of the metallocene compounds of the invention and subsequent stabilization with subsequent formation of a non-coordinating anion include: ammonium salts substituted with three alkyls such as;

triethylammoniumtetrafenylborate tripropylammoniumtetrafenylborate tri (n-butyl) ammoniumtetrafenylborate trimethylammoniumtetrakis (p-tolyl) borate trimethylammoniumtetrakis (o-tolyl) borate tributylammoniumtetrakis (pentafluorophenyl) borate tripropylammonium borate ptracislammonium borate p-triphopylamonate Tributylammonium tetrakis (p-trifluoromethylphenyl) borate tributylammonium tetrakis (pentafluorophenyl) borate tri (n-butyl) ammonium tetrakis (p-tolyl) borate a *> Targets S oel j

N, N-dialkylanilinium salts such as;

N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate N, N-dimethylaniliniumtetrakis (heptafluoraphthyl) borate N, N-dimethylaniliniumtetrakis (perfluoro-4-biphenyl) borate N, N-dimethylaniliniumtetrafenylborate

N, N-diethylanilinium tetrafenylborate

N, N-2,4,6-pentamethylaniliniumtetrafenylborate and the like;

dialkylammonium salts such as;

di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate dicyclohexylammonium tetrafenylborate and the like;

and triarylphosphonium salts such as;

triphenylphosphonium tetrafenylborate tri (methylphenyl) phosphonium tetrafenylborate tri (dimethylphenyl) phosphonium tetrafenylborate and the like.

Other examples of suitable anionic precursors include carbonium ion precursors and a compatible non-coordinating anion. These include;

tropiliumtetrakis (pentafluorophenyl) borate triphenylmethiliumtetrakis (pentafluorophenyl) borate benzene (diazonium) tetrakis (pentafluorophenyl) borate tropiliumphenyltris (pentafluorophenyl) borate triphenylmethyliumphenyl (trispentafluorophenyl) borate pentene benzene (diazonium) -tetrafluorophenyl) borate triphenylmethylium tetrakis (2,3,5, β-tetrafluorophenyl) borate benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate tropilium tetrakis (3,4,5-trifluorophenyl) borate • 9 ·

9 · · *. * · ·. · · ·

9 9 benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate tropilium tetrakis (3,4,5-trifluorophenyl) triphenylmethyliumtetrakis (3,4,5-trifluorophenyl) aluminate benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) aluminate trifluorophenyl) tropilium tetrakis (1,2,2-trifluorethenyl) borate triphenylmethyliumtetrakis (1,2,2-trifluorethenyl) borate benzene (diazonium) tetrakis (1,2,2-trifluorethenyl) tropilium tetrakis (2,3,4,5) -tetrafluorophenyl) borate triphenylmethyliumtetrakis (2,3,4,5-tetrafluorophenyl) borate benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate and the like;

Where metal ligands contain halide groups such as (methylphenyl) silylene (tetramethylcyclopentadienyl) (tert-butylamido) zirconium dichloride, which under standard conditions are not capable of ionizing cleavage, they can be converted by known alkylation reactions using organometallic compounds such as lithium or aluminum hydrides or alkylAl or alkyl Li, alkylalumoxanes, Grignard reagents and the like. See EP-A-0,500,944, EP-A1-0,570,982 and EP-Al-0,612,768 for methods describing the reaction of alkyl aluminum compounds with metallocene dihalides before or simultaneously with activating anionic compounds. For example, the aluminum alkyl compound may be mixed with the methalocene before being placed in the reaction vessel. However, since alkyl aluminum is also suitable as a scavenger, its use in excess of the stoichiometric amount required to alkylate the metallocene allows it to be added to the reaction medium simultaneously with the metallocene compound. Normally, the alumoxane would not be added together with the metallocene to prevent premature activation, but may be added to the reaction vessel directly in the presence of polymerizable monomers when serving as both scavenger and alkylation activator.

In addition, the known alkylalumoxanes are suitable as catalyst activators, especially for halide-containing metallocenes

44

4 4 4

4 4 ·

4 4 4

4 4 4

44 ligands. The alomoxane component useful as the catalyst activator is typically an oligomeric aluminum compound represented by the general formula (R-Al-O) _n , which is a cyclic compound, or R (R-Al-O) _n AlR ₂ , which is a linear compound. In the general formula, R is an alkyl radical C1 to C5, for example methyl, ethyl, propyl, butyl or pentyl and n is an integer from 1 to about 50. Most preferably, R is methyl and is at least 4, which represents methylalumoxane (MAO). Alumoxanes can be prepared by a variety of methods known in the art. For example, the alkylaluminum may be reacted with water dissolved in an inert organic solvent, or may be contacted with a hydrated salt such as hydrated copper sulfate suspended in an inert organic solvent to form an alumoxane. Regardless of the method of preparation, the reaction of an alkyl aluminum with a limited amount of water provides a mixture of linear and cyclic alumoxane variants.

Although the most popular scavenger used in the present invention is trialkylaluminum, other scavengers may be used as described below. The term scavanging compounds as used herein and in the claims means compounds effective in removing polar impurities from the solvent used in the reaction. These impurities may inadvertently be introduced with any component of the polymerization reaction, particularly with the solvent, monomer and comonomer, and negatively affect the activity and stability of the catalyst. This may result in a decrease in activity or even inactivation, especially when the catalyst system is a metallocene-based pair of non-coordinating anion. Polar impurities or catalyst poisons are water, oxygen, oxygenated hydrocarbons, metallic impurities, and so on. It is preferred to take appropriate precautions before introducing them into the reaction vessel, for example by chemical treatment or by careful separation procedures, but nevertheless it is normally required to introduce at least a small amount of scavenger into the polymerization process. Typically, the scavenger is an organometallic compound such as an organometallic compound of Group 13 of 5,153,157, 5,241,025, EP-A-638 and WO-A. · · · · · · · · · · · · · · · · · · · · · · ·

91/09882 and WO-A-94/03506, mentioned above, and WO-A-93/14132. By way of example, compounds such as triethylaluminum, triethylborane, triisobutylaluminum, isobutylaluminum oxane having bulky substituents covalently bonded to a metal or metalloid center can be mentioned and have the advantage of minimizing unwanted interactions with the active catalyst. When alumoxane is used as an activator, no additional trap is needed. The amount of scavenger usable with the metallocene-non-coordinating anion cation pair in the polymerization reaction is minimized to the amount required to enhance activity.

The metallocene-based catalyst and activator can be introduced into the reactor either separately or in a premix (premixed).

Catalyst systems particularly suitable for the polymerization of ethylene and propylene allow a combination of high activity, good alpha-olefin and diene incorporation into the chain, and a sufficiently high molecular weight polymer for elastomeric applications at economically interesting reaction temperatures. Catalyst systems particularly suitable for achieving these goals include catalysts selected from the group consisting of μ (CH ₃ ) ₂ Si (indenyl) ₂ Hf (CH ₃ ) ₂ ;

μ- (CH ₃ ) ₂ Si [tetramethylcyclopentadienyl] [adamantylamido] Ti (CH ₃ ) ₂ , or μ- (C ₆ H ₅ ) ₂ Si [cyclopentadienyl] [fluorenyl] Hf (CH ₃ ) ₂ .

Although the most popular scavenger used in the present invention is trialkylaluminum, other scavengers may be used as described below. The term scavenging compounds as used in this application and in the claims means compounds effective in removing polar impurities from the mixture fed to the reactor. These impurities may inadvertently be introduced with any component of the polymerization reaction, particularly with the solvent, monomer and comonomer, and negatively affect the activity and stability of the catalyst. The result may be a decrease in activity or even deactivation, especially when the catalyst system is a pair of metallocene-based cations - a non-coordinating anion. Polar impurities or catalyst poisons are water, oxygen, oxygenated hydrocarbons, metallic impurities, and so on. It is preferred to take appropriate precautions before introducing them into the reaction vessel, for example by chemical treatment or by careful separation procedures, but nevertheless it is normally required to introduce at least a small amount of scavenger into the polymerization process. Typically, the trap is an organometallic compound such as the Group 13 organometallic compound of 5,153,157, 5,241,025, EP-A-638 and WO-A91 / 09882 and WO-A-94/03506 mentioned above, and WO-A-93/14132. By way of example, compounds such as triethylaluminum, triethylborane, triisobutylaluminum, isobutylaluminum oxane having bulky substituents covalently bonded to a metal or metalloid center may be mentioned and have the advantage of minimizing undesirable interactions with the active catalyst. When alumoxane is used as an activator, no additional trap is needed. The amount of scavenger usable with the metallocene-non-coordinating anion cation pair in the polymerization reaction is minimized to the amount required to enhance activity.

The rubber proportions of the mixture from sequential reactors are generally present as small, i.e. microscopic particles, within the continuous matrix of thermoplastic resin, although co-continuous morphology or phase inversion is also possible depending on the quantity ratio of rubber to plastic. It is desirable that the rubber be at least partially crosslinked and preferably completely crosslinked. It is preferred that the rubber be crosslinked by a dynamic vulcanization process. The term dynamic vulcanization as used in this application and claims means vulcanizing or curing the rubber in admixture with a thermoplastic resin in which the rubber is vulcanized under shear conditions and at a temperature at which the mixture is liquid. The rubber is thus both crosslinked and dispersed in fine particles inside the thermoplastic resin matrix, although, as mentioned above, other morphological structures may exist. Dynamic vulcanization occurs by mixing the components of the thermoplastic elastomer at elevated temperatures in conventional mixers such as roller mills, a Banbury and Brabender mixer, continuous mixers, mixer screw extruders and the like. Unique • ·

The advantage of the dynamically cured compositions is that, regardless of the rubber component being partially or fully vulcanized, the composition can be processed or reworked by conventional processing methods for plastics such as extrusion, injection molding and injection molding. pressing. Solid waste and evaporated volatile constituents can be collected and recycled.

The terms fully vulcanized, fully cured and fully crosslinked used in the application and claims mean that the vulcanizable rubber component has cured or crosslinked to a state in which the elastomeric properties of the reticulated rubber are similar to the elastomeric properties of the rubber in its normal vulcanized state separately from the thermoplastic elastomer composition. The degree of cure can be described in terms of gel contents or extractables. The rubber component may be described as fully vulcanized when less than about 5% and preferably less than 3% of the rubber capable of being vulcanized by hydrosilylation is extracted from the product thermoplastic elastomer by a solvent suitable for the rubber. Alternatively, the degree of vulcanization is expressed in terms of crosslinking density. All of these descriptions are known in the art, for example, in U.S. Patents 5,100,947 and 5,157,081, both of which are incorporated herein by reference.

The compositions can be processed and reprocessed by conventional plastics processing techniques such as extrusion, injection molding and compression molding. Those of ordinary skill in the art will be able to cope with the appropriate amount ratios, types of vulcanization systems, and vulcanization conditions required to effect rubber vulcanization. The rubber may be vulcanized using different amounts of vulcanizing agent, different temperatures and different vulcanization times for optimal crosslinking. Any known rubber vulcanization system may be used as long as it is suitable under the vulcanization conditions for a specific olefinic rubber or a combination of rubbers used together with the polyolefin. Said vulcanizing agents include sulfur, sulfur donors, metal oxides, resin systems, peroxide-based systems, platinum or peroxide hydrosilation, and the like;

9

9 9 9

9 9 9

99 both with or without accelerators and auxiliary agents.

DETAILED DESCRIPTION OF THE INVENTION

The polymerization was carried out in two stirred 1-liter stirred-tank reactors with continuous feed of raw materials into the system and continuous collection of products. The first reactor could also be operated separately. Solvents (hexane) and monomers (ethylene, propylene and ENB) were purified through alumina bed and molecular sieves. The toluene for catalyst preparation was also purified by the same technique. All feed materials were pumped into the reactors by a metering pump except ethylene, which in the gaseous state flowed under its own pressure to the flow regulator.

The reactor temperature was controlled by circulating water in the cooling jacket. The reactor pressure was maintained above the saturated vapor pressure above the reactant mixture, thereby keeping the reactants in the liquid phase. The reactors were fully charged with liquid reactants.

The ethylene and propylene feed were combined into a single stream and then mixed with a stream of precooled hexane which had been cooled to 0 ° C. If ENB was used, it was also connected to the hexane stream before the monomers. The triisobutyl aluminum trap hexane solution was also added to the combined solvent / monomer stream prior to entering the reactor to further reduce the concentration of any catalyst poison. Molar ratio

TIBA / metallocene was typically 10-60. The mixture of catalyst components in toluene was separately pumped into the reactor and fed through the second inlet. The polymer solution leaving the first reactor was entering the second reactor. The monomer solution in hexane was fed into a second reactor through a separate orifice. The product from the second reactor was discharged through a pressure reducing valve which reduced the pressure to atmospheric. As a result, the excess monomers in the solution passed into the vapor phase, which was vented from the top of the liquid-vapor separator. The liquid phase drained from the bottom of the separator and collected to recover the polymer. The polymer was recovered from the solution by either stripping the solution or stripping it. By steam or by drying or evaporation of the solvent under heat and vacuum.

Polymers from the first and second reactors were characterized by Mooney viscosity (Mooney viscometer, ASTM D1648), ethylene content (FTIR, ASTM D3900), ENB content (FTIR, ASTM D6047), melting point and / or glass transition temperature (DSC) described herein. ) and molecular weight (GPC gel permeation chromatography, described herein). The polymer analysis of the second reactor shows the properties of the whole polymer mixture.

The Cellular Permeation Chromatography (GPC) methods used to determine the properties of the products of the invention have been described in several publications, particularly in U.S. Patent 4,989,436, which is incorporated herein by reference in accordance with US Patent Law. Molecular weight and composition measurements are described in G. Ver Strate, C. Cozewith, S. Ju, Macromolecules, Vol. 21, p. 3360 (1988), which is incorporated herein by reference in accordance with US patent law. Differential scanning calorimetry (DSC) was also used to characterize the products of the invention in a conventional manner by loading a sample without deformation into a calorimeter at 20 ° C, heat treatment at room temperature for 40 hours, cooling the sample to -75, scanning to 180 ° C. at 10 ° C / min

-75 ° C and repeat scan. T _g , T _m and latent heat of fusion were determined. In some cases, the second scan does not detect crystallinity in low melting polymer products, as it can develop for many hours even at low temperatures.

Atomic force microscopy (AFM) was used to determine the number of polymer phases present in the final product after recovery from solution in the reactor. AFM analysis is performed with the Digital Instruments Dimension 3000 operating under environmental conditions. The instrument worked in tapping mode and mapped the height, amplitude and phase shift. The height analysis gives the overall topography of the sample. The amplitude analysis provides a representation of the differential height and is sensitive to changes in height, but not to its absolute height. The phase shift display maps the surface z

4 »

4 • 4 • 4

4 · 4 · 4 V 4 V 4

4 4 · 4 4 4 • 4 4 4 • 4 44 in terms of modulus of elasticity and chemical nature. Silicon arms (225 μπι long and 30 μιη wide) with force constants between 0.4 and 5 N / m were used in these assays. When tapping in air, the arm oscillated with a frequency slightly below its resonant frequency and an RMS amplitude of between 3.5 and 4.0 Volts (measured by a position-sensitive detector). When analyzing the sample, the amplitude of the RMS was set to approximately 30% of the amplitude of the RMS arm oscillating in the air. Prior to analysis, elastomeric samples at -150 ° C were cryogenically treated using an ultramicrotome. The samples were allowed to warm to room temperature in a nitrogen-filled dissector and then analyzed at room temperature.

Samples of the polymer solution from the first and second reactors were analyzed for polymer concentration. From these measurements and from the reactor flow rates, it was possible to determine the polymerization rate in both reactors by means of material balances. Then, the degree of monomer conversion was calculated from the polymerization rate and polymer composition data for the first reactor alone and for both reactors together. The following balance equations were used to calculate the polymerization rate and polymer composition in the second reactor itself:

PR2 = PRt-PR1

F1 = PR1 / PRt

E2 = (Et- (FlxEl)) / (1-F1)

D2 = {Dt- (FlxD1)} / (1-F1)

MN2 = (1-F1) / (MNt-F1 / MN1)

MW2 = (Mwt-F1 * MW1) / (1-F1) where:

Equation 1 Equation 2 Equation3 Equation 4 Equation 5 Equation 6

PR1 = polymerization rate in the 1st reactor

PR2 = polymerization rate in the 2nd reactor

PRt = total polymerization rate

E1 = Ethylene content of the 1st reactor polymer

E2 = Ethylene content of the 2nd reactor polymer

Et = Ethylene content of the polymer from the whole reactor D1 - Diene content of the polymer from the 1st reactor

D2 = The diene content of the 2nd reactor polymer is 2 · 1 · 2 · 1 · 2 · 2 · · 2 · · · · · · · · · · · · · · · · · · · · · · · · · * * * * «

Dt = Diene content of the polymer from the entire reactor

Fl = All polymer fraction produced in reactor 1

MNI = Numeric medium molecular mass polymer of 1. reactor MN2 = Numeric medium molecular mass polymer of 2. reactor Mnt = Numeric medium molecular mass polymer of all over reactor

MW1 = Weight reactor medium molecular mass polymer of 1. MW2 = Weight reactor medium molecular mass polymer of 2. MWt = Weight medium molecular mass polymer of all over

reactor

A series of polymerizations were performed to demonstrate the process and products of the invention. All reactor conditions, polymer prepared in reactor 1 (R1) and total product are based on real measurements made on polymer from reactor 1 and polymer blend leaving reactor 2. The results for reactor 2 (R-2) alone were calculated from these data using of the above formulas.

Example 1 (121C)

Polymerization in sequential reactors was carried out with a catalyst of dimethylsilylbisindenylhafnium dichloride (Catalyst A) mixed with an activator of N, N-dimethylaniliniumtetrakis (pentafluorophenyl) boron (DMPFB). The catalyst components were dissolved in toluene in a 1: 1 molar ratio. Table 1 shows the reactor conditions and feed rate. The catalyst feed rate in this table applies to catalyst A only, and catalyst efficiency is calculated by dividing the polymerization rate by catalyst feed rate A. The first reactor was fed with a mixture of ethylene and propylene, but the second reactor was fed only with ethylene. The polymer produced in the first reactor had an ethylene content of 15.5% and the polymer in the second reactor had a content of 55% ethylene. Molecular weight of polymers

prepared in both reactors was similar so that the product mixture did not have an expanded MWD. The polymer from Reactor 1 was semi-crystalline due to propylene crystallinity, but the polymer prepared in Reactor 2 was amorphous.

Example 2 (125A)

The polymerization was carried out with Catalyst A as in Example 1 except that diene (ENB) was fed into the second reactor to make the product a terpolymer. The polymer from the first reactor was a semi-crystalline copolymer containing 17% by weight of ethylene melting above 29.6-99 ° C. The polymer from the second reactor was an amorphous terpolymer containing 50.6% by weight of ethylene and 3.29% by weight of ENB.

The reactor conditions and polymerization results are shown in Table 1.

Example 3 (127A, B, C)

Catalyst A was subjected to a number of polymerizations under similar conditions to Example 1 except that in runs A through C, increasing amounts of ethylene were fed into the second reactor. Table 1 shows the reaction conditions and the polymerization results. Due to the increasing feed of ethylene feed to the second reactor, the fraction of all polymer produced in the first reactor decreased from 36% to 20% and the ethylene content of the polymer from the second reactor increased from 47.4% to 61% by weight. Thus, by adjusting the feed rate of the feed to the second reactor, the composition and amount of the second component in the mixture can easily be varied. The same amount could not be obtained using the vanadium catalyst of the earlier patents due to the lower catalyst concentration in the second reactor.

Example 4 (131C)

The polymerization was carried out with the same catalyst and in the same manner as in Example 1 in the preparation of the terpolymer mixture. Table 1 shows the reactor conditions and polymerization results. In this polymerization, ENB monomers were fed to both reactors. The polymer formed in the first reactor

had an ethylene content of 18.8% by weight and 3.53% 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)

The polymerization was carried out with the same catalyst and in the same manner as in Example 4 in the preparation of the terpolymer mixture. However, the temperatures in the reactors are higher than in previous experiments and the second reactor has a temperature of 65 ° C compared to 40 ° C. Table 1 shows reactor conditions and polymerization results. In this example, the polymers produced in both reactors were amorphous and the polymer produced in the first reactor had 30.3% ethylene, while the polymer produced in the second reactor had 53.1% by weight ethylene. The MWD of the final product expanded due to the different molecular weights of the polymers produced in the two reactors. The Mw / Mn ratio was 2.84.

Example 6 (272A)

The polymerization was carried out with the same catalyst and in the same manner as in Example 1 except that the catalyst was dimethylsilyltetracyclopentadienylada / mantylamidotitanium dichloride (Catalyst B). As in Example 1, it was fed into the reactor at a 1: 1 molar ratio with DMPFB dissolved in toluene. The copolymerization was carried out at reactor temperatures of 30 ° C and 75 ° C. The reactor conditions and polymerization results are shown in Table 1. Hydrogen was added to the first reactor to reduce the molecular weight of the polymer. In the first reactor, an amorphous copolymer with 32.9 wt% ethylene was formed, while in the second reactor a semi-crystalline copolymer with 79.5% ethylene was formed. 64% by weight of the product was produced in the first reactor. The MWD of the final product was narrow with a Mw / Mn ratio of 1.94.

Example 7 (A, B, C, D).

Catalyst B was subjected to a number of polymerizations using the method of Example 6 to prepare mixtures of the extended MWD copolymer and terpolymer. In this example, the reactor was equilibrated under primary conditions (run A). After sampling the product, diene was added to both reactors, the terpolymer mixture was prepared, and the reactor was re-equilibrated before the second sample was taken (run B). The same process was repeated in Runs C and D. The reactor conditions and polymerization results are shown in Table 1. In Runs A and B, the high ethylene blend component was prepared in a second reactor. In runs C and D, the compositions were reversed and the high ethylene component was produced in the first reactor.

Also, in runs C and D, hydrogen was added to the first reactor as a chain transfer agent to prepare a low molecular weight product. The polymers prepared in runs A, B and C had a broad MWD as indicated by Mw / Mn values of 4.5 to 9.8.

Example 8 (319B, C)

This run was performed with Catalyst B in the manner of Example 1 to demonstrate the advantages of loading monomer into both reactors using sequential reactors. In run B, sequential reactors were used, but no monomer feedstock was fed into the second reactor. The reactor conditions and polymerization results are shown in Table 1. In the second reactor, the polymerization rate was low due to the low monomer concentration and the polymer composition was practically the same for the polymers from both reactors. In run C, the reactor conditions were the same except that monomer was now added to the second reactor. Compared to the initial B, the polymerization rate and catalyst efficiency were improved to obtain a polymer blend with one component containing -7.6% by weight of ethylene and the other containing 39.3% by weight of ethylene.

Example 9 (268B, 272A, 307C, 318A, 320C, 293A)

A series of polymerizations were performed using the method of Example for the preparation of polymer blends in which the two components were largely immiscible and the final product was a two-phase blend after recovery from solution.

The reactor conditions and polymerization results are given in

Products produced in Runs 268A and 293A are mixtures of two substantially amorphous polymers prepared with catalysts A and B. The products prepared in Runs 272A and 320C are mixtures of an amorphous component and a component having a high ethylene content and characterized by ethylene crystallinity. The polymers in Runs 307C and 318C were prepared with Catalyst A and comprise a component showing propylene crystallinity and a higher ethylene content component that does not exhibit propylene crystallinity.

All polymers were analyzed by atomic force microscopy (AFM) to determine the number of phases present. As shown by the result for polymer 318C in Figure 1, the polymer product was a biphasic mixture. All other products in this example gave similar results.

Example 10

A number of reactor mixtures were dynamically vulcanized in a Brabender mixer by stirring the mixture until the plastic phase had melted and the torsion was leveled. Now the vulcanization system was added and stirring was continued for 4 minutes. The material was stirred at 180 ° C at 100 rpm and the temperature rose to approximately 200 ° C during vulcanization. Then the products were removed from the Brabender mixer, pressed and evaluated for physical properties.

Table 4 shows the elastic properties and composition.

Table 1. Reactor operation conditions

DSC rozme- of melting ° c 41,7- 71.0 29,6- 99 33-100 29,4- 97.6 CM CM heat thaw J / g 8.3 22.6 12.9 10.97 15.5 GPC Mw / M n 1.93 1.85 and 1.92 2.28 2.54 2.38 X " i ° 286 what σ> 225 237 227.3 209.2 £ x? 148 107 117 104 89.4 87.9 monomer conversion% effective- nost Cat. g / g 17477 38805 56283 16335 19526 35861 17209 30353 47562 17609 41799 59408 13243 54612 67855 conv die- nu O O O O 28.4 28.4 O O O O O O O O O conv C3 = 27.1 AND 53.6 O) 24.9 23.4 41.9 26.4 35.8 55.6 26.6 62.5 CM b- " Lf) 20.2 76.4 59.3 conv C2 = IO O IN" i 78,5 AND 80.5 127.6 35.9 42.3 120.3 72.5 75.9 134.6 8‘SZ 77.9 95.1 r- what 82.7 reactor feed g / h Cat. 0.0044 Xt ^ ř O O O 0.0044 0.0044 0.0044 dien O O O O 9.98 9.98 O O O O O O O O O C3 = 240 AND O 240 240 O 240 I 242 O 242 242 O 242 242 O 242 C2 = 120 what 9.6 120 130 10.2 90 100 ALIGN! 10.2 150 160 10.2 180 190 or ¹ E θ ΐ ^c ε ⁷³ N temperature Noc: 2 ° C O CM O O CM O M · O CM O Tt O CM O Tf O CM WHAT m flj O < < < < < -j T &> £ i N 54.9 69.7 75.2 dien v polyme- ru wt% O O O O 3.29 67.4 O 39.2 O O C2 = h and polyme- ru wt% 15.5 54.9 42.7 l · - IN" 50.6 35.3 what 47.4 36.1 what h- O WHAT 47,4 · m what in- WHAT 52.3 speed polyme- race g / h 76.9 170.0 247.0 CM h- 86.1 158.0 76.2 134.0 210 00 b- 185 263 5837 T ” CM 300 reactor R-1 R-2 total CM R-1 R-2 total 1 Qi R-2 total R-1 R-2 I I i total V ^- 1 Qi R-2 total SW »And> Ex. 121C Ex. 125A Ex. 127A 127B 127C

319C R-1 89 76.2 4.35 B 62 10.2 0 Πθ875 I 16.5 I 0.0064 60.1 Γ27 23.5 13865

Ø7 87 ^ 6 ~ 39/3 ~ 2J 90 T / 77 15 240 Ó ŠJJ ΪΪΛ Ϊ87 Ϊ3653 total 176,7 57,9 3,53 Ϊ5 Ϊ7Α 123 315 16/5 80/2 22 / š 37,8 27518 ·· 99 ► ♦ * ♦ »· · ♦

Table 2. Reactor conditions for example

Mw / Mw lall / dri 1,123 1.09 1.96 68 * i- 1.04 1.07 1,02 Mw they lied 223 CM 91.8 104 148 I 270 AND 576 Mw / Mn lall / dri 2.26 2.34 1.96 1.89 2.42 6.40 2.45 Mw / Mn dri / dri 2.01 2.14 2.03 1.94 2.32 I 5.98 AND 2.39 © T X cl ω O CL O Mw dři i 198! σ> O T ' IN" 10 O) 0 * 901- 142.0 252 562 Mn dri 98.6 92.9 46.9 54.7 WHAT 42.2 235 monomer conversion% read ta ° £ -2 °> 13962 19411 33373 20453 12287 32740 24662 30279 54941 31170 AND '16150 AND_ 47320 17478 25269 42746 25105 34470 59575 conv die- nu O CM O) CM 27.2 v ~ r-T in 33.8 O 79.3 79.3 O O O 34.0 40.2 60.6 0 0 0 conv. | C3 = 24.8 25.5 44.7 WHAT it 60.97 54.63 j _1 51.3 ⁶⁵ ' 70,5 j _AND 53.5 AND 6 * 0 i 24.2 37.5 UÝ 40.6 52.8 IN" 0 X " 75.3 j conv C2 = T ~ CN 10 58.5 76.6 10 66.6 143 | 62.1 66.3 92.4 49 j 96.1 66.8 89.3 96.1 65.2 92.6 94.4 AND monomer feed rate g / h Cat. 800 * 0 0,0066 | 0,0084 0.0057 0.006 0.005 .1 c 0 Φ O 25.1 25.1. O CM 7.02 27.0 O 12.9 12.9 O O O »0 0 10 ° r ° 0 0 0 11 what O 375 O 375 3 $ 32.4 WHAT 00 360 42 402 104 486 590 71.5 243 315 10 WHAT 32.4 l 197 AND C2 = 36.6 120 157 55.2 100 ALIGN! 155 10 234 249 CM WHAT IN" O 132 108 10 123 60 0 0 T ' 0 what spraying H2 moi / hr 0.013 O O 0.003 O 0 0 temperature Noc: 2 ° C 30 O 00 O what 10 r- O what 80 CM WHAT 10 62 WITH 0 what 75 "type Cat. < what < < CQ CQ ML 125 ° 26.9 10.3 ’Ί CD CM 10 ' 11.8 what what 3 Φ 0. - a. ^0.00 I 4.69 2.73 4.06 4.59 4.26 4.05 2.23 0.00 0.00 0.00 5.66 3.05 4.12 0.00 0 0 0 " 0.00 % C2 vEP -1 8 * 91- 48.6 35.3 32.9 79.5 50.4 10.4 58.3 36.8 68.7 5.32 1 47.1 72.9 30.9 48.1 T ' WHAT 64.5 50.4 speed polyme- race g / h (0 T ' T ~ 155.1 266.6 134 00 O what 214.4 205.9 252.8 458.8 177.7 t— CM O> 269.7 104.9 151.6 256.5 126.3 173.4 299.7 T ' oc CM and: total 5 R2 total Σ CM Q £ total in- and: R2 total ce CM and: total IN Qi R2 total run 268B 272A 307C 318C 320C 293A

Table 3

Composition of a mixture of reactors in series

Polymer Folders Ingredients product Ethylene% wt. EDN% wt. DSC Tm (° C) DSC / Hf J / g Mixture A 45, 68 3.35 127 30 m-ipp Reactor 1 46.5 0 0 133 74 m-EPDM Reactor 2 53.5 85, 4 6.27 Mixture B 46.09 4.33 128 25 m-ipp Reactor 1 38.76 0 0 134 73 m-EPDM Reactor 2 61.24 75.3 7.07

and ·· ·· ·· ·· • · ».

• · co co co co co co co co

Table 4. Dynamic vulcanizate properties

what 0 0 T- 33.33 CM CM WHAT 50/50 54A 3.95 257 1.99 25.9 4,5 Γ \ | 0 r-. it CM CM it n CM 00 WITH WHAT 0 66, CM r> 0 (O xt ’ T ” M · CM Xt 00 WHAT T ' T ” 100 ALIGN! 33.33 CM CM what 74A 12.5 287 5.20 22.9 5.5 CM- xt O 0 , 33 and 63 CD CD rí WHAT <0 ío what 0 0 Q what n WHAT CD 0 § what 0 0 CD t— what what IO 00 133.3 CM CM what 50/50 54A 2.76 201 1.85 40.9 L 5.5 WHAT Q O) 0 WHAT WHAT h- what" what CM CM it xt WHAT T ' 0 m b- 00 ’ 0 m lf> CM WHAT- < xt xt r- m it what what T— CM CM what δ CM in- 42 xt 10 ’ 0 Xt CM t ^- xt LO 133.3 52A 2.12 h- T ^- 110 and xt Q CM WHAT T ” xt <0 ’ CM l · - xt O O CD it in Xt WHAT IO h- xt n t- m xt what what' it T ~ 45I δ 52 CD N CM (6.9 CM 00 Q xt δ 88 ' uu IN" xt what WHAT h- O) Q 10 0 IN" it' t *. CM 0 what 00 IN" what IN" what h- and) F- > 0 IT and. C ω ω ω 0 O 0 0 2 of of 2 C LU LU UJ ω 0 xo O C 0 xt what what x> 0 > v > c WHAT xr WHAT Ό 00 IT x: 3 □ 3 of 7) CM ylen ylen C φ LU G? Φ C Φ CM AND eth eth £ Φ WHAT Sch 0 of- CM T ' m o> what CM gS sS tř * <r 3 ” "O CM xt 0 O tD m- Φ WHAT 5 Q CL PDM with 46 PDM with 48 3% ethyl ontel) resin 0 finový olej) CM O l · - 00 AND of % IT 0412) % (ASTM % (ASTM lohexane LU O LU O LU O m <0 Ό CL 'IT 2 IT Q 0 5 CM 5 H 3 QJ cycl O O O 5. O CL 045 (alkylphenolo \ X) Q ω '>> SW Φ S A (86.9 iPP / 1 with B (63.4 iPP / 1 with C (33.3 iPP / 1 / η 70A (EPDI ax® 6723 (IPP those D008M (IF zinc 0 OF CM par® 150MLW 3St (Shore And No tensile strength ost,% (ASTM lul 100 MPa (A deformation v deformation v clay extractable pattern > φ E what smé smě WHAT CL LU 0 and. Arisl oxide SnC SP1 C □ ω G £ limit tažn δ E persisted persisted under i

x:

Claims (14)

PATENT CLAIMS A method of dynamically vulcanizing a polymer blend from solution polymerization, comprising the steps of: a. introducing the first group of monomers and solvent into predetermined amounts into the first reactor; b. adding the metallocene catalyst to the first reactor; c. operating the first reactor to polymerize the first monomer group to a polymer-containing stream; d. introducing the stream from (c) to a second reactor; e. introducing the second group of monomers in predetermined amounts into the second reactor and adding a solvent as necessary; f. operating a second reactor to polymerize the second monomer group and prepare a second polymer; g. mixing the resulting first and second polymers under heat and shear conditions such that the mixture flows; and h. adding a curative composition to one of the polymers to at least partially cross-link said polymer, wherein the first and second monomer groups are selected from the group consisting of ethylene, higher alpha-olefins and unconjugated diene, and wherein the monomer ratios in the first a second reactor such that the first polymer contains 0-85% by weight ethylene, the second polymer 0-85% by weight ethylene and the polymer blend 6-85% by weight ethylene, and wherein more than 50% by weight of the total amount of catalyst added to all reactors is added to of the first reactor. The process according to claim 1, wherein 100% by weight of the total amount of catalyst added to all the reactors is added to the first reactor. Method according to claim 1, characterized in that 9 9 9 99 9 9 99 99 9 9 9 9 9 9 9 9 9 9 9 9 The higher alpha-olefin is propylene. The process of claim 1, wherein the relative ratios of the monomers in the first and second reactors are controlled such that the ethylene content of the first and second polymers is different in 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. 5. The process of claim 1 wherein the polymer components are immiscible and the product is a biphasic mixture. with e degrees (f) 6. The process of claim 1 wherein the monomer relative ratios in the first and second reactors are controlled such that one of the polymers contains 0-20% by weight of ethylene, is semi-crystalline due to the presence of isotactic propylene sequences, and has a melting point of 40 to 160 ° C, while the second polymer is amorphous. 7. The process of claim 6 wherein the amorphous polymer is a diene-containing terpolymer. The method of claim 7, wherein the terpolymer comprises ethylene, propylene, and diene. The process of claim 1 wherein the unconjugated diene is selected from the group consisting of 5-ethylidene-2-norbornene, 1,4-hexadiene, dicyclopentadiene, norbornadiene, 5-vinyl-2-norbornene, and mixtures thereof. 10. The process of claim 1 wherein the catalyst is capable of producing stereoregular polypropylene. The method according to claim 10, characterized in that isotactic stereoregularity is achieved. 12. The method of claim 1, wherein the dynamically vulcanized composition has a permanent tensile strain of less than 50% as determined by ASTM D412. 13. The process of claim 1 wherein in step (h) a vulcanizing agent comprising a phenolic resin system is used to completely cross-link said polymer. A dynamic vulcanizate prepared by the method of claim