MXPA06010584A - Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation - Google Patents

Abstract

A composition for use in forming a multi-block copolymer, said copolymer containing therein two or more segments or blocks differing in chemical or physical properties, a polymerization process using the same, and the resulting polymers, wherein the composition comprises the admixture or reaction product resulting from combining:(A) a first metal complex olefin polymerization catalyst, (B) a second metal complex olefin polymerization catalyst capable of preparing polymers differing in chemical or physical properties from the polymer prepared by catalyst (A) under equivalent polymerization conditions, and (C) a chain shuttling agent.

Description

COM CATALYZER POSITION THAT UNDERSTANDS ENLACÉ AGENT FOR THE FORMATION OF MULTIPLE COPOLYMERS ETHYLENE BLOCKS Cross Reference Statement This application claims the benefit of the Provisional Application of the United States of America Number 60 / 553,906, filed on March 1, 2004. For the purposes of United States patent practice, the content of this provisional application is incorporated herein by reference.

BACKGROUND OF THE INVENTION The present invention relates to compositions for polymerizing one or more monomers or mixtures of monomers, such as ethylene, and one or more comonomers, in order to form an interpolymer product having unique physical properties, a process for the preparation of these interpolymers, and the resulting polymer products. In another aspect, the present invention relates to methods for using these polymers in applications that require unique combinations of physical properties. In still another aspect, the invention relates to articles prepared from these polymers. The polymers of the invention comprise two or more different regions or segments (blocks), which cause the polymer to possess unique physical properties. These multi-block copolymers and polymer blends comprising them, are they are usefully employed in the preparation of solid articles, such as molded articles, films, sheets, and foamed objects, by molding, extrusion, or other processes, and are useful as components or ingredients in adhesives, laminates, polymer blends, and other uses final. The resulting products are used in the manufacture of automotive components, such as profiles, fenders, and moldings; packaging materials; insulation of electrical cables, and other applications. It has long been known that polymers containing a block-like structure often have superior properties compared to random copolymers and mixtures thereof. For example, the triblock copolymers of styrene and butadiene (SBS), and the hydrogenated versions thereof (SEBS) have an excellent combination of resistance to! heat and elasticity. Other block copolymers are also known in the art. In general, block copolymers known as thermoplastic elastomers (TPE) have desirable properties due to the presence of "soft" or elastomeric block segments connecting "hard" blocks, either crystallized or glazed, in the same polymer. At temperatures up to the melting temperature or up to the glass transition temperature of the hard segments, the polymers demonstrate an elastomeric character. At higher temperatures, the polymers become flowable, exhibiting a thermoplastic behavior. Known methods for preparing block copolymers include anionic polymerization and radical polymerization free controlled. Unfortunately, these methods for the preparation of block copolymers require the addition of monomers in sequence and batch processing, and the types of monomers that can be usefully employed in these methods are relatively limited. For example, in the anionic polymerization of styrene and butadiene to form a block-type copolymer of SBS type, each polymer chain requires a stoichiometric amount of initiator, and the resulting polymers have a molecular weight distribution, Mw / Mn, which is extremely narrow, for example from 1.0 to 1.3. Additionally, anionic and free radical processes are relatively slow, resulting in poor process economy. It would be desirable to produce block copolymers in a catalytic manner, that is, in a process wherein more than one polymer molecule is produced per catalyst or initiator molecule. In addition, it would be highly desirable to produce block copolymers from olefin monomers, such as ethylene, propylene, and higher alpha-olefins, which are generally not suitable for use in anionic or free radical polymerizations. In some of these polymers, it is highly desirable that some or all polymeric blocks comprise amorphous polymers, such as a copolymer of ethylene and a comonomer, especially amorphous random copolymers comprising ethylene and an alpha-olefin having 3, and especially 4 or more carbon atoms. Finally, it would be highly desirable to be able to use a continuous process for the production of block copolymers. Previous investigators have stated that certain homogeneous coordination polymerization catalysts can be used to prepare polymers having a substantially "block-like" structure, suppressing chain transfer during polymerization, for example, conducting the polymerization process in the absence of a chain transfer agent, and at a sufficiently low temperature so that chain transfer is essentially eliminated by the removal of hydride-β, or other chain transfer processes. Under such conditions, it was said that sequential addition of different monomers resulted in the formation of polymers with sequences or segments of different monomer content. Several examples of these catalyst compositions and processes are reviewed by Coates, Hustad, and Reinartz, in Angew. Chem .. Int. Ed .. 41, 2236-2257 (2002) as well as in the United States Patent of North American Issue US-A-2003/01 14623. In an inconvenient manner, these processes require the addition of monomers in sequence, and result in the production of only one polymer chain per active catalyst center, which limits the productivity of the catalyst. catalyst. In addition, the requirement of relatively low process temperatures increases the operating costs of the process, making these processes unsuitable for commercial implementation. Moreover, the catalyst can not be optimized for the formation of each type of polymer respective, and therefore, the entire process results in the production of polymeric blocks or segments of less than maximum efficiency and / or quality. For example, in general, the formation of a certain amount of prematurely terminated polymer is inevitable, which results in the formation of mixtures having inferior properties of the polymer. In accordance with the above, under normal operating conditions, for block copolymers prepared in sequence having an Mw / Mn of 1.5 or greater, the resulting distribution of block lengths is relatively non-homogeneous, not much when at a distribution. probable. Finally, block copolymers prepared in sequence must be prepared in a batch process, limiting the speeds and increasing the costs with respect to the polymerization reactions carried out in a continuous process. For these reasons, it would be highly desirable to provide a process for producing olefin copolymers in well-defined blocks or segments, in a process using coordination polymerization catalysts capable of operating at high catalytic efficiencies. In addition, it would be desirable to provide a process and the resulting segmented block or copolymers, wherein the insertion of terminal blocks or block sequencing within the polymer, can be influenced by appropriate selection of the process conditions. Finally, it would be desirable to provide a continuous process for producing multi-block copolymers.

The use of certain alkyl compounds of metals and other compounds, such as hydrogen, as chain transfer agents to interrupt chain growth in olefin polymerizations, is well known in the art. In addition, it is known to use such compounds, especially alkyl aluminum compounds, as scavengers or as cocatalysts in olefin polymerizations. In Macromolecules. 33, 91 92-91 99 (2000), the use of certain trialkyl alumium compounds as chain transfer agents in combination with certain paired zirconocene catalyst compositions, resulted in polypropylene blends containing small amounts of polymeric fractions that They contain both isotactic and atactic chain segments. In Liu and Rytter, Macromolecular Rapid Comm .. 22, 952-956 (2001) and Bruaseth and Rytter, Macromolecules. 36, 3026-3034 (2003), mixtures of ethylene and 1 -hexene were polymerized by a similar catalyst composition containing an aluminum-io trimethyl chain transfer agent. In the last reference, the authors summarized the prior art studies as follows (some citations omitted): "The mixture of two metallocenes with a known polymerization behavior can be used to control the polymer microstructure. carried out several studies of the polymerization of ethene by mixing two metallocenes.The common observations were that, by combining catalysts that separately give polyethylene with different Mw, you can obtain polyethylene with a wider MWD and in some cases bimodal. [Sjoares and Kim (J. Polym, Sci., Part A: Polvm. Chem .. 38, 1408-1432 (2000)) developed a criterion in order to test the bimodality of MWD of polymers made by catalysts of a single double site, as exemplified by the copolymerization of ethene / 1 -hexene of the mixtures of Et (lnd) 2 ZrCl 2 / Cp 2 HfCl 2, and Et (lnd) 2 ZrCl / CGC (limited geometry catalyst) supported on silica. Heiland and Kaminsky (Makromol, Chem. 1 93, 601-61 0 (1992)) studied a mixture of Et (l nd) 2 ZrCl 2 and the hafnium analog in the copolymerization of ethene and 1-butene. These studies do not contain any indication of the interaction between the two different sites, for example, by reabsorbing a chain terminated at the alternative site. However, these reports have been issued for propene polymerization. Chien et al. (J. Polym, Sci., Part A: Polvm. Chem .. 37, 2439-2445 (1 999), Makromol .. 30, 3447-3458 (1 997)) studied the polymerization of propene by homogeneous binary zirconocene catalysts. A mixture of isotactic polypropylene (i-PP), atactic polypropylene (a-PP), and a stereoblock fraction (i-PP-ba-PP) was obtained, with a binary system comprising an isospecific precursor and an unspecific precursor. with a borate and TI BA as cocatalyst. By using a binary mixture of isospecific and syndiospecific zirconocenes, a mixture of isotactic polypropylene (i-PP), syndiotactic polypropylene (s-PP), and a stereoblock fraction (i-PP-b-s-PP) was obtained. It was proposed that the mechanism for the formation of the stereoblock fraction involves the exchange of propagation chains between the two different catalytic sites. Przybyla and Fink (Acta Polvm .. 50, 77-83 (1999)) used two different types of metallocenes (isospecific and sindiospecific) supported on the same silica for the polymerization of propene. They reported that, with a certain type of silica support, the chain transfer between the active species of the catalyst system was presented, and the PP stereoblock was obtained. Lieber and Brintzinger (Macromol.3, 91 92-9199 (2000)) have proposed a more detailed explanation of the way in which the transfer of a growing polymer chain from one type of metallocene to another occurs. They studied the polymerization of propene by means of catalyst mixtures of two different ansa-zirconocenes. First the different catalysts were studied individually with respect to their tendency towards the exchange of alkyl-polyimeryl with the aluminum alkyl activator, and then in pairs with respect to their ability to produce polymers with a stereoblock structure. They reported that the formation of stereoblock polymers by a mixture of zirconocene catalysts with different stereoselectivities, is contingent upon an efficient polymeryl exchange between the Zr catalyst centers and the Al centers of the cocatalyst. Brusath and Rytter then gave their own observations. using paired zirconocene catalysts to polymerize ethylene / 1 -hexene mixtures, and reported the effects of the influence of the double-site catalyst on the polymerization activity, the incorporation of the comonomer, and the microstructure of the polymer, using a methylalumoxane cocatalyst. Analysis of the above results indicates that Rytter et al. Possibly failed to utilize combinations of catalyst, cocatalyst, and third components that were capable of reabsorbing the polymer chain from the chain transfer agent on both active catalytic sites, i.e. Two-way reabsorption. Although it is indicated that the chain termination due to the presence of trimethyl aluminum possibly arose with respect to the polymer formed from the minimum comonomer that incorporated the catalyst, and after possibly exchanging polyimeryl with the more open catalytic site followed by a continuous polymerization, evidence of the inverse flow of polymer ligands seemed to be lacking in the reference. In fact, in a later communication, Rytter et al., Polymer, 45, 7853-7861 (2004), it was reported that in fact no chain transfer took place between the catalyst sites in the first experiments. Similar polymerizations were reported in International Publication No. WO98 / 34970. In the Patents of the United States of North America Numbers 6,380,341 and 6,169,151, it was said that the use of a "fluxional" metallocene catalyst, which is a metallocene capable of having a relatively easy conversion between two stereoisomeric forms having different polymerization characteristics, such as Different reactivity ratios result in the production of olefin copolymers which have a "blocked" structure. In a disadvantageous manner, the respective stereoisomers of these metallocenes generally do not have a significant difference in polymer formation properties, and are unable to form both highly crystalline and amorphous block copolymer segments, for example, from a mixture of given monomers, under fixed reaction conditions. Moreover, because the relative proportion of the two "fluxional" forms of the catalyst can not be varied, there is no capacity, using the "fluxional" catalysts, to vary the composition of the polymer block or the proportion of the respective blocks. Finally, the methods of the prior art for the copolymerization of olefin blocks have been unable to easily control the sequencing of the different polymeric blocks, and in particular to control the nature of the block or terminator segment of a multi-block copolymer. . For certain applications, it is desirable to produce polymers that have terminal blocks that are highly crystalline, that are functionalized or more easily functionalized, or that possess other distinctive properties. For example, it is believed that polymers in which the segments or terminal blocks are crystalline or glazed have a better abrasion resistance and better thermal properties, such as tensile strength, elastic recovery, and compression setting. In addition, the polymers where the blocks that have amorphous properties are internal or are primarily connected between the crystalline or glazed blocks, have better elastomeric properties, such as better retraction force and recovery, particularly at elevated temperatures. In JACS, 2004, 126, 1 0701 -1 071 2, Gibson et al. Discuss the effects of "catalyzed living polymerization" on the molecular weight distribution. The authors define the living polymerization catalysed in this way: "... if the chain transfer to aluminum is the only transfer mechanism and the exchange of the growing polymer chain between the transition metal and the aluminum centers is very fast and reversible, the polymer chains will appear to be growing on the aluminum centers.This can then be reasonably described as a chain reaction catalyzed on aluminum ... An attractive manifestation of this type of chain growth reaction is a distribution of Poisson of the molecular weights of the product, as opposed to the distribution of Sch ulz-FIory that occurs when the transfer of β-H accompanies the propagation ". The authors reported the results for the catalyzed living homopolymerization of ethylene, using a catalyst containing iron in combination with Zn Et2, Zn Me2, or Zn (i-Pr) 2. The homolytic alkyls of aluminum, boron, tin, lithium, magnesium, and lead did not induce catalytic chain growth. The use of GaMe3 as cocatalyst resulted in the production of a polymer which has a narrow molecular weight distribution. However, after analysis of the time-dependent product distribution, the authors concluded that this reaction "was not a simple catalyzed chain growth reaction". The reference does not disclose the use of two or more catalysts in combination with a chain-linking agent to make multi-block copolymers. Similar processes employing individual catalysts have been described in the Patents of the United States of North America Numbers 5,21 0,338; 5,276,220, and 6,444,867. Previous workers have claimed to have block copolymers formed using a single Ziegler-Natta type catalyst in multiple reactors configured in series; see, for example, Patents of the United States of North America Nos. 3,970.71 9 and 4,039,632. Additional processes and polymers based on Ziegler-Natta are disclosed in the United States Patents of North America Nos. 4,971, 936; 5,089,573; 5,11,8767; 5,118,868; 5, 134,209; 5,229,477; 5,270,276; 5,270.41 0; 5,294,581; 5,543,458; 5.550, 1 94; and 5,693, 71 3, as well as in European Patents Nos. EP-A-470, 171 and EP-A-500,530. Despite the advances of the above investigators, there remains a need in the art for a polymerization process that is capable of preparing block copolymers, especially multiblock copolymers, and more especially linear multiblock copolymers, in high yield and selectivity. Moreover, it would be desirable to provide an improved process to prepare multiblock copolymers, especially linear multi-block copolymers, of two or more olefin monomers, such as ethylene, and one or more comonomers, by the use of a linking agent. In addition, it would be desirable to provide this improved process that is capable of preparing multi-block copolymers, especially linear multi-block copolymers, having a relatively narrow molecular weight distribution. In addition it would be desirable to provide an improved process for the preparation of copolymers having more than two segments or blocks. Additionally, it would be desirable to provide a process for identifying combinations of catalysts and chain binding agents capable of making these multi-block copolymers. Still further, it would be desirable to provide a process for the independent control of the order of the different polymer blocks, especially a process for preparing olefin block copolymers containing terminal blocks having a high crystallinity and / or functionality. Finally, it would be desirable to provide an improved process for the preparation of any of the above desirable polymeric products in a continuous process, without the sequential addition of the monomers being required. In a highly desirable manner, this process allows independent control of the amount and / or identity of the binding agents and / or catalysts used.

Brief Description of the Invention In accordance with the present invention, a composition is now provided for use in the polymerization of an addition polymerizable monomer, preferably two or more addition polymerizable monomers, especially ethylene and at least one copolymerizable comonomer, to form a segmented copolymer. (multiple block copolymer), said copolymer containing two or more, preferably three or more segments or blocks differing in one or more chemical or physical properties as disclosed herein further, the composition comprising the mixture or reaction product resulting from combining: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers that differ in the chemical or physical properties of the polymer prepared by the catalyst (A) under equivalent polymerization conditions, and (C) a chain-linking agent, and preferably the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst having a high rate of incorporation of comonomer, (B) a second olefin polymerization catalyst having an index of incorporation of comonomer men or at 95 percent, preferably less than 90 percent, more preferably less than 25 percent, and most preferably less than 10 percent of the comonomer incorporation index of the catalyst (A), and (C) a chain binding agent. In another embodiment of the invention, there is provided a method for selecting a mixture of catalysts (A) and (B) and chain-linking agent (C), capable of producing multi-block copolymers according to the invention, especially these ethylene copolymers comprising in a polymerized form. In a further embodiment of the present invention, a process for preparing a segmented copolymer is provided, especially comprising this ethylene copolymer and optionally one or more additional polymerizable monomers by addition of ethylene, this process comprising contacting the ethylene and optionally or not more polymerizable monomers by addition of different ethylene, under conditions of addition polymerization, with a composition comprising: the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst having a high comonomer incorporation index, (B) ) a second olefin polymerization catalyst having a comonomer incorporation index of less than 90 percent, preferably less than 50 percent, more preferably less than 5 percent of the comonomer incorporation index of the catalyst (A), and (C) a chain binding agent. Preferably, the above process takes the form of a process in continuous solution to form block copolymers, especially multiblock copolymers, preferably linear multiple block copolymers of two or more monomers, more especially ethylene and an olefin of 3 to 20 carbon atoms or cyclo-olefin, and a very special way ethylene and an a-olefin of 4 to 20 carbon atoms, using multiple catalysts that are unable to have interconversion. That is, the catalysts are chemically different. Under continuous solution polymerization conditions, the process is ideally suited for the polymerization of monomer mixtures at high monomer conversions. Under these polymerization conditions, the linkage from the chain-linking agent to the catalyst is advantageously compared with the growth of the chain, and multi-block copolymers are formed, especially linear multi-block copolymers according to the invention. , with a high efficiency. In another embodiment of the invention, a segmented copolymer (multi-block copolymer) is provided, this ethylene copolymer in particular comprising a polymerized form, said copolymer containing two or more, preferably three or more different segments in the content of comonomer or density or other physical or physical property. In a highly preferable manner, the copolymer has a molecular weight distribution, Mw / Mn, less than 3.0, preferably less than 2.8. In still another embodiment of the invention, functionalized derivatives of the segmented copolymers or multiple previous blocks. In a still further embodiment of the present invention, there is provided a polymer blend comprising: (1) an organic or inorganic polymer, preferably an ethylene or propylene homopolymer and / or an ethylene or propylene copolymer and a copolymerizable comonomer , and (2) a multi-block copolymer according to the present invention, or prepared according to the process of the present invention. In a desirable embodiment, the component. (1) is a matrix polymer comprising high density polyethylene or isotactic polypropylene, and component (2) is an elastomeric multi-block copolymer. In a preferred embodiment component (2) comprises occlusions of the matrix polymer formed during the mixing of components (1) and (2).

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of the polymer chain link process involving two catalyst sites. Figure 2 shows delta DSC-CRYSTAF graphs as a function of DSC Fusion Enthalpy for Examples 1 to 1 9, Comparative Polymers A-F, and conventional ethylene-octene copolymers. Figures 3 to 27 are DSC heating curves and the corresponding CRYSTAF reports for the polymers of the Examples 1 to 1 9 and Comparative Polymers A-F, including peak temperature assignments and fraction integrations weight for the areas corresponding to the respective peak temperatures. Fig. 28 is a low resolution micrograph showing the crystal structure of different comparative polymers, as well as polymers prepared by using different amounts of chain linking agent according to the invention. Figure 29 is a high resolution micrograph showing the morphology of a comparative ethylene / 1-ketene copolymer, as well as three multiblock copolymers prepared according to the invention. FIGURE 30 illustrates the performance of the 300 percent pull cycle for samples prepared from the polymer of Example 1 7. FIGURE 31 illustrates the Reticulated Fiber Tension Relaxation, the polymer of Example 1 1 and FIG. Comparative G at 21 ° C and at 41 ° C. Figures 32 and 33 are graphs of the number average molecular weight (Mn) of the polymer, as a function of the yield for the polymerizations conducted in Examples 27 and 28, respectively. Figure 34 is a plot of the peak melting temperature against density for ethylene / 1-octene copolymers of multiple blocks of the invention (line), as well as for typical conventional ethylene / 1-octene copolymers (curve) . Figure 35 is a graph of the storage modulus as a function of temperature for ethylene / 1-ketene copolymers and of comparative propylene / ethylene, and for two ethylene / 1-ketene multi-block copolymers of the invention, made with different amounts of chain-linking agent. Figures 36 to 49 are DSC heating curves, and the corresponding reports CRYSTAF, for the polymers of the Examples 29 to 33 and the Comparative M-P, respectively, including the peak temperature assignments and the weight fraction integrations for the areas corresponding to the respective peak temperatures. Figure 50 shows delta charts DSC-CRYSTAF as a function of the DSC Fusion Enthalpy for the polymers of Examples 29 to 33, the Comparative Polymers M-P, and the conventional ethylene / octene copolymers. Figures 51 to 53 are microscopic images of atomic force of microtome samples of injection molded plates of impact-modified isotactic polypropylene, corresponding to samples a, b, and d of Table 13, respectively. Figure 54 is a graph of the octene content of the ethylene / 1-ketene copolymer fractionated by TREF against the TREF elution temperature of the fraction for the polymer of Example 5 and the Comparative polymers E and F. Figure 55 is a plot of the octene content of the fractions of the ethylene / 1-ketene copolymer fractionated by TREF against the TREF elution temperature of the fraction for the polymer of Example 5 and for Comparative F.

Detailed Description of the Invention All references to the Periodic Table of the Elements herein, will refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, I nc. , 2003. Also, any reference to a Group or Groups, will be to the Group or Groups reflected in this Periodic Table of the Elements, using the I UPAC system for the numbering of the groups. Unless otherwise reported, implied or by context, or as is customary in the art, all parts and percentages are weight-based. For the purposes of patent practice the United States, the content of any patent, patent application, or publication referenced herein, is hereby incorporated by reference in its entirety (or the equivalent United States version of North America thereof is hereby incorporated by reference) especially with respect to the disclosure of synthetic techniques, definitions (to the extent that they are not inconsistent with any definitions provided herein), and general knowledge in the art. . The term "comprising" and its derivatives, is not intended to exclude the presence of any component, step, or additional procedure, whether or not it is disclosed herein. In order to avoid any doubt, all of the compositions claimed herein through the use of the term "comprising" may include: any additive, adjuvant, or additional compound, either polymeric or otherwise, unless otherwise advised. In contrast, the term "essentially consisting of" excludes from the scope of any subsequent text any other component, step, or procedure, except those that are not essential for operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or enlisted. The term "or", unless otherwise reported, refers to members listed individually, as well as in any combination. The term "polymer" includes both conventional homopolymers, ie, homogeneous polymers prepared from a single comonomer, such as copolymers (interchangeably referred to herein as polyethers), the polymers being prepared by the reaction of at least two monomers, or that otherwise contain chemically differentiated segments or blocks in them, even when they are formed from a single monomer. More specifically, the term "polyethylene" includes homopolymers of ethylene and copolymers of ethylene and one or more α-olefins of 3 to 8 carbon atoms, wherein the ethylene comprises at least 50 mole percent. The term "crystalline", if used, refers to a polymer that possesses a first-order transition or a crystalline melting point (Tm) determined by differential scanning calorimetry (DSC) or an eq uivalent technique. The term can be used in a way interchangeable with the term "semicrystalline". The term "amorphous" refers to a polymer that lacks a crystalline melting point, determined by differential scanning calorimetry (DSC) or an equivalent technique. The term "multi-block copolymer" or "segmented copolymer" refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks"), preferably joined in a linear manner, i.e., a polymer that comprise chemically differentiated units that are joined end to end with respect to the polymerized ethylenic functionality, rather than in a pendent or grafted form. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the size of the cristite attributable to a polymer of that composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long-chain branching or hyper-branching, homogeneity, or any other chemical or physical property. Compared with block copolymers of the prior art, including copolymers produced by addition of monomers in sequence, fluxional catalysts, or anionic polymerization techniques, the copolymers of the invention are characterized by unique distributions of the polydispersity of the polymer (PDI or Mw). / Mn), block length distribution, and / or block number distribution, due, in a preferred embodiment, to the effect of the binding agents in combination with multiple catalysts. More specifically, when they occur in a continuous process, the polymers desirably possess a PDI of 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. When they are produced in a batch or semi-batch process, the polymers desirably have a PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to 2.0, and in a very high fashion. preferable from 1 .4 to 1 .8. The term "multi-block copolymer of ethylene" means a multi-block copolymer comprising ethylene and one or more copolymerizable comonomers, wherein ethylene comprises a plurality of the polymerized monomer units of at least one block or segment in the polymer, preferably at minus 90 mole percent, more preferably at least 95 mole percent, and more preferably at least 98 mole percent of said block. Based on the weight of the total polymer, the multi-block ethylene copolymers of the present invention preferably have an ethylene content of 25 to 97 percent, more preferably 40 to 96 percent, even more preferably 55 to 95 percent , and more preferably from 65 to 85 percent. Because the respective distinguishable segments or blocks formed from two or more monomers are joined in individual polymer chains, the polymers can not be completely fractionated using selective extraction techniques. conventional For example, polymers containing regions that are relatively crystalline (high density segments) and regions that are relatively amorphous (lower density segments) can not be selectively extracted or fractionated using different solvents. In a preferred embodiment, the amount of extractable polymer using either a dialkyl ether or an alkane solvent is less than 10 percent, preferably less than 7 percent, more preferably less than 5 percent, and in a very preferable less than 2 percent of the total weight of the polymer. In addition, the multi-block copolymers of the invention desirably possess a PDI that conforms to a Schutz-Flory distribution instead of a Poisson distribution. The use of the present polymerization process results in a product having both a polydisperse block distribution and a polydisperse distribution of block sizes. This ends the formation of the polymeric products that have improved and distinguishable physical properties. The theoretical benefits of a polydispersed block distribution have been modeled and discussed earlier in Potemkin, Phvsical Review E (1 998) 57 (6), pages 6902-6912, and Dobrynin, J. Chem. Phys. (1 997) 1 07 (2), pages 9234-9238. In a further embodiment, the polymers of the invention, especially those made in a continuous solution polymerization reactor, possess a more likely distribution of block lengths. The most preferred polymers according to the invention are the multi-block copolymers containing four or more blocks or segments, including the terminal blocks.

The following mathematical treatment of the resultant polymers is based on the theoretically derived parameters that are believed to apply to the present invented polymers, and demonstrate that, especially in a well-blended continuous reactor, the polymer block lengths Resulting prepared using two or more catalysts, each will conform to a more probable distribution, derived in the following way, where pj is the probability of propagation with respect to the block sequences from catalyst i. The theoretical treatment is based on assumptions and conventional methods known in the art, and used in the prediction of the effects of polymerization kinetics on molecular architecture, including the use of mass action reaction velocity expressions that are not affected for the lengths of chains or blocks. These methods have been previously disclosed in W. H. Ray, J. Macromol Sci., Rev. Macromol. Chem .. C8, 1 (1972) and A. E. Hamielec and J. F. MacGregor, "Polymer Reaction Engineering", K. H. Reichert and W. Geisler, Editors, Hanser, M unich, 1 983. In addition, it is assumed that adjacent sequences formed by the same catalyst form a single block. For the catalyst i, the fraction of the sequences of length n is given by X¡ [n], where n is an integer from 1 to infinity, representing the number of monomer units in the block. X¡ [n] = (1 -p¡) p¡ (n "1) most probable distribution of block lengths.

N¡ = 1 average block length in number. 1 - . 1 P. Each catalyst has a probability of propagation (pi) and forms a polymeric segment having a unique average length and distribution of blocks. In a more preferred embodiment, the probability of propagation is defined as: pj = RpN1 for each catalyst i =. { 1, 2 ....}. , where, Rp [i] + Rt [i] + Rs [i] + [C] Rp [i] = speed of monomer consumption by the catalyst i, (moles / liter), Rt [i] = speed total chain transfer and termination for the catalyst i, (moles / liter), Rs [i] = chain link speed with the dormant polymer for other catalysts, (moles / liter), and [C] = concentration of the catalyst i (moles / liter). Sleeping polymer chains refer to polymer chains that are linked to a CSA. The total monomer consumption or the propagation velocity of the polymer Rp [i], is defined using an apparent velocity constant, multiplied by a total monomer concentration, [M], as follows: Rp [i] =? [M] [Q] The total chain transfer rate is given more forward, including the values for the chain transfer to hydrogen (H2), the elimination of beta hydride, and the chain transfer to the chain-linking agent (CSA). The residence time in the reactor is given by?, And each subscribed k-value is a velocity constant. Rt [i] =? kH2i [H2] [C.] +? kßl [C]] +? ka? [CSA] [C] For a double catalyst system, the chain link speed of the polymer between catalysts 1 and 2 is given as follows: Rs [1] = Rs [2] =? ka 1 [CSA]? ka2 [C,] [C2]. If more than two catalysts are used, then the terms and the theoretical complexity in the relation are added for the result of Rs [i], but the final conclusion that the resulting distributions of block lengths are the most likely, that is without be affected As used herein with respect to a chemical compound, unless specifically indicated otherwise, the singular includes all isomeric forms, and vice versa (eg, "hexane" includes all isomers of hexane, both in an individual way as a collective). The terms "compound" and "complex" are used interchangeably herein to refer to organic, inorganic, and organometallic compounds. The term "atom" refers to the smallest constituent of an element, irrespective of the ionic state, that is, whether or not it carries a charge or a partial charge, whether or not it is laced to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. The preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se, and Ge. The term "hydrocarbyl" refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, or non-cyclic species. Examples include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, and alkynyl groups. "Substituted hydrocarbyl" refers to a hydrocarbyl group that is substituted with one or more non-hydrocarbyl substituent groups. The terms "heteroatom-containing hydrocarbyl" or "heterohydrocarbyl" refer to the univalent groups in which at least one atom other than hydrogen or carbon is present, together with one or more carbon atoms and one or more hydrogen atoms. The term "heterocarbyl" refers to groups that contain one or more carbon atoms and one or more heteroatoms, and do not contain hydrogen atoms. The bond between the carbon atom and any heteroatom, as well as the bonds between any two heteroatoms, can be a single or multiple covalent bond, or a coordinator or other donor bond. Accordingly, an alkyl group substituted with a heterocycloalkyl group, heterocycloalkyl substituted by aryl, heteroaryl, heteroaryl substituted by alkyl, alkoxy, aryloxy, dihydro-carbylboryl, dihydro-carbyl-phosphino, dihydro-carbyl-amino, trihydro-carbyl- silyl, thiohydro-carbyl, or hydrocarbyl-seleno, is within the scope of the term heteroalkyl. Examples of suitable heteroalkyl groups include cyano-methyl groups, benzoyl-methyl, (2-pyridyl) -methyl, and trifluoromethyl. As used herein, the term "aromatic" refers to a polyatomic cyclic conjugate ring system containing (4d + 2) tt-electrons, wherein d is an integer greater than or equal to 1. The term "fused", as used herein with respect to a ring system containing two or more polyatomic ring elements that, with respect to at least two rings thereof, at least one pair of adjacent atoms is included in both rings. The term "aryl" refers to a monovalent aromatic substituent which may be an individual aromatic ring or multiple aromatic rings that fuse with each other, bind covalently, or bind to a common group, such as a methylene or ethylene moiety. Examples of the aromatic rings include phenyl, naphthyl, anthracenyl, and biphenyl ilo, among others. "Substituted aryl" refers to an aryl group, wherein one or more hydrogen atoms bonded to any carbon atom, are replaced by one or more functional groups, such as alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen , halogen alkyl (CF3), hydroxyl, amino, phosphide, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons that are fused to the aromatic rings, linked in a covalent manner, or linked to a group common, such as a methylene or ethylene fraction. The common linker group can also be a carbonyl as in benzophenone, or oxygen as in diphenylether, or Nitrogen in diphenylamine. The term "comonomer incorporation index" refers to the percentage of comonomer incorporated in a polymer prepared under representative ethylene / comonomer polymerization conditions, by the catalyst under consideration, in the absence of other polymerization catalysts, ideally under polymerization conditions in continuous solution of steady state in a diluent of hydrocarbon at 100 ° C, at an ethylene pressure of 4.5 MPa (reactor pressure), with more than 92 (more preferably more than 95) percent conversion of ethylene, and more than 0.01 percent comonomer conversion. The selection of metal complexes or catalyst compositions that have the greatest difference in the rates of incorporation of comonomers results in copolymers from two or more monomers having the greatest difference in the properties of blocks or segments, such as density. In certain circumstances, the rate of incorporation of comonomers can be directly determined, for example, by the use of nuclear magnetic resonance spectroscopic techniques. However, frequently, any difference in the incorporation of comonomers can be determined indirectly. For polymers formed from multiple monomers, this can be carried out by different techniques based on the reactivities of the monomers. For the copolymers produced by a given catalyst, the relative amounts of comonomer and monomer in the copolymer, and consequently of the copolymer composition, they are determined by the relative reaction rates of comonomer and monomer. Mathematically, the molar ratio of the comonomer to the monomer is given by: [comonomero _ Rp2 O) F,. [monomer J J .polymer P1 Here, Rp2 and Rp? are the polymerization rates of the comonomer and the monomer, respectively, and F2 and F1 are the molar fractions of each in the copolymer. Because F? + F2 = 1, we can reconfigure this equation to: The individual polymerization rates of the comonomer and the monomer are typically complex functions of temperature, catalyst, and monomer / comonomer concentrations. At the limit, as the concentration of comonomer in the reaction medium drops to 0, Rp2 decreases to zero, F2 becomes zero, and the polymer consists of pure monomer. In the limiting case of no monomer in the reactor, Rp-becomes zero, and F2 is 1 (provided that the comonomer can polymerize only). For most homogeneous catalysts, the ratio of the comonomer to the monomer in the reactor largely determines the composition of the polymer, as determined according to either the Terminal Copolymerization Model or the Penultimate Model.

Copolymerization. For random copolymers, where the identity of the last inserted monomer dictates the rate at which the following monomers are inserted, the terminal copolymerization model is employed. In this model, we have the insertion reactions of the type: -Mf + Mt-y *? ... M p * (3) where C * represents the catalyst, M, represents the monomer i, and k, is the velocity constant of the speed equation: The molar fraction of comonomer (i = 2) in the reaction medium is defined by the equation: A simplified equation can be derived for the composition of the comonomer as disclosed in George Odian, Principles of Polymerization, Second Edition, John Wiley and Sons, 1970, as follows: From this equation, the molar fraction of the comonomer in the polymer depends exclusively on the mole fraction of the comonomer in the reaction medium, and two proportions of temperature-dependent reactivity in terms of the constants of Insertion speed as: v2 (7). ?, 2 / f.M Alternatively, in the penultimate copolymerization model, the identities of the last two monomers inserted into the growing polymer chain dictate the subsequent insertion rate of the monomer. The polymerization reactions are of the form: - • - M. jC + Mk - "-l? ... MfMjMkC '(8) and the individual velocity equations are: R ^ = kl? ~ M i = C¡ [Ml¡] (9). The comonomer content can be calculated (again as it is disclosed in Jorge Odian, Supra.) As: where X is defined as: xCzA (I1) A and the reactivity ratios are defined as: - - X 21] r? ~ km 2I2 (12). ~ _ * 22_¡ "? «J 22 2 ~~ '1 ~ * 221 For this model, also the composition of the polymer is a function only of the reactivity rates dependent on the temperature and the mole fraction of the comonomer in the reactor. The same is also true when the reverse insertion of comonomer or monomer can occur, or in the case of the interpolymerization of more than two monomers. Reactivity ratios for use in the above models can be predicted using well-known theoretical techniques, or can be derived empirically from the actual polymerization data. Suitable theoretical techniques are disclosed, for example, in B.G. Kyle, Chemical and Process Thermodynamics, Third Edition, Prentice-Hall, 1999 and Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pages 1 197-1203. Commercially available software programs can be used to assist in the derivation of reactivity ratios from experimentally derived data. An example of this software is Aspen Plus from Aspen Technology I nc., Ten Canal Park, Cambridge, MA 02141 -2201 EUA. Based on the foregoing theoretical considerations, the present invention can be alternatively described as a composition for use in the polymerization of two or more addition polymerizable monomers, especially ethylene and at least one copolymerizable comonomer, to form a segmented copolymer of high molecular weight (multi-block copolymer), said copolymer containing two or more, preferably three or more different segments or blocks in one or more chemical or physical properties, as disclosed further herein, the composition comprising the mixture or the reaction product resulting from the combination of: (A) a first polymerization catalyst of olefin, (B) a second olefin polymerization catalyst capable of preparing polymers different in their chemical or physical properties from the polymer prepared by the catalyst (A) under equivalent polymerization conditions, and (C) a chain-linking agent, and wherein: ri of the first olefin polymerization catalyst (r1A), and r-l of the second olefin polymerization catalyst (rß), are selected in such a way that the ratio (r1A / r? ß) under the conditions of polymerization is 0.5 or less, preferably 0. 25 or less, more preferably 0.125 or less, still more preferably 0.08 or less, and most preferably 0.04 or less. Additionally, now a process is provided, preferably a solution process, and more preferably a continuous solution process, for use in the polymerization of two or more addition polymerizable monomers, especially ethylene and at least one polymerizable copolymer, to form a high molecular weight segmented copolymer (multi-block copolymer), said copolymer containing two or more, preferably three or more, thereof different segments in one or more chemical or physical properties, as are further disclosed herein, the process comprising the steps of combining two or more addition polymerizable monomers, especially ethylene and at least one copolymerizable comonomer under the polymerization conditions , the composition comprising the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing different polymers in their chemical or physical properties , from the polymer prepared by the catalyst (A), under equivalent polymerization conditions, and (C) a chain-linking agent; and recovering the polymer product, wherein: ri of the first olefin polymerization catalyst (r1ñ), and ri of the second olefin polymerization catalyst (r1B), are selected such that the ratio (r1A / r1B) under the conditions of polymerization is 0.5 or less, preferably 0.25 or less, more preferably 0.125 or less, still more preferably 0.08 or less, and most preferably 0.04 or less. In addition, a composition is now provided for use in the polymerization of two or more polymerizable monomers by addition (referred to as monomers and comonomers, respectively), especially ethylene and at least one copolymerizable comonomer, for forming a high molecular weight segmented copolymer (multi-block copolymer), said copolymer containing two or more, preferably three or more different segments or blocks in one or more chemical or physical properties, as disclosed further in present, the composition comprising the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing different polymers in their chemical properties or of the polymer prepared by the catalyst (A), under equivalent polymerization conditions, and (C) a chain equivalent polymerization agent; wherein: the comonomer content in mole percent of the copolymer resulting from the first olefin polymerization catalyst (F-?), and the comonomer content in mole percent of the copolymer resulting from the second olefin polymerization catalyst (F2), are selected such that the ratio (F1 / F2) under the polymerization conditions is two or more, preferably four or more, more preferably 10 or more, still more preferably 15 or more, and most preferably 20 or more. Additionally, now a process is provided, preferably a solution process, more preferably a continuous solution process, for use in the polymerization of two or more addition polymerizable monomers (referred to as monomers and comonomers, respectively), especially ethylene and at least one copolymerizable comonomer, to form a high molecular weight segmented copolymer (multi-block copolymer), this copolymer containing two or more, preferably three or more different segments or blocks in one or more chemical or physical properties, as disclosed further herein, the process comprising the steps of combining, under the polymerization conditions: (A) a first olefin polymerization catalyst, (B) a second polymerization catalyst of olefin capable of preparing polymers different in their chemical or physical properties from the polymer prepared by the catalyst (A), under equivalent polymerization conditions, and (C) a chain-linking agent; wherein: the comonomer content in molar percentage of the copolymer resulting from the first olefin polymerization catalyst (Fi), and the comonomer content in molar percentage of the copolymer resulting from the second olefin polymerization catalyst (F2), are selected from such that the ratio (F1 / F2) under the polymerization conditions is two or more, preferably four or more, more preferably 1.0 or more, still more preferably 15 or more, and preferably 20 or more, under the polymerization conditions, and recover the polymer product. Monomers Suitable monomers for use in the preparation of the polymers of the present invention include ethylene and one or more additional polymerizable monomers of ethylene. Examples of suitable comonomers include straight or branched chain α-olefins of 3 to 30, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-ketene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cycloolefins from 3 to 30, preferably from 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1, 4,5, 8-dimethane - 1, 2,3,4,4a, 5, 8,8a-octahydronaphthalene, di- and poly-olefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1, 7 octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene; aromatic vinyl compounds, such as mono- or poly-alkylstyrenes (including styrene, o-methyl-styrene, m-methyl-styrene, p-methyl-styrene, or, p-dimethyl-styrene, o-ethylstyrene, m-ethylstyrene) , and p-ethylstyrene), and derivatives containing functional groups, such as methoxy-styrene, ethoxy-styrene, vinyl-benzoic acid, methyl vinyl-benzoate, vinyl-benzyl acetate, hydroxy-styrene, o-chloro- styrene, p-chloro-styrene, divinyl-benzene, 3-phenyl-propene, 4-phenyl-propene, a-methyl-styrene, vinyl chloride, 1,2-difluoro-ethylene, 1,2-dichloro-ethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1-propene. Chain Linking Agents The term "binding agent" refers to a compound or a mixture of compounds used in the composition of the present invention that is capable of causing the exchange of polimepium between at least two sites of active catalyst, catalysts included in the composition under the conditions of polymerization. That is, the transfer of a polymer fragment occurs both to and from one or more of the active catalyst sites. In contrast to a binding agent, a "chain transfer agent" causes the termination of the growth of the polymer chain, and adds up to a one-time transfer of the growing polymer from the catalyst to the transfer agent. Preferably, the linking agent has a RA-B / RB-A activity ratio of 0.01 to 1 00, more preferably 0.1 to 10, more preferably 0.5 to 2.0, and very highly preferable of 0.8 to 1.2, where RA-B is the transfer rate of polymeryl from the active site of catalyst A to the active site of catalyst B via the linking agent, and RB-A is the reverse transfer rate of polymeryl , that is, the exchange rate starting from the active site of catalyst B to the active site of catalyst A via the linking agent. Desirably, the intermediate formed between the linking agent and the polymeryl chain is sufficiently stable so that the chain termination is relatively rare. Desirably, less 90 percent, preferably less than 75 percent, more preferably less than 50 percent, and most desirably less than 10 percent bonding polymer products are terminated before obtaining three distinguishable polymer segments or blocks. Ideally, the chain link speed (defined as the time required to transfer a polymer chain from a catalyst site to the chain linker and then back to a catalyst site) is equivalent to, or faster than, the polymer termination speed, even up to 10 or even faster than the polymer termination speed. This allows the formation of polymeric block on the same time scale as the polymer propagation. By selecting different combinations of catalysts having different rates of comonomer incorporation, as well as different reactivities, and by pairing different bonding agents or agent mixtures with these catalyst combinations, polymer products can be prepared having segments of different densities or comonomer concentrations, different block lengths, and different numbers of these segments or blocks in each copolymer.

For example, if the activity of the binding agent is low relative to the propagation velocity of the polymeric catalyst chain of one or more of the catalysts, multiple block copolymers or polymer blends of a block length more may be obtained. long Conversely, if the link is very fast in relation to the propagation of the polymer chain, a copolymer having a more random chain structure and shorter block lengths is obtained. An extremely fast bonding agent can produce a multi-block copolymer which has substantially random copolymer properties. By appropriate selection of both the catalyst mixture and the linking agent, relatively pure block copolymers, copolymers containing relatively large polymer segments or blocks, and / or mixtures of the above with different homopolymers and / or copolymers can be obtained. of ethylene. For this invention, a suitable composition comprising Catalyst A, Catalyst B, and a chain-linking agent can be selected by the following multi-step procedure especially adapted for block differentiation based on the incorporation of the comonomer: . One or more polymerizable monomers are polymerized by addition, preferably olefin, using a mixture comprising a potential catalyst and a potential chain binding agent. This polymerization test is desirably carried out using a batch or semi-batch reactor (ie, without re-supplying catalyst or binding agent), preferably with a relatively constant monomer concentration, operating under polymerization conditions in solution, typically using a molar ratio of the catalyst to the chain-linking agent from 1: 5 to 1: 500. After forming an adequate amount of polymer, The reaction is terminated by the addition of a catalyst poison, and the properties of the polymer (Mw, M n), and Mw / Mn or PDI are measured). I. Previous polymerization and polymer test are repeated for several different reaction times, providing a series of polymers having a range of yields and values PDI. II I. Catalyst / bonding agent pairs that demonstrate significant polymer transfer, both to and from the bonding agent, are characterized by a polymer series wherein the minimum PDI is less than 2.0, more preferably less than 1.5. , and in a very preferable way less than 1 .3. In addition, if the chain link is being introduced, the Mn of the polymer will increase, preferably almost linearly, as the conversion increases. The most preferred catalyst / linker pairs are those that give the Mn of the polymer as a function of the conversion (or polymer yield) that fits a line with statistical precision (R2) of more than 0.95, preferably more than 0.99. Then, steps l-1 are carried out for one or more additional pairings of potential catalysts and / or supposed linkage agents. A suitable composition is then selected which comprises Catalyst A, Catalyst B, and one or more chain agents according to the invention, such that the two catalysts each suffer chain link with one or more of the chain agents. chain link, and Catalyst A has an index of higher comonomer incorporation (i.e. otherwise capable of selectively forming the polymer) compared to Catalyst B under the selected reaction conditions. More preferably, at least u of the chain linkers undergo polymer transfer in both the forward and reverse directions (as identified in the previous test) with both Catalyst A and Catalyst B. In addition, it is preferable that the chain-linking agent does not reduce the catalyst activity (measured by weight of the polymer produced per weight of catalyst per unit time) of any catalyst (compared to the activity in the absence of a linking agent). ) by more than 60 percent, more preferably this catalyst activity is not reduced by more than 20 percent, and most preferably, the catalyst activity of at least one of the catalysts is increased by comparing it with catalyst activity in the absence of a lace agent. Alternatively, it is also possible to detect the desirable catalyst / linker pairs by performing a series of polymerizations under conventional batch reaction conditions, and by measuring the resulting number-average molecular weights, PDI, and the yield of the polymer or production speed. Suitable binding agents are characterized by netting the resulting M n without significantly expanding the PDI, or without losing activity (reduction in performance or speed).

The above tests are easily adapted to fast production sifting techniques using automated reactors and analytical probes, and to the formation of polymer blocks having different distinctive properties. For example, a number of potential candidate binding agents can be previously identified or synthesized in situ by the combination of different organometallic compounds with different proton sources, and the compound or reaction product is added to a polymerization reaction using a olefin polymerization catalyst composition. Several polymerizations are conducted at different molar proportions of the binding agent to the catalyst. As a minimum requirement, suitable binding agents are those that produce a minimum PDI of less than 2.0 in variable performance experiments, as described above, so long as they do not significantly adversely affect the activity of the catalyst, and that preferably they improve the activity of the catalyst, as described in the foregoing. With respect to the method for identifying, a priori, a linking agent, the term refers to a compound that is capable of preparing the multiblock copolymers currently identified, or usefully employed under the polymerization conditions disclosed herein. In a highly desirable manner, according to the invention, multiple block copolymers having an average number of blocks or segments are formed by average chain (as defined as the average number of blocks of different composition divided by the Mn of the polymer) greater than 3.0, more preferably greater than 3.5, still more preferably greater than 4.0, and less than 25, preferably less than 1 5, more preferably less than 10.0, and most preferably less than 8.0. Suitable lace agents for use herein include compounds of Group 1, 2, 12, or 13 metals, or complexes containing at least one hydrocarbyl group of 1 to 20 carbon atoms, preferably compounds of aluminum, gallium, or zinc substituted by hydrocarbyl containing 1 to 1 2 carbon atoms in each hydrocarbyl group, and the reaction products thereof with a source of protons. Preferred hydrocarbyl groups are alkyl groups, preferably linear or branched alkyl groups of 2 to 8 carbon atoms. The most preferred linking agents for use in the present invention are trialkyl aluminum and dialkyl zinc compounds, especially triethyl aluminum, tri- (isopropyl) aluminum, tri- (isobutyl) aluminum, tri- ( normal hexyl) -aluminium, tri- (normal octyl) -auminium, triethyl-gallium, or diethyl-zinc. Additional suitable bonding agents include the reaction product or mixture formed by the combination of the above organometallic compound, preferably a tri-alkyl (1 to 8 carbon atoms) -aluminium, or di-alkyl- (1 at 8 carbon atoms) -zinc, especially triethylaluminum, tri- (isopropyl) -aluminium, tri- (isopropyl) -aluminium, tri- (hexy! or normal) -Iuminium, tri- (normal octyl) -aluminium, or diethyl zinc, with less of a stoichiometric amount of a secondary amine or a hydroxyl group, especially bis- (trimethylsilyl) -amine, terbutyl- (dimethyl) -siloxane, 2-hydroxy-methyl-pyridine, di- (normal pentyl) -amine, , 6-di- (tert-butyl) -phenol, ethyl- (1-naphthyl) -amine, bis- (2,3,6,7-dibenzo-1-azaciumheptanamine), or 2,6-diphenyl-phenol. Desirably, enough amine or hydroxyl reagent is used so that one hydrocarbyl group per metal atom remains. The primary reaction products of the above preferred combinations for use in the present invention as linking agents are di- (bis-trimethylsilyl) -amide) of n-octyl-aluminum, bis (dimethyl- (tert-butyl) -syloxide) isopropyl-aluminum, and di- (pyridinyl-2-methoxide) of n-octyl-aluminum, bis (dimethyl- (tert-butyl) -siloxane) of isobutyl-aluminum, bis (di- (trimethylsilyl) -amide of isobutyl-aluminum io , di- (pyridin-2-methoxide) of n-octyl-aluminum, bis- (di- (pentyl norl) -amide) of isobutyl-aluminum, bis (2,6-diterbutyl-phenoxide) of n-octyl- aluminum, di- (ethyl- (1-naphthyl) -amide) of n-octyl-aluminum, bis- (tert-butyl-dimethyl-silioxide) of ethyl-aluminum, di- (bis- (trimethylsilyl) -amide) of ethylaluminum, bis (2,3,6,7-dibenzo-1-azacycloheptanamide) of ethylaluminum, bis (2, 3,6,7-dibenzo-1-azacycloheptanamide) of n-octyl-aluminum, bis- (dimethyl) - (tert-butyl) -n-octyl-aluminum-oxide, (2,6-diphenyl-phenoxide) ethyl-zinc, and ethyl-zinc (tert-butoxide). However, a suitable binding agent for a catalyst or a combination of catalysts may not necessarily be as good or even satisfactory for use with a different catalyst or catalyst combination.

Some potential linkers may adversely affect the performance of one or more catalysts, and may be undesirable to also be used for that reason. In accordance with the above, the activity of the chain binding agent is desirably balanced with the catalytic activity of the catalysts to achieve the desirable properties of the polymer. In some embodiments of the invention, the best results can be obtained by using binding agents having a chain link activity (measured by the chain transfer rate) that is less than the maximum possible rate. However, in general, the preferred bonding agents possess the highest polymer transfer rates, as well as the highest transfer efficiencies (reduced chain termination incidences). These binding agents can be used in reduced concentrations, and can still achieve the desired degree of lace. In addition, these linking agents result in the production of shorter polymer block lengths possible. In a highly desirable manner, chain binding agents with a single exchange site are employed, due to the fact that the effective molecular weight of the polymer in the reactor is reduced, thereby reducing the viscosity of the reaction mixture, and thus reducing operating costs. Catalysts Suitable catalysts for use herein include any compound or combination of compounds that is Adapt to prepare polymers of the composition or of the desired type. Both heterogeneous and homogeneous catalysts can be used. Examples of heterogeneous catalysts include well-known Ziegler-Natta compositions, especially Group 4 metal halides supported on metal halides of Group 2, or mixed halides and alkoxides, and well-known vanadium chromium-based catalysts. . However, preferably, for ease of use, and for the production of narrow molecular weight polymer segments in solution, the catalysts for use herein are homogeneous catalysts comprising a relatively pure organometallic compound or a metal complex, especially compounds or complexes based on metals selected from Groups 3 to 10, or of the lanthanide series of the Periodic Table of the Elements. It is preferred that any catalyst employed herein does not significantly affect the performance of the other catalyst under the conditions of the present polymerization. Desirably, no catalyst is reduced in activity by more than 25 percent, more preferably more than 10 percent, under the conditions of the present polymerization. The metal complexes for use herein, which has a high comonomer incorporation index (catalyst A), include the transition metal complexes selected from Groups 3 to 1 5 of the Periodic Table of the Elements, which contain one or more delocalized p-linked ligands, or ligands of polyvalent Lewis base. Examples include metallocene, half-metallocene, of limited geometry, and polyvalent pyridylamine, or other complexes of polychelant base. The complexes are illustrated generically by the formula: M KkXxZz, or a dimer thereof, wherein: M is a metal selected from Groups 3 to 15, preferably 3 to 10, more preferably 4 to 8, and in a very preferable way from Group 4 of the Periodic Table of the Elements; K, independently in each presentation, is a group that contains delocalized p-electrons, or one or more pairs of electrons through which K is laced with M, this group containing up to 50 atoms without counting the hydrogen atoms; optionally, two or more K groups can be joined together, forming a bridged structure, and optionally one or more groups K can be linked with Z, with X, or both with Z and with X; X, independently in each presentation, is a monovalent anionic fraction that has up to 40 atoms that are not hydrogen; optionally, one or more X groups may be linked together, thereby forming a divalent or polyvalent anionic group, and optionally, one or more X groups and one or more Z groups may be linked together, thereby forming a fraction that is both covalently linked to M, and coordinated to it; Z, independently in each presentation, is a neutral Lewis base donor ligand of up to 50 non-hydrogen atoms, containing at least one pair of electrons not shared through which Z coordinates with M; k is an integer from 0 to 3; x is an integer from 1 to 4; z is a number from 0 to 3; and the sum of k + x is equal to the formal oxidation state of M. Suitable metal complexes include those containing 1 to 3 anionic or neutral p-linked ligand groups, which may be cyclic or non-cyclic delocalized p-linked ligand moieties. Examples of these p-linked groups are the diene and dienyl groups, allyl groups, boratabenzene groups, phosphols, and non-cyclic or non-cyclic conjugated or non-conjugated arene groups. The term "p-linked" means that the ligand group is bound to the transition metal by sharing electrons from a partially delocalized p-bond. Each atom in the delocalized p-linked group can be independently substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substituted heteroatoms wherein the heteroatom is selected from the groups 14 to 16 of the Periodic Table of the Elements, and these hydrocarbyl substituted heteroatom radicals are further substituted with a heteroatom containing Group 1 5 or 1 6. In addition, two or more of these radicals can together form a system of fused ring, including partially or completely hydrogenated fused ring systems, or they can form a metallocycle with the metal. Within the term "hydrocarbyl" are included the straight, branched, and cyclic carbon atoms of 1 to 20 carbon atoms, the aromatic radicals of 6 to 20 carbon atoms, the alkyl substituted aromatic radicals of 7 to 20 carbon atoms , and alkyl radicals substituted by aryl of 7 to 20 carbon atoms.

Suitable hydrocarbyl substituted heteroatom radicals include the mono-, di-, and tri-substituted boron, silicon, germanium, nitrogen, phosphorus or oxygen radicals, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. carbon Examples include the N, N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, tert-butyl-dimethyl-silyl, methyldi (tert-butyl) -silyl, triphenyl-germyl, and trimethyl-germyl groups. Examples of the heteroatom containing fractions of Group 1 5 or 16 include the amino, phosphino, alkoxy moieties, or thioalkyl, or its divalent derivatives, for example the amide, phosphide, alkyleneoxy, or thioalkylene groups bonded to the transition metal or the lanthanide metal, and linked to the hydrocarbyl group, to the p-linked group, or to the heteroatom substituted by hydrocarbyl. Examples of suitable anionic delocalized p-linked groups include the cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, the phosphine and boratabenzyl groups, as well as their inertly substituted derivatives. , especially hydrocarbyl substituted derivatives of 1 to 10 carbon atoms or substituted by tris (1 to 10 carbon atoms) of silyl thereof. The preferred anionic delocalized p-linked groups are cyclopentadienyl, pen tameti I-cyclope nta-diene, tetramethi-cyclope nadienyl, tetramethyl-silylcyclopentadienyl, indenyl, 2,3-dimethyl-indenyl, fluorenyl, 2- methyl-indenyl, 2-methyl-4-phenyl-indenyl, tetrahydrofluorenyl, octahydro-fluorenyl, 1-indanyl, 3-pyrrolidine-inden-1-yl, 3,4- (cyclopenta (/) phenanthren-1 - ilo, and tetrahydro-indenyl Boratabenzene ligands are anionic ligands that are benzene analogs containing boron.They were previously known in the art, having been described by G. Herberich et al., in Organometallics, 14, 1, 471-480 (1995) Preferred boratabenzene ligands correspond to the formula: wherein R1 is an inert substituent, preferably selected from the group consisting of hydrogen, hydrocarbyl, silyl, halogen or germyl, this R1 having up to 20 atoms not counting hydrogen, and optionally two adjacent R1 groups may be attached between yes. In complexes involving divalent derivatives of these delocalized p-linked groups, one atom thereof is linked by means of a covalent bond or a divalent group covalently bonded to another atom of the complex, thereby forming a bridged system.

The phosphols are anionic ligands that are analogs of a cyclopentadienyl group containing phosphorus. Previously they were known in the art, having been described by International Publication Number WO 98/50392, and elsewhere. Preferred phosphol ligands correspond to the formula: wherein R1 is as defined above. Preferred transition metal complexes for use herein correspond to the formula: MKkXxZz, or a dimer thereof, wherein: M is a Group 4 metal; K is a group containing delocalized p-electrons through which K is linked to M, this group containing up to 50 atoms without counting the hydrogen atoms; optionally two K groups can be joined together forming a bridged structure; and optionally a K can be linked with X or Z; X, in each presentation, is a monovalent anionic fraction that has up to 40 non-hydrogen atoms; optionally one or more groups X and one or more K groups are linked together to form a metallocycle; and optionally additionally one or more X groups and one or more Z groups are linked together, thereby forming a fraction that is both covalently linked to M and coordinated the same; Z, independently in each presentation, is a neutral Lewis base donor ligand of up to 50 non-hydrogen atoms, containing at least one pair of unshared electrons through which Z coordinates with M; k is an integer from 0 to 3; x is an integer from 1 to 4; z is a number from 0 to 3; and the sum of k + x is equal to the formal oxidation state of M. Preferred complexes include those that contain either one or two K groups. The last complexes include those that contain a bridging group that binds to both K groups. The preferred bridging groups are those corresponding to the formula (ER'2) e, wherein e is silicon, germanium, tin or carbon; RS independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, this R 'having up to 30 carbon or silicon atoms, and e is from 1 to 8. Preferably, RS independently in each presentation, it is methyl, ethyl, propyl, benzyl, tertbutyl, phenyl, methoxy, ethoxy, or phenoxy. Examples of complexes containing two K groups are the complexes corresponding to the formula: wherein: M is titanium, zirconium, or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4; R3, in each presentation, is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, and combinations thereof, this R3 having up to 20 non-hydrogen atoms, or the groups Adjacent R3 together form a divalent derivative (i.e., a hydrocarbaryl, siladiyl, or germadiyl group), thereby forming a fused ring system, and X ", independently in each presentation, is an anionic ligand group of up to 40 atoms which are not hydrogen, or two groups X "together form a divalent anionic ligand group of up to 40 non-hydrogen carbon atoms, or are together a conjugated diene having from 4 to 30 non-hydrogen atoms linked by means of delocalized p-electrons with M, on which, M is in the formal oxidation state +2, and RS E, e are as defined above. Exemplary bridged ligands containing two p-linked groups are: dimethylbis- (cyclopentadienyl) -silane, dimethylbis- (tetramethyl-cyclopentadienyl) -silane, dimethylbis- (2-ethyl-cyclopentadien-1-yl) -silane, dimethylbis- (2-tert-butyl-cyclopentadien-1-yl) - silane, 2, 2-bis- (tetramethyl-cyclopentadiene and I) -propane, dimethylbis- (inden-1 -yl) -silane, dimethylbis- (tetrahydro-inden-1 -yl) -silane, dimethylbis- (fluoren-1-yl) -silane, dimethylbis- (tetrahydro-fluoren-1-yl) -silane, d-methylbis- (2-methyl-4-phen-linden-1-yl) -silane, d imeti l-bis - (2-methyl-inden-1-yl) -silane, dimethyl- (cyclopenta-dienyl) - (fluoren-1-yl) -silane, dimethyl- (cyclopenta-dyl) - (octahydro-fluoren-1 - L) -silane, d imeti I- (cyclopenta-dienyl) - (tetrahydro-fluoren-1-yl) -silane, (1,1-, 2,2-tetramethyl) -1,2-bis- (cyclopentadienyl) ) -disilane, (1, 2-bis- (cyclopentadienyl) -ethane, and dimethyl- (cyclopentadienyl) -1- (fluoren-1-yl) -methane The X groups "are selected from the hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl, and aminohydroca groups ribut, or two X groups "together form a divalent derivative of a conjugated diene, or otherwise together form a neutral p-linked conjugated diene. The most preferred groups X are hydrocarbyl groups of 1 to 20 carbon atoms Examples of the metal complexes of the above formula suitable for use in the present invention include: bis (cyclopentadienyl) -zirconium-dimethyl, bis (cyclopentadienyl) ) -zirconium-dibenzyl, bis (cyclopentadienyl) -zirconium-methyl-benzyl, bis (cyclopentadienyl) -zirconium-methyl-phenyl, bis (cyclopentadienyl) -zirconium-diphenyl, bis (cyclopentadienyl) -titanium-allyl, methoxide bis (cyclopentadienyl) zirconium methyl, bis (cyclopentadienyl) zirconium methyl, bis (pentamethyl cyclopentadienyl) zirconium dimethyl, bis (pen tameti I-ciclope ntadien yl) -titanium-d imeti as chloride, bis (indenyl) -zirconium-dimethyl, indenyl-fluorenyl-zirconium-dimethyl, bis (indenyl) -zirconium-methyl- (2- (dimethylamido) -benzyl, bis (indenyl) -zirconium-methyl-trimethylsilyl, bis (tetrahydroindenyl) ) zirconium-methyl-trimet¡lsililo, bis (pentamethylcyclopentadienyl) -z¡rcon¡o benc¡lo methyl, bis (pentamethyl-cyclopentadiene yl) zirconium dibenzyl methoxide, bis (pentamethylcyclopentadienyl) -zirconio- methyl, bis (pentamethyl-cyclopentadienyl) -zirconium-methyl chloride, bis (methyl-ethyl-cyclopentadienyl) -zirconium-dimethyl, bis (butyl-cyclopentadienyl) -zirconium-d-benzyl, bis (tert-butyl-cyclopentadiene) - zirconium-dimethyl, bis (ethyltetra-methyl-cyclopentadienyl) -zirconium-dimethyl, bis (methyl-propyl-cyclopentadienyl) -zircon-io-dibenzyl, bis (trimethylsilyl-cyclopentadienyl) -zirconium -di benzyl dimetilsililbis- dihydrochloride (cyclopentadienyl) zirconium dichloride, dimetilsililbis- (cyclopentadienyl) zirconium dimethyl, dimethyl sililbis- (tetramethyl-cyclopentadienyl) -titanio- (III) -allyl dichloride, dimethyl sililbis- (tertbutyl -cyclopentadienyl) -zirconium, dimethylsilylbis- (n-butylcyclopentadienyl) -zirconium dichloride, (dimethylsilylbis- (tetramethyl-cyclo-pentadienyl) -titanium (III) -2- (dimethylamino) - benzyl, (d imeti lsiliIbis- (n-butilciclo-pentadienyl) titanium (III) -2- (dimethylamino) - benzyl dimetilsiIilbis- dihydrochloride (inden yl) zirconium dimethyl-sililbis- (indenyl) zirconium dimethyl , dimethylsilylbis- (2-methylindenyl) -zirconium-d-imethyl, dimethylsilylbis- (2-methyl-4-phenyl-n-nyl) -zirconium-d-imethyl, dimethylsilylbis- (2-methylindenyl) -zirconium-1,4-diphenyl-1 , 3-butadiene, d-imeti-lysilylbis- (2-methyl-4-phen-linden-il) -zirconium- (11) -1,4-diphenyl-1, 3-butadiene, dimethyl-dichloride- (4) , 5,6,7-tetrahydroinden-1-yl) -zirconium, dimethylsilylbis- (4,5,6,7-tetrahydroinden-1-yl) -zirconium-dimethyl, dimethylsilylbis- (tetrahydroindenyl) -zirconium- ( ) -1, 4-diphenyl-1, 3-butadiene dimetilsililbis- (tetramethylcyclopentadienyl) zirconium-d imetilo, dimetilsililbis- (fluorenyl) zirconium dimethyl, dimetilsililbis- (tetrahydrofluorenyl) zirconium bis (trimethylsilyl), ethylenebis - (indenyl) -zirconium, ethylene bis- (indenyl) -zirconium-dimethyl, ethylenebis- dichloride- (4,5,6,7-t) idroindenil etrah) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, (isopropylidene) - (cyclopentadienyl) - (fluorenyl) zirconium dibenzyl, d imeti lsilil- (I-ciclope tetrameti ntadien il) - (fluorenil) -zirconium-d imeti lo. An additional class of metal complexes used in the present invention corresponds to the above formula, or a dimer thereof, wherein M, K, X, x, and z are as defined above, and Z is a substituent of up to 50 non-hydrogen atoms, which, together with K, forms a metallocycle with M. Preferred Z substituents include groups containing up to 30 non-hydrogen atoms, comprising at least one atom which is oxygen, sulfur, boron, or a member of Group 14 of the Periodic Table of the Elements directly attached to K, and a different atom selected from the group that consists of nitrogen, phosphorus, oxygen, or sulfur, which is covalently bound to M. More specifically, this class of Group 4 metal complexes used in accordance with the present invention includes the "limited geometry catalysts" corresponding to the formula: wherein: M is titanium or zirconium, preferably titanium in the formal oxidation state +2, +3, or +4; K1 is a group of delocalized p-ligand optionally substituted with from 1 to 5 g R2, R2 moieties, in each presentation, is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen , and combinations thereof, this R2 having up to 20 non-hydrogen atoms, or the adjacent R2 groups together form a divalent derivative (i.e., a hydrocarbyl, siladiyl, or germadiyl), thereby forming a ring system fused, each X is a halogen, hydrocarbyl, hydrocarbyloxy, or silyl group, this group having up to 20 non-hydrogen atoms, or two X groups together form a neutral conjugated diene of 5 to 30 carbon atoms, or a divalent derivative of the same; x is 1 or 2; and is -O-, -S-, -NR '-_ -PR'-; X "is SiRS, CR'2, CR'2CR'2, CR '= CRS CR'2SiR'2, or GeR'2, wherein: RS independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof , this R 'having up to 30 carbon or silicon atoms. Specific examples of the complexes of metals of limited geometry above include the corresponding compounds of the formula: wherein: Ar is an aryl group of 6 to 30 atoms, not counting hydrogen; R4, independently in each presentation, is hydrogen, Ar, or a different group of Ar, selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbyl-germyl, halide, hydrocarbyloxy, tri h id rock rb i Is i I oxylo, bis- (trih idrocarbil-syl) -amino, di- (hydrocarbyl) -amino, hydrocarbonylamino, hydrocarbyl imino, di (hydrocarbyl) phosphino, hydrocarbhalloylphosphino, hydrocarbyl sulphide, hydrocarbyl substituted by halogen, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by trihydrocarbylsilyl, hydrocarbyl substituted by trihydrocarbylsiloxyl, hydrocarbyl substituted by bis (trihydrocarbylsilyl) -amino, hydrocarbyl substituted by di- (hydrocarbyl) -amino, hydrocarbyl substituted by hydrocarbylamino; hydrocarbyl substituted by di (hydrocarbyl) -phosphine, hydrocarbyl substituted by hydrocarbylenephosphine, or hydrocarbyl substituted by hydrocarbyl sulfide, this group having R up to 40 atoms without counting the hydrogen atoms, and up to two adjacent R4 groups may be linked together, forming a group of polycyclic fused ring; M is titanium; X 'is SiR62, CR62, SiR62Si R62, CR62CR62, CR6 = CR6, CR62SiR62, BR6, BR6L ", or GeR62; Y is -O-, -S-, -N R5-, -PR5-, -NR52, or - PR52; R5, independently in each presentation, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilyl-hydrocarbyl, this group having R5 up to 20 different hydrogen atoms, and optionally two groups R5, or R5 together with Y or Z, form a ring system; R6, independently in each presentation, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, -NR52, and combinations thereof, this R6 having up to 20 atoms that are not of hydrogen, and optionally two groups R6, or R6 together with Z, form a ring system; Z is a neutral diene or a monodentate or polydentate Lewis base optionally linked to R5, R6, or X; X is hydrogen, a monovalent anionic ligand group having up to 60 atoms without counting hydrogen, or two X groups are joined together thus forming a divalent ligand group; x is 1 or 2; z is 0, 1, or 2. Preferred examples of the above metal complexes are substituted in either the 3-position or the 4-position of a cyclopentadienyl or indenyl group, with an Ar group. Examples of the above metal complexes include: (3-phenylcyclopentadien-1-yl) -dimethyl- (tert-butyl-amido) -silane-titanium dichloride, (3-f in yl-cyclo pen tadien-1-yl) - di meti l- (terbutyl lamido) -sily non-titanium-dimethyl, (3-phenylcyclopentadien-1-yl) -dimethyl- (terbutylamido) -silane-titanium- (ll) -1,3-diphenyl-1, 3-butadiene; (3- (pyrrol-1-yl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium dichloride, 3- (pyrrol-1-yl) -cyclopentadien-1-yl) -dimethyl- ( terbutylamido) -silane-titanium-dimethyl, (3- (pyrrol-1-yl) -cyclopentad-1-yl) -d-imeti-l- (t-butylamido) -silane-ti- tanium- (II) -1, 4-diphenyl-1,3-butadiene, (3- (1-methylpyrrole) -3-i!) - cyclopentadien-1-yl) -dimethyl dichloride (terbutylamido) -silane-titanium, (3- (1-methylpyrrol-3-yl) -cyclopentadien-1-yl) -dimethyl- (tert-butyl-amido) -silane-titanium-dimethyl, (3- (1-methylpyrrol- 3-yl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium- (II) -1,4-diphenyl-1,3-butadiene, (3,4-diphenyl-cyclopentadiene-1-dichloride) il) -dimethyl- (terbutylamido) -silane-titanium, (3,4-diphenylcyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, (3,4-diphenylcyclopentadien-1-yl) -dimethyl - (tert-butylamido) -silane-titanium- (ll) -1,3-pentadiene, (3- (3-N, N-dimethylamino) -phenyl) -cyclopentadien-1-yl) -di methyldichloride I- (terbutylamido) -if the non-tita nio, (3- (3-N, N-dimethylamino) -phenyl) -cyclopentadien-1-yl) -dimethyl- (terbuti la mido) -if the non-titanium- di methylo, (3- (3-N, N-dimethylamino) -phenyl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium- (II) -1,4-diphenyl-1, 3 -butadiene, (3- (4-methoxypheni) -4-methylcyclopentadien-1-yl) -dimethyl- dichloride (te rbuti la mido) -if the non-tita nio, ( 3- (4-methoxyphenyl) -4-methylcyclopentadien-1-yl) -dimethyl- (tert butylamido) -silyl-titanium-dimethyl, (3- (4-methoxyphenyl) -4-methylcyclopentadien-1-yl) -dimethyl- (terbutylamido) -silyano-titanium- (ll) -1,4-diphenyl-1,3-butadiene, (3-phenyl-4-methoxycyclopentadien-1-yl) -dimethyl- (terbutylamido) dichloride - silane-titanium, (3-phenyl-4-methoxycyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, (3-phenyl-4-methoxycyclopentadien-1-yl) -dimethyl- (tert-butylamido) - titanium-titanium- (ll) -1,4-diphenyl-1,3-butadiene, (3-phenyl-4- (N, N-dimethylamino) -cyclopentadien-1-yl) -dimethyl- (terbutylamido) dichloride - silane-titanium, (3-phenyl-4- (N, N-dimethylamino) -cyclopentadien-1-yl) -dimethyl- (te rb uti mido) -if the non-titanium-di methylo, (3-phenyl) -4- (N, N-dimethylamino) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium- (II) -1,4-diphenyl-1,3-butadiene, 2-methyl- dichloride (3,4-di- (4-methylphenyl) -cyclopentadien-1-yl) -dimetiI- (te rb uti lam ido) -if the non-tita nio, 2-methyl- (3,4-di- (4 -methylphenyl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, 2-methyl- (3,4-di- (4-methylphenyl) -cyclopentadien-1-yl) -dimethyl- ( terbutylamido) -silane-titanium- (ll) -1,4-diphenyl-1,3-butadiene, dichloride ((2,3-d-fe-l-l) -4- (N, N-dimethylamine) -cyclo -pen tadien-1 -il) -di methyl- (tert-butylamido) -silyano-titanium, ((2,3-diphenyl) -4- (N, N-dimethylamino) -cyclopentadiene-1-l) -dimethyl- (tert-butylamido) -siolone -titanium-d-methyl, ((2,3-diphenyl) -4- (N, N-dimethylamino) -cydo-pentadien-1-yl) -dimethyl- (tert-butylamido) -sily n-tite nio- (l I) - 1,4-diphenyl-1,3-butadiene, (2,3,4-triphenyl-5-methyl-cyclopentad-1-yl) -dimethyl-tert-butylamido-silane-titanium dichloride, (2, 3, 4-trif in l-5-met i Iciclopentad ¡en- 1 -il) -di meti l- (terbuti lam do) -if the non-titanium-dimethyl, (2,3,4 -triphenyl-5-methylcyclopentadien-1-yl) -dimetiI- (terbutylamido) -saluminium- (II) -1,4-diphenyl-1,3-butadiene, 3- (phenyl-4-methoxycyclopentadiene) dichloride -1-yl) -dimethyl- (tert-butylamido) -silane-titanium, 3- (phenyl-4-methoxycyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, 3- (phenyl-4-) m etoxi cid open tadien-1 -il) -di meti l- (terb uti lam id o) -si lañótitanio- (ll) -1, 4-diphenyl-1,3-butadiene, dichloride (2,3-diphenyl) -4- (n-butyl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium, (2,3-diflume-4- (n-butyl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, (2,3-diphenyl-4- (n-butyl) -cyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium- (II) -1, 4- diphenyl ilo-1, 3-butadiene, (2,3,4,5-tetraphenylcyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium dichloride, (2, 3,4,5-tetraphenylacyclopentadiene-1) -yl) -dimethyl- (tert-butylamido) -silane-titanium-dimethyl, and (2, 3,4,5-tetraphenylcyclopentadien-1-yl) -dimethyl- (tert-butylamido) -silane-titanium- (ll) -1 , 4-diphen-l, 3-butadiene. Additional examples of metal complexes suitable for use as catalyst (A) herein, are polycyclic complexes corresponding to the formula: where M is titanium in the formal oxidation state +2, +3, or +4; R7, independently in each presentation, is hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbyl) -amino, hydrocarbylamino, di (hydrocarbyl) -phosphino, hydrocarbylene-phosphino, hydrocarbyl sulphide, hydrocarbyl substituted by halogen , hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by silyl, hydrocarbyl substituted by hydrocarbylsiloxyl hyd, hydrocarbyl substituted by hydrocarbylsilylamino, hydrocarbyl substituted by di (hydrocarbyl) amino, hydrocarbyl substituted by hydrocarbonylamino, hydrocarbyl substituted by di- (hydrocarbyl) -phosphino, hydro rocarbyl substituted by hydrocarbylene phosphino, or hydrocarbyl substituted by hydrocarbyl sulphide, this group R7 having up to 40 atoms without hydrogen, and optionally two or more of the above groups can together form a divalent derivative; R8 is a divalent hydrocarbylene or substituted hydrocarbylene group which forms a system fused with the rest of the metal complex, this R8 containing from 1 to 30 atoms without counting hydrogen; Xa is a divalent moiety, or a moiety comprising a -s bond, and a pair of two neutral electrons capable of forming a covalent-covalent bond with M, this Xa boron comprising, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur, or oxygen; X is a monovalent anionic ligand group having up to 60 atoms, excluding the class of ligands which are groups of cyclized delocalized p-linked ligands, and optionally two X groups together form a divalent ligand group; Z, independently in each presentation, is a neutral binder compound having up to 20 atoms; x is 0, 1, or 2; and z is 0 or 1. Preferred examples of these complexes are the 3-phenyl substituted s-indecenyl complexes corresponding to the formula: The s-indecenyl complexes substituted by 2,3-dimethyl corresponding to the formulas: or the 2-methyl substituted s-indecenyl complexes corresponding to the formula: Additional examples of the metal complexes that are usefully employed as the catalyst (A) according to the present invention include those of the formula: Specific metal complexes include: (8-methylene-1,8-dihydrodibenzo [e, .. ^ - ulen-1-yl) -N- (1,1-dimethylethiimethylsilanamide-titanium-Ol, 4-diphenyl- 1,3-butadiene, (8-methylene-1, 8-dihydrodibenzo [e, ft] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (ll) -1, 3-pentadiene, (8-methylene-1,8-dihydrodibenzo [e, 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (III) -2- (N, N-dimethylamino) -benzyl, (8-methylene-1,8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1, 1-dimethylethyl) -dimethylsilanamide-titanium- (IV) dichloride, (8-Methylene-1, 8-dihydro-d-benzo [e, fr] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (IV) -dimethyl, (8- methylene-1, 8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (IV) -dibenzyl, (8-difluoromethylene-1,8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (ll) -1,4-diphenyl-1,3-butadiene, (8-difluoromethylene-1, 8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (ll) -1,3-pentadiene, (8-difluoromethylene-1,8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (II) -2- (N, N-dimethylamino) -benzyl, (8-difluoromethylene) dichloride 1,8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethyethyl) -dimetils ilanamide-titanium- (IV), (8-difluoromethylene-1,8-dihydrodibenzo [e, 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilyanamide-titanium- (IV) -dimethyl, (8-difluoromethylene-1,8-dihydrodibenzo [e, / 7] azulen-1-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (IV) -dibenzyl, (8-methylene-1, 8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1, 1-di meti leti I) - dimethylsilanamide-titanium- (II) -1,4-diphenyl-1 , 3-butadiene, (8-methylene-1, 8-dihydrodibenzo [e, / 7] azulen-2-yl) -N- (1, 1-dimethylethyl) -dimethyl-silanamide-titanium- (ll) -1, 3-pentadiene, (8-methylene-1, 8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1, 1-d imeti leti I) - dimethylsilyanamide-titanium- (III) -2- ( N, N-dimethylamino) -benzyl, (8-methylene-1, 8-dihydrodibenzo [e, /?] Azulen-2-yl) -N- (1, 1- dimethylethyl) -d imeti isilanamide-titanium- dichloride (IV), (8-methylene-1, 8-dihydrodibenzo [e, 7] azuIen-2-yl) -N- (1, 1-di meti leti I) - dimethylsilanamide-titanium- (IV) -d imeti lo, (8-methylene-1, 8-dihydrodibenzo [e, / 7] azulen-2-yl) -N- (1,1-dimethylethyl) -d imeti Isi Pan amida-tita nio- (IV) -di benzyl, (8-difluoromethiien-1, 8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1, 1-dimethylethyl) -d imeti Is i nam ida-tita nio- (l I) - 1,4-diphen-1, 3-butadiene, (8-difluoromethylene-1,8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide- titanium- (ll) -1,3-pentadiene, (8-difluoromethylene-1,8-dihydrodibenzo [e,?] azulen-2-yl) -N- (1,1-dimethylethyl) -dimethylsilanamide-titanium- (III) ) -2- (N, N-dimethylamino) -benzyl, (8-difluoromethyl-1, 8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1, 1-d imeti letiI) dichloride - dimethylsilanamide-titanium- (IV), (8-difluoromethylene-1, 8-dihydrodibenzo [e, 7] azulen-2-yl) -N- (1,1-dimethylethyl) -di meti Isi nam id a-tita nio - (IV) -di meti lo, (8-difluoromethylene-1, 8-dihydrodibenzo [e, ft] azulen-2-yl) -N- (1, 1-dimethylethyl) -dimethylsilanamide-titanium- (IV) -dibenzyl , and mixtures thereof, especially mixtures of positional isomers.

Other illustrative examples of metal complexes to be used according to the present invention correspond to the formula: where M is titanium in the formal oxidation state +2, +3, or +4; T is -NR9- or -O-; R9 is hydrocarbyl, silyl, germyl, dihydrocarbyl-boryl, or halohydrocarbyl, or up to 10 atoms without counting hydrogen; R10, independently in each presentation, is hydrogeno, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbyl-silylhydrocarbyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbyl) -amino, hydrocarbylamino, di- (hydrocarbyl) -phosphino, hydrocarbyl- phosphino, hydrocarbyl sulphide, hydrocarbyl substituted by halogen, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by silyl, hydrocarbyl substituted by hydroxybylsiloxyl, hydrocarbyl substituted by hydrocarbylsilylamino, hydrocarbyl substituted by di- (hydrocarbyl) -amino, hydrocarbyl substituted by hydrocarbylene, hydrocarbyl substituted by di- (hydrocarbyl) phosphino, hydrocarbyl substituted by hydrocarbylene phosphino, or hydrocarbyl substituted by hydrobiisulfide, this group R10 having up to 40 atoms without counting the hydrogen atoms, and optionally two or more of the groups R1 Anterior adjacent 0s may together form a divalent derivative, thereby forming a saturated or unsaturated fused ring; Xa is a divalent moiety lacking delocalised p-electrons, or this fraction comprising a s-bond and a pair of two neutral electrons capable of forming a covalent-covalent bond with M, comprising this X 'boron, or a member of the Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur, or oxygen; X is a monovalent anionic ligand group having up to 60 atoms, excluding the class of ligands that are groups of cyclic ligands linked to M through delocalized p-electrons, or two X groups are together a divalent anionic ligand group; Z, independently in each presentation, is a neutral binder compound having up to 20 atoms; x is 0, 1, 2, or 3; and z is 0 or 1. In a highly preferable manner, T is = N (CH3), X is halogen or hydrocarbyl, x is 2, X 'is dimethylsilane, z is 0, and R10 is at each presentation hydrogen, a hydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbon group -bilenamino, hydrocarbyl substituted by dihydrocarbylamino, or hydrocarbyl substituted by hydrocarbylamino of up to 20 atoms without counting hydrogen, and optionally two R10 groups can be linked together. Illustrative metal complexes of the above formula which may be employed in the practice of the present invention further include the following compounds: (terbutylamido) -dimethyl- [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (11) -1,4-diphenyl-1,3-butadiene, (terbutylamido) -dimethyl- [6,7] ] -benzo- [4,5: 2S3 ') - (1-methyl-isoindole) - (3H) -inden-2-yl) -silyano-titanium- (II) -1, 3-pentadiene, (terbutylamido) ) -dimethyl- [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3 H) -inden-2-yl) -silane-titanium- (III) -2- (N, N-dimethylamino) -benzyl, dichloride. of (terbutylamido) -dimethyl- [6,7] -benzo- [4,5: 2 \ 3 ') - (1-methyl-isopyol) - (3H) -inden-2-yl) -silane-titanium- (IV), (terbutylamido) -dimethyl- [6,7] -benzo- [4, 5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -d-imethyl, (tert-butylamido) -dimethyl- [6, 7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane -titanium- (IV) -dibenzyl, (tert-butylamido) -dimethyl- [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silyna-titan io- (IV) -bis- (trimethyl-silyl), (cyclohexylamido) -d imeti l- [6,7] -benzo- [4, 5: 2 \ 3 ') - (1-methyl- isoindol) - (3H) -inden-2-yl) -silane-titanium- (ll) -1,4-diphenyl-1,3-butadiene, (cyclohexyl-amyl) -dimethyl- [6,7 ] -benzo- [4,5: 2 \ 3 ') - (1-methyl-isoindole) - (3H) -inden-2-yl) -silane-titanium- (II) -1,3-pentadiene, (cyclohexylamido) -dimethyl- [6, 7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) - inden-2-yl) -silyano-titanium- (III) -2- (N, N-dimethylamino) -benzyl, (cyclohexylamido) -dimethyl- [6,7] -benzo- dichloride [4,5: 2 \ 3 ') - (1-methyl-isoindoI) - (3H) -inden-2-yl) -silane-titanium- (IV), (cyclohexylamido) -dimethyl- [6,7] -benzo- [4, 5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -dimethoxy, (cyclohexylamido) -dimethyl- [6,7] -benzo - [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -dibenzyl, (cyclohexylamido) -dimethyl- [6,7 ] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -bis- (trimethyl-silyl), (terbutylamido) -di- (p -methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -siolone- titanium- (II) -1,4-diphenyl-1,3-butadiene, (terbutylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2 \ 3 ') - ( 1-methyl-isoindole) - (3H) -inden-2-yl) -silane-titanium- (11) -1,3-pentadiene, (terbutylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (III) -2- (N, N-dimethylamino) -benzyl, dichloro (terbutylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2 ', 3') - (1-methyl-isoindol) - (3H) -inden-2- il) -silane-titanium- (IV), (terbutylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindole) - (3H) -inden-2-yl) -silane-titanium- (IV) -dimethyl, (tert-butylamido) -di- (p-methylphenyl) - [6, 7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -dibenzyl, (terbutylamido) -di- (p-methylphenyl) - [6,7] -benzo- [ 4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) -bis- (trimethylsilyl), (cyclohexylamido) -di- (p- methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (ll) -1, 4 -diphenyl-1, 3-butadiene, (cyclohexylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindole) - (3H) -inden-2-yl) -si-Nanano titanium- (ll) -1,3-pentadiene, (cyclohexylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2 \ 3 ') - (1-methyl- isoindol) - (3H) -inden-2-yl) -silane-titanium- (III) -2- (N, N-dimethylamino) -benzyl, dichloride of (cyclohexylamido) -di- (p-methylphenyl) - [6 , 7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -s-alan-titanium- (IV), (cyclohexylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) -silane-titanium- (IV) - dimethyl, (cyclohexylamido) -di- (p-methylphenyl) - [6,7] -benzo- [4,5: 2S3 ') - (1-methyl-isoindol) - (3H) -inden-2-yl) - titanium-titanium- (IV) -dibenzyl, and (cyclohexylamido) -di- (p-methylphenyl) - [6, 7] -benzo- [4,5: 2 3 ') - (1-methyl-isoindol) - ( 3H) -inden-2-yl) -silane-titanium- (IV) -bis (trimethyl-silicon). Illustrative Group 4 metal complexes that can be employed in the practice of the present invention further include: (terbutylamido) - (1, 1-dimethyl-2,3,4,9, 1 0 -? - 1, 4,5,6,7,8-hexah idro-naphthalenyl) -dimethyl-silane-titanium-d imeti lo, (terbutylamido) - (1, 1, 2, 3-tetramethi 1-2,3, 4, 9, 1 0 -? - 1, 4, 5,6,7, 8-hexah id ro-n afta le ni I) -di meti Is i the non-titanium-di meti lo, (te rb uti lam id o) - (tetramethyl-? 5-cyclope ntadien il) -d imeti I-if the no-tita nor o-dibenzyl, (te rbu tila mido ) - (tetramethyl-? 5-cyclope ntadien il) -d imeti l-sila non-titanium-dimethyl, (terbutylamido) - (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl-titanium-dimethyl, (terbutylamido) - (tetramethyl-? 5-indenyl) -dimethyl-silane-titanium-d-imethyl, (terbutylamido) - (tetramethyl-? 5-cyclopentadienyl) -dimethyl-silane-titanium- (III) -2- (dimethylamino) -benzyl, (te rbu ti lam o) - (tetra methylo-? 5-cyclope ntadien il) -di meti I-if the no-tita ni o- (lll) -alilo, (te rb uti lam ido) - (tetramethyl-? 5-cyclopentan-il) -d imeti ls ilan o-titan io- ( lll) -2,4-dimethylpentadienyl, (te rb uti lam id o) - (tetramethyl-? 5-cyclope ntadien il) -d imeti ls i la no-tita nio- (l I) - 1, 4-diphenyl- 1, 3-butadiene, (terbutylamido) - (tetramethyl-? 5-cyclopentadienyl) -dimethyl-silane-t-tatano- (ll) -1,3-pentadiene, (terbutylamido) - ( 2-Methylindenyl) -dimethyl-silane-titanium- (ll) -1,4-dif-i-1, 3-butadiene, (terbutylamido) - (2-methylindenyl) -dimethyl-silane-titanium- (II) ) -2,4-hexadiene, (tert-butylamido) - (2-methylindenyl) -dimethyI-silane-titanium- (IV) -2,3-dimethyl-1,3-butadiene, (terbutylamido) - (2-methylindenyl) - dimethylsilane-titanium- (IV) -isoprene, (terbutylamido) - (2-methylindenyl) -dimethyl-silane-titanium- (IV) -1,3-butadiene, (terbutylamido) - (2,3-dimethylindenyl) -dimethyl-silane-titanium- (IV) -2,3-dimethyl-1,3-butadiene, (terbutylamido) - (2,3-dimethylindenyl) -d imeti l- silane-titanium- (IV) -isoprene, (tert-butylamido) - (2,3-d-imethylindenyl) -dimethyl-silane-titanium- (IV) -d-imethyl ester, (tert-butylamido) - (2,3-dimethylindenyl) -dimethyl-silane-titanium- (IV) -dibenzyl, (terbutylamido) - (2,3-dimethylindenyl) -dimethyl-silane-titanium- (IV) -1,3-butadiene, (terbutylamido) - (2,3-dimethylindenyl) -dimethyl-silane-titanium- (II) -1, 3-pentadiene, (tert-butylamido) - (2,3-dimethylindenyl) -dimethyl-silane-titanium- (II) - 1, 4-dif in il-1,3-butadiene, (terbutylamido) - (2-methylindenyl) -dimethyl-silane-titanium- (ll) -1, 3-petadiene, (terbutylamido) - (2-methylindenyl) -dimethyl-silane-titanium- (IV) -dmethyl, (terbutylamido) - (2-methylindenyl) -d imeti l-s and non-titanium- (IV) -d i benzyl, (terbuti lam ido) - (2-methyl-4-phen-linden il) -dimetiI-silane-titanium- (l I) -1, 4-diphenyl-1,3-butadiene, (terbutylamido) - (2-methyl) 4-phenyliminyl) -d-imethylsilane-titanium- (ll) -1,3-pentadiene, (tert-butylamido) - (2-methyl-4-phenylenedyl) -dimethyl-silane-titanium- (II) - 2,4-hexadiene, (te rb uti mido) - (tetra methylo-? 5-cyclope ntadien il) -dimethyl-s ila non-tita nio- (IV) -1, 3-butadiene, (te rb uti lam id o) - (tetramethyl-? 5-cyclope ntadien il) -d imeti ls i the no-tita ni o- (IV) -2,3-dimethyl-1,3-butadiene, (te rb uti mido) - (tetra methylo-? 5-cyclopentadiene) -di meti I-silan o-tita ni o- (IV) -isoprene, (tertbutylamido) - (tetramethyl-? 5-cyclopentadienyl) -dimethyl-silane- titanium- (ll) -1,4-dibenzyl-1,3-butadiene, (tert-butylamido) - (tetramethyl-? 5-cyclopentadienyl) -dimethyl-silane-titanium- (ll) -2,4-hexadiene, ( terbutylamido) - (tetramethyl-? 5-cyclopentadienyl) -dimethyl-silane-titanium- (II) -3-methyl-1,3-pentadiene, (terbutylamido) - (2,4-dimethylpentadien-3-yl) -dimethyl-silane-titanium-d-imethyl, (te rb uti lam id o) - (6,6-d imeti I-cyclohexanediyl) -di meti I-if non-tita nio-dimetil, (te rbuti lam id o) - (1, 1 -dimeti 1-2,3, 4,9, 1 0 -? - 1, 4,5,6,7,8-hexah idro-naphthalen-4-yl) -dimethyl-silane-titanium-d-imethyl, (terbutylamido) - (1, 1, 2, 3-tetramethyl-2, 3, 4, 9, 1 0 -? - 1, 4, 5,6,7, 8-hexahydro-naphthalen-4-yl) -di meti l- if the non-titanium-di meti lo, (terb uti lam ido) - (tetra meti l-? 5-cicIo pe ntadien i l-metilfen i ls i la no-tita nio- (IV) -dimetilo, (terb uti lam ido) - (tetramethyl-? 5-cyclopentad ie ni l -methylphen i l- if the non-tita n io- (II) 1,4-diphenyl-1,3-butadiene, 1 - (terbutylamido) -2- (tetramethyl-? 5-cyclopentadienyl) -etandiyl-titanium- (IV) -dimethyl, and 1 - (te rbuty lam ido) -2- (tetra methylo-? 5-cyclope ntadien il) -etandii I-tita nio- (II) -1,4-diphenyl-1,3-butadiene Other delocalised p-linked complexes, especially those containing other Group 4 metals, will, of course, be apparent to those skilled in the art, and are given to know, in among other places, in: Patent Numbers WO 03/78480; WO 03/78483; WO 02/92610; WO 02/02577; US 2003/0004286; and US 6,515, 155; 6,555,634; 6, 1 50.297; 6,034,022; 6,268,444; 6, 01, 5,868; 5,866,704; and 5,470,993. Additional examples of metal complexes that are usefully employed as the catalyst (A), are the complexes of the polyvalent Lewis bases, such as the complexes corresponding to the formula: reference wherein Tb is bridging group, preferably containing two or more different hydrogen atoms, Xb and Y are each independently selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus; more preferably both X and Yb are nitrogen, Rb and R S independently in each presentation, are hydrogen or hydrocarbyl groups of 1 to 50 carbon atoms which optionally contain one or more heteroatoms or inertly substituted derivatives thereof. Non-limiting examples of suitable R and Rb 'groups include the alkyl, alkenyl, aryl, aralkyl, (poly) alkylaryl, and cycloalkyl groups, as well as the derivatives substituted by nitrogen, phosphorus, oxygen, and halogen thereof . Specific examples of suitable Rb and Rb 'groups include methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethylphenyl, 2,6-di (isopropyl) -phenyl, 2,4,6-trimethylphenyl, pentafluorophenyl, , 5-trifluoromethylphenyl, and benzyl; g is O or 1; Mb is a metallic element selected from Groups 3 to 1 5 of the Lantánidos series of the Periodic Table of the Elements. Preferably, Mb is a metal of Groups 3 to 1 3, more preferably M is a metal of Groups 4 to 1 0; L is a monovalent, divalent, or trivalent anionic ligand, containing 1 to 50 atoms, not counting hydrogen. Examples of suitable Lb groups include halide, hydride, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) -amido, hydrocarbylolamido, di (hydrocarbyl) -phosphide; hydrocarbon sulfide; hydrocarbyloxy; tri (hydrocarbylsilyl) -alkyl; and carboxylates. The most preferred L groups are alkenyl of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, and chloride; h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, the value of h x j being selected to provide a load balance; Z is a group of neutral ligand coordinated with Mb, and containing up to 50 atoms without hydrogen. Preferred Zb groups include aliphatic and aromatic amines, phosphines and ethers, alkenes, alkadienes, and inertly substituted derivatives thereof. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di (hydrocarbyl) -amine, tri (hydrocarbyl) -silyl, and nitrile groups. Preferred Zb groups include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene; f is an integer from 1 to 3; two or three of T, Rb, and RbS can be linked together to form a single or multiple ring structure; h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3; Indicates any form of electronic interaction, vWW especially coordinated or covalent links, including multiple links; the arrows indicate coordinated links; and dotted lines indicate optional double links. In one embodiment, it is preferred that R have a relatively low steric hindrance with respect to Xb. In this embodiment, the most preferred Rb groups are straight chain alkyl groups, straight chain alkenyl groups, branched chain alkyl groups wherein the nearest branch point is at least 3 atoms removed from Xb, and derivatives substituted by halogen , dihydrocarbylamino, alkoxy, or trihydrocarbylsilyl thereof. The highly preferred Rb groups in this embodiment are the straight chain alkyl groups of 1 to 8 carbon atoms. At the same time, in this embodiment, Rb 'preferably has a relatively high steric hindrance with respect to Yb. Non-limiting examples of the Rb 'groups suitable for this embodiment include alkyl or alkenyl groups containing one or more secondary or tertiary carbon centers, cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups, oligomeric, polymeric, or cyclic groups organic or inorganic, and derivatives substituted by halogen, dihydrocarbylamino, alkoxy, or trihydrocarbylsilyl thereof. Preferred Rb groups in this embodiment contain from 3 to 40, more preferably from 3 to 40, and most preferably from 4 to 20 atoms, not counting hydrogen, and are branched or cyclic. The examples of the preferred Tb groups are the structures that correspond to the following formulas: wherein: each Rd is a hydrocarbyl group of 1 to 10 carbon atoms, preferably methyl, ethyl, normal propyl, isopropyl, tertiary butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. Each Re is hydrocarbyl of 1 to 10 carbon atoms, preferably methyl, ethyl, propyl normal, isopropyl, tertiary butyl, phenyl, 2,6-dimethylpihenyl, benzyl, or tolyl. In addition, two or more groups Rd or Re, or mixtures of groups Rd and Re may together form a polyvalent derivative of a hydrocarbyl group, such as 1,4-butylene, 1,5-pentylene, or a hydrocarbyl group or heterohydric multicyclic ring fused heterocarbon, such as naphthalen-1,8-diyl.

Preferred examples of the above polyvalent Lewis base complexes include: wherein Rd 'in each presentation, is independently selected from the group consisting of hydrogen and hydrocarbyl groups of 1 to 50 carbon atoms which optionally contain one or more heteroatoms, or inertly substituted derivatives thereof, or in addition optionally, two adjacent Rd 'groups can together form a divalent bridge group. d 'is 4; M 'is a Group 4 metal, preferably titanium or hafnium, or a metal of Group 1 0, preferably Ni or Pd; Lb 'is a monovalent ligand of up to 50 atoms without counting hydrogen, preferably haloal or hydrocarbyl, or two Lb' groups together are a divalent or neutral ligand group, preferably a hydrocarbylene group of 2 to 50 carbon atoms, hydrocarbyl , or diene. The polyvalent Lewis base complexes for use in the present invention include in particular Group 4 metal derivatives, especially hafnium derivatives of the hydrocarbylamine substituted heteroaryl compounds corresponding to the formula: wherein: R 1 1 is selected from an alule, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing from 1 to 30 atoms without counting hydrogen, or a divalent derivative thereof; T1 is a divalent bridging group of 1 to 41 different hydrogen atoms, preferably 1 to 20 different hydrogen atoms, and more preferably a methylene or silane group substituted by mono- or di-hydrocarbyl of 1 to 20 carbon atoms. carbon; and R12 is a heteroaryl group of 5 to 20 carbon atoms containing Lewis base functionality, especially a pyridin-2-yl group, or a substituted pyridin-2-yl group, or a divalent derivative of the same; M1 is a Group 4 metal, preferably hafnium; X1 is a group of anionic, neutral, or dianionic ligand; x 'is a number from 0 to 5, which indicates the number of these groups x1; the links, optional links, and electron donation interactions are represented by lines, dotted lines, and arrows, respectively. Preferred complexes are those wherein the formation of the ligand results from the removal of hydrogen from the amine group, and optionally from the loss of one or more additional groups, especially from R12. In addition, the donation of electrons from Lewis base functionality, preferably a pair of electrons, provides additional stability to the metal center. Preferred metal complexes correspond to the formula: where: M1, X1, xS R1 1 and T1 are as defined above, R13, R14, R15 and R16 are hydrogen, halogen, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, silyl group of up to 20 atoms without hydrogen, or adjacent R13, R14, R15, or R16 are can join together, thus forming merged ring derivatives, links, optional links, and electron pair donation interactions, are represented by lines, dashed lines, and arrows, respectively. The most preferred examples of the above metal complexes correspond to the formula: wherein: M1, X1, and x 'are as defined above, R13, R14, R15 and R16 are as defined above, preferably R13, R14, R15 and R16 are hydrogen or alkyl of 1 to 4 carbon atoms, and R16 is aryl of 6 to 20 carbon atoms, more preferably naphthalenyl; Ra, independently in each presentation, is alkyl of 1 to 4 carbon atoms, and a is from 1 to 5, more preferably Ra in two positions ortho to the nitrogen, is isopropyl or tertiary butyl; R17 and R1 8, independently in each presentation, are hydrogen, halogen, or an alkyl group of 1 to 20 carbon atoms or aryl, more preferably one of R17 and R8 is hydrogen and the other is an aryl group of 6. at 20 carbon atoms, especially 2-isopropyl, phenyl, or a fused polycyclic aryl group, more preferably an anthracenyl group, and the bonds, optional bonds, and electron pair donation interactions, are represented by dashed lines, lines, and dates, respectively. The highly preferred metal complexes for use herein as the catalyst (A), correspond to the formula: wherein X1 is in each presentation halide, N, N-dimethylamido, or alkyl of 1 to 4 carbon atoms, and preferably X1 in each presentation is methyl; Rf, independently in each presentation, is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms, or two adjacent Rf groups are joined together thus forming a ring, and f is 1 to 5; and Rc, independently in each presentation, is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms, or two adjacent Rc groups are joined together, thereby forming a ring, and is from 1 to 5. The most highly preferred examples of metal complexes to be used as the catalyst (A) according to the present invention, are the complexes of the following formulas: wherein Rx is alkyl of 1 to 4 carbon atoms or cycloalkyl, preferably methyl, isopropyl, tertiary butyl, or cyclohexyl; and X1 is in each presentation halide, N, N-dimethylamido, or alkyl of 1 to 4 carbon atoms, preferably methyl. Examples of the metal complexes usefully employed as the catalyst (A) according to the present invention include: [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (o-tolyl) - (α-naphthalene-2-diyl- (6-pyridin-2-diyl) -methane)] -hafnium-dimethyl; [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (o-tolyl) - (α-naphthalene-2-diyl- (6-pyridin-2-diyl) -methane)] -hafnium-di (N, N-dimethylamido); [N- (2,6-di- (1-methylethyl) -phenyl) -ami o) - (o-tolyl) - (α-naphthalene-2-diyl- (6-pyridin-2-diyl) - dichloride - methane)] - hafnium; [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (2-isopropylphenyl) - (α-naphthalen-2-diyl) - (6-pyridin-2-diyl) -methane) ] hafnium-dimethyl; [N- (2,6-di- (1-methylethyl) -phenyl] -amido) - (2-isopropylphenyl) - (α-naphthalen-2-diyl) - (6-pyridin-2-diyl) -methane) ] hafnium-di (N, N-dimethylamido); [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (2-isopropyl-phenyl) - (α-naphthalen-2-diyl) - (6-pyridin-2-diyl) dichloride ) -methane)] hafnium; [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (phenanthren-5-yl) - (α-naphthalen-2-diyl) - (6-pyridin-2-diyl) - methane)] hafnium-dimethyl; [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (phenanthren-5-yl) - (α-naphthalen-2-diyl) - (6-pyridin-2-diyl) - methane)] hafnium-di (N, N-dimethylamido); and [N- (2,6-di- (1-methylethyl) -phenyl) -amido) - (phenanthren-5-yl) - (α-naphthalene-2-diyl) - (6-pyridin-2-dichloride. diyl) -methane)] hafnium; Under the reaction conditions used to prepare the metal complexes used in the present invention, the hydrogen of the 2-position of the a-naphthalene group substituted in the 6-position of the pyridin-2-yl group, is subject to elimination, thus conforming exclusively metal complexes in which the metal is bonded in a covalent manner with both the resulting amide group and position 2 of the a-naphthalene group, as well as being stabilized by coordination with the atom of nitrogen of the pyridinyl through the electron pair of the nitrogen atom. Additional suitable metal complexes of polyvalent Lewis bases for use herein include the compounds corresponding to the formula wherein: R20 is an aromatic, or inertly substituted, aromatic group, containing from 5 to 20 atoms without counting hydrogen, or a derivative polyvalent thereof; T3 is a hydrocarbylene or silane group having from 1 to 20 atoms without counting hydrogen, or an inertly substituted derivative thereof; M3 is a Group 4 metal, preferably zirconium or hafnium; G is an anionic, neutral, or dianionic ligand group; Preferably a halide, hydrocarbyl, or dihydrocarbylamide group having up to 20 atoms is hydrogen; g is a number from 1 to 5, which indicates the number of such G groups; and electron donation links and interactions are represented by lines and arrows, respectively. Preferably, these complexes correspond to the formula: wherein: T 3 is a divalent bridging group of 2 to 20 atoms not counting hydrogen, preferably an alkylene group of 3 to 6 carbon atoms substituted or unsubstituted; and Ar2, independently in each presentation, is an arylene group, or an arylene group substituted by alkylene or by aryl of 6 to 20 atoms without counting hydrogen; M3 is a Group 4 metal, preferably hafnium or zirconium; G, independently in each presentation, is a group of anionic, neutral, or dianionic ligand; g is a number from 1 to 5, which indicates the number of such G groups; and electron donation interactions are represented by arrows. Preferred examples of the metal complexes of the above formula include the following compounds: where M3 is Hf or Zr; Ar 4 is aryl of 6 to 20 carbon atoms, or inertly substituted derivatives thereof, especially 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1 H-pyrrol-1-yl , or anthracen-5-yl, and T4, independently in each presentation, comprises an alkylene group of 3 to 6 carbon atoms, a cycloalkylene group of 3 to 6 carbon atoms, or an inertly substituted derivative thereof; R21, independently in each presentation, is hydrogen, halogen, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms without counting hydrogen; and G, independently in each presentation, is halogen or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms without hydrogen, or two G groups are a divalent derivative of the above hydrocarbyl or trihydrocarbylsilyl groups. Especially preferred are compounds of the formula: wherein Ar 4 is 3,5-di (isopropyl) -phenyl, 3,5-di (isobutyl) -phenyl, dibenzo-1 H -pyrroyl-1-yl, or anthracen-5-yl, R 21 is hydrogen, halogen, or alkyl of 1 to 4 carbon atoms, especially methyl, T4 is propan-1,3-diyl, or butan-1,4-diyl, and G is chloro, methyl or benzyl. A more highly preferred metal complex of the above formula is: The above polyvalent Lewis base complexes are conveniently prepared by conventional methods of metalation and ligand exchange, involving a source of the Group 4 metal and the source of neutral polyfunctional ligand. In addition, the complexes can also be prepared by means of an amide removal and hydrocarbylation process, starting from the corresponding Group 4 metal tetra-amide, and a hydrocarbylating agent, such as trimethylaluminum. Other techniques can also be used. These complexes are known from the disclosures of, among others, Patent Nos. 6,320,005; 6, 103.657; WO 02/38628; WO 03/40195; and US 04/0220050. It is also known that catalysts that have properties of high comonomer incorporation, re-in situ the olefins of long chain preparations, which result incidentally during polymerization through the removal of ß-hydride and the chain termination of the growing polymer, or other process. The concentration of these long chain olefins is particularly improved by using the conditions of continuous solution polymerization at high conversions, especially ethylene conversions of 95 percent or more, more preferably to ethylene conversions of 97 percent or more. Under these conditions, a small but detectable amount of the olefin-terminated polymer can be reincorporated into a growing polymer chain, resulting in the formation of long chain branches, i.e., branches of a greater carbon atom length. which would result from another deliberately added comonomer. Moreover, these chains reflect the presence of other comonomers present in the reaction mixture.

That is, the chains can also include short chain or long chain branching, depending on the composition of the comonomer of the reaction mixture. The long chain branching of olefin polymers is further described in U.S. Patent Nos. 5,272,236; 5,278, 272, and ,665,800. In one aspect of the invention, the level of long chain branching in the product is significantly suppressed or completely eliminated by the use of chain linking agents that cause essentially all polymer chains to be terminated with the chain link, and not by training of vinyl groups that can be reincorporated to form a long chain branching. In this embodiment, the resulting polymer block is highly linear, leading to convenient properties. Alternatively, and more preferably, branching, including hyper-branching, can be induced in a particular segment of the present multi-block copolymers by the use of specific catalysts known to result in a "walking chain" "in the resulting polymer. For example, certain partially-halogenated, bridged, homogeneous bis-indenyl-zirconium, or bis-indenyl-zirconium catalysts, disclosed in Kaminski et al., J, may be used. Mol. Catal. A: Chemical. 102 (1995) 59-65; Zambelli et al., Macromolecules, 1 988, 21, 61 7-622; o Dias and collaborators, J. Mol. Catal. A: Chemical. 1 85 (2002) 57-64, to prepare branched copolymers from individual monomers, including ethylene. It is also known that higher transition metal catalysts, especially nickel and palladium catalysts, lead to hyper-branched polymers (whose branches are also branched) as disclosed in Brookhart et al., J. Am. Chem. Soc, 1 995, 1 1 7, 64145-641 5. In one embodiment of the invention, the presence of this branching (long chain branching, addition-1, 3, or hyper-branching) in the polymers of the invention , can only be confined to the blocks or segments resulting from the activity of the catalyst A. In accordance with the foregoing, in one embodiment of the invention, a multi-block copolymer containing different blocks or segments may be produced in the face of such a branch in combination with other segments or blocks substantially lacking this branch. (especially high density or highly crystalline polymer blocks), from a reaction mixture containing a single monomer, that is, without the addition of a deliberately added comonomer. In a highly preferable manner, in a specific embodiment of the invention, a multi-block copolymer comprising alternatingly unbranched homopolymer segments of ethylene, and branched polyethylene segments in particular ethylene / propylene copolymer segments, can be prepared from of an initial reaction mixture consisting essentially of ethylene as the addition polymerizable monomer. The presence of this branching in the multi-block copolymers of the invention can be detected by certain physical properties of the resultant copolymers, such as surface imperfections red during melt extrusion (reduced melt fracture), reduced melting point, Tg, for the amorphous segments, compared to an unbranched polymeric segment, and / or the presence of addition-1, 3 or hyper-branching sequences, as detected by n-nuclear magnetic resonance techniques. The amount of the above types of branching present in the polymers of the invention (as a portion of the blocks or segments that contain them), is usually in the range of 0.01 to 10 branches per 1, 000 carbon atoms. Suitable metal compounds to be used as the catalyst (B) include the foregoing metal compounds mentioned with respect to the catalyst (A), as well as other metal compounds, with the proviso that, in one embodiment of the invention, they incorporate the comonomer in a relatively poor manner, compared to the catalyst (A). In accordance with the above, in addition to the previously identified metal complexes, the following additional metal complexes can be used. Derivatives of Groups 4 to 10 corresponding to the formula: wherein: M2 is a metal of Groups 4 to 10 of the Periodic Table of the Elements, preferably Group 4, Ni (l l) or Pd (l l) metals, more preferably zirconium; T2 is a group that contains nitrogen, oxygen, or phosphorus; X2 is halogen, hydrocarbyl, or hydrocarbyloxy; t is one or two; x "is a number selected to provide charge equilibrium, and T2 and N are linked by a bridging ligand.These catalysts have been previously disclosed in J.

Am. Chem. Soc. 118, 267-268 (1996), J. Am. Chem. Soc. 117, 6414-6415 (1995), and Orqanometallics. 16, 1514-1516, (1997), among other disclosures. Preferred examples of the above metal complexes to be used as the catalyst (B) are aromatic di-imine and aromatic dioxy-imine complexes of Group 4 metals, especially zirconium, corresponding to the formula: wherein: M2, X2, and T2 are as defined above; Rd, independently in each presentation, is hydrogen, halogen, or Re; and Rc, independently in each presentation, is hydrocarbyl of 1 to 20 carbon atoms, or a derivative substituted by heteroatom, especially substituted by F, N, S, or P thereof, more preferably hydrocarbyl of 1 to 10 carbon atoms or a derivative substituted by F or N thereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl, piperidyl, perfluorophenyl, cycloalkyl, (poly) alkylaryl, or aralkyl. The most preferred examples of metal complexes previous to be used as the catalyst (B) are the aromatic zirconium dioxy imine complexes, corresponding to the formula: wherein: X2 is as defined above, preferably hydrocarbyl of 1 to 10 carbon atoms, more preferably methyl or benzyl; and Re 'is methyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethyl-cyclohexyl, 2-pyrrolyl, N-metii-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl, benzyl, o-tolyl, 2,6-dimethylphenyl, perfluorophenyl , 2,6-di (isopropyl) phenyl, or 2,4,6-trimethylphenyl. The above complexes to be used as catalyst (B) also include certain phosphinimine complexes, which are given to know in European Patent No. EP-A-890581. These complexes correspond to the formula: [(Rf) 3-P = N] fM (K2) (Rf) 3-f, wherein: Rf is a monovalent ligand, or two Rf groups are together a monovalent ligand, preferably Rf is hydrogen or alkyl of 1 to 4 carbon atoms; M is a Group 4 metal; K2 is a group containing delocalized p-electrons through which K2 is linked to M, this group containing up to 50 atoms without counting the hydrogen atoms, and f is 1 or 2. The expert will appreciate that, in other embodiments of the invention, the criteria for selecting a combination of the catalysts (A) and (B), can be any other property distinctive of the resulting polymeric blocks, such as combinations based on tacticity (isotactic / syndiotactic, isotactic / atactic, or syndiotactic / atactic), content of regio-error, or combinations thereof. Cocatalysts Each or not of the metal complex catalysts (A) and (B) (also referred to interchangeably herein as procatalysts), can be activated to form the active catalyst composition, by combining it with a cocatalyst, preferably a cation forming cocatalyst, a strong Lewis acid, or a combination of the same. In a preferred embodiment, the linking agent is used for the purposes of linking the chain, and as the cocatalyst component of the catalyst composition. The metal complexes are desirably made catalytically active by their combination with a cation-forming cocatalyst, such as those previously known in the art for use with olefin polymerization complexes of metals of Group 4. Cation-forming cocatalysts suitable for use in the present include neutral Lewis acids, such as compounds of Group 1 3 substituted by hydrocarbyl of 1 to 30 carbon atoms, especially tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds, and halogenated (including perhalogenated) derivatives thereof, which have 1 to 10 carbon atoms in each hydrocarbyl group, or halogenated hydrocarbyl, more especially perfluorinated tri (aryl) -boron compounds, and in a very special way tris (pentafluoro-phenyl) borane; non-coordinating, non-polymeric ion-forming compounds (including the use of these compounds under oxidizing conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silylium, or sulfonium salts of compatible non-coordinating anions, or salts of ferrocenium, lead, or anion silver compatible non-coordinators; and combinations of the cation-forming cocatalysts and prior techniques. Activating cocatalysts and activation techniques above have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277, 003; US-A-5, 1 53, 1 57; US-A-5,064,802; US-A-5,321, 1 06; US-A-5,721,185; US-A-5,350,723; US-A-5,425,872; US-A-5,625,087; US-A-5,883,204; US-A-5,91,9983; US-A-5,783,512; WO 99/1 5534, and WO99 / 42467. As the activating cocatalysts, combinations of neutral Lewis acids can be used, especially the combination of a trialkyl-aluminum compound having 1 to 4 carbon atoms in each alkyl group, and a halogenated tri (hydrocarbyl) boron compound. that has from 1 to 20 carbon atoms in each hydrocarbyl group, especially tris (pentafluorophenyl) borane, other combinations of these mixtures of neutral Lewis acid with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, in particular tris (pentafluorophenyl) borane, with a polymeric or oligomeric alumoxane. The preferred molar proportions of the metal complex: tris (pentafiuorophenyl) borane: alumoxane are from 1: 1: 1 to 1: 5: 20, more preferably from 1: 1: 1.5 to 1: 5: 1 0. The Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible non-coordinating anion, A ". As used herein, the "non-coordinating" term means an anion or a substance that is not coordinated with the precursor complex containing Group 4 metal and the catalytic derivative derived therefrom, or that only it coordinates weakly with these complexes, remaining in this way sufficiently labile to be displaced by a neutral Lewis base. A non-coordinating anion refers specifically to an anion which, when functioning as a charge anion equilibrium in a cationic metal complex, does not transfer an anionic substituent or fragment thereof to this cation, thereby forming neutral complexes. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes, and do not interfere with the desired subsequent polymerization, or with other uses of the complex. Preferred anions are those which contain a single coordinating complex comprising a metal or metalloid core carrying charge, whose anion is capable of balancing the charge of the active catalyst species (the metal cation) that can be formed when the two components are combined. Also, this anion must be sufficiently labile to be displaced by olefinic, diolefinic, and acetylenically unsaturated compounds or other neutral Lewis bases, such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions comprising coordination complexes containing a single metal or metalloid atom are, of course, well known, and many, particularly compounds containing a single boron atom in the anion portion, are available commercially Preferably, these cocatalysts can be represented by the following general formula: (L * -H) g + (A) 9- wherein: L * is a neutral Lewis base; (L * -H) + is a conjugated Bronsted acid of L *; A9"is a non-coordinating compatible anion having a charge of g-, and g is an integer from 1 to 3. More preferably, A9" corresponds to the formula: [M'Q4] -; wherein: M 'is boron or aluminum in the formal oxidation state +3; and Q, independently in each presentation, is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, hydrocarbyl substituted by halogen, hydrocarbyloxy substituted by halogen, and silyl hydrocarbyl radicals substituted by halogen (including perhalogenated hydrocarbyl radicals, perhalogenated idrocarbyloxy, and perhalogenated silylhydrocarbyl), this Q having up to 20 carbon atoms, with the proviso that in no more than one presentation Q is halu ro. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Patent No. US-A-5,296,433. In a more preferred embodiment, d is 1, that is, the counter-ion it has a single negative charge and is A. "Activating cocatalysts comprising boron, which are particularly useful in the preparation of the catalysts of this invention, can be represented by the following general formula: (L * -H) + (BQ4) - wherein: L * is as defined above, B is boron in a formal oxidation state of 3, and Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated rochycellular silylhydrate group of up to 20 atoms not are hydrogen, with the proviso that, on no more than one occasion, Q is hydrocarbyl The preferred Lewis base salts are the ammonium salts, more preferably the trialkyl ammonium salts containing one or more alkyl groups from 12 to 40 carbon atoms.Of more preferable, Q is in each presentation a fluorinated aryl group, especially a pentafluorophenyl group.Examples, but not limiting, of the boron compounds that can be in using as an activating cocatalyst e? the preparation of the improved catalysts of this invention are tri-substituted ammonium salts, such as: titanium ester (pentafluorophenyl) -trimethylammonium borate, titanium ester (pentafluorophenyl) -triethylammonium stearate, titanium ester (pentafluoro-phenyl) -tripropylammonium borate, titanium ester (pentafluorophenyl) -tri- (n-butyl) -ammonium borate, titanium ester (pentafluorophenyl) -trium (sec-butyl) -ammonium ester, N, N-dimethylanilinium (pentafluorophenyl) -borate ester, N, N-dimethylanilinium n-butyltris- (pentafluorophenyl) -borate ester, benzyltris - N, N-dimethylanilinium (pentafluorophenyl) borate, titanium ester (4- (t-butyldimethylsilyl) -2,5,5,6-tetrafluorophenyl) -borate N, N-dimethylaminoium, titanium ester (4-tri-isopropylsilyl) -2, 3,5,6-tetrafluorophenyl) -borate of N, N-dimethylanilinium, pentafluorofenoxitris- (pentafluorophenyl) -borate of N, N-dimethylanilinium, N, N-diethylanilinium titanium (pentafluorophenyl) ester, N, N-dimethyl-2,4,6-trimethylanilinium titanium ester (pentafluorophenyl) borate, dimethyloctadecylammonium titanium (pentafluorophenyl) borate ester, ester titanium (pentafIuorophenyl) -methyldioctadecylammonium borate, dialkylammonium salts, such as: di- (isopropyl) ammonium titanium (pentafluorophenyl) -borate ester, titanium (pentafluorophenyl) -methioctadecylammonium borate ester, titanium ester (pentafluorophenyl) ) - methyl octodecyl ammonium borate, and titanium ester (pentafluorophen? 'I) - dioctadecylammonium borate; tri-substituted phosphonium salts, such as: triphenylphosphonium (pentafluorophenyl) -tertrate, titanium (pentafluorophenyl) -borate-methylcyclodecylphosphonium ester, and titanium (pentafiorucophenyl) -tertrate (2,6-dimethylphenyl) ester. -phosphonium, di-substituted oxonium salts, such as: diphenyloxonium titanium (pentafluorophenyl) -borate ester, di (o-tolyl) oxonium titanium (pentafluorophenyl) borate ester, di (octadecyl) -oxonium titanium (pentafluorophenyl) -borate ester, di-substituted sulfonium salts, such as: titanium ester (pentafluorophenyl) -di (o-tolyl) -sulfonium borate, and titanium (pentaflourophenyl) -meryloctadecylsulfonium borate ester. Preferred cations (L * -H) + are methyldioctadecylammonium cations, dimethyloctadecyl ammonium cations, and ammonium cations derived from mixtures of trialkylamines containing 1 or 2 g alkyl groups of 14 to 18 carbon atoms. . Another suitable ion-forming activating cocatalyst comprises a salt of a cationic oxidizing agent and a compatible non-coordinating anion represented by the formula: (Oxh +) g (A9-) h, wherein: Oxh + is a cationic oxidizing agent having a charge of h +; h is an integer from 1 to 3; and A9"and g are as defined above, Examples of the cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag + 'or Pb + 2. Preferred embodiments of A9" are the anions previously defined with respect to activating cocatalysts. containing a Bronsted acid, especially titanium ester (pentafluorophenyl) -borate. Another suitable ion-forming activating cocatalyst comprises a compound which is a salt of a carbenium ion and a compatible non-coordinating anion represented by the formula: [C] + A- where: [C] + is a carbenium ion of 1 to 20 carbon atoms; and A "is a compatible non-coordinating anion having a charge of 1. A preferred carbenium ion is the triphenyl cation, ie, triphenylmethyl, or an additional suitable ion-forming activating cocatalyst comprises a compound which is a salt of a silyl ion, and a compatible non-coordinating anion represented by the formula: (Q13Si) + A "where: Q1 is hydrocarbyl of 1 to 10 carbon atoms, and A" is as defined above. Preferred silyl salts are titanium-pentafluorophenyl-borate trimethyl silyl ester, triethylsilyl titanium pentafluorophenyl silyl ester, and ether-substituted adducts thereof Silylium salts have been previously reported in a J-gene form. Chem. Soc. Chem. Comm., 1993, 383-384, as well as Lambert, JB et al., Organometallics, 1 994, 1 3, 2430-2443.The use of the above silylium salts as activating cocatalysts for tasting addition polymerization catalysts is disclosed in U.S. Patent No. US-A-5,625,087. Certain complexes of alcohols, mercaptans, silanols, and oximes with tris (pentafluorophenyl) borane, are also activators of effective catalysts, and may be used in accordance with the present invention. These cocatalysts are disclosed in U.S. Pat. No. 5,296,433. Activating cocatalysts suitable for use herein also include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO), trifluorbutylaluminum modified methylalumoxane (MAO M), or isobutylalumoxane; alumoxanes modified by Lewis acid, especially alumoxanes modified by perhalogenated tri (hydrocarbyl) -aluminum, or by perhalogenated tri (hydrocarbyl-boron), having from 1 to 10 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group, and more especially the alumoxanes modified by tris (pentaflourophenyl) borane. These cocatalysts were previously disclosed in U.S. Patent Nos. 6,214,760; 6, 1, 60, 146; 6, 140, 521, and 6,696,379. A class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, disclosed further in U.S. Patent No. 6,395,671, can be suitably employed to activate the metal complexes of the present invention for the polymerization of olefin In general, these cocatalysts (illustrated by those having anions of imidazolide, substituted imidazolide, imidazolinide, substituted imidazolin, substituted benzimidazolide, or substituted benzimidazolide) can be illustrated as follows: wherein: A * + is a cation, especially a cation containing proton, and is preferably a cation of trihydrocarbyl ammonium containing one or two alkyl groups of 1 to 40 carbon atoms, especially a methyldi cation (alkoxy of 14 to 20 carbon atoms) -ammonium, Q3, independently in each presentation, is hydrogen or a halogen, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl group, (including mono-, di-, and tri) - (hydrocarbyl) silyl) of up to 30 atoms without counting hydrogen, preferably alkyl of 1 to 20 carbon atoms, and Q2 is tris (pentafluorophenyl) borane or tris (pentafluorophenyl) aluman.

Examples of these catalyst activators include the trihydrocarbyl ammonium salts, especially the methyldi (C14 to 20 carbon atoms) -ammonium salts of: bis (tris (pentafluorophenyl) borane) imidazolide, bis (tris (pentafluoro-phenyl) borane) -2-undecyl imidazolide, bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolide, bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) -imidazolide, bis (tris (pentafluorophenyl) borane) ) -4,5-bis (heptadecyl) -imidazolide, bis (tris (pentafluorophenyl) borane) imidazolinide, bis (tris (pentafluorophenyl) borane) -2-undecylimidazolinide, bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) -imidazolinide, bis (tris ( pentafluorophenyl) borane) -4,5-bis (heptadecyl) -imidazolinide, bis (tris (pentafluorophenyl) borane) -5,6-dimethylbenzimidazolide, bis (tris (pentaf luo rof in i I) borane) -5, 6-bis (one decile) - benzimidazole ida, bis (tris (pentafluoropheniI) alumano) -imidazolide, bis (tris (pentafluorophenyl) alumano) -2-undecyl-imidazolide, bis (tris (pentafluorophenyl) alumano) -2-heptadecylimidazolide, bis (tris) (pentafluorophenyl) aluman) -4,5-bis (undecyl) -imidazoide, bis (tris (pentafluorophenyl) aIuman) -4,5-bis (heptadecyl) -imidazolide, bis (tris (pentafluorophenyl) aluman) -imidazolinide, bis ( tris (pentafluorophenyl) aluman) -2-undecylimidazolinide, bis (tris (pentafluorophenyl) aluman) -2-heptadeci I imidazolinide, bis (tris (pentafluorophenyl) aluman) -4,5-bis (undecyl) -imidazolinide, bis (tris) (pentafIuorophenyl) alumano) -4,5-bis (heptadecyl) - imidazolinide, bis (tris (pentafluorophenyl) aluman) -5,6-dimethylbenzimidazolide, and bis (tris (pentafluorophenyl) aluman) -5,6-bis (undecyl) benzimidazolide. Other activators include those described in PCT Publication Number WO 98/07515, such as tris (2,2 \ 2"-nonafluorobiphenyl) fluoroaluminate The invention also contemplates combinations of activators, for example alumoxanes and ionizing activators in combinations, see, for example, European Patent Number EP-A-0, 573120, the publications of the TCP Numbers WO 94/07928 and WO 95/14044, and the United States Patents of North America Numbers 5, 153, 157 and 5,453,410. PCT Publication No. WO 98/09996 describes activating catalyst compounds with perchlorates, periodates, and iodates, including their hydrates. PCT Publication No. WO 99/1 81 35 describes the use of organo-boron-aluminum activators. PCT Publication Number WO 03/1 01 71 discloses catalyst activators which are Bronsted acid adducts with Lewis acids. Other activators or methods for activating a catalyst compound are described, for example, in U.S. Patent Nos. 5,849, 852; 5,859,653; 5,869,723; in the European Patent EP-A-61 5981, and in the Publication of the TCP Number WO 98/32775. All activators of the above catalysts, as well as any other known activator for transition metal complex catalysts, can be used alone or in combination according to the present invention; however, to obtain the best results, cocatalysts containing alumoxane are avoided. The molar ratio of catalyst / cocatalyst employed preferably is in the range of 1: 1 0000 to 1 00: 1, more preferably 1: 5000 to 10: 1, most preferably of 1: 1,000 to 1: 1. Alumoxane, when used by itself as an activating cocatalyst, is used in a large amount, generally at least 1 00 times the amount of metal complex on a molar basis. Tris (pentafluorophenyl) borane, when used as an activating cocatalyst, is used in a molar ratio to the complex of metal from 0.5: 1 to 1 0: 1, more preferably from 1: 1 to 6: 1, and most preferably from 1: 1 to 5: 1. The remaining activating cocatalysts are generally employed in an approximately equimolar amount with the metal complex. The process of the invention employing the catalyst A, the catalyst B, or not or more cocatalysts, and the chain binding agent C, can be further elucidated with reference to Figure 1, where the site of the activated catalyst A, 1 0, which, under polymerization conditions, forms a polymer chain, 13, attached to the site of the active catalyst, 1 2. In a similar manner, the active catalyst site B, 20, produces a differentiated polymer chain , 23, linked to the site of the active catalyst, 22. A chain bonding agent C1, linked to a polymer chain produced by the active catalyst B, 14, exchanges its polymer chain, 23, for the polymer chain, 1 3, attached to the site of the catalyst A. The additional growth of the chain under polymerization conditions, causes the formation of a multi-block copolymer, 1 8, attached to the site of the active catalyst A. In a similar manner, the chain-linking agent C2, attached to a polymer chain produced by the site of the active catalyst A, 24, exchanges its polymer chain, 1 3, by the polymer chain, 23, attached to the catalyst site B. Additional growth of the chain under polymerization conditions, causes the formation of a multiblock copolymer, 28, attached to the site of the active catalyst B The multiple block copolymers in growth are repeatedly exchanged between the active catalyst A and the active catalyst B by means of the linking agent C, resulting in the formation of a block or segment of different properties, provided that exchange occurs with the site of the opposite active catalyst. The growing polymer chains can be recovered while attached to a chain binding agent, and can be functionalized if desired. Alternatively, the resulting polymer can be recovered by cleavage of the site of the active catalyst or the binding agent, through the use of a proton source or other aniqilator agent. It is believed (without wishing to be bound by this belief) that the composition of the respective segments or blocks, and especially of the end segments of the polymer chains, can be influenced through the selection of process conditions and other variables. process. In the polymers of the invention, the nature of the end segments is determined by the relative rates of transfer or chain termination for the respective catalysts, as well as by the relative chain link speeds. Possible chain termination mechanisms include, but are not limited to, ß-hydrogen removal, ß-hydrogen transfer to the monomer, ß'-methyl removal, and chain transfer to hydrogen or another chain terminator reagent, such as an organosilane or a chain-raising agent. In accordance with the above, when a low concentration of chain binding agent is used, most ends of the polymer chain will be generated in the polymerization reactor by u of the above chain termination mechanisms, and the relative chain termination velocities for the catalysts (A) and (B) will determine the predominant chain terminator fraction. That is, the catalyst having the fastest rate of chain termination will produce relatively more chain end segments in the finished polymer. In contrast, when a high concentration of chain binding agent is employed, most of the polymer chains within the reactor and upon leaving the polymerization zone are bound or bound to the chain binding agent. Under these reaction conditions, the relative chain transfer rates of the polymerization catalysts, and the relative chain link velocity of the two catalysts, primarily determine the identity of the chain terminator fraction. If the catalyst (A) has a faster chain transfer, and / or a chain link speed faster than the catalyst (B), then most of the chain end segments will be those produced by the catalyst (A ). In intermediate concentrations of chain binding agent, the three factors mentioned above are instrumental in determining the identity of the final polymer block. The above methodology can be extended to the analysis of polymers of multiple blocks having more than two types of blocks, and to control the average block lengths and block sequences for these polymers. For example, using a mixture of catalysts 1, 2, and 3 with a chain bonding agent, for which each type of catalyst makes a different type of polymer block, a linear block copolymer is produced with three different block types. Additionally, if the ratio of the link speed to the propagation velocity for the three catalysts follows the order 1 > 2 > 3, then the average block length for the three block types will follow the order > 3 > 2 > 1, and there will be fewer instances of type-2 blocks adjacent to type-3 blocks than type-1 blocks adjacent to type-2 blocks. It follows that there is a method to control the block length distribution of the different types of blocks. For example, by selecting the catalysts 1, 2, and 3 (wherein 2 and 3 produce substantially the same type of polymer block), and of a chain linker, and the link rate follows the order 1 >; 2 > 3, the resulting polymer will have a bimodal distribution of block lengths made from catalysts 2 and 3. During the polymerization, the reaction mixture comprising one or more monomers is contacted with the catalyst composition activated in accordance with any suitable polymerization conditions. The process is characterized by the use of elevated temperatures and pressures. Hydrogen can be used as a chain transfer agent for molecular weight control according to known techniques, if desired. As in other similar polymerizations, it is highly desirable that the monomers and solvents used are one PU high enough that deactivation of the catalyst does not occur. Any suitable technique can be employed for the purification of monomers, such as devolatilization under reduced pressure, contact with molecular sieves or alumina of high surface area, or a combination of the above processes. The skilled person will appreciate that the proportion of the chain-linking agent to one or more catalysts and / or monomers in the process of the present invention can be varied in order to produce polymers that differ in one or more chemical or physical properties. Supports may be employed in the present invention, especially in paste or gas phase polymerizations. Suitable supports include oxides of solid metals, in particulates, of high surface area, metalloid oxides, mixtures thereof (interchangeably referred to herein as an inorganic oxide). Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn2O3, aluminosilicates, borosilicates, clays, and mixtures thereof. Suitable supports preferably have a surface area, determined by nitrogen porosimetry using method B. E.T. , from 1 0 to 1, 000 m2 / g bouquet, and preferably from 1 00 to 600 m2 / gram. The average particle size is usually from 0.1 to 500 microns, preferably from 1 to 200 microns, more preferably from 1.0 to 1.000 microns. In one embodiment of the invention, the present catalyst composition and the optional support can be spray dried, or otherwise recovered in a particulate solid form, to provide a composition that is easily transported and handled. Suitable methods for spray drying a paste containing liquid are well known in the art and are usefully employed herein. The preferred techniques for spray drying the catalyst compositions for use herein are described in U.S. Patent Nos. 5,648.31 0 and 5,672,669. The polymerization is desirably carried out as a continuous polymerization, preferably a continuous solution polymerization, wherein the catalyst components, linking agents, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to the reaction zone, and the polymer product is continuously removed from it. Within the scope of the terms "continuous" and "continuously", as they are used in this context, are the processes where there are intermittent additions of reagents and product removal at small regular or irregular intervals, so that, through the time, the overall process is substantially continuous. The catalyst compositions can be conveniently employed in a high pressure, solution, paste, or gas phase polymerization process. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components in a liquid diluent in which the polymer is soluble under the conditions of polymerization employed. This process using an extremely fine silica dispersion agent or similar to produce this homogeneous catalyst dispersion wherein the metal complex or the cocatalyst is only poorly soluble is disclosed in the U.S. Patent of North America. US-A-5,783.51 2. A process in solution for preparing the novel polymers of the present invention, especially a continuous solution process, preferably carried out at a temperature between 80 ° C and 250 ° C , more preferably between 1 00 ° C and 21 0 ° C, and most preferably between 1 1 0 ° C and 21 0 ° C. A high pressure process is normally carried out at temperatures of 1 00 ° C to 400 ° C, and at pressures above 500 bar (50 M Pa). A pulp process typically utilizes an inert hydrocarbon diluent and temperatures from 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. The preferred temperatures in a paste polymerization are from 30 ° C, preferably from 60 ° C to 1 1 5 ° C, preferably up to 1 00 ° C. The pressures are usually in the range from atmospheric (1 00 kPa) to 500 psi (3.4 MPa). In all of the above processes, continuous or substantially continuous polymerization conditions are preferably used. The use of these polymerization conditions, especially the continuous solution polymerization processes that employ two or more active polymerization catalyst species, allow the use of elevated reactor temperatures, which results in economical production of multi-block or segmented copolymers in high yields and efficiencies. Reaction conditions of both homogeneous type and plug flow type can be employed. The latter conditions are preferred when it is desired to thin the block composition. Both catalyst compositions (A) and (B) can be prepared as a homogeneous composition by adding the required metal complexes to a solvent in which the polymerization is conducted, or in a diluent compatible with the last reaction mixture. The desired cocatalyst or activator, and the linking agent, may be combined with the catalyst composition either before, simultaneously with, or after, the combination with the monomers to be polymerized and any additional reaction diluents. At all times, the individual ingredients, as well as any active catalyst composition, should be protected from oxygen and moisture. Consequently, the catalyst components, the binding agent, and the activated catalysts, must be prepared and stored in an atmosphere free of oxygen and moisture, preferably in a dry inert gas, such as nitrogen. Without limiting the scope of the invention in any way, a means to carry out this polymerization process is as follows. In a stirred vessel reactor, monomers that are to be polymerized are continuously introduced, together with any solvent or diluent. The reactor contains a liquid phase composed substantially of monomers, together with any solvent or diluent and the dissolved polymer. Preferred solvents include hydrocarbons of 4 to 10 carbon atoms or mixtures thereof, especially alkanes, such as hexane, or mixtures of alkanes, as well as one or more of the monomers used in the polymerization. The catalysts (A) and (B), together with the cocatalyst and the chain-linking agent, are introduced in a continuous or intermittent manner into the liquid phase of the reactor and any recycled portion thereof. The temperature and pressure of the reactor can be controlled by adjusting the solvent / monomer ratio, the rate of catalyst addition, as well as by heating cooling coils, jackets, or both. The polymerization rate is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of the ethylene to the comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. Optionally, the molecular weight of the polymer product is controlled by controlling other polymerization variables, such as temperature, monomer concentration, or by the above-mentioned chain transfer agent, as is well known in the art. Upon exiting the reactor, the effluent is contacted with a catalyst killer, such as water, steam, or an alcohol. The The polymer solution is optionally heated, and the polymer product is recovered by the flash evaporation of the gaseous monomers, as well as the solvent or residual diluent at a liquid pressure, and if necessary, further devolatilization is conducted in the equipment, as a exusion of devolatilization. In a coninuous process, the average residence time of the tracer and the polymer in the reactant is in general from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours. In an aligning manner, the lower polymerization can be carried out in a conformed cycle reaction with or without a monomer, calychator, or gradient of bonding agent structured between different regions thereof, optionally accompanied by the separate addition of cayalisers and / or chain transfer schedule, and is operated under adiabatic or non-adiabatic solution polymerization conditions, or combinations of the above conditions of the reactant. Examples of suitable cycle reactors and a variety of operating conditions suitable for use with them will be found in the United States of America's Pairs. Numbers 5,977,251; 6, 31 9,989, and 6,683, 149. Although it is not as desired, the cayalizing composition can also be prepared and used as a heterogeneous materializer by the adsorption of the required components on an inorganic or inert organic solid, as shown in Figure 1. Unveiled. In a preferred embodiment, a heigeogenic heater is prepared by co-precipitating the complex of meia and the reaction product of an inorganic compound inert and an activator that contains hydrogen, especially the reaction product of a compound of 1 to 4 aluminum atoms and an ammonium salt of a hydroxyaryl (penofluorophenyl) borafo, ial as an ammonium salt of (4-hydroxy-3,5-dibuterryl-phenyl) -ris (peniafluorophenyl) -boraio. When prepared in a heigeogenic or soporific form, the caplizing composition can be used in a passfaction or gas phase polymerization. As a practical limitation, the polymerization in the past takes place in liquid diluents in which the polymeric production is insubstantially insoluble. Preferably, the diluent for the pass-through polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, hydrous carbonates, such as effano, propane, or biano, from iodo or in parie, such as diluyenfe, can be used. As with a solution polymerization, the α-olefin comonomer or a mixture of α-olefin monomer differents of the iodine or the diluent may be used. More preferably, at least one major part of the diluent comprises the α-olefin monomer (s) to be polymerized. Preferably, to be used in the gas phase polymerization processes, the soporfe material and the resulfant caffeizer have an average particle diameter of 20 to 200 microns, more preferably 30 to 1 50 microns, and in a very preferable manner from 50 microns to 1 00 microns. Preferably, to be used in the passivation polymerization processes, the support has a particle diameter. average from 1 miera to 200 micras, more preferably from 5 micras to 100 micras, and most preferably from 10 micras to 80 micras.

The gas phase polymerization process suitable for use herein is substantially similar to known commercially large scale processes for the manufacture of polypropylene, ethylene / α-olefin copolymers, and other olefin polymers. The gas phase process employed can be, for example, a type employing a mechanically agitated bed or a fluidized bed with gas as the polymerization reaction zone. The process is preferred wherein the polymerization reaction is carried out in a true cylindrical polymerization reagent which confers a fluidized bed of polymeric particles supported or suspended above a perforated plate or fluidization grid by a flow of fluidizing gas. The gas used to fluidize the bed comprises the monomer or the monomers to be polymerized, and also serves as a heat exchange medium to remove the heat from the bed reaction. Hot gases emerge from the top of the reactor, usually through a zone of reassurance, also known as a zone of velocity network, which has a diameter wider than the fluidized bed, and where the fine particles introduced into the stream of gas have the opportunity to gravitate back to the bed. It may also be convenient to use a cyclone to remove uly-fine particles from the hot gas stream. Then the gas is normally recycled to the bed by means of a veníilador or compressor and one or more heat exchangers to separate the gas from the heat of the polymerization. A preferred method for cooling the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid into the bed to provide an evaporative cooling effect, often referred to as an operation in the condensation mode. The volatile liquid used in this case can be, for example, a volatile liquid inert, for example a saftered hydrocarbon having from 3 to 8, preferably from 4 to 6, carbon atoms. In case the monomer or the comonomer itself is a volatile liquid, or can be condensed to provide this liquid, it can be fed to the bed in order to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas, which is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. Then the evaporated liquid emerges from the reactor as part of the hot recycle gas, and flows to the compression / heat exchange part of the recycle. The recycle gas is cooled in the heat exchanger, and, if the femperaf to which the gas cools is below the dew point, the liquid will precipitate from the gas. This liquid is desirably recycled in a continuous manner to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example, in Pafeníes Numbers EP-89691; US 4,543,399; WO 94/25495 and US Pat. No. 5,352,749. A particularly preferred method for recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to re-inject this liquid directly into the bed, preferably using a method that generates fine gofas of the liquid in the bed. This process type is described in International Publication Number WO-94/28033. The polymerization reaction that was present in the fluidized bed with gas is cayalized by means of coninuous or semi-conical addition of the coating composition according to the invention.

The coating composition can be subjected to a prepolymerization step, for example by mediating the polymerization of a small amount of olefin monomer in an inert liquid diluent, to provide a cationizing compound comprising soporific cahilizer particles also hardened in the polymer particles of olefin The polymer is produced directly in the fluidized bed by the polymerization of the monomer or monomer mixture on the fluidized particles of the catalyst composition, the soporided catalyst composition, or the prepolymerized anionic catalyst composition of the bed. The initiation of the polymerization reaction is achieved by using a bed of preformed polymeric particles, which are preferably similar to the desired polymer, and the bed is conditioned by drying with inert gas or nitrogen before infusing the composition, the monomers, and any other gases that one wishes to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or a condensable gas inert, when operating in the gas phase condensation mode. The produced polymer is discharged in a conical or semi-conical manner from the fluidized bed as desired. The gas phase processes most suitable for the practice of this invention are continuous processes that provide the continuous supply of reactants to the reaction zone of the reactor, and the removal of the products from the reaction zone of the reactor, thus providing a medium environment of continuous state at the macro-scale in the reacfor reaction zone. The products are easily recovered by their exposure at reduced pressure and optionally at elevated temperatures (devolatilization) according to known techniques. Normally, the fluidized bed of the gas phase process is operated at temperatures greater than 50 ° C, preferably 60 ° C to 1 10 ° C, and most preferably 70 ° C to 1 10 ° C. Examples of the gas phase processes which are adaptable to be used in the process of this invention are disclosed in Pafenfes of the United States of North America Nos. 4,588,790; 4,543,399; 5,352, 749; 5,436,304; 5,405,922; 5,462, 999; 5,461, 123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5, 1 06,804; 5,556,238; 5,541, 270; 5,608.01 9; and 5.61 6.661. As mentioned earlier, the present invention also includes the derivatized derivatives of copolymers of multiple blocks. Examples include melamine polymers, wherein the metal is the remnant of the tracer or of the chain linker employed, as well as additional derivatives thereof, for example, the reaction product of a polymer plated with an oxygen source and then with water to form a hydroxyl-terminated polymer. In another embodiment, water or other dampening device that conignes progens is added, to dissociate some or all of the polymer-bonding agent bonds, thereby converting at least a portion of the polymer into a hydroxyl-terminated polymer. Additional examples include olefin-terminated polymers formed by the use of hydrogen or other suitable chain terminator which results in the removal of β-hydride and ethylenic unsaturation in the resulting polymer. In an embodiment of the invention, the multiple block copolymer can be functionalized by means of a maleation (reaction with maleic anhydride or its equivalence), a melamination (as with a lithium alkyl reaction), optionally in the presence of a Lewis base, especially an amine, such as telramefil-efilen-diamine), or mediating the incorporation of a diene or olefin masked in a copolymerization process. After the polymerization involving a masked olefin, the masking group, for example a trihydrocarbylsilane, can be removed, exposing in this manner a more easily functionalized remanence. Techniques for polymer functionalization are well known, and are disclosed, for example, in the United States Patenle North America Number USP 5,543,458, and elsewhere. Because a substantial fraction of the polymer product leaving the reactor is terminated with the chain-linking agent, further functionalization is relatively easy. The polymeric species may be used in well-known chemical reactions, such as those suitable for other compounds of aluminum alkyl, alkyl-gallium, alkyl-zinc, or alkyl-Group 1, to form amine-, hydroxy-, epoxy- ketone, ester, nitrile, and other functionalized polymeric products. Examples of suitable reaction techniques which are adaptable for use herein are described in Negishi, "Organomeallics in Organic Synítesis", Volumes 1 and 2 (1980), and in other conventional examples in organomegalic and organic synεis. Polymeric Products Using the present process, novel polymers, especially olefin interpolymers, are easily prepared, including the copolymers of multiple blocks of one or more olefin monomers. In a desirable alpha fashion, the polymers are inerpolymers comprising, in a polymerized form, epylene and at least one comonomer of α-olefins of 3 to 20 carbon atoms, and optionally one or more additional copolymerizable comonomers. The preferred α-olefins are the a-olefins of 3 to 8 carbon atoms. Suitable comonomers are selected from diolefins, cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, and aromatic compounds of vinylidene. In a more particular manner, the present invented polymers include the following specific embodiments. In a first embodiment, the invention is an interpolymer having at least one melting point, Tm, in degrees Celsius, and a density, d *, in grams / cubic centimeter, where the numerical values of the variables correspond to the ratio : Tm > 2002.9 + 4538.5 (d *) - 2422.2 (d *) 2, and where the interpolmer has an Mw / Mn of 1.7 to 3.5. In a second embodiment, the invention is an interpolymer having at least a melting point, Tm, in degrees Celsius, and density, d *, in grams / cubic centimeter, where the numerical values of the variables correspond to the ratio : Tm > 6288.1 + 1 3141 (d *) - 67203 (d *) 2. In a third embodiment, the invention is an interpolymer having at least a melting point, Tm, in degrees Celsius, and a density, d *, in grams / cubic centimeter, where the numerical values of the variables correspond to the ratio : Tm > 858.91 -1 825.3 (d *) + 1 1 12.8 (d *) 2. In a fourth embodiment, the invention comprises an inerpolymer comprising, in a polymerized form, ethylene and an α-olefin of 3 to 8 carbon atoms, this interpolymer having a delta amount (DSC peak plus all the lower CRYSTAF peak). ) greater than the quantity, y *, defined by the equation: y * > 0.1299 (? H) +62.81, preferably the equation: y * > 0.1 299 (? H) +64.38, and more preferably the equation: and * > 0.1 299 (? H) +65.95, at a heat of fusion of up to 1 30 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer (ie, the peak must represent at least 5 percent of the accumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C, and? H is the numerical value of the heat of fusion in J / g. Still more preferably, the highest CRYSTAF peak comprises at least 10 percent of the cumulative polymer. Figures 3 to 27 and 36 to 49 show the curves of DSC and CRYSTAF for many examples of the invention, as well as many comparative polymers. The peaks used to calculate the delia amount, y *, are idenified in each figure along with the integrated area below the curve (which indicates the cumulative polymer percentage). Figures 2 and 50 will show the graphical data. for the examples of the invention, as well as for the comparative examples. The peak areas and the integrated peak tempera- tures are calculated by the computed drawing pro- gram supplied by the instrument manufaer. The diagonal line shown for the comparative polymers of ethylene and random ocean corresponds to the equation y * = - 0. 1299 (? H) + 62.81. In a fifth embodiment, the invention is an interpolymer having a tensile strength greater than 1 0 M Pa, preferably a tensile strength >; 1 1 MPa, more preferably a tensile strength > 1 3 MPa, and an elongation to the breaking of at least 600 percent, more preferably at least 700 percent, and in a highly preferable way at least 800 percent, and in a more highly preferable way than at least 900 percent, at a separation rate of the crossed head of 1 1 centimeters / minute. In a sixth embodiment, the invention is a inferpolymer having a delta canine (highest DSC peak temperature (measured from the baseline) minus CRYSTAF peak temperaure beyond (ie, numerical value more than dW / dT) ) greater than 48 ° C, and a heat of fusion greater than or equal to 130 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer (ie, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an idenifiable CRYSTAF peak, then the temperature of CRYSTAF is 30 ° C. Still more preferably, the highest CRYSTAF peak comprises at least 10 percent of the cumulative polymer. Figures 3 to 27 and 36 to 49 show the curves of DSC and CRYSTAF for many examples of the invention, as well as for many comparative polymers. The peaks used to calculate the delta quality, and *, are identified in each figure along with the integrated area below the curve (which indicates the cumulative polymer percentage). In Figures 2 and 50, the vertical line illustrates? H = 1 30 J / g, and the horizontal line illustrates y * = 48 ° C. In a seventh embodiment, the invention is an interpolymer having a storage modulus ratio, G '(25 ° C) / G' (1 00 ° C), from 1 to 50, preferably from 1 to 20, more preferably from 1 to 1 0, and a setting by compression at 70 ° C less than 80 by percent, preferably less than 70 percent, especially less than 60 percent, down to a compression setting of 0 percent. In an eighth embodiment, the invention is an interpolymer having a heat of fusion of less than 85 J / g, and a resistance to gland blockage equal to or less than 1 00 pounds / foot2 (4800 Pa), preferably equal or less than 50 pounds / foot2 (2400 Pa), especially equal to or less than 5 pounds / foot2 (240 Pa), and as low as 0 pounds / foot2 (0 Pa). In a ninth embodiment, the invention is a non-crosslinked elastomeric inlerpolymer comprising, in a polymerized form, at least 50 molar percent of ethylene, which has a compression setting at 70 ° C less than 80 percent, preferably less at 70 percent, and more preferably less than 60 percent. In a tenth embodiment, the invention is an olefin in-polymer, preferably comprising ethylene and one or more copolymerizable comonomers in a polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical (blocked interpolymer), more preferably a multiple block copolymer, this block inlerpolymer having a molecular fraction that elutes between 40 ° C and 1 30 ° C when fractionated using TREF, characterized in that this fraction has a molar comonomer content higher, preferably when less than 5 percent higher, more preferably at least 1 0 percent higher, than that of a comparable random ethylene interpolymer fraction that elutes between the same temperatures, where this comparable random ethylene interpolymer comprises same comonomers, and have a melt index, density, and molar comonomer content (based on the entire polymer) within 10 percent of those of the blocked interpolymer. Preferably, the Mw / M n of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer, and / or the comparable interpolymer has a total comonomer content within 10 percent by weight of that of the blocked interpolymer. The comonomer content can be measured using any suitable technique, preferring the techniques based on nuclear magnetic resonance (NMR) spectroscopy. Moreover, for polymers or polymer blends having relatively broad TREF curves, the polymer is preferably fractionated first by using TREF in fractions, each having an eluted temperature range of 10 ° C or less. That is, an eluted fraction has a collection window of 1 0 ° C or less. Using technical means, the polymers consist of at least one fraction having a higher comonomer content than a corresponding fraction of the comparable interpolymer. Preferably, for the interpolymers of ethylene and 1-ketene, the blocked interpolymer has a comonomer content of the fraction of TREF eluting between 40 ° C and 1 30 ° C more than, equal to, the amount (-0.201 3) T + 20.07, more preferably more than, or equal to, the amount (-0.201 3T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared as measured in ° C. Figure 54 graphically illustrates the above embodiment of the invention for the blocked epylene and 1-inert polymers. octene, where a graph of the comonomer content coniras the TREF elution temperature for several comparable ethylene / 1-ketene interpolymers (alloy copolymers), fitted to a line representing (-0.201 3) T + 20.07 (solid line The line for equation (-0.201 3) T + 21 .07 is illustrated by a dotted line The comonomer connotes are also illustrated for fractions of various blocked ethylene / 1-olene interpolymers of the invention (copolymers. of multiple blocks.) All fractions It is interpolymerically blocked having a content of 1-ketene significantly more than any line to the equivalent elution parameters. This result is characteristic of the multiblock copolymers of the invention, and is believed to be due to the presence of differentiated blocks within the polymer chains, which have a tanforal or amorphous nature. Figure 55 graphically displays the TREF curve and the comonomer content of the polymer fractions for Example 5 and Comparative F. The peak that elutes from 40 ° C to 1 30 ° C, preferably from 60 ° C to 95 ° C. ° C for both polymers, is divided into three parts, eluting each parie on an inervave of temperament less than ° C. The real damages for Example 5 are represented by íriángulos. The experimenter will appreciate that an appropriate calibration curve can be consumed for inermers that comprise different monomers, and a line is used as a comparison adjusted to the TREF values obtained from the comparative inermers of the same monomers, preferably random copolymers made using a meíaloceno or oíra homogenous cayalizadora composition. The blocked inert polymers corresponding to the present invention are characterized by a molar comonomer condenide greater than the value determined from the calibration curve at the same elution temperature of TREF, preferably at least 5 percent higher, more preferably at least 1 0 percent higher. For the copolymers of ethylene and an α-olefin, the polymers of the invention preferably have a PDI of at least 1.7, more preferably at least 2.0, and most preferably at least 2.6, up to a maximum value from 5.0, more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; a heat of fusion of 80 J / g or less, an ethylene content of at least 50 weight percent, a temperature of crissalization Tg, less than -25 ° C, more preferably less than -30 ° C, and / or one and one only Tm. The polymers can be characterized additionally by a depth of penetration of the thermomechanical analysis at 1 millimeter to a temperature of at least 90 ° C, as well as a flexural modulus from 3 kpsi (20 M Pa) to 1 3 kpsi (90 M Pa). Alternatively, the present polymers can have a penetration depth of the thermomechanical analysis of 1 millimeter at an hour of at least 1 04 ° C, as well as a flexure modulus of at least 3 kpsi (20 MPa). The interpolymers of the invention can be further characterized by having a setting setting at 70 ° C of less than 80 percent, preferably less than 70 percent, more preferably less than 60 percent. The polymers of the invention can also be characterized as having an abrasion resistance (or loss of volume) of less than 90 cubic millimeters. Additionally, the polymers of the invention may have, alone or in combination with any other properties disclosed herein, a storage module, GS when the register (G ') is greater than or equal to 400 KPa, preferably greater than or equal to 1.0 MPa, a a temperaure of 1 00 ° C. Moreover, the olefin polymers of the invention possess a relatively flat storage modulus as a function of the temperature in and store it from 0 ° C to 1 00 ° C (illustrated in Figure 35), which is characteristic of copolymers. of blocks, and unknown now for a copolymer of total olefin, especially a copolymer of ethylene and one or more aliphatic α-olefins of 3 to 8 carbon atoms. (The term "relative flat object", in this context, means that the G 'record (in Passages) decreases by less than an order of magnitude between 50 ° C and 1 00 ° C, preferably between 0 ° C and 1 00 ° C). Additionally, The polymers of the invention can have a melt index, 12, of 0.01 to 2,000 g branches / 10 minutes, preferably 0.01 to 1,000 grams / 10 minutes, more preferably 0.01 to 500 grams / 10 minutes, and especially from 0.01 to 1 00 grams / 10 minutes. The polymers of the invention can have molecular weights, Mw, of 1000 grams / mol a ,000,000 grams / mol, preferably from 1,000 g / gram to 1,000,000 grams / mol, preferably from 1,000,000 / mol to 500,000 g / mol, and especially from 1,000,000 / mol to 300,000 grams / mol. The density of the polymers of the invention may be from 0.80 to 0.99 grams / cm 3 and preferably for polymers containing ethylene, from 0.85 grams / cm 3 to 0.97 grams / cm 3. The polymers of the invention can be differentiated from conventional random copolymers, physical mixtures of polymers, and block copolymers prepared by the addition of monomers in sequence, fluxional catalysts, and living anionic or cationic polymerization techniques. In particular, in comparison with an alloy copolymer of the same monomers and the same monomer content at a chirality or equivalent modulus, the polymers of the invention have a better heat resistance (more alpha) as measured by the melting point, a temperaure of penetration TMA plus alpha, a resistance to the traction to alpha temperaure plus alpha, and / or a modulus of storage of deviation to alpha femperaíura higher, determined by dynamic mechanical analysis. Compared with an alloy copolymer comprising the same monomers and monomer content, the polymers of the Invention have a lower compression set, in particular at higher femperaires, a lower stress relaxation, a higher resistance to drag, a higher tear resistance, a more alpha blocking resistance, a more rapid set-up due to the Cryphalization imaging beyond (solidification), higher recovery (particularly at high temperatures), better resistance to abrasion, a refraction force beyond, and better acceptance of oil and filler. The present polymers also exhibit a unique branching and branching distribution ratio. That is, the present polymers have a relatively large difference between the highest peak temperature measured using CRYSTAF and DSC as a function of the heat of fusion, especially by comparing random copolymers comprising the same monomers and level of monomers or physical mixtures of polymers, such as a mixture of a high density polymer and a lower density copolymer, at an equivalent overall density. It is believed that the unique characteristic of the polymers of the invention is due to the unique distribution of the denim block comonomer of the polymer base structure. In particular, the polymer desirably comprises alternating blocks of different comonomer content (including homopolymer blocks). The polymers desirably comprise a block number and / or size distribution of the polymer blocks of different density or comonomer content, which is a Schultz-Flory distribution type. In addition, the polymers of the invention also have a peak melting point and a crystallization temperature profile which, in a unique way, is independent of the density / modulus morphology of the polymer. In a preferred embodiment, the microcrystalline order of the polymers demonstrates spherulites and characteristic sheets that can be distinguished from random or block copolymers, even in PDI values less than 1.7, or even less than 1.5, down to less of 1 .3. The unique crystalline morphology of the polymers of the invention is believed to result in good barrier properties due to the increased torsion of the crystalline morphology, which makes the polymers suitable for use in packaging and seal applications., such as coverings of boíellas covers and films to produce meat and food packaging. Figure 28 contains low resolution optical microg raphies of pressed films showing the micro-crustal structure of three multi-block copolymers of the present invention (all having a density of about 0.88), but made with different levels of chain binding agent. , which exhibit a varied spherulitic structure, as well as fresher comparative polymers, a substantially linear ethylene / 1 -inocene copolymer (copolymer Affinity R of a density of 0.875 grams / cm3, available from The Dow Chemical Company), a linear polyielylene having a density of 0.94 grams / cm3, and a mixture of polyethylene made with double cafalers in a single reactor (mixture within the reacfor). Figure 29 contains four scanning electron micrographs of alpha resolution (1 00 nanometer scale), three films of the above samples of the polymers of the invention made with alio, medium, and low levels of chain binding agent in the reactor, as well as a comparative photomicrograph of the ethylene copolymer / 1-substantially linear cytogen (Affinity ™ copolymer of a density of 0.875 grams / cm 3). The comparison of three polymer photographs of the invention shows in general a reduction in the thickness and length of the sheets with increasing levels of chain binding agent. Moreover, the present polymers can be prepared using techniques to influence the degree or level of blocking. That is, the amount of comonomer and the length of each block or polymer segment can be altered by controlling the ratio and type of catalysts and binding agent, as well as the polymerization temperature, and you will hear polymerization variables. A surprising benefit of this phenomenon is the discovery that, as the degree of blocking increases, the optical properties, the resistance to tearing, and the recovery properties at high temperature of the resulting polymer are improved. In particular, the nebulosity is reduced, while transparency, tear strength, and high temperature recovery properties are increased, as the average number of blockages in the polymer is increased. By selecting the binding agents and catalyst combinations that have the desired chain transfer capacity (high link speeds with low levels of termination chain), other forms of polymer termination are effectively suppressed. In accordance with the above, little, if any, removal of ß-hydride is observed in the polymerization of ethylene / α-olefin comonomer mixtures according to the invention, and the resultant crystalline blocks are highly, or substantially completely, linear, with little or no long chain branching. Another surprising benefit of the invention is that polymers in which the chain ends are highly crystalline can be prepared in a selective manner. In elastomer applications, the reduction of the relative amount of polymer that ends with an amorphous block reduces the effect of intermolecular dilution on the crystalline regions. This result can be obtained by the choice of chain binding agents and catalysts that have an appropriate response to the hydronogen or other chain-terminating agents. Specifically, if the catalyst that produces the high crystalline polymer is more suscepible to the chain termination (such as mediating the use of hydrogen) than the catalyst responsible for producing the least crystalline polymer segmenium (such as through a co-monomer addition, regio-error, or atactic polymer formation), then the high-crystalline polymer segments will preferentially populate the polymeric end portions. Not only the resulting finished groups are crystalline, but, after completion, the site of the high polymer forming catalyst Chrysalyne is once again available to restart the formation of the polymer. Accordingly, the polymer initially formed is another polymeric allialy crystalline segment. In accordance with the foregoing, both ends of the resulting multi-block copolymer are preferably highly crystalline. The ability of multi-block polymers made from ephelene and a comonomer such as 1-ketene to retain the properties of high melting point, is illustrated with reference to Figure 34, which is a graph of the crystalline melting point as a function of density (comonomer content). At lower densities, temperatures of crystal fusion not reduced significantly, comparing with those of the multiblock copolymers of higher density according to the invention (line), mieníras conventional aleaforios copolymers normalmeníe follow a curve well known that reflects the loss of peak crystalline fusion temperature as density is reduced. Other highly desirable compositions according to the present invention are elastomeric interpolymers of ethylene, one -olefin of 3 to 20 carbon atoms, especially propylene, and optionally one or more diene monomers. Preferred .alpha.-olefins for use in this embodiment of the present invention are designated by the formula CH2 = CH R *, wherein R * is a linear or branched alkyl of 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-1 -pentene, and 1-octene. A particularly preferred α-olefin is propylene. The propylene-based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in the preparation of these polymers, especially type polymers EPDM of multiple blocks include cyclic or polycyclic dienes, straight chain or branched, conjugated or unconjugated, containing 4 to 20 carbon atoms. Preferred dienes include 1, 4- peníadieno, 1, 4-hexadiene, 5-ethylidene-2-norbornene, diciclopeníadieno, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene. Because aq ue polymers coníienen diene contain alternating segments or blocks coníienen greater or lesser quantities of the diene (including none) and a-olefin (including none), you can reduce tofal amount of diene and a-olefin without losing the properties Subsequent polymer Because the diene monomers and olefin are incorporated preferentially in a type of bloq ue polymer, rather than a uniform or randomly throughout the polymer, uíilizan in a more efficient manner, and subsequently the crosslinking density of the polymer can be better controlled. These crosslinkable elastomers and cured products have convenient properties, including higher fraction strength and better elastic recovery. Furthermore, in a preferable manner, the multi-block elastomeric polymers of this embodiment of the invention, come a ethylene content of 60 to 90 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 1.0 to 40 percent, based on the total weight of the polymer. Preferred polymers are high molecular weight polymers, having a weight average molecular weight (Mw) of from 1,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000, and a polydispersity of less than 3.5, more preferably less than 3.0, and a Mooney viscosity (ML (1 +4125 ° C) of 1 to 250. More preferably, these polymers have an ethylene content of 65 to 75 percent , a diene content of 0 to 6 percent, and an a-olefin content of 20 to 35 per cent. The polymer can exfender with aceiíe with 5 to about 75 percent, preferably 10 to 60 percent, more preferably 20 to 50 percent, based on the toíal weight of the composition, of a aceiíe of procesamienío . Suitable oils include any oil that is conventionally used in the manufacture of extended EPDM rubber formulations. Examples include both naphthenic and paraffinic oils, with paraffinic oils being preferred. In a highly desirable manner, a rubber formulation of Curable EPDM is prepared by incorporating one or more curing agents, June with conventional accelerators or other adjuvants. The proper processing agencies are based on sulfur. Examples of suitable sulfur-based curing agents include, but are not limited to, sulfur, disulphide tetramethylthiuram (TMTD), dipentamethylenethiuram tetrasulfide (DPTT), 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazole disulfide (MBTS), zinc-2-mercaptobenzotiazolato (ZMBT), zinc diethyldithiocarbamate zinc (ZDEC), zinc dibutilditiocarbamalo ( ZDBC), dipentamethylenethiuram tetrasulfide (DPTT), N-tert-butylbenzothiazole-2-sulfanamide (TBBS), and mixtures thereof. A preferred curing system includes a combination of sulfur, MBT, and TMTD. Desirably, the above components are employed in amounts of 0.1 to 5 percent, based on the total weight of the composition. A preferred elastomeric composition in accordance with this embodiment of the invention, may also include carbon black. Preferably, the carbon black is present in the amount of 10 to 80 percent, more preferably 20 to 60 percent, based on the total weight of the composition. Additional components of the presently useful formulations employed in accordance with the present invention include other different ingredients, in amounts that do not impair the properties of the resulting composition. These ingredients include, but are not limited to, activators, such as calcium or magnesium oxide.; fatty acids, such as stearic acid and salts thereof; fillers and reinforcements, such as calcium or magnesium carbonate, silica, and aluminum silicates; plasticizers, such as dialkyl esters of dicarboxylic acids; aniidegradaníes, softeners; waxes; and pigments.

Uses and Fiinal Uses The polymers of the invention can be usefully employed in a variety of conventional iodoplastic manufacturing processes to produce useful articles, including objects comprising at least one layer of film, such as a single layer film, or when less one layer in a multilayer film prepared by casting, blown, calender, or extrusion coating processes; molded articles, such as articles blow molded, injection molded, or rotomolded; exirusions; fibers; and fabrics spun or not spun. Thermoplastic compositions comprising the present polymers include blends with other naïve or synthetic polymers, additives, reinforcing agents, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, blowing agents, and plasmifiers. Fibers of multiple components, such as core / sheath fibers, having an outer surface layer, comprising, at least in part, one or more polymers of the invention are of particular utility. Fibers that can be prepared from the present polymers or blends include short fibers, tow, multiple components, sheath / core, uroids, and single filament. Suitable fiber-forming processes include centrifugal sing or meltblowing techniques, as disclosed in United States Pat. Nos. 4,430,563, 4,663,220, 4,668, 566, and 4,322,027; the fibers spun in gel, as US Pat. No. 4,41 3,110,0 disclose spun and uned fabrics, as disclosed in the U.S. Patent No. 3,485,706, of the United States of America. Structures made from fine fibers, including blends with other fibers, such as polyester, nylon, or cotton, thermoformed articles, extruded configurations, including profile extrusions and co-extrusions, calendered goods, and drawn yarns or fibers, crooked, or curly. The novel polymers described herein are also useful for wire and cable coating operations, as well as in leaf extrusion for different forming operations, and molded articles by forming, including the use of injection molding, molding processes. by blowing, or rotomolding processes. Compositions comprising the olefin polymers can also be formed into manufactured articles, such as those mentioned previously, using conventional polyolefin processing techniques, which are well known to those skilled in the field of polyolefin processing. Dispersions (both aqueous and non-aqueous) can also be formed using the present polymers or formulations comprising them. Whipped foams comprising the polymers of the invention can also be formed, as disclosed in PCT Application No. 2004/02793, filed on August 25, 2004. The polymers can also be crosslinked by means known per se, as the use of peroxide, electron beam, silane, azide, or other crosslinking technique. The polymers may also be modified chemically, as a mediator (for example, by the use of maleic anhydride (MAH), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification. Additives and adjuvants can be included in any formulation comprising the present polymers. Suitable additives include fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, wire or mesh. steel, and nylon or polyester rope, nanometer sized particles, clays, etcérara; viscose, oil extenders, including paraffinic or naphthenic; and other natural and synthetic polymers, including other polymers according to the invention. Polymers suitable for blending with the polymers of the invention include thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers. Exemplary polymers for blending include polypropylene (both impact modifier polypropylene, isocyclic polypropylene, aiatic polypropylene, and random ethylene / propylene copolymers), different types of polyethylene, including high pressure, free radical LDPE, Ziegler-Natta LLDPE , PE of metallocene, including PE of multiple reactors (mixtures "inside the reactor" of PE Ziegler-Natta and Pe of metallocene, such as the products disclosed in the Patents of the United States of North America Numbers 6,545,088; 6,538,070; 6,566,446; 5,844,045; 5,869,575; and 6,448,341), ethylene-vinyl acetate block copolymers (EVA), ethylene / vinyl alcohol copolymers, polyesirene, impact modified polystyrene, ABS, styrene / butadiene block copolymers, and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyureia. Homogeneous polymers, such as olefin plasmomers and elastomers, ethylene and propylene-based copolymers (for example, the polymers available under the trade designation VERSI FYMR available from The Dow Chemical Company and VISTAMAXX ™ available from ExxonMobil), may also be useful as components in the blends comprising the instant polymers.

Suitable end uses for the above products include films and elastic fibers; soft items to the tacid, such as toothbrush handles and handles of aparaíos; packaging and profiles; adhesives (including hot melt adhesives and pressure sensitive adhesives); footwear (including shoe soles and shoe backs); interior parts and profiles of cars; foam articles (open and closed cell tans), impact modifiers for other thermoplastic polymers, such as high density polyethylene, isotactic polypropylene, or other olefin polymers; coated fabrics; soles; pipelines; exterior cornices; coverings of covers; floors; and viscosity index modifiers, also known as pour point modifiers, for lubricants.

In a highly preferred embodiment of the invention, the thermoplastic compositions comprising a polymer of feropolymeric mayrix, especially isocyclic polypropylene, and an elasomeric copolymer of multiple blocks of ethylene and a copolymerizable comonomer according to the invention, are uniquely capable of forming n-core-shell type particles having hard crystalline or semi-crystalline blocks in the shape of a core surrounded by soft or elastomeric blocks forming a "shell" around the clogged domains of the hard polymer. These particles are formed and dispersed within the matrix polymer by the forces incurred during the composition or blend of the melt. It is believed that this highly desirable morphology results due to the unique physical properties of the multi-block copolymers that make compatible polymer regions, such as the matrix, and the elastomer regions of higher comonomer content of the copolymer multiple blocks, self-assemble in fusion due to thermodynamic forces. It is believed that tearing forces during mixing produce separate regions of matrix polymer encased by elastomer. Upon solidification, these regions become the occluded elasphemer particles housed in the polymeric matrix. Particularly desirable mixtures are mixtures of thermoplastic polyolefin (TPO), thermoplastic elastomer blends (TPE), fermoplastic vulcanisites (TPV), and styrenic polymer blends. The mixtures of TPE and TPV can be prepare by combining the multi-block polymers of the invention, including their functionalized or unsaturated derivatives, with an optional rubber, including conventional block copolymer copolymers, especially a SBS block copolymer, and optionally a re-cure or vulcanization agent . The TPO mixtures are generally prepared by mixing the multi-block copolymers of the invention with a polyolefin, and optionally a re-linking or vulcanizing agent. The above mixtures can be used in the formation of a molded object, and the resulting molded article is optionally cross-linked. A similar procedure using different components has been previously disclosed in the US Pat. No. USP 6, 797,779. Conventional block copolymers suitable for this application, desirably have a Mooney viscosity (ML 1 + 4 @ 100 ° C) in the range of 10 to 135, more preferably 25 to 1 00, and more preferably 30 to 80. Suitable polyolefins include especially linear or low density polyethylene, polypropylene (including the atactic, isotactic, syndiotactic, and modified impact versions thereof), and poly (4-methyl-1 -pentelene). Suitable styrenic polymers include polystyrene, rubber modified polystyrene (H I PS), styrene / acrylonitrile copolymers (SAN), halo modified HA (ABS or AES), and styrene-maleic anhydride copolymers. Mixtures can be prepared by mixing or kneading Respective components at a temperature around or above the temperature of the melting point of one or both components. For most multi-block copolymers, this temperature may be 1 30 ° C, more generally above 145 ° C, and most preferably above 1 50 ° C. It is possible to employ typical polymer mixer or kneader equipment which is capable of achieving the desired temperatures and melt plasticization of the mixture. These include mills, mixers, extruders (both single screw and twin screw), Banbury mixers, calenders, and the like. The sequence of the mixture and the method may depend on the final composition. A combination of Banbu and batch mixers and continuous mixers can also be used, such as a Banbury mixer followed by a mill mixer, followed by an extruder. Typically, a TPE or TPV composition will have a more alpha charge of crosslinkable polymer (typically the conventional block copolymer conferring unsaturation) compared to the TPO compositions. In general, for the TPE and TPV compositions, the weight ratio of the block copolymer to the multi-block copolymer can be from about 90: 1 0 to 10:90, more preferably from 80:20 to 20:80, and from a very preferable way from 75:25 to 25:75. For TPO applications, the weight ratio of the multi-block copolymer to the polyolefin can be from about 49:51 to about 5:95, more preferably from 35:65 to about 1 0:90. For styrenic polymer applications modified, the weight ratio of the multi-block copolymer to the polyolefin can also be from about 49:51 to about 5:95, more preferably from 35:65 to about 10:90. The proportions can be changed by changing the viscosity ratios of the different components. There is considerable literature that illustrates the techniques for changing phase continuity by changing the viscosity ratios of the constituents of a mixture, and a person experienced in this field can consult it if necessary. The mixing compositions can confer processing aids, plasfificants, and process aids. The process oils have a certain ASTM designation, and the paraffinic, naffinic, or aromatic process oils are all suitable for use. In general, from 0 to 150 parples are used, more preferably from 0 to 1000 parts, and most preferably from 0 to 50 parts of oil per 1000 parts of the total polymer. Higher amounts of oil may tend to improve the processing of the resulting product at the expense of some physical properties. Additional processing aids include conventional waxes, salts of fatty acids, such as calcium stearate or zinc spherale, (poly) alcohols, including glycols, (poly) -alcohol-ethers, including glycol-esters, (poly) esters, including (poly) glycol esters, and metal salt derivatives, especially Group 1 or 2 metal, or zinc thereof. It is known that unhydrogenated rubbers, such as those They comprise the polymerized forms of butadiene or isoprene, including the block copolymers (hereinafter diene), have a lower resistance to ultraviolet light, to ozone, and to oxidation, in comparison with the fibers for the most part or highly saíurados. In general pneumatic applications made from compositions containing higher concentrations of diene-based rubbers, it is known to incorporate carbon black to improve the stability of the person, together with anti-ozone additives, and anti-oxidants. The multi-block copolymers according to the present invention, which have extremely low levels of unsaturation, find a particular application as a protective surface layer (coated, coextruded, or laminated), or weather resistant film, adhered to articles formed from conventional diene elastomer modified polymeric compositions. For conventional applications of TPO, TPV, and TPE, carbon black is the additive of choice for the absorption of ultraviolet light and for the properties of destabilization. Exemplary examples of smoke cancers include ASTM N 1 1 0, N 121, N220, N231, N234, N242, N293, N299, N31 5, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, and IM991. These carbon blacks have iodine uptake in the inoculum of 9 to 145 grams / kilogram, and average pore volumes in the range of 1 0 to 1 50 cm3 / 1 00 grams. In general, blacks are employed of smoke in smaller particle sizes, to the extent that sewing considerations allowed. For many of these applications, the present multi-block copolymers and mixtures thereof require little or no carbon black, thus allowing considerable design freedom to include alternating pigments or no pigments. One possibility is the tires of multiple shades, or the tires that match the color of the vehicle. The compositions, including the thermoplastic mixtures according to the invention, may also contain anhydrous or anoxidizing agents, which are known to a rubber chemist of ordinary experience. Chemicals can be physical proiectors, such as waxy materials that reach the surface and protect that part of oxygen or ozone, or they can be chemical protectors that react with oxygen or ozone. Suitable chemical protectants include styrene phenols, butylated octyl phenol, di (dimethylbenzyl) phenol butylated, p-phenylenediamines, butylated reaction products of p-cresol and dicyclopentadiene (DCPD), polyphenolic antioxidants, hydroquinone derivatives, quinoline, antioxidants diphenylene, thioester antioxidants, and mixtures thereof. Some trade names representative of these products are the antioxidant WingstayMR S, the antioxidant PolystayMR 100, the antioxidant PolystayMR 100 AZ, the antioxidant PoIystayMR 200, the antioxidant WingstayMR L, the antioxidant WingstayMR LHLS, the antioxidant WingstayM R K, the antioxidant WingstayMR 29, the antioxidant antioxidant WingstayMR SN-1, and the antioxidants lrganoxMR. In some applications, the antioxidants and anti-ozonants used will preferably not stain and will be non-migratory. To provide additional stability against ultraviolet radiation, hindered amine light stabilizers (HALS) and ultraviolet absorbers can also be used. Suitable examples include Tinuvin ™ 123, Tinuvin ™ 144, Tinuvin ™ 622, Tinuvin ™ 765, Tinuvin ™ 770, and Tinuvin ™ 780, available from Ciba Specialty Chemicals, and ChemisorbIVIR, available from Cytex Plastics, Houston TX, USA. Additionally, a Lewis acid with a HALS compound may be included for the purpose of achieving superior surface quality, as disclosed in US Pat. No. 6,051, 681. For some compositions, an additional mixing process may be employed to pre-disperse antioxidants, amphotericizers, carbon black, absorbents of ultraviolet light, and / or stabilize them to light, to form a masterbatch, and subsequently to form the mixtures. Polymeric to parfir of the same. Suitable crosslinking agents (also referred to as curing or vulcanizing agents) for use herein include the sulfur-based, peroxide-based, or phenolic-based compounds. Examples of the above materials are found in the art, including in the Patents of the United States of North America Numbers: 3,758,643; 3,806,558; 5,051, 478; 4, 1 04.21 0; 4,135,535; 4,202,801; 4,271, 049; 4.340, 684; 4,250,273; 4,927,882; 4.31 1, 628; and 5,248, 729. When sulfur-based curing agents are used, accelerators and cured acfivators can also be used. Accelerators are used to control the time and / or temperature required for dynamic vulcanization, and to improve the properties of the reticulated resulfant article. In one mode, a single accelerator or primary accelerator is used. The primary accelerators can be used in thal quantities in the range of about 5 to about 4., preferably from about 0.8 to about 1.5 phr, based on the total weight of the composition. In another embodiment, combinations of a primary and a secondary accelerator could be used, the primary accelerator being used in smaller quantities, such as from about 0.05 to about 3 phr, with the objection of activating and improving the properties of the cured article. Accelerator combinations generally produce arrays that have properties that are a bit better than those produced by the use of a single accelerator. In addition, delayed action accelerators can be used, which are not affected by normal processing temperatures, and yet, produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retardances could also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, fiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthines. From preference, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a compound of guanidine, dithiocarbamalo, or thiouram. Auxiliary processing latches and curing activators, such as stearic acid and ZnO, can also be used. When peroxide-based coating agents are used, co-builders or co-catalysts can be used in combination with them. Suitable co-agents include dimethylolpropane iarylate (TM PTA), trimethylolpropane methacrylate (TMPTMA), triallyl cyanide (TAC), triallyl isocyanurate (TAIC), among others. The use of peroxide refinulants and optional coagents used for partial or complete dynamic vulcanization is known in the art, and is disclosed, for example, in the publication "Peroxide Vulcanization of Elastomer", Volume 74, Number 3, July -August 2001 When the multi-block copolymer-containing composition is at least partially refined, the degree of cross-linking can be measured by dissolving the composition in a solvency for the specified duration, and calculating the non-exirable gel or composition percentage. The percentage of gel normally increases when the levels of crosslinking are increased. For articles cured according to the invention, the percentage of gel content is desirably in the range of 5 to 1 00 percent. The multi-block copolymers of the invention, as well as the mixtures thereof, possess better processability, compared to the prior art compositions, and are believed to be that this is due to the lower melt viscosity. Accordingly, the composition or mixture demonstrates an improved surface appearance, especially when formed in a molded or extruded article. At the same time, the compositions and mixtures thereof uniquely possess improved melt strength properties, thus allowing the present multi-block copolymers to mix the same, especially the TPO mixtures, to be used for foam and thermoforming applications, where fusion strength is currently inadequate. The thermoplastic compositions according to the invention may also contain organic or inorganic fillers, or other additives, such as starch, talc, calcium carbonate, glass fibers, polymeric fibers (including nylon, cotton, rayon, polyester, and polyaramide), metal fibers, flakes or particles, silicates in expandable layers, phosphates or carbonates, such as clay, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon hairs, carbon fibers, nanoparticles including nanotubes, wollastonite, graphite, zeolites, and ceramics, such as silicon carbide, silicon oxide, or tifanias. It is also possible to use silane-based or other coupling agents for a better binding of the filler. The thermoplastic compositions of this invention, including the above mixtures, can be processed by conventional molding techniques, such as injection molding, extrusion molding, self-forming, beveled molding, over-molding, molding. of insert, blow molding, and other techniques. Films, including multilayer films, can be produced by casting or laying processes, including blown film processes. Test Methods In the above characterization disclosure and in the following examples, the following analytical techniques are employed: GPC Method for Samples 1-4 and AC An automated liquid handling robot equipped with a heated needle set at 160 ° is used C, to add enough 1, 2,4-trichlorobenzene dispersed with 300 μmol of l onol to each dry polymer sample, to give a final concentration of 30 milligrams / milliliter. A small glass stirring rod is placed in each tube, and the samples are heated at 160 ° C for 2 hours, on a heated orbital shaker rotating at 250 revolutions per minute. Then the concentrated polymer solution was diluted to 1 milligram / milliliter, using the automated fluid handling robot and the calibrated needle set at 1 60 ° C. A Symyx Rapid GPC system is used to determine the molecular weight data for each sample. A Gilson 350 pump is used, established at a flow rate of 2.0 milliliters / minute, to pump 1, 2-dichlorobenzene purged of stabilized helium with 300 ppm of lonol as the mobile phase through three Plgel columns of 10 microns (μm). ) M ixed B of 300 millimeters x 7.5 millimeters placed in series, and heated to 1 60 ° C. A Deiector Polymer Labs ELS 1 000 is used with the Evaporator set at 250 ° C, the Nebulizer it is stable at 1 65 ° C, and the flow rate of nitrogen is established at 1.8 SLM and at a pressure of 60-80 psi (400-600 kPa) N2. The polymer samples are heated to 1 60 ° C, and each sample is injected in a 250 microliter cycle using the liquid handling robot and a heated needle. Serial analysis of the polymer samples is used using two switched sites and inlaid injections. The data from the samples are collected and analyzed using the Symyx Epoch ™ software. The peaks are manually integrated, and the uncorrected molecular weight information is reported against a standard polystyrene calibration curve. The DSC melting peak is measured as the maximum in the heat flow velocity (W / g) with respect to the linear baseline drawn between -30 ° C and the end of the melt. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of the melt, using a linear baseline. CRYSTAF Method Standard The branching distributions are determined by fractionation of crystallization analysis (CRYSTF), using a C RYSTAF 200 unit, available from PolymerChar, Valencia, Spain. The samples are dissolved in 1, 2, 4-trichlorobenzene at 160 ° C (0.66 milligrams / milliliter) for 1 hour, and are destabilized at 95 ° C for 45 minutes. Sampling temperatures are in the range of 95 ° C to 30 ° C, at a cooling rate of 0.2 ° C / min uto. An infrared detector is used to measure the concentrations of the polymer solution. The cumulative soluble concentration is measured as The polymer is crystallized, while the temperament is red. The analogous derivative of the cumulative profile reflects the short chain branching distribution of the polymer. The peak temperature and the CRYSTAF area are identified by the peak analysis module included in the Software CRYSTAF (Version 2001. b, PolymerChar, Valencia, Spain). The CRYSTAF peak discovery routine identifies a peak temperature as a maximum in dW / dT, and the area between the largest positive inflections on either side of the peak identified in the derived curve. To calculate the CRYSTAF curve, the preferred processing parameters are with a temperature limit of 70 ° C and with smoothing parameters above the temperature limit of 0.1, and below the threshold value of 0.3. DSC Standard Method (Excluding samples 1-4 and A-C) Differential Scanning Calorimetry results are determined using a TAI model Q 1 000 DSC equipped with an RCS cooling accessory and a self-sampler. A flow of nitrogen purge gas of 50 milliliters / minute is used. The sample is compressed to a thin film, and fired in the press at about 75 ° C, and then cooled with ambient air temperature (25 ° C). Then 3 to 10 milligrams of the material was run on a disk of 6 millimeters in diameter, weighed precisely, placed on a light aluminum tray (approximately 50 milligrams), and then curled. The technical behavior of the sample is investigated with the following profile of femperairy. The sample quickly heated to 180 ° C, and remained isothermal for 3 minutes, in order to remove any previous thermal history. The sample was then cooled to -40 ° C at a cooling rate of 10 ° C / min, and kept at -40 ° C for 3 minutes. Then the sample is heated to 50 ° C at a heating rate of 10 ° C / minute. The cooling and second heating curves will be recorded. The DSC melting peak is measured as the maximum in the heat flow velocity (W / g) with respect to the linear baseline drawn between -30 ° C and the end of the melt. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of the melt, using a linear baseline. Abrasion Resistance Abrasion resistance is measured on compression molded plates in accordance with ISO 4649. The average value of three measurements is reported. The plates for the test are 6.4 millimeters thick, and are compression molded using a hot press (Carver Model # 4095-4PR1 001 R). The granules are placed between the sheets of polyfluoro-fluoroethylene, heated at 1 90 ° C to 55 psi (380 kPa) for 3 minutes, followed by 1.3 M Pa during 3 min., And then 2.6 M Pa for 3 minutes. The plates are then cooled in the press with cold running water at 1.3 M Pa for 1 minute, and removed for the test. GPC Method (Excluding Samples 1-4 and A-C) The gel permeation chromatographic system consisted of either a Polymer Laboratories Model PL-21 0 or an insírumento Polymer Laboratories Model PL-220. The column and the carrousel comparisons are operated at 140 ° C. Three columns M ixtas-B Polymer Laboratories of 1 0 microns are used. The solvenle is 1, 2, 4-trichlorobenzene. The samples are prepared in a concentration of 0.1 grams of polymer in 50 milliliters of solvenite containing 200 ppm of butylated hydroxy-luene (BHT). The samples are prepared by shaking lightly for 2 hours at 160 ° C. The injection volume ufilized is 1 00 microliters, and the flow rate is 1.0 milliliters / minute. The calibration of the established GPC column is carried out with 21 narrow molecular weight distribution polystyrene standards, with molecular weights in the range of 580 to 8,400,000, configured in six "cocktail" mixtures, with at least a dozen of separation between the individual molecular weights. The slats are acquired at Polymer Laboratories (Shropshire, United Kingdom United). The polystyrene standards are prepared in 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. First the mixtures of narrow standards are passed, and with the aim of reducting the component of higher molecular weight, to minimize the deg radation. The peak molecular weights of the polystyrene standard are converted to molecular weights of polyethylene using the following equation (as described in Williams and Ward, J. Polvm, Sci .. Polvm.

Le, 6, 621 (1 968)): Mp? | E.iieno = 0.431 (Mp0, iestireno). The equivalent molecular weight calculations of polyethylene are carried out using the Viscotek TriSEC Version 3.0 software. Compressive Setting Compression setting is measured according to ASTM D395.

The sample is prepared by stacking round discs of 25.4 millimeters in diameter, with a thickness of 3.2 millimeters, 2.0 millimeters, and 0.25 millimeters, to reach an ionic thickness of 12.7 millimeters. The discs are cut from compression molded plates of 12.7 centimeters x 12.7 centimeters, molded with a hot press under the following conditions: zero pressure for 3 minutes at 190 ° C, followed by 86 MPa for 2 minutes at 1 90 ° C, followed by cooling inside the press with running cold water at 86 MPa. Density Samples are prepared for density measurement according to ASTM D 1 928. Measurements are made within 1 hour of sample compression, using ASTM D792, Me- dia B. Flexural Module / Secant Module / Storage Module Samples they are compression molded using ASTM D1 928. The 2 percent flexural and secant modules are measured in accordance with ASTM D790. The storage module is measured in accordance with ASTM D 5026-01, or an equivalent technique. Optical Properties Films 0.4 mm thick are compression molded, using a hot press (Carver Model # 4095-4PR1 001 R). The The granules were placed in the polyterefluoroethylene sheets, heated at 190 ° C to 55 psi (380 kPa) for 3 minutes, followed by 1.3 MPa for 3 minutes, and then 2.6 MPa for 3 minutes. Then the film is cooled in the press with cold water running at 1.3 MPa during 1 minute. Compression molded films are used for optical measurements, fraction behavior, recovery, and stress relaxation. Transparency is measured using the BYK Gardner Haze-gard, as specified in ASTM D 1 746. The gloss at 45 ° is measured using the BYK Gardner Glossmeyer M icrogloss 45 °, as specified in ASTM D-2457. The internal nebulosity is measured using the BYK Gardner Haze-gard based on ASTM D 1 003 procedure A. Mineral oil is applied to the surface of the film to remove surface scratches. Mechanical Properties - Traction, Hysteresis, and Tear The stress-strain behavior in the uniaxial tension is measured using microtensile samples from ASTM D 1 708. The samples are scraped with an Instron at 500% min "1 to 21 ° C. traction and elongation at break from an average of five samples Hysteresis at 100 per cent and at 300 per cent is determined from the cyclic load up to 100 per cent and 300 per cent using samples ASTM D 1 708 micro-sensors with an instrumentation lnSyronMR The sample is loaded and discharged at 267% min "1 for three cycles at 21 ° C. Cyclic experiments are conducted at 300 percent and at 80 ° C using an environmental chamber. In the experiment at 80 ° C, allow the sample to equilibrate for 45 minutes at the test temperature before testing. In the cyclic experiment at 21 ° C, with 300 percent pull, the shrinkage stress is recorded at a fraction of 1 50 percent from the first discharge cycle. The recovery percentage is calculated for all the experiments from the first discharge cycle using the fraction to which the load returned to the baseline. The recovery percentage is defined as: Zf - is% recovery = x 1 00 e. * Where, zf is the fraction taken for the cyclic load, and is the traction when the load returns to the baseline during the first discharge cycle. Stress relaxation is measured at a fraction of 50 percent and at 37 ° C for 12 hours, using an inflow of water equipped with a medium-ambient chamber. The calibration geometry was 76 millimeters x 25 millimeters x 0.4 millimeters.

After balancing at 37 ° C for 45 minutes in the environmental chamber, the sample was sifted to a fraction of 50 percent at 333% min. "1 The stress was recorded as a function of time for 12 hours. of tension after 1 2 hours was calculated using the formula: Lo - L-? 2% Stress Relaxation = x 1 00 Lo where L0 is the load at a fraction of 50 percent at time zero, and L 2 is the load at a 50 percent pull after 1 2 hours. They are carried out, experiment of tearing with tensile notch on samples that have a density of 0.88 grams / cm3 or less, using an instrumentation lnsíronMR. The geometry consists of a calibration section of 76 millimeters x 1 3 millimeters x 0.4 millimeters, with a notch cut of 2 millimeters in the sample, at the same time as the length of the sample. The sample is squeezed at 508 millimeters min "1 to 21 ° C until it breaks The tear energy is calculated as the area under the stress elongation curve up to the fraction at maximum load. minus three samples TMA Thermal Mechanical Analysis (Peneration Temperaure) is carried out on compression-molded discs of 30 millimeters in diameter x 3.3 millimeters in thickness, formed at 1 80 ° C and at a molding pressure of 10 MPa for 5 hours. The instrument used is a TMA 7, available on PerkinElmer.In the test, a probe is applied with a handpiece of a radius of 1.5 mm (P / N N519-0416). to the surface of the sample disc with a force of 1 N. The temperature rises to 5 ° C / minute from ° C. The penetration distance of the probe is measured as a function of temperature. The experiment ends when the probe has penetrated 1 millimeter into the sample. DMA The Dynamic Mechanical Analysis (DMA) is measured on compression molded discs formed in a hot press at 180 ° C and at a pressure of 10 M Pa for 5 minutes, and then cooled with water in the press at 90 ° C / minute. The test is conducted using an ARES controlled traction rheometer (TA instruments) equipped with double cantilever fittings for the deflection test. A plate of 1.5 millimeters is compressed and cut into a bar measuring 32 x 1 2 millimeters. The sample was fastened in both exfers to the accessories separated by 10 millimeters (grid spacing? L), and subjected to successive femperature steps from -1 00 ° C to 200 ° C (5 ° C per step). At each temperature, the torsion modulus G 'is measured at an angular frequency of 1 0 rad / s, maintaining the amplitude of the traction, against 0.1 percent and 4 percent to ensure that the torque is sufficient, and that the measurement remains in the linear regime. An initial static force of 10 g grams (self-tension mode) is maintained to prevent the sample from loosening when thermal expansion occurs. As a consequence, the spacing of the grid? L increases with the temperature, in particular above the melting or softening point of the polymer sample. The test stops at the maximum temperature, or when the gap between the accessories reach 65 millimeters. Granule Locking Resistance Granules (150 grams) are loaded into a 2"(5 centimeter) diameter hollow cylinder made of two halves held together by a hose clamp 2.75 lbs. kilograms) to the granules in the cylinder at 45 ° C for 3 days After 3 days, the granules are consolidated together in a cylindrical stopper The plug is removed from the shape, and the blocking force is measured of g ranulo loading the cylinder of granules locked in compression using an instrument lnstronM R to measure the compression force necessary to break the cylinder into granules Fusion index The melt index, or l2, is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg Melt index, or l10, is also measured according to ASTM D 1 238, Condition 190 ° C / 10 kg ATREF Fraction analysis by elution with elevation of analytical temperature (ATREF ) is driven from according to the method described in the United States of America Packet Number USP 4,798,081. The composition to be analyzed is dissolved in trichlorobenzene, and left to crystallize in a column containing an inert support (a shot of stainless steel), slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. uto. The column is equipped with an infrared detector. Then an ATREF chromatogram curve is generated by eluting the crystallized polymer sample from the column, slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 ° C to 120 ° C, at a rate of 1.5 ° C / min. . Polymer Fractionation Using TREF Large-scale TREF fractionation is carried out by dissolving 15 to 20 grams of polymer in 2 liters of 1, 2,4-trichlorobenzene (TCB), agitating for 4 hours at 160 ° C. The polymer solution is forced by nitrogen at 15 psig (100 kPa) onto a steel column 3 inches by 4 feet (7.6 centimeters x 3.6 meters) packed with a mixture of 60:40 (volume.volume) of glass beads from technical grade, spherical, 30-40 mesh (600 to 425 microns) (available from Potiers Industries, HC 30 Box 20, Brownwood, TX, 76801), and 0.028-inch (0.7 millimeter) stainless steel wire cut diameter (available from Pellets, Inc. 63 Industrial Drive, Noríh Tonawanda, NY, 14120). The column is immersed in a thermally controlled oil jacket, initially set at 160 ° C. The first is cooled first ballistic to 125 ° C, then cooled slowly to 20 ° C at 0.04 ° C per minute, and is maintained for 1 hour. Fresh TCB is inflated to approximately 65 milliliters / minute, while the temperature is maintained at 0.167 ° C per minute. Portions of approximately 2,000 milliliters of the eluent are collected from the preparation TREF column in a heated fraction collector from station 16. The polymer is concentrated in each fraction using a rotary evaporator, until approximately 50 to 1000 milliliters of the polymer solution remain. The concentrated solutions are allowed to stand overnight before adding an excess of methanol, filtering, and rinsing (approximately 300 to 500 milliliters of meianol, including the final rinse). The filtration step is carried out on an assisted filtration station, by vacuum in position 3 using a filter paper coated with 5.0 micron polyphentrafluoroethylene (available from Osmonics Inc., Caf # Z50WP04750). The filtered fractions are dried overnight in a vacuum oven at 60 ° C, and are weighed on an analytical balance after an additional test. 13C NMR analysis The samples are prepared by adding 3 grams of a 50/50 sample of terachlorethane-d2 / orio dichloro-benzene to 0.4 grams of sample in a 1 0 mm nuclear magnetic resonance tube.

The samples are dissolved and homogenized by heating the tube and its contents to 50 ° C. The data is collected using a spectrophotometer J EOL EclipseM R 400 MHz, or a Varian UMity PlusMR spectrometer at 400 MHz, corresponding to a resonance frequency of 13C of 1 00.5 MHz. The data is acquired using 4,000 transients per damage file with a pulse repetition delay of 6 seconds. Multiple data files are added in order to achieve the minimum signal to noise for quantitative analysis. The spectral amplitude is 25,000 Hz with a minimum file size of 32 K damage points. The samples are analyzed at 1 30 ° C in a 1 0 mm broadband probe. The incorporation of comonomer is determined using the triad method of Randall (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys. C29, 201-31 7 (1989) Atomic Force M icroscope (AFM) collect sections of the sample material using a Leica UCTMR microtome with a cryo-camera FC operated at -80 ° C. A diamond blade is used to section all the sample material to a thickness of 1 20 nanometers. freshly dissociated mica surfaces, and mounted on metal support discs for standard AFM samples with a double carbon tape The sections are examined with a NanoScope IVM R Multi-Mode AFM, in the vibration mode with phase defection. The nano-sensor pointers are used in all experiments Specific Modes The following specific embodiments of the invention and combinations thereof are especially desirable, and are outlined herein with the object to provide a detailed disclosure for the appended claims. 1 . A composition comprising the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers that differ in their chemical or physical properties , of the polymer prepared by the catalyst (A), under equivalent polymerization conditions, and (C) a chain binding agent. 1 a. A composition comprising the mixture or the reaction product results from the combination of: (A) a first olefin polymerization catalyst having a high comonomer incorporation index, (B) a second olefin polymerization catalyst having a comonomer incorporation rate less than 95 percent, preferably less than 90 percent, more preferably less than 25 percent, and most preferably less than 1.0 percent of the rate of incorporation of the catalyst comonomer (A) , and (C) a chain link agency. 2. A method for selecting a mixture of (A) and (B) and chain linkage (C) binders according to mode 1) and 1 a), which is capable of producing a multi-block copolymer, in counting a mixture of olefin or a mixture of monomers with this mixture under olefin polymerization conditions. 3 A process for the preparation of a multi-block copolymer, which comprises contacting one or more polymerizable monomers by addition under addition polymerization conditions, with a composition comprising: the resulting reaction mixture or product. the combination of: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers that differ in their chemical or physical properties, of the polymer prepared by the catalyst (A), under equivalent polymerization conditions, and (C) a chain-linking agent . 3a. A process for the preparation of a multi-block copolymer, which comprises contacting one or more polymerizable monomers by addition under addition polymerization conditions, with a composition comprising: the reaction mixture or product resulting from the combination of: (A) a first olefin polymerization catalyst having a high comonomer incorporation index, (B) a second capable olefin polymerization catalyst having a comonomer incorporation index of less than 90 percent, preference less than 50 percent, more preferably less than 5 percent of the comonomer incorporation index of the catalyst (A), and (C) a chain-linking agent. 4. A multi-block copolymer comprising, in polymerized form, one or more addition polymerizable monomers, said copolymer containing therein, two or more, preferably one or more segments or blocks differing in their comonomer content, crystallinity , tacitity, homogeneity, density, melting point or glass transition temperature, this copolymer preferably having a molecular weight distribution, Mw / M n, less than 3.0, more preferably less than 2.8. 4a. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more copolymerizable copolymers, containing copolymer therein, two or more, preferably three or more segments or blocks differing in their comonomer content, crystallinity , facticity, homogeneity, density, melting point or glass transition temperature, this copolymer preferably having a molecular weight distribution, Mw / Mn, less than 3.0, more preferably less than 2.8. 5. A functionalized derivative of the multiple block copolymer of mode 4. 6. A functionalized derivative of the multi-block copolymer of mode a. 7. An olefin interpolymer having at least one melting point, Tm, in degrees Celsius, and a density, d *, in grams / cm3, where the numerical values of the variables correspond to the ratio: Tm > 2002.9 + 4538.5 (d *) - 2422.2 (d *) 2, and wherein the interpolymer has an Mw / Mn of 1.7 to 35. 8. An interpolymer comprising, in a polymerized form, ethylene and an α-olefin from 3 to 8 carbon atoms that has at least one melting point, Tm in degrees Celsius, and a density, d *, in grams / cm3, where the numerical values of the variables correspond to the ratio: Tm > 2002.9 + 4538.5 (d *) - 2422.2 (d *) 2. 9. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more copolymerizable comonomers, having at least a melting point, Tm, in degrees Celsius, and a density, d *, in grams / cm3, where the numeric values of the variables correspond to the relation: Tm > 2002.9 + 4538.5 (d *) - 2422.2 (d *) 2. 1 0. An olefin interpolymer having an Mw / M n of 1.7 to 35, a delta amount (highest DSC peak minus the highest CRYSTAF peak) greater than the quantity, and *, defined by the equation : y * > -0.1299 (? H) + 62.81, preferably the equation: y * > -0.1299 (? H) + 64.38, and more preferably the equation: y * > -0.1299 (? H) + 65.95, and a heat of fusion of up to 1 30 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer, and if less than percent of the polymer is u? peak of CRYSTAF idenifiable, then the temperature of CRYSTAF is 30 ° C, and? H is the numerical value of the heat of fusion in J / g. 1 0a. An interpolymer comprising, in a polymerized form, and an α-olefin of 3 to 8 carbon atoms, this interpolymer having a delta amount (highest DSC peak minus highest CRYSTAF peak) greater than the amount, and *, defined by the equation: and * > 0.1 299 (? H) +62.81, preferably the equation: y * > 0.1 299 (? H) +64.38, and more preferably the equation: y * > 0.1 299 (? H) + 65.95, and a heat of fusion of up to 1 30 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C, and? H is the numerical value of the heat of fusion in J / g. 1 0b. A multi-block copolymer having a delta amount (highest DSC peak minus CRYSTAF peak plus alio) greater than the amount, and *, defined by the equation: y * > 0.1299 (? H) +62.81, preferably the equation: y * > 0.1299 (? H) +64.38, and more preferably the equation: y * > 0.1 299 (? H) + 65.95, and a heat of fusion of up to 1 30 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer, and if less than percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C, and? H is the numerical value of the heat of fusion in J / g. eleven . An olefin interpolymer having a strength above 1.0 M Pa, preferably a tensile strength > 1 1 M Pa, more preferably a tensile strength > 13 M Pa, and an elongation to the break of at least 600 percent, more preferably at least 700 percent, most preferably at least 800 percent, and very highly preferable at least 900 percent, at a crosshead clearance rate of 1 1 centimeter /minute. 1 1 a. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more copolymerizable comonomers, having a strength at a fraction above 10 MPa, preferably a tensile strength > 1 1 MPa, more preferably a tensile strength > 13 MPa, and an elongation at break of at least 600 percent, more preferably at least 700 percent, in a highly preferable way of at least 800 percent, and in a very highly preferable way of at least 900 percent, at a crosshead clearance rate of 1 1 centimeters / minute. 12. An olefin interpolymer having a delta amount (highest DSC peak (measured from baseline) minus highest CRYSTAF peak) greater than 48 ° C, and a heat of fusion greater than or equal to 1 30 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C. 1 2a. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more comonomers copolymerizable, which has a delta amount (highest DSC peak (measured from the baseline) minus CRYSTAF peak plus alio) greater than 48 ° C, and a heat of fusion greater than or equal to 130 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ° C. 1 3. An olefin interpolymer having a storage modulus ratio, G '(25 ° C) / G' (1 00 ° C), from 1 to 50, preferably from 1 to 20, more preferably from 1 to 1 0, and a compression setting at 70 ° C less than 80 percent, preferably less than 70 percent, especially less than 60 percent, down to a compression setting of 0 percent. 13a. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more copolymerizable comonomers, having a storage modulus ratio, G '(25 ° C) / G' (1 00 ° C), from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10, and a setting by compression at 70 ° C of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, going down to a setting by compression of 0 percent. 14. An olefin interpolymer having a heat of fusion less than 85 J / g, preferably less than 80 J / g, and a blockage strength of the granule equal to or less than 1 00 pounds / square foot (4800 Pa), preferably equal to or less than 50 pounds / square foot (2400 Pa), in special equal to or less than 5 pounds / square foot (240 Pa), and as low as 0 pounds / square foot (0 Pa). 14 to. A multi-block copolymer comprising, in a polymerized form, ethylene and one or more copolymerizable comonomers, having a heat of fusion of less than 85 J / g, preferably less than 80 J / g, and a resistance to blocking of the granule equal to or less than 1 00 pounds / square foot (4800 Pa), preferably equal to or less than 50 pounds / square foot (2400 Pa), especially equal to or less than 5 pounds / square foot (240 Pa), and so low as of 0 pounds / square foot (0 Pa). 5. An olefin interpolymer, elastomeric, non-crosslinked, comprising, in a polymerized form, at least 50 mole percent ethylene, which is set by compression at 70 ° C less than 80 percent, preference less than 70 percent, more preferably less than 60 percent. 1 5a. A multi-block elastomeric copolymer, non-crosslinked, comprising, in a polymerized form, at least 50 mole percent of ethylene, having a setting setting at 70 ° C of less than 80 percent, preferably less than 70 percent, more preferably less than 60 percent. 16. A polymer according to any of the embodiments 4 to 1 5, 4a, 5a, 1 0a-1 5a, 1 0b, or which can be prepared by the method of mode 3 or 3a, which contains a single point of crystalline fusion (Tm) measured by DSC. 1 7. A polymer according to any of the modalities 4-15, 4a, 5a, 10a-15a, 10b, or that can be prepared by the method of mode 3 or 3a, which has a penetration depth of the thermomechanical analysis of 1 millimeter at a temperature of at least 90 ° C , preferably at a temperature of at least 100 ° C, and a flexural modulus of 3 kpsi (20 MPa) at 13 kpsi (90 MPa). 18. A polymer according to mode 16, having a depth of penetration of the thermomechanical analysis of 1 millimeter at a temperature of at least 90 ° C, preferably at a temperature of at least 100 ° C, and a flexural modulus of 3 kpsi (20 MPa) at 13 kpsi (90 MPa). 19. A polymer according to any of the embodiments 4-15, 4a, 5a, 10a-15a, 10b, or that can be prepared by the method of mode 3 or 3a, which has a volume loss by resistance to abrasion in accordance with ISO 4649 less than 90 cubic millimeters. 20. A polymer according to mode 16, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters. 21. A polymer according to the modality 17, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters. 22. A polymer according to mode 18, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters. 23. A polymer according to any of the embodiments 4-15, 4a, 5a, 10a-15a, 10b, or which can be prepared by the mode 3 or 3a method, which has a volume loss due to abrasion resistance of according to ISO 4649 less than 90 cubic millimeters, and that has a storage module, GS that the record (G ') is greater than or equal to 0.4 KPa, preferably greater than or equal to 1 .0 M Pa, at a temperaure of 1 00 ° C. 24. A polymer according to the modality 1 6, which has a volume loss due to abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters, and which has a storage module, which is the record ( G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 MPa, at a temperaure of 1 00 ° C. 25. A polymer according to the modality 17, which has a volume loss due to abrasion resistance according to ISO 4649 less than 90 cubic millimeters, and that has a storage module, GS such that the register (G ') is greater than or equal to 0.4 MPa, preferably greater than or equal to 1.0 M Pa, at a temperature of 100 ° C. 26. A polymer according to the modality 1 8, which has a volume loss due to abrasion resistance according to ISO 4649 less than 90 cubic millimeters, and which has a storage module, GS such that the registration (G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 M Pa, at a temperaure of 1 00 ° C. 27. A polymer according to the modality 1 9, which has a loss of volume due to resistance to abrasion according to ISO 4649 less than 90 cubic millimeters, and which has a storage module, GS such that the record (G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 M Pa, at a tempera- 1 00 ° C. 28. A polymer according to the embodiment 20, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters, and which has a storage modulus, GS such that the record (G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 M Pa, at a temperature of 1 00 ° C. 29. A polymer according to mode 21, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 cubic millimeters, and having a storage modulus, GS such that the record (G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 M Pa, at a temperature of 1 00 ° C. 30. A polymer according to the embodiment 22, which has a volume loss due to abrasion resistance according to ISO 4649 less than 90 cubic millimeters, and having a storage modulus, GS such that the record (G ') is greater than or equal to 0.4 M Pa, preferably greater than or equal to 1.0 M Pa, at a temperature of 1 00 ° C. 31 A cross-linked derivative of a polymer according to any of the embodiments 4-1 5, 4a, 5a, 1 0a-1 5a, 1 0b, or which may be prepared by the method of mode 3 or 3a. 32. A crosslinked derivative of a polymer according to the mode 1 6. 33. A re-cyclic derivative of a polymer according to the mode 1 7. 34. A cross-linked derivative of a polymer according to the mode 1 8. 35. A crosslinked derivative of a polymer according to the modality 19. 36. A crosslinked derivative of a polymer according to the modality 20. 37. A reliculated derivative of a polymer according to the embodiment 21. 38. A cross-linked derivative of a polymer according to mode 22. 39. A cross-linked derivative of a polymer according to mode 23. 40. A re-branched derivative of a polymer according to mode 24. 41. A cross-linked derivative of a polymer according to mode 25. 42. A cross-linked derivative of a polymer according to mode 26. 43. A cross-linked derivative of a polymer according to mode 27. 44. A crosslinked derivative of a polymer according to the embodiment 28. 45. A cross-linked derivative of a polymer according to the embodiment 29. 46. A re-cyclic derivative of a polymer according to the modality 30. 47 A polymer according to any of the embodiments 4-1 5, 4a, 5a, 1a-1a, 5a, 1b, or which can be prepared by the mode 3 or 3a method, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed arithmetic, a fiber, a non-spun fabric, an injection molded article, an article molded by blown, a roto-molded article, or an adhesive. 48. A polymer according to the embodiment 1 6, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a gum-molded article, or an adhesive. 49. A polymer according to the modality 1 7, or a composition comprising the same in the form of a film, at least a layer of a multilayer film, when less a layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow-molded article, a roto-molded article, or an adhesive. 50. A polymer according to the embodiment 18, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 51 A polymer according to the embodiment 19, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a gum-molded article, or an adhesive. 52. A polymer according to the embodiment 20, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a rofo-molded article, or an adhesive. 53. A polymer according to mode 21, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, a molded article by injection, a blow molded article, a roto-molded article, or an adhesive. 54. A polymer according to the embodiment 22, or a composition comprising thereon in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 55. A polymer according to the embodiment 23, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 56. A polymer according to the embodiment 24, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection-molded ale, a blow-molded ale, a roto-molded ale, or an adhesive. 57. A polymer according to the mode 25, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, one ale foamed, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 58. A polymer according to the embodiment 26, or a composition comprising the same in the form of a film, at least in a layer of a multilayer film, at least in a layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 59. A polymer according to the embodiment 27, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 60. A polymer according to mode 28, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 61 A polymer according to the embodiment 29, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection-molded ale, a blow-molded ale, a roto-molded ale, or an adhesive. 62. A polymer according to the embodiment 30, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, one foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 63. A polymer according to the embodiment 31, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least a layer of a laminated ale, a foamed ale , a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 64. A polymer according to the embodiment 32, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 65. A polymer according to the embodiment 33, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 66. A polymer according to the embodiment 34, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated ale, a foamed ale, a fiber, a non-spun fabric, an injection molded ale, a blow molded ale, a roto-molded ale, or an adhesive. 67. A polymer according to the embodiment 35, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article , or an adhesive. 68. A polymer according to the embodiment 36, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 69. A polymer according to the embodiment 37, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least a layer of a laminated article, a foamed article , a fiber, a non-spun fabric, an injection molded article, a blow molded article, a gum-molded article, or an adhesive. 70. A polymer according to the embodiment 38, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or a adhesive. 71 A polymer according to the embodiment 39, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection-molded article, a blow-molded article, a roto-molded article, or an adhesive. 72. A polymer according to the embodiment 40, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article , a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 73. A polymer according to embodiment 41, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 74. A polymer according to the embodiment 42, or a composition comprising the same in the form of a film, at least a layer of a multilayer film, when less a layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow-molded article, a roto-molded article, or an adhesive. 75. A polymer according to the embodiment 43, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a gum-molded article, or an adhesive. 76. A polymer according to the embodiment 44, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed arycle, a fiber, a non-spun fabric, an injection-molded article, a blow-molded article, a roll-molded article, or an adhesive. 77. A polymer according to the embodiment 45, or a composition comprising thereto in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a gum-molded article, or an adhesive. 78. A polymer according to the embodiment 46, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed arycle, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive. 79. A composition according to embodiment 1 or 1 a, wherein the linking agent is a trihydrocarbyl-aluminum or dihydrocarbyl-zinc compound, which contains from 1 to 12 carbon atoms in each hydrocarbyl group. 80. A composition according to claim 79, wherein the linking agent is triefil-aluminum or diethyl-zinc. 81 A composition according to the embodiment 1 or 1 a, wherein the catalyst (A) comprises a complex comprising a transition metal selected from Groups 4 to 8 of the Periodic Table of the Elements, and one or more ligands p-linked delocalised, or polyvalent Lewis base ligands. 82. A composition according to mode 81, wherein the catalyst (A) corresponds to the formula: where: R1 1 is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives of the same, that they contain from 1 to 30 atoms without counting hydrogen, or a divalent derivative thereof; T1 is a divalent group of from 1 to 41 different hydrogen atoms, preferably from 1 to 20 different hydrogen atoms, and more preferably a methylene or silane group substituted by mono-, or di-hydrocarbyl of 1 to 20 carbon atoms. carbon; and R12 is a heteroaryl group of 5 to 20 carbon atoms containing Lewis base functionality, especially a pyridin-2-yl group, or a substituted pyridin-2-yl group, or a divalent derivative thereof; M1 is a Group 4 metal, preferably hafnium; X1 is a group of anionic, neutral, or dianionic ligand; x 'is a number from 0 to 5, which indicates the number of such groups x1; and the links, optional links, and electron donor donations, are represented by lines, punched lines, and arrows, respectively. 83. A composition according to the embodiment 82, wherein the catalyst (B) corresponds to the formula: where: M2 is a metal of Groups 4 to 10 of the Periodic Table of the Elements; T2 is a group that contains nitrogen, oxygen, or phosphorus, X2 is halogen, hydrocarbyl, or hydrocarbyloxy; t is 1 or 2; x "is a number selected to provide a load balance, and T2 and N are linked by a bridging ligand 84. A process according to modality 3 or 3a, which is a continuous process. 86. A process according to the modality 85, where ethylene and one or more copolymerizable comonomers are polymerized 87. A process according to the modality 86, in accordance with the modality 84, which is a process in solution. where the ethylene conversion in the reactor is at least 95 percent. 88. A process according to the mode 84, wherein the catalyst (A) corresponds to the formula: wherein: R1 1 is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof, containing from 1 to 30 atoms without counting hydrogen, or a divalent derivative thereof; T1 is a divalent bridging group of 1 to 41 different hydrinogen atoms, preferably from 1 to 20 different hydrogen atoms, and more preferably a methylene or silane group substituted by mono-, or di-hydrocarbyl of 1 to 20 carbon atoms; and R12 is a heteroaryl group of 5 to 20 carbon atoms containing Lewis base functionality, especially a pyridin-2-yl group, or a substituted pyridin-2-yl group, or a divalent derivative thereof; M1 is a Group 4 metal, preferably hafnium; X1 is a group of anionic, neutral, or dianionic ligand; x 'is a number from 0 to 5, which indicates the number of such groups x1; and the links, optional links, and electron donation interactions, are represented by lines, dotted lines, and arrows, respectively. 89. A process according to the modality 88, where the cafalizador (B) corresponds to the formula: where: M2 is a metal of Groups 4 to 10 of the Periodic Table of the Elements; T2 is a group containing nitrogen, oxygen, or phosphorus, X2 is halogen, hydrocarbyl, or hydrocarbyloxy; t is 1 or 2; x "is a number selected to provide a load balance, and T2 and N are linked by a bridging ligand 90. A multi-block copolymer, which comprises, in a polymerized form, ethylene and a copolymerizable comonomer. 91 An olefin polymer having a relatively flat storage modulus, characterized in that the G 'register (in Passages) decreases by less than an order of magnitude between 50 ° C and 1 00 ° C. 92. A process according to mode 3 or 3a, wherein the proportion of the chain-linking agent to one or more catalysts and / or monomers is varied in order to produce polymers that differ in one or more chemical properties or physical 93. A polymer blend comprising: (1) an organic or inorganic polymer, preferably an ethylene or propylene homopolymer and / or a copolymer of ethylene and a copolymerizable comonomer, and (2) a polymer according to any of the modalities 4-1 5, 4a, 5a, 1 0a-1 5a, 1 0b, or that can be prepared by the method of mode 3 or 3a. 94. A polymer blend according to the embodiment 93, wherein the component (1) is an organic thermoplastic polymer. 95. A polymer blend according to mode 94, wherein component (1) is a propylene homopolymer. 96. A polymer blend according to embodiment 95, wherein component (1) is highly isotactic polypropylene. 97. A polymer blend according to the embodiment 93, wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers. 98. A polymeric mixture according to mode 94, in wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers. 99. A polymer blend according to embodiment 95, wherein component (2) is an elastomeric copolymer of ephemeral and one or more copolymerizable comonomers. 1 00. A polymer mixture according to the embodiment 96, wherein the component (2) is a elastomeric copolymer of ethylene and one or more copolymerizable comonomers. 1 01. A polymer blend according to the embodiment 93, wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein. 102. A polymer blend according to the embodiment 94, wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein. 103. A polymer blend according to embodiment 95, wherein component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of component (1) therein. 1 04. A polymeric mixture according to the embodiment 96, wherein the component (2) is an elasomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein. 1 05. A polymer mixture according to the modality 93, in wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein, these occlusions being formed after the fusion mixture of the components (1) ) and (2). 06. A polymer blend according to the embodiment 94, wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein, forming these occlusions after the fusion mixture of the components (i) and (2). 07. A polymeric mixture according to the embodiment 95, wherein the component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of the component (1) therein. , these occlusions are formed after the fusion mixture of the components (1 and 2) . 1 08. A polymer blend according to embodiment 96, wherein component (2) is an elastomeric copolymer of ethylene and one or more copolymerizable comonomers, in the form of particles containing occlusions of component (1) therein, forming these occlusions after the fusion mixture of the components ( 1 and 2) . 09. A process for the preparation of a polymer mixture, which comprises: (1) an organic or inorganic thermoplastic polymer, preferably an ethylene or propylene homopolymer and / or a copolymer of ethylene and a copolymerizable comonomer, and (2) an elastomeric polymer in the form of particles containing occlusions of the component (1) therein, this process comprising blending the components (1) and (2) under conditions of shear stress, to form occlusions of the component (1) in dispersed particles of the component (2). 1 1 0. The process of mode 1 09, where component (1) is isotactic polypropylene. 1 1 1 The process of the 1 1 0 mode, wherein the component (2) is a copolymer of ethylene and a copolymerizable comonomer. The experfo will appreciate that the invention disclosed herein can be practiced in the absence of any component, step or ingredient that has not been disclosed in a specific manner. Examples The following examples are provided as an optional illustration of the invention, and should not be construed as limiting. The term "during the night", if used, refers to a time of approximately 1 6 to 1 8 hours; the term "ambient temperature" refers to a temperature of 20 ° C to 25 ° C; and the term "mixed alkanes" refers to a commercially obtained mixture of aliphatic hydrocarbons of 6 to 9 carbon atoms, available under the trade designation Isopar EM R, from Exxon Chemicals I nc. In the event that the name of the compound herein does not conform to its structural representation, will control the structural representation. The synthesis of all the metal complexes, and the preparation of all the sifting experiments, were carried out in an atmosphere of dry nitrogen, using dry box techniques. All the solvents used were HPLC grade, and dried before use. MMAO refers to modified methylalumoxane, a tri-isobutyl aluminum modified methylalumoxane commercially available from Akzo-Noble Corporation. The catalyst (A1) is [N- (2,6-di (1-methylethi) phenyl) -amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-di-1) - methan)] hafnium-dimethyl, prepared in accordance with the teachings of the Patent Numbers WO 03/40195, 2003US0204017, USSN 10 / 429,024, filed May 2, 2003, and International Publication-Number WO 04/24740.

Catalyst (A2) is [N- (2,6-di (1-methylethyl) -phenyl) -amido) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2-diyl) methan)] hafnium dimethyl, prepared in accordance with the teachings of the Patent Numbers WO 03/40195, 2003US0204017, USSN 10 / 429,024, filed May 2, 2003, and International Publication Number WO 04/24740.

The catalyst (A3) is bis [N, N '"- (2,4,6-tri (methyl-phenyl) -amido) -ethylenediamine-hafnium-dibenzyl.

The catalyst (A4) is bis ((2-oxoyl-3- (dibenzo-1 H -pyrrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) cyclohexan-12-diyl-zirconium- (IV ) -dibenciIo, prepared substantially in accordance with the teachings of the Patenfe de los Esfados Unidos de Norleamérica Number US-A-2004/0010103.

The catalyst (B1) is 1,2-bis- (3,5-diterbutyl-phenylene) - (1 - (N- (1-methylethyl) imino) methyl) - (2-oxoyl) -zirconium-dibenzyl.

The preparation of the catalyst (B1) is conducted as follows. a) Preparation of (1-methylethyl) - (2-hydroxy-3,5-di (terbufil) -phenyl) -methylimine 3,5-Dylebutyl-alkylaldehyde (3.00 grams) is added to 10 milliliters of isopropylamine. The solution becomes rapidly bright yellow. After stirring at ambient temperature for 3 hours, volatiles are removed in vacuo to give a bright yellow crystalline solid (97 percent yield). b Preparation of 1,2-bis- (3,5-di-butylphenyl) - (1 - (N- (1-methylethyl) imino) methyl) - (2-oxoyl) -zirconium-dibenzyl A solution of (1-methyl-ethyl) (2-Hydroxy-3,5-di (ferbutyl) -phenyl) imine (605 milligrams, 2.2 mmol) in 5 milliliters of toluene, lenfamenfe is added to a solution of Zr (CH2Ph) 4 (500 milligrams, 1.1) millimoles) in 50 milliliters of toluene. The resulting dark yellow solution is stirred for 30 minutes. The solvent is removed under reduced pressure to give the desired product as a reddish brown solid.

The catalyst (B2) is 1,2-bis- (3,5-di-butylphenyl) - (1 - (N- (2-methyl-cyclohexyl) -imino) -methyl) - (2-oxoyl) -zirconium-dibenzyl.

The preparation of the caulk (B2) is conducted as follows. a) Preparation of (1- (2-mephylcyclohexyl) -ylethyl) - (2-oxoyl-3,5-di (terbuyl) -phenylimine) 2-Methylcyclohexylamine (8.44 milliliters, 64.0 mmol) is dissolved in mephanole (90 milliliters), and di-boroyl-salicyl-aldehyde (1.00 grams, 42.67 mmol) was added.The reaction mixture was stirred for 3 hours, and then cooled to -25 ° C for 12 hours.The resulting yellow solid precipitate was collected. The filtrate is filtered, and washed with cold methanol (15 milliliters, 2 times), and then dried under reduced pressure.The yield is 11.1 grams of a yellow solid.1H NMR is consistent with the desired product as a mixture of isomers b) Preparation of bis- (1 - (2-mephyl) cyclohexyl) ethyl) - (2-oxoyl-3,5-di (ferbufil) -phenyl) -imino) -zircon-dibenzyl A solution of (1- (2-mephylcyclohexyl) -ethyl) - (2-oxoyl-3,5-di (tert-butyl) phenyl) imine (7.63 grams, 23.2 mmol) in 200 milliliters of toluene, is added slowly to a solution of Zr (CH2Ph) 4 (5.28 grams, 1 1.6 millimoles) in 600 milliliters of toluene. The resulting dark yellow solution is stirred for 1 hour at 25 ° C. The solution is diluted further with 680 milliliters of toluene, to give a solution having a concentration of 0.00783 M. The catalyst (C1) is (terbufylamido) -dimethyl (3-N-pyrrolyl-1, 2,3,3a, 7a-β-inden-1-yl) -silane-iitanium-dimethyl, prepared substantially according to the techniques of the Paíente of the United States of North America Number USP 6,268,444: The catalyst (C2) is (lerbutylamido) -di (4-methylphenyl) - (2-methyl-1, 2,3,3a, 7a -? - inden-1-yl) -silane-thiomanium-dimethyl, prepared substantially from in accordance with the teachings of the Patenfe of the United States of America Number US-A-2003/004286: The catalyst (C3) is (ε-butylamido) - (di (4-methyl-phenyl) - (2-methyl- 1, 2,3,3a, 8a -? - s-indacen-1-yl) -silane-thifanium-dimethyl, prepared in accordance with the teaching of the United States of America No. US-A-2003 / 004286: The catalyst (D1) is bis (dimethyldisiloxane) - (inden-1-yl) -zirconium dichloride, available from Sigma-Aldrich: Cocatalyst 1. A mixture of methidoid salts (alkyl of 14 to 18 carbon atoms) - ammonium ester ester (peniafluorophenyl) borate (hereinafter referred to as Armenian bora), prepared by the reaction of a long chain trialkylamine (Armeen ™ M2HT, available from Akzo-Nobel, Inc.), HCl, and Li [B (C6F5) 4], substantially as disclosed in US Pat. No. 5,919,9883, Example 2. Cocatalyst 2. Mixed alkyl salt of 14 to 18 atoms carbon-dimethylammonium bis (irish (penfafluoro-phenyl) -aluman) -2-undecyl imidazolide, prepared in accordance with the Patenfe of the United States of America No. USP 6,395, 671, Example 1 6. Linking Agents. The binding agencies employed include diethyl zinc (DEZ, SA1), di (isobutyI) -zinc (SA2), di (n-hexyl) -zinc (SA3), aluminum-aluminum (TEA, SA4), aluminum-aluminum ( SA5), trietyl-gallium (SA6), bis (dimethyla- (terbuyl) -siloxane) of isobutyl-aluminum (SA7), bis (di (trimethylsilyl) amide) of isobutyl-aluminum (SA8), di (pyridin-2) mephoxide) of n-octyl-aluminum (SA9), bis (n-octadecyl) -isobufil-aluminium (SA1 0), bis (di- (n-penyl) amide) of isobuyl-aluminum io (SA1 1), bis- (2,6-diterbuyl-phenoxide) of n-octyl-aluminum (SA12), di- (ethyl (1-naphthyl) -amide) of n-ocyl-aluminum (SA1 3), bis (terbuyl-dimethyl-silioxide) of aluminum-aluminum (SA14), di- (bis (yrylylsilyl) -amide) ethyl-aluminum (SA1 5), bis (2, 3,6,7-dibenzo-1-azacyclo-hepyanamide) ethyl-aluminum ( SA1 6), bis- (2, 3,6,7-dibenzo-1-azacycloheptanamide) of n-oleyl-aluminum (SA1 7), bis (dimei? 'I (boerbuyl) siloxide) of n-ocyyl- aluminum (SA18), ethyl-zinc (2,6-diphenyl-phenoxide) (SA19), and efil-zinc (ferbutoxide) (S) TO 20). Example 1 -4, Components A-C General Conditions of High Production Parallel Polymerization. The polymerizations are conducted using a parallel production alpha polymerization (PPR) reamer available from Symyx Technologies, I nc. , and operated substantially in accordance with the Patents of the United States of North America Numbers 6,248,540; 6,030,917; 6,362,309; 6,306,658; and 6,316,663. Ethylene copolymerizations are conducted at 1 30 ° C and at 200 psi (1.4 MPa) with ethylene on demand, using 1.2 equivalents of cocaine analyzer 1, based on the tofal catalyst used (1.1 equivalents when M MAO is present). A series of polymerizations is conducted in a parallel pressure reactor (PPR) comprised of 48 individual reactor cells in a 6x8 array, which are adapted with a pre-weighed glass tube. The workload in each reactor cell is 6,000 microliters. The temperature and pressure of each cell is controlled with agitation provided by individual stirring blades. The monomer gas and the shut-off gas are connected directly to the PPR unit, and controlled by automatic valves. The liquid reagents are added robotically to each cell of the reactor by means of syringes, and the solvent of the deposit is of mixed alkanes. The order of addition is of mixed alkane solvent (4 milliliters), ethylene comonomer, 1-octene (1 milliliter), cocatalyst 1 or 1 / M MAO cocatalyst mixture, bonding agent, and catalyst or mixture of cayalisers. When a mixture of cocatalyst 1 and M MAO is used, or a mixture of two caffeizers, the reagents are pre-mixed in a small vial immediately after adding the reactant. When a reagent is omitted in one experiment, the order of earlier addition is maintained in a different manner. The polymerizations are conducted for approximately 1 to 2 minutes, until the previously determined ethylene consumption is reached. After shutting down with CO, the reactors are cooled, and the glass tubes are discharged. The tubes are transferred to a centrifugal / vacuum drying unit, and dried last 12 hours at 60 ° C. The tubes containing dry polymer are weighed, and the difference between this weight and the unbalanced weight gives the net yield of the polymer. The results are contained in Table 1. In Table 1 and in any other part of the application, the comparisons are indicated by an asferisk (*). Examples 1 to 4 demonstrate the synthesis of linear block copolymers of the present invention, as evidenced by the formation of a very narrow Mw, an essentially monomodal copolymer when DEZ is present, and a bimodal product of broad molecular weight distribution ( a mixture of polymers produced separately) in the absence of DEZ. Due to the fact that it is known that the Catalyst (A1) incorporates more oil than the Catalyst (B1), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on the branching or the density. Table 1 Contain d or d chain of 6 carbon atoms or its peri or 1000 atoms of carbon or 2D? str? b uc? on molecular weight, bi modal It can be seen that the polymers produced according to the invention have a relatively narrow polydispersity (Mw / Mn), and a higher content of block copolymer (trimer, tetramer, or greater) than the polymers prepared in the absence of the link. Additional characterization data for the polymers of Table 1 are determined by referring to the figures. More specifically, the DSC and ATREFF results show the following: The DSC curve of Figure 3 for the polymer of Example 1, shows a melting point (Tm) of 1-1.5 ° C with a heat of fusion of 1 58.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 34.5 ° C, with a peak area of 52.9 percent. The difference between the DSC Tm and the Tcrystaf is 81.2 ° C. The DSC curve in Fig. 4 of the polymer of Example 2 shows a peak with a melting point (Tm) of 1.07 ° C with a heat of fusion of 214.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 46.2 ° C, with a peak area of 57.0 percent. The difference between the DSC Tm and the Tcrystaf is 63.5 ° C. The DSC curve in Fig. 5 of the polymer of Example 3 shows a peak with a melting point (Tm) of 120.7 ° C with a heat of fusion of 160.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 66.1 ° C, with a peak area of 71.8 percent. The difference between the DSC Tm and the Tcrystaf is 54.6 ° C. The DSC curve in Figure 6 of the polymer of Example 4 shows a peak with a melting point (Tm) of 1 04.5 ° C with a heat of fusion of 70.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 30 ° C, with a peak area of 18.2 per cent. The difference between the DSC Tm and the Tcrystaf is 74.5 ° C.

The DSC curve in Figure 22 (Comparative A) shows a melting puncture (Tm) of 90.0 ° C with a heat of fusion of 86.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 48.5 ° C, with a peak area of 29.4 percent. Both values are consistent with a resin that is low density. The difference between the Tm of DSC and the Tcrystaf is 41.8 ° C. The DSC cuve in Figure 23 (Comparative B) shows a melting point (Tm) of 129.8 ° C with a heat of fusion of 237.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 82.4 ° C, with a peak area of 83.7 percent. Both values are consistent with a resin that is of high density. The difference between the DSC Tm and the Tcrystaf is 47.4 ° C. The DSC curve in Figure 24 (Comparative C) shows a melting point (Tm) of 1 25.3 ° C, with a heat of fusion of 143.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C, with a peak area of 34.7 percent, as well as a lower crystalline peak at 52.4 ° C. The separation between the two peaks is consistent with the presence of a high crystalline polymer and a low crystalline polymer. The difference between Tm of DSC and Tcrystaf is 43.5 ° C. Examples 5-1 9, Compounds D-F, Polymerization in Continuous Solution, Catalyst A1 / A2 + DEZ Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. The mixed alkane solvent is supplied purified (lspparR E, available from ExxonMobil Inc.), ethylene at 2.70 pounds / hour (1.22 kilograms / hour), 1-ketene, and hydrogen (when used) to a 3.8-liter reactor equipped with a jacket for the temperature control, and an internal thermocouple. The solvent feed to the reactor is measured by a mass flow controller.

A variable speed diaphragm pump controls the flow velocity and pressure of the solvent to the reactor. At the pump discharge, a sidestream is taken to provide discharge flows for the injection lines of the catalyst and the cocatalyst 1, and the reactor agitator. These flows are measured by Micro-Motion mass flow meters, and controlled by control valves, or by means of manual adjustment of needle valves. The resin solvent is combined with 1-amino, ethylene, and hydrogen (when used), and fed into the reactor. A mass flow confrolator is used to supply hydrogen to the reactor as necessary. The temperature of the solvent / monomer solution is controlled by the use of a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The solutions of the catalyst component are introduced using pumps and mass flow meters, and are combined with the solvent discharged from the catalyst, and introduced into the bottom of the reactor. The reactor is filled with liquid at 500 psig (3.45 M Pa) with vigorous agiiation. The product is removed through the outlet lines of the top of the reactor. All the output lines from the reactor are steam tracked and isolated. The polymerization is determined by the addition of a small amount of water at the start line, together with any other additives or additives, and passing the mixture through a static mixer. The product stream is then heated by passing it through a heat exchanger prior to devolatilization. The polymer product is recovered by extrusion, using a devolatilization extruder, and a water-cooled granulator. The values and results of the process are contained in Table 2. The selected properties of the polymer are given in Table 3.

The resulting polymers are tested by DSC and ATREFF as with the above examples. The results are as follows: The DSC curve in Figure 7 (polymer of Example 5) shows a peak with a melting point (Tm) of 1 1 9.6 ° C., with a heat of fusion of 60.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 47.6 ° C, with a peak area of 59.5 percent. The delta between the Tm DSC and the Tcryslaf is 72.0 ° C. The DSC curve in Figure 8 (polymer of Example 6) shows a peak with a melting point (Tm) of 15.2 ° C, with a heat of fusion of 60.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 44.2 ° C, with a peak area of 62.7 percent. The delta between the Tm DSC and the Tcrystaf is 71.0 ° C. The DSC curve in Figure 9 (polymer of Example 7) shows a peak with a melting point (Tm) of 121.3 ° C, with a heat of fusion of 69.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 49.2 ° C, with a peak area of 29.4 percent. The delta between the Tm DSC and the Tcrystaf is 72.1 ° C. The DSC curve in Fig. 10 (polymer of Example 8) shows a peak with a melting point (Tm) of 123.5 ° C, with a heat of fusion of 69.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.1 ° C, with a peak area of 12.7 percent. The delta between the Tm DSC and the Tcryslaf is 43.4 ° C. The DSC curve in Fig. 1 1 (polymer of Example 9) shows a peak with a melting point (Tm) of 1 24.6 ° C, with a heat of fusion of 73.5 J / g. The corresponding CRYSTAF curve shows the highest peak at 80.8 ° C, with a peak area of 16.0 percent. The delta between the Tm DSC and the Tcrystaf is 43.8 ° C. The DSC curve in Fig. 1 2 (polymer of Example 1 0) shows a peak with a melting point (Tm) of 1 1 5.6 ° C, with a heat of fusion of 60.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.9 ° C, with a peak area of 52.4 per cent. The delfa between the Tm DSC and the Tcrystaf is 74.7 ° C. The DSC curve in Figure 13 (polymer of Example 1 1) shows a peak with a melting point (Tm) of 13.6 ° C, with a heat of fusion of 70.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 39.6 ° C, with a peak area of 25.2 percent. The delta between the Tm DSC and the Tcrysíaf is 74.1 ° C. The DSC curve in Figure 14 (polymer of Example 12) shows a peak with a melting point (Tm) of 1 13.2 ° C, with a heat of fusion of 48.9 J / g. The corresponding CRYSTAF curve does not show a peak equal to or greater than 30 ° C. (Tcrystaf for the purposes of additional calculation, is set at 30 ° C). Delía eníre Tm DSC and Tcrystaf is 83.2 ° C. The DSC curve in Figure 15 (polymer of Example 1 3) shows a peak with a melting point (Tm) of 14.4 ° C, with a heat of fusion of 49.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 33.8 ° C, with a peak area of 7.7 percent. The delta between the Tm DSC and the Tcrystaf is 84.4 ° C. The DSC curve in Figure 1 6 (polymer of Example 14) shows a peak with a melting point (Tm) of 120.8 ° C, with a heat of fusion of 27.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 72.9 ° C, with a peak area of 92.2 per cent. The delta between the Tm DSC and the Tcrystaf is 47.9 ° C. The DSC cuve in Fig. 17 (polymer of Example 1 5) shows a peak with a melting point (Tm) of 14.3 ° C, with a heat of fusion of 36.2 J / g. The corresponding CRYSTAF curve shows the highest peak at 32.3 ° C, with a peak area of 9.8 percent. The delta between the Tm DSC and the Tcrystaf is 82.0 ° C. The DSC curve in Figure 18 (polymer of Example 16) shows a peak with a melting point (Tm) of 1 1 6.6 ° C, with a heat of fusion of 44.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 48.0 ° C, with a peak area of 65.0 percent. The delta between the DSC Tm and the Tcrystaf is 68.6 ° C. The DSC curve in Figure 1 9 (polymer of Example 1 7) shows a peak with a melting point (Tm) of 16.0 ° C, with a heat of fusion of 47.0 J / g. The corresponding CRYSTAF curve shows the highest peak at 43.1 ° C, with a peak area of 56.8 per cent. The delía between the Tm DSC and the Tcrystaf is 72.9 ° C. The DSC cuve in Fig. 20 (polymer of Example 18) shows a peak with a melting point (Tm) of 1 20.5 ° C, with a heat of fusion of 141.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 70.0 ° C, with a peak area of 94.0 percent. The delta between the Tm DSC and the Tcrystaf is 50.5 ° C. The DSC cuve in Figure 21 (polymer of Example 1 9) shows a peak with a melting point (Tm) of 1 24.8 ° C, with a heat of fusion of 74.8 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.9 ° C, with a peak area of 79.9 percent. The delta between the Tm DSC and the Tcrystaf is 45.0 ° C. The DSC curve in Figure 25 (Comparative D) shows a peak with a melting point (Tm) of 37.3 ° C, with a heat of fusion of 31.6.

J / g. The corresponding CRYSTAF curve does not show peak equal to or above 30 ° C. Both values are consistent with a resin that is low density. The delta between the Tm DSC and the Tcrystaf is 7.3 ° C. The DSC curve in Figure 26 (Comparative E) shows a peak with a melting point (Tm) of 1 24.0 ° C, with a heat of fusion of 179. 3 J / g. The corresponding CRYSTAF curve shows the highest peak at 79.3 ° C, with a peak area of 94.6 percent. Both values are consistent with a resin that is high density. The delta between the Tm DSC and the Tcrystaf is 44.6 ° C. The DSC curve in Fig. 27 (Comparative F) shows a peak with a melting point (Tm) of 124.8 ° C., with a heat of fusion of 90.4 J / g. The corresponding C RYSTAF curve shows the highest peak at 77.6 ° C, with a peak area of 9.5 percent. The separation between the two peaks is consistent with the presence of a high crystalline polymer as a low crislallic polymer. The delta between the DSC Tm and the Tcrystaf is 47.2 ° C. Physical Properties Testing Polymeric samples are evaluated to determine their physical properties, such as their high temperature resistance properties, as evidenced by the TMA temperature test, resistance to blockage of the granule, recovery at high temperature, setting by compression at high temperature, and storage module ratio, G (25 ° C) / G '(100 ° C). The tests include several commercially available polymers: the Comparative G * is a substantially linear ethylene / 1-ketene copolymer (AFFINITY R KC8852G, available from The Dow Chemical Company), Comparative H * is a substantially linear, elastomeric ethylene / 1-ketene copolymer (AFFINITY ™ EG8100, available from The Dow Chemical Company), Comparative I is an ethylene / 1-copolymer linear susfancialmenle ocíeno (Affinity PL1840, available from The Dow Chemical Company), Comparative J is a styrene / butadiene / styrene-hydrogenated triblock copolymer (KratonMR G1652, available from KRATON Polymers), Comparative K is a thermoplastic vulcanizate (TPV, a polyolefin blend containing dispersed therein). crosslinked elastomer). The results are presented in Table 4.

Table 4. High Temperature Mechanical Properties In Table 4, Comparative F (which is a physical mixture of the two resulting polymers simultaneously using the A1 catalysts and B 1) has a penetration temperature of 1 millimeter of about 70 ° C, while Examples 5 to 9 have a penetration temperature of 1 millimeter of 100 ° C or higher.

Additionally, Examples 1 to 19 all have a penetration temperature of 1 millimeter greater than 85 ° C, the majority having a TMA temperature of 1 millimeter greater than 90 ° C, or even greater than 1 00 ° C. It is a sample that the novel polymers have a better dimensional stability at higher temperatures, compared with a physical mixture. Comparative J (a commercial SEBS) has a good TMA temperature of 1 millimeter of about 107 ° C, but it has very bad setting by compression (high temperature 70 ° C) of about 1 00 percent and also failed to recover (the sample broke) during a recovery of traction from 300 percent to alpha temperaure (80 ° C). Thus, the exemplified polymers have a unique combination of properties not available even in some commercially available high performance thermoplastic elastomers. In a similar manner, Table 4 shows a low proportion of the storage modulus (good), G '(25 ° C) / G' (1 00 ° C) for the invented polymers, of 6 or less, while a physical (Comparative F) has a storage module ratio of 9, and a random ethylene / octene copolymer (Comparative G) of a similar density, has a storage module ratio an order of magnitude (89). It is desirable that the storage modulus ratio of a polymer be as close to 1 as possible. These polymers will be relatively unaffected by temperature, and fabricated articles made from these polymers can be usefully employed over a wide temperature range. This characteristic of low storage modulus ratio and temperature independence is particularly useful in elastomer applications, such as in pressure sensitive adhesive formulations. The data in Table 4 also demonstrate that the polymers of the invention possess better resistance to blockage of the granule. In particular, Example 5 has a resistance to blocking of the granule of O MPa, meaning that it flows freely under the conditions tested, comparing with Comparatives F and G, which show a considerable blockage. Resistance to blockage is important, because the bulk shipment of polymers that have great resistance to blocking, can result in the product forming lumps or sinking with itself on its storage or shipment, giving as a result poor handling properties. The setting by high temperature compression (70 ° C) for the invented polymers is generally good, meaning generally that it is less than about 80 percent, preferably less than about 70 percent, and especially less than about 60 percent. In contrast, Comparatives F, G, H, and J all have a compression setting at 70 ° C of 100 percent (the maximum possible value, indicating that there is no recovery). Good setting by high temperature compression (under numerical values) is especially necessary for applications such as gaskets, window profiles, O-rings, and the like. ( do not Table 5. Mechanical Properties at Ambient Temperature NJ OO stolen at 51 centimeters / minute. 2 Measured at 38 ° C for 12 hours.

Table 5 shows the results for the mechanical properties for the new polymers, as well as for different comparison polymers, at ambient temperatures. It can be seen that the present polymers have very good abrasion properties when tested in accordance with ISO 4649, generally showing a volume loss of less than about 90 mm 3, preferably less than about 80 mm 3, and especially less than about 50 mm 3. mm3. In this test, the most alias numbers indicate a higher volume loss, and consequently, a lower abrasion resistance. The tear strength, as measured by the tensile notch tear resistance of the polymers of the invention, is generally 1,000 mJ or more aya, as shown in Table 5. Tear resistance of invented polymers it can be as high as 3,000 mJ, or even as high as 5,00 mJ. Comparative polymers generally have tensile strengths no greater than 750 mJ. Table 5 also shows that the polymers of the invention have a better retraction tension with a fraction of 150 percent (demonstrated by higher values of refractive ion) than some of the comparative samples. The Comparative Examples F, G, and H have a refractive index value with a fraction of 1 50 per cent of 400 kPa or less, while the polymers of the invention have refractive voltage values with a 150 percent tensile strength. 500 400 kPa (Example 1 1), until they were ally as about 100 kPa (Example 17). Polymers having refractive index values of 150 percent higher would be very useful for elastic applications, such as fibers and elastic fabrics, especially non-spun fabrics. Other applications include diapers, hygiene, and applications of medical clothing belts, such as drawstrings and elastic bands. Table 5 also shows that tension relaxation (with a 50 percent pull) is also improved (less) for the polymers of the invention, comparing, for example, with Comparative G. The lower stress relaxation means that the polymer retains its strength better in applications such as diapers and other clothing where it is desired to refer elastic properties for long periods of time to body temperatures. Optical Test Table 6. Optical Properties of Polymers The optical properties reported in Table 6 are based on compression molded films that substantially lack orientation. The optical properties of the polymers can be varied over wide ranges, due to the variation in the size of the chrysalis, which results from the variation in the chain linkage agent used in the polymerization. Exiractions of Multiple Block Copolymers Exduction studies of the polymers of Examples 5, 7, and Comparative E are conducted. In the experiments, the polymer sample is weighed in a glass frit extraction thimble, and fitted to a Kumagawa type extractor. The extractor with the sample is purged with nitrogen, and a 500 milliliter round bottom flask is charged with 350 milliliters of diethyl ether. Then the flask is adapted to the extractor. The ether warms while it is agifando. The time in which the ether begins to condense in the thimble is recorded, and the extraction under nilrogen is allowed to proceed for 24 hours. At this time, the heating is stopped, and the solution is allowed to cool. Any ether remaining in the extracíor is returned to the maíraz. The ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are allowed to dry with nitrogen. Any residue is transferred to a weighted bottle using successive washes of hexane. The combined hexane washings are then evaporated with another nitrogen purge, and the residue is dried under vacuum overnight at 40 ° C. Any remaining ether in the extractor is purged to dry with nitrogen.

Then a second maíraz with a clean round bottom loaded with 350 milliliters of hexane was connected to the extractor. The hexane is heated to reflux with stirring, and is kept under reflux for 24 hours, after which it is first noticed that hexane is condensed in the thimble. Then the caleleníamienfo is deíiene, and the maíraz is let cool. Any hexane resfante in the exíractor is transferred back to the mafraz. The hexane is removed by evaporation in vacuo at room temperature, and any remaining residue in the flask is transferred to a weighted flask using successive washes of hexane. The hexane in the flask is evaporated by a nitrogen purge, and the residue is dried under vacuum overnight at 40 ° C. The polymer sample remaining in the thimble after the extractions, is transferred from the thimble to a weighted bottle, and dried under vacuum overnight at 40 ° C. The results are summarized in Table 7. Table 7 1 Demined by 13 C NMR. Article Manufacturing and Testing Fibers The polymer samples of Example 1 1, Example 17, and Comparative G, are spun in a 24-fiber multi-filament bundle with round cross-sections, in a fiber spinning line (Fourne) equipped with 24 25x1 spindles mm, a temperature of the spinning head of 260 ° C, a melting temperature of 302 ° C, and a winding speed of 70 meters / minute. Other spinning conditions are listed in Table 8. The denier of the resulting bundle is approximately 95 to 100 denier (g / 9000 m). Table 8 The fibers are crosslinked by passing six times through an electron beam crosslinking machine operating at an electron beam dosage of 32 KGy / pass, giving a total dosage level of 192 KGy. Between each pass, the fibers are cooled to -10 ° C. The behavior of the fraction of the non-recycled and re-cycled fibers is measured according to BISFA Tesi Methods for Bare Elastic Yarns, Chapter 6: Tensile Properties (Test Methods for Bisephane Elastic Threads, Chapter 6: Traction Properties), using the fasteners of Option C, and the testing speed of Option A. Tenacity and elongation at breakdown are reported from an average of five replicates. The recovery behavior of the reticulated fibers is also Measure using the BISFA Tesi Methods for Bare Elastic Yarns, Chapter 7: Viscoelastic Properies Procedure A (Test Methods for Naked Elastic Fibers BISFA, Chapter 7: Viscoelastic Properties, Procedure A), where the fiber is loaded cyclically to a fraction of the 300 percent. The percentage of permanent deformation is calculated at the beginning of the sixth cycle, as specified in the test method. The results of the performance of the fraction cycle of 300 per cent for the fibers prepared from the polymer of Example 1 7, are shown in Figure 30. The stress relaxation of the crosslinked fibers is measured from a tension of 10%. percent at alternating temperatures of 21 ° C and 40 ° C. In the experiment, thirteen loops of the beam fibers are mounted with a circumference of 324 millimeters, on an I nstron test machine, by means of two hooks, resulting in a calibrated length of 162 millimeters. The sample is stretched to 1 0 percent traction at an elongation rate of 1 00 percent / minute at 21 ° C, and then maintained for 10 minutes. The subsequent thermal imaging is: 1 0 minutes at 40 ° C in a water bath, 1 0 min. At 21 ° C in air, 1 0 min. At 40 ° C in a water bath, and 10 minutes at 21 ° C in air. The time to transfer the sample to the water bath and the air cooling chamber is 6 seconds. During the process, the load is monitored. The percentage of change of load from the load to 35 min. And the load to 45 min. Is calculated using the formula: L (í = 35 min) -L (f = 45 min)% load change = L (í = 35 min) where L (t = 35 min) and L (í = 45 min) are the loads at 35 minutes and 45 minutes, corresponding to the average periods of the last exposures to the water bath at 40 ° C and the air at 21 ° C, respectively. The resins are shown in Figure 31. The properties of the fiber are also tabulated in Table 9. Table 9. Fiber Properties In the fibers prepared from innate Example 1 1 as Comparative G, the crosslinking results in an increase in the idonacity with some loss of elongation. Both examples show a permanent deformation of approximately 135 per cent. In Figure 31, Example 1 1 exhibits a lower stress relaxation than Comparative G, as well as being less sensitive to temperature. The percentage of charge change between 40 ° C (35 minutes) and 21 ° C (35 minutes) is listed in Table 9. The fiber prepared from the polymer of Example 1 1 shows only a change of 4 percent in the load, while the fiber of Comparative G exhibits a change of 25 percent. The sensitivity to low temperature in the relaxation of tension is important to maintain a long life of shelf of the fiber coils. Sensitivity to high temperature in tension relaxation can lead to coil defects during storage in a storage facility that does not have controlled climate, because the fiber relaxes and tightens alternately due to temperature fluctuations . This can lead to problems, such as poor fiber unwinding behavior and fiber breaks in the downstream processing of the fiber. Foams Polymer blends are mixed by fusion (Example 5) and a commercially available ethylene / acetone vinyl acetate copolymer, ElvaxMR 460, which contains 18 percent acetates, and which has a melt index of 2, available from DuPont Inc. , and Comparative L, with an azide blowing agent (AZ130, an azodicarbonamide blowing agent available from Uniroyal, Inc.), zinc oxide, stearic acid, and a peroxide crosslinking agent (diterbuyl peroxypropyl peroxide). isopropylbenzene, 40 percent active on a silica porr, peroxide PerkadoxMR 1440, available from Akzo Nobel, Inc.), are compression molded into plates, and allowed to expand. Mix Condition: Roller Mill @ 1 30 ° C 1 0 min Molding and Foaming Condition: The sheets from the roller mill were preheated to 90 ° C in an oven for 1 5 minutes, then fed to a previously heated mold at 1 80 ° C, compressed (mechanical safety), and s They cure at this temperature for 10 minutes. When removed, the samples are allowed to expand. The The formulations (weight in parity) are given in Table 10. Table 10 The test of properties on the resulting foam strands is conducted as follows: the density of the foam is measured according to ASTM 792, the abrasion resistance is measured according to ISO 4649, the shrinkage at temperafure is measured Once the sample has been subjected to 70 ° C for 40 minutes according to SATRA PM70, the setting by compression at ambient temperature is measured after 1.5 and 24 hours of subjecting the sample to a temperature of 50 ° C for 6 hours. hours in accordance with ISO 815, the Shore A hardness is measured according to ISO 868, the split tear is measured according to the SATRA TM65 standards, and the strength to the fraction and the elongation are measured in accordance with DIN 53504. The results are reported in Table 1 1. Table 11: Properties of Reticulated Foams The results of Table 1 1 show that the properties The formulations and mechanics of the cross-linked foam prepared from Example 7 are better than those of a similarly prepared foam made from Comparative L. In particular,, the foam prepared from Example 7 has a lower shrinkage, a lower compression setting, and a split tear and elongation than the comparative foam. These properties make the polymers of the invention suitable for use in many performance foam applications, such as shoe soles, floors, and building maferials. Reticulated Films Uilizing Electrostatic Beam Compression molded films of 0.4 millimeter thickness are reliculated under a nitrogen atmosphere using an electron beam radiation crosslinking unit (Sterigenics, San Diego). A total electron beam dosage of 22.4 M rad is applied using a series of 7 passes through an electron beam at 3.2 Mrad per pass. All the examples showed a level of gelation between 75 and 90 percent, measured according to ASTM D-2765. The mechanical properties of the irradiated films are substantially unaffected by crosslinking. Although the examples of the invention and comparatives exhibit similar final properties, the examples of the invention exhibit a higher percentage of recovery, shrinkage tension and stress relaxation than the comparative samples. The results are given in Table 12.

Table 12: Properties of Reticulate Films with Electron Beam Impact Modification of Polypropylene A series of impact-modified isotactic polypropylene blends containing 20 percent by weight of ethylene / octene elastomer is prepared in a Haake mixer supplied with a Leistritz 1 8-millimeter twin-screw extruder (L / D = 30), a K-TRON K2VT20 twin screw propeller feeder, two cooled water recirculation bath shut-off tanks, and a Berlyn PEL-2 4-blade strand chopper. The polypropylene used in all samples is PP-314-02Z h PP, available from The Dow Chemical Co., which has an M FR of 2 decigrams / minute, measured in accordance with ASTM D 1238 (230 ° C, 2.16 kg) . A water circulator is connected to the jacket of the feed throat of the extruder, and is set at 20 ° C to prevent the polymer from melting and bridging the feed throat. The temperature zones of the extruder are set at 120 ° C, 165 ° C, 190 ° C, 230, and 230 ° C, respectively. The die of the extruder is set to 230 ° C. Prior to extrusion, a lid supplied with a nitrogen line is placed on top of the feed hopper. The transition area from the discharge of the feeder to the cone of the feed throat of the extruder is sealed with heavy aluminum foil. The extruder is preheated, calibrated, and vacuum-dried for several minutes with nitrogen flowing through the entire system to purge it of oxygen. Samples of 3 kilograms are prepared for fusion mixing by manually turning the combined components into a plastic bag before extrusion. Injection-molded test rods are prepared from the polymer samples, and tested for the Izod notched impact at 23 ° C in accordance with ASTM D-256, and the flexural modulus according to ASTM D-790. The conditions of the injection molding are as follows. The samples are injection molded at a melting temperature of 243 ° C, packing time of 6.7 seconds at a pressure of 3,400 psi (23 M Pa), holding time of 12 seconds at a pressure of 3,400 psi (23 MPa) , and a total cycle time of 28 sec undos. The details of the components and the results are contained in Table 1 3. Table 13 * Comparative, it is not an example of the invention. 1AFFI N ITYM R EG81 00: 0.87 grams / cm3, 1 gram / 1 minute (12), available from The Dow Chemical Co. 2ENGAG EMR VP8770: 0.885 g bouquets / cm3, 1 g bouquet / 1 0 minutuses (12), available from The Dow Chemical Co. The results of Table 1 3 indicate that the multiple block copolymers of the invention are effective as impact modifiers when mixed with isotactic polypropylene. Surprisingly, a sample made with the polymer of Example 5, made with a more alpha proportion of total chain linker / catalyst, which results in a greater number of blocks per polymer molecule (a more "blocked" polymer ") shows a modulus and impact resistance still lower than sample b, which is composed of the polymer of Example 8, which is a less" blocked "polymer. This observation indicates that the blocking level, as controlled by the chain linkage agent caníidad, in the multi-block copolymers of the invention, can greatly affect the rigidity / hardness balance of the polymer blends. Further evidence of the difference in the properties of the polymer blends can be seen from a comparison of Figures 51 to 53, which are microscopic atomic force images of microtome samples stained with osmium tetroxide from injection molded plates. , ayd, respectively. In microg raphies, the dark areas are the copolymer elastomer of ethylene / octene, while the lighter areas are the matrix of propylene homopolymers. It can be seen, from the micrographs, that the multi-block copolymers made with low molar proportions of CSA to the cafalizador (low "blocking" copolymers), in a surprising way produce a core-shell morphology in the mixtures (Figure 51). The CSA high-proportion multi-block copolymers (Figure 52) exhibit apparently solid elastomer domains, similar in appearance to the resins obtained using conventional elyne / ocene impaction modifiers (Figure 53). The advantages of the unique morphology shown in Figure 51 (extruded rubber morphology) include: excellent rigidity / hardness balance, high impact efficiency (lower amount of rubber to achieve a given duress), and higher strength when brushing (lower tendency to stress whitening). Moreover, the refractive index of the elastomer is easily varied by controlling the amount of present occlusions. Esio allows having a greater capacity to match the refractive index of the elastomer with the matrix polymer, resulting in mixtures that exhibit a better balance of optical transfer, rigidity, hardness, and brushing resistance. Additionally, these blends (i.e., the blends comprising lower block multiple block copolymers) exhibit a higher heat distortion temperature, better morphological stability (retention of polymer properties after multiple processing steps). ).

Previously, these properties could only be obtained in a mixture comprising additional components, such as mixtures of three components of the elastomer, high density polyethylene, and isotopic polypropylene. Preparation of Blown Film Samples Multiblock copolymer samples (Example 14) and a conventional ethylene / ocphene copolymer (Comparative I) are formed into single layer films by using a line of blown laboratory film. The polymer samples are melted in an extruder, passed through a ring die, expanded with air, cooled, and slit into bidirectional oriented films. The film formation conditions are given in Table 14. Table 14. Blown film conditions: Sample I * Example 14 Zone 1, ° C 176 176 Zone 2, ° C 206 204 Zone 3, ° C 21 6 204 Zone 4, ° C 216 210 Sieve Changer ° C 221 210 Adapter ° C 232 21 0 Die 1, ° C 232 21 0 Die 2, ° C 232 210 Screw speed, rpm 48.3 49.2 Melting temperature, ° C 234 234 Consumption of energy of the 12 9 Extruder, Amps. Pressure (MPa) 9600 7600 Nipple speed 4.4 5.2 M / second. Air blower, M3 / minute 0.8 0.7 Film thickness, mm 0.05-0.06 0.04-0.05 Samples of the resulting films are tested to determine their resistance to normalized film tearing in the cross direction (CD) and in the direction of the machine (MD) in accordance with ASTM D1922; the blocking properties according to ASTM D3354-96; and the coefficient of friction (COF), in accordance with ASTM D1894-01. The results are given in Table 15. Table 15. Blown Film Properties 1Affinity ™ PL 1840, available from The Dow Chemical Company. The film prepared from the polymer of Example 15 shows a higher tear in the cross direction as well as in the machine direction than the film made from the Comparative Polymer I. Additionally, it exhibits a more balanced tear (lower proportion of CD / MD) than the comparative film. Both the block force and COF for the film made of Example 14 are lower than those for Comparative I. This combination of Film properties indicate that films made from multiple copolymers according to the invention, have a higher tear strength and a higher resistance to blockage than films made from conventional ethylene / ocine copolymers. Preparation of Extended Polymer Mixtures with Aceifene Compound mixtures are prepared at 1 90 ° C in a previously heated Haake Reomixlvl R 600 mixer, of a volume of 69 milliliters. The rotors are rotated at an impulse speed of 50 revolutions per minute, while the polymer is added, and processed in a melt. By monitoring the torque of the mixer, the fusion is verified. Once the polymer melt is carried out, a paraffinic oil (RENOILM R 625, available from Renkert Oil, Inc.) is added by syringe to the molten polymer. Once the oil addition has been completed, the tamper seal on the melting is lowered, and the mixing is continued for 1.5 minutes. The photographic mass of oil and polymer is 55 grams. Then the rotors are stopped, the container is opened, and the resultant mixture is removed, flattened, and cooled in a press. Mixed and unmixed polymers are compression molded into 5"x5" x0.125"(125x125x3 mm) plates on a lamination press, under the following conditions: 1) 3 minutes without pressure at 1 90 ° C, 2) 2 minutes to the force of the roller of 30,000 pounds (1 33 kN) to 1 90 ° C, and then 3) 3 minutes at 25 ° C, with a force of the roller of 30,000 pounds (1 3 kN). The resulting plates are measured to determine the Shore A hardness with a manual durometer, and to determine the heat resistance (TMA). The hardness results reported are the average of five measurements in durations of 1 and 5 seconds made at random points on the surface of the plate. The results are reported in Table 16. Table 1 6: Properties of Extended Polymers with Oil A substantially linear, elastomeric ethylene / 1-ketene copolymer, Affinity EG81 00, available from The Dow Chemical Company.

The results of Table 1 6 indicate that the polymer of the invention has a Shore A duo similar to that of the comparative polymer, but shows an approximate TMA temperature. 40 ° C plus alia. Surprisingly, the extended polymer with 30 percent by weight of oil has a Shore A hardness similar to the comparative polymer filled with 40 percent oil, but has a TMA tempera- ture greater than 30 ° C higher. This result shows that the polymer of Example 1 7 exhibits an acceptance of more alpha oil and a better retention of thermal and mechanical properties, such as the heat resistance measured by the TMA temperature, and the tensile strength, compared to the comparative polymer H. This combination of low hardness and high temperature TMA is useful in many applications of soft elasomers, such as soft molded articles to the tacit, and the applications of pressure sensitive adhesives. Example 20. Period for Selecting the Catalyst Pair A / Linking Agent A series of epylene / 1-ketene copolymerizations is conducted, using different molar proportions of catalyst / binding agent, and monomer conversions. The cocatalyst used in all polymerizations is Cocatalyst 2. The resulting polymers are measured to defer the molecular weight (Mw and Mn) using G PC. The polydispersity index (PD I = Mw / Mn) is calculated for each polymer. The results are tabulated in Table 17 and plotted in Figure 32. In Figure 32, the line is the statistical adjustment to the data with an R2 value of 0.961. i) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 10 psi (0.77 MPa) with ethylene. Octene (100 microliters) is added via a syringe, followed by a cocatalyst mixture (4.2 mM in toluene, 0.100 milliliters, 420 nanomoles) and diethyl zinc (10 micromoles). Catalyst (A) (3.5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added via a syringe. After 15 seconds, the reaction is quenched by the addition of CO. The glass insert is removed and the volatile components are removed under vacuum. Polymer yield = 0.0938 grams. Mw = 14.560; Mn = 8.267; PD I = 1 .76. ii) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene. Octene (100 microlol) is added via a syringe, followed by a cocatalyst mixture (4.2 mM in toluene, 0.100 milliliters, 420 nanomoles) and diethyl zinc (10 micromoles). Catalyst (A) (3.5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added via syringe. After 30 seconds, the reaction is turned off by the addition of CO. The glass insert is removed, and the volatile components are removed under vacuum. Polymer yield = 0.1173 grams. Mw = 16,677; Mn = 9,774; PDI = 1.71. iii) A 6 milliliter reaction vessel, which contains a glass bottle insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene. Oxygen (100 microliters) is added by syringe, and then a cocatalyst mixture (4.2 mM in toluene, 0.100 milliliters, 420 nanomoles) and diefil-zinc (10 micromoles). Catalyst (A) (3.5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added via syringe. After 51 seconds, the reaction is turned off by the addition of CO. The glass insert is removed, and the volatile components are removed in vacuo. Polymer yield = 0.1360 grams. Mw = 20.557; Mn = 12.773; PDI = 1.61. iv) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene.

Octene (100 microliters) is added via a syringe, and then a cocatalyst mixture (4.2 mM in toluene, 0.100 milliliters, 420 nanomoles) and diethyl zinc (10 micromoles). Catalyst (A) (3.5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added by syringe. After 98 seconds, the reaction is quenched by the addition of CO. The glass insert is removed, and the volatile components are removed in vacuo. Polymer yield = 0.1 748 grams. Mw = 26,379; Mn = 13, 161; PDI = 2.00. v) A 6-milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 1 1 0 psi (0.77 M Pa) with ethylene. By means of a syringe, octene (1 00 microlives) is added, and then a mixture of cocaíalizador (4.2 mM in íolueno, 0.100 milliliters, 420 nanomoles) and diethyl-zinc (10 micromoles). Catalyst (A) (3.5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added via syringe. After 291 seconds, the reaction is turned off by the addition of CO. The glass insert is removed, and the volatile components are removed under vacuum. Polymer yield = 0.21 91 g branches. Mw = 33,777; M n = 1 8, 201; PDI = 1 .86. vi) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2.70 milliliters), and then pressurized to 1 1 0 psi (0.77 M Pa) with ethylene. Syringes are added (1 00 microlives), and then a coca-cocaizer mixture (4.2 mM in toluene, 0.100 milliliters, 420 nanomoles) and diethyl zinc (10 micromoles). The caíalizador (To) (3,5 mM in toluene, 0.100 milliliters, 350 nanomoles) was added via a syringe. After 1 201 seconds, the reaction is quenched by the addition of CO. The glass insert is removed, and the volatile components are removed in vacuo. Polymer yield = 0.2681 grams. Mw = 46.539; Mn = 24,426; PDI = 1 .91. Table 1 7 These results demonstrate that the behavior of chain linkage (exchange of polyimeryl both forward and reverse) between the Catalyst (A) and the diethyl zinc chain-linking agent, occurs during the polymerization, due to the fact that the Mn of the resulting polymer increases linearly with the polymer yield, while the PDI remains less than or equal to two for all polymerizations. Example 21 Method for Selecting the Catalyst Pair B2 / Linking Agent A series of ethylene / 1-ketene polymerizations are conducted, using different molar proportions of catalyst / linking agent and monomer conversions with the cocatalyst 2. The resulting polymers are measured for determine the molecular weight (Mw and Mn) using GPC. The polydispersity index is calculated (PDI = Mw / M n) for each polymer. The results are tabulated in Table 1 8 and are plotted in Figure 33. In Figure 33, the line is the statistical fit to the data with a value of R2 of 0.995. i) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2,334 ml), and then presumed at 1 1 0 psi (0.77 M Pa) with ethylene. Using a syringe, one adds oxygen (200 microliters), and then one m < cocaine analyzer (1.8 mM in toluene, 0.233 milliliters, 41 9 nanomoles) and diethyl zinc (1.0 micromoles). Catalyst (B2) (1.5 mM in ileum, 0.233 milliliters, 350 nanomoles) was added via syringe. After 18 sec, the reaction is quenched by the addition of CO. The glass insert is removed and the volatile components are removed under vacuum. Polymer yield = 0.0542 grams. Mw = 7,626; M n = 5.281; PDI = 1 .44. ii) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2,334 milliliters), and then pressurized to 10 psi (0.77 MPa) with ethylene. Using a syringe, add octene (200 microliters), then a cocatalyst mixture (1.8 mM in toluene, 0.233 milliliters, 419 nanomoles) and diethyl zinc (10 micromoles). The catalyst (B2) (1.5 mM in toluene, 0.233 milliliters, 350 nanomoles) was added via syringe. After 39 seconds, the reaction is quenched by the addition of CO. The glass insert is removed and the volatile components are removed in vacuo. Polymer yield = 0.0769 grams. Mw = 1 0.501; Mn = 7, 523; PDI = 1 .40. iii) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2,334 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene. Medianie a syringe, add ocíeno (200 micololl), and then a mixture of cocalalizador (1.8 mM in toluene, 0.233 milliliters, 419 nanomoles) and diethyl-zinc (10 micromoles). The caíalizador (B2) (1.5 mM in toluene, 0.233 milliliters, 350 nanomoles) was added by means of a syringe. After 59 seconds, the reaction is turned off by the addition of CO. The glass insert is removed and the volatile components are removed under vacuum. Polymer yield = 0.1071 grams. Mw = 15,840; Mn = 10,971; PDI = 1.44. iv) A 6-milliliter reaction vessel, containing a glass bottle insert, is charged with mixed alkanes (2,334 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene. Medianie a syringe, add ocíeno (200 micololl), and then a mixture of cocafalizador (1.8 mM in toluene, 0.233 milliliters, 419 nanomoles) and diethyl-zinc (10 micromoles). The caplizer (B2) (1.5 mM in toluene, 0.233 milliliters, 350 nanomoles) was added via syringe. After 103 seconds, the reaction is turned off by the addition of CO. The glass insert is removed and the volatile components are removed in vacuo. Polymer yield = 0.1365 grams. Mw = 21,664; Mn = 12,577; PDI = 1.72. v) A 6-milliliter reaction vessel, containing a glass bottle insert, is charged with mixed alkanes (2,334 milliliters), and then pressurized to 110 psi (0.77 MPa) with ethylene.

By means of a syringe, octene (200 microlipres) is added, followed by a cocatalyst mixture (1.8 mM in toluene, 0.233 milliliters, 419 nanomoles) and diethyl zinc (10 micromoles). The catalyst (B2) (1.5 mM in ileum, 0.233 milliliters, 350 nanomoles) was added via syringe. After 173 seconds, the reaction is quenched by the addition of CO. The glass insert is removed and the volatile components are removed under vacuum. Polymer yield = 0.1829 grams. Mw = 25.221; Mn = 16.245; PDI = 1.55. vi) A 6 milliliter reaction vessel, containing a glass jar insert, is charged with mixed alkanes (2,334 milliliters), and then pressurized to 10 psi (0.77 MPa) with ethylene. Octene (200 microliters) is added via a syringe, and then a cocatalyst mixture (1.8 mM in toluene, 0.233 milliliters, 419 nanomoles) and diethyl zinc (10 micromoles). The catalyst (B2) (1.5 mM in toluene, 0.233 milliliters, 350 nanomoles) was added via syringe. After 282 seconds, the reaction is quenched by the addition of CO. The glass insert is removed and the volatile components are removed in vacuo. Polymer yield = 0.2566 grams. Mw = 35,012; Mn = 23.376; PDI = 1 .50. Table 18 These results demonstrate that chain linkage (forward tannic polymorphism inverse and reverse) interaction in Catalyst (B2) and diethyl zinc chain-linking agent occurs during polymerization, due to the fact that that the M n of the resulting polymer increases linearly with the yield of the polymer, while the PDI is still less than 2, and usually less than 1.5 for all polymerizations. Example 22. Combination Selection of Catalyst / Linkage Agents The reaction conditions of the Examples 1 to 4, using different catalyst, cocatalyst 1, and potential binding agents. More than 500 reactions are carried out. The resulting ethylene / 1-ketene copolymers are tested to determine their Mn and PDI, and the rate of polymer production, compared to the velocities obtained from a conrol which uses M MAO instead of the linking agent. The best compositions are then selected based on a combination of higher molecular weight reduction (Mn), greater reduction in PDI, and less reduction (or actual increase) in the polymerization rate. Table 1 9 shows the selected combinations that show the best results (classified by the reduction of M n).

Table 1 9 Referring to Table 1 9, suitable combinations of catalyst and linking agent can be selected. It should be emphasized that the preferred catalyst / linker combinations, in different embodiments, can be selected based on a desired objective, such as the maximum reduction in Mn, or the improvement in production speed, together with a reduction of M n more modest. Additionally, the above results are based on a single catalyst / linker combination, while in practice, the effect, "where appropriate, of the presence of one or more additional catalysts, or of the use of continuous polymerization conditions, in the selection of a combination of catalysts and linking agents. Example 23. Formation of Multifunctional Copolymer Blocks A 1 liter reactor is charged with 600 milliliters of dry deoxygenated hexane and 40 millimoles of diethyl zinc and heated to 100 ° C under nitrogen, then the reactor is pressurized to 10 psi (70 kPa) with ethylene. inject a mixture of 10 micromoles of the catalyst (A1), 10 micromoles of the catalyst (B1), and 50 micromoles of MAO M into the reactor, and ethylene was fed on demand to maintain 10 psi (70 kPa) during 40 minutes The reactor is then vented and cooled to room temperature and purged with nitrogen for 20 minutes, while purging vigorously with nitrogen, a stream of air is introduced into the bottom of the reactor for 1 hour, and the pulp is stirred. result for 1 additional hour. The paste is then removed from the reaction product of the reaction, stirred with water, and dried to give 25.5 grams of polymer. The GPC analysis reveals Mw = 1 271, Mn = 1 01 8, Mw / M n = 1 .25. The 1 H NMR analysis reveals a conversion of 27 percent of the possible chain ends ferminated in zinc to the hydroxyl-chain exine of the chain. Examples 24-28. Copolymerization of Ethylene / 1-Bienene Polymerizations are carried out in continuous solution, following the procedure described above for Examples 5 to 1 9, with the following exceptions; the comonomer used in all examples is 1-butene, and for Example 25, a mixture of DEZ and MAO (molar ratio of 99: 1) is used as the chain-linking agent (CSA). The details of the process and the results are given in Table 1 9. It can be seen that the mixture of chain binding agents results in an improvement of approximately 40 percent in efficiency, while substantially similar products are prepared ( density = 0.88, 1 2 = 2). The properties of the selected polymer are given in Tables 21 to 24. The thermal properties of the polymer are as follows: The DSC curve of Figure 36 for the polymer of Example 24, shows a peak with a melting point of 14.9 ° C. C, with a heat of fusion of 44.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 42.6 ° C, with a peak area of 48.4 percent. The difference between the Tm DSC and the Tcrystaf is 72.3 ° C. The DSC cuve of Fig. 37 for the polymer of Example 25, shows a peak with a melting point of 14.5 ° C, with a heat of fusion of 41.5 J / g. The corresponding CRYSTAF curve shows the highest peak at 41 .0 ° C, with a peak area of 24.2 percent. The difference between the Tm DSC and the Tcrystaf is 73.5 ° C. The DSC curve of Fig. 38 for the polymer of Example 26 shows a peak with a melting point of 16.7 ° C, with a heat of fusion of 45.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.2 ° C, with a peak area of 6.1 percent. The difference between the Tm DSC and the Tcrysíaf is 76.5 ° C.

The DSC curve of Figure 39 for the polymer of Example 27, shows a peak with a melting point of 18.4 ° C, with a heat of fusion of 47.1 J / g. The corresponding CRYSTAF curve shows the highest peak at 40.2 ° C, with a peak area of 6.1 percent. The difference between the Tm DSC and the Tcrystaf is 79.8 ° C. The DSC curve of Figure 40 for the polymer of Example 28, shows a peak with a melting point of 121.3 ° C, with a heat of fusion of 143.4 J / g. The corresponding CRYSTAF curve shows the highest peak at 74.4 ° C, with a peak area of 96.6 per cent. The difference between the Tm DSC and the Tcrystaf is 46.9 ° C. t t o Table 20. Process Conditions Standard cm / minute 2N- (2,6-di (1-methylethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-di (6-pyridin-2-diyl) methane) )] hafnium-dimethyl. 3bis (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (tert-butyl) phenyl) imino) zirconium-dibenzyl. 4 The chain link agent (CSA) was DEZ without added MAO. The chain link agent (CSA) was a mixture of DEZ and MAO in a molar ratio of 99: 1. 6Molar proportion in the reactor. Speed of polymer production. 8 Percentage of ethylene conversion in the reactor. 9 Efficiency, kilograms of polymer / grams of M, where g Hf + g Zr. ? \ 3 Ül O Table 21. Physical Properties Test Table 22. High Temperature Mechanical Properties of Ethylene-Butene Copolymer Table 23. Mechanical Properties at Ambient Temperature of Ethylene-Butene Copolymer Table 24. Optical Properties of Ethylene-Butene Copolymer Examples 29-33. Comparative M-P The reaction conditions of Examples 1 to 4 are substantially repeated to prepare copolymers of ethylene and a variety of aliphatic comonomers (1 -hexene, 1-ketene, 1 -decano, 1,5-hexadiene, and 4-methyl-1-pentene). The chain liaison agent used is frioctil-aluminum (SA5). MAO is used to replace the chain link agent for the M-P Comparatives. The details of the process are mentioned in Table 25. The properties of the polymers are contained in Table 26. Table 25. Process Data The thermal properties of the resulting polymers are as follows: The DSC cuvette of Fig. 41 for the polymer of Example 29, shows a peak with a melting point of 121.6 ° C, with a heat of fusion of 1. 38.7 J / g. The corresponding CRYSTAF curve shows the highest peak at 61.0 ° C, with a peak area of 17.8 percent. The difference between the Tm DSC and the Tcrystaf is 60.6 ° C. The DSC curve of Fig. 42 for the polymer of Example 30, shows a peak with a melting point of 123.3 ° C, with a heat of fusion of 146.3 J / g. The corresponding CRYSTAF curve shows the highest peak at 50.6 ° C, with a peak area of 25.4 percent. The difference between the Tm DSC and the Tcrystaf is 72.7 ° C.

The DSC cuve of Fig. 43 for the polymer of Example 31 shows a peak with a melting point of 120.7 ° C, with a heat of fusion of 160.3 J / g. The corresponding CRYSTAF curve shows the highest peak at 52.3 ° C, with a peak area of 95.1 percent. The difference between the Tm DSC and the Tcrystaf is 68.4 ° C. The DSC curve of Figure 44 for the polymer of Example 32, shows a peak with a melting point of 122.9 ° C, with a heat of fusion of 83.2 J / g. The corresponding CRYSTAF curve shows the highest peak at 64.1 ° C, with a peak area of 95.2 percent. The difference between the Tm DSC and the Tcrystaf is 58.7 ° C. The DSC curve of Figure 45 for the polymer of Example 33, shows a peak with a melting point of 120.8 ° C, with a heat of fusion of 177.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 64.1 ° C, with a peak area of 95.7 percent. The difference between the Tm DSC and the Tcrystaf is 56.7 ° C. The DSC curve of Figure 46 for the polymer of Comparative M *, shows a peak with a melting point of 121.9 ° C, with a heat of fusion of 1 1 2.3 J / g. The corresponding CRYSTAF curve shows the highest peak at 78.9 ° C, with a peak area of 36.1 percent. The difference between the Tm DSC and the Tcrystaf is 43. 0 ° C. The DSC curve of Figure 47 for the polymer of the Comparative N *, shows a peak with a melting point of 121.7 ° C, with a heat of fusion of 85.5 J / g. The corresponding CRYSTAF curve shows the highest peak at 30.0 ° C, with a peak area of 69.7 percentS The difference between the Tm DSC and the Tcrystaf is 91.7 ° C. However, it should be noted that the Mw / Mn for this comparative example is 1 5, and it is much larger than for the examples of the invention. The DSC curve of Figure 48 for the polymer of the Comparative O *, shows a peak with a melting point of 122.6 ° C, with a heat of fusion of 34.9 J / g. The corresponding CRYSTAF curve shows the highest peak at 81. 1 ° C, with a peak area of 40.4 percent. The difference between the Tm DSC and the Tcrystaf is 41.5 ° C. The DSC curve of Figure 49 for the Comparative P * polymer shows a peak with a melting point of 121.9 ° C, with a heat of fusion of 148.2 J / g. The corresponding CRYSTAF curve shows the highest peak at 82.8 ° C, with a peak area of 33.3 percent. The difference between the Tm DSC and the Tcrystaf is 39. 1 C. Figure 50 is a plot of the difference in the Peak DSC Timer-CRYSTAF peak temperature, as a function of the DSC Enthalpy for Examples 29-33, the MP Comparative Polymers, and the ethylene-ocine copolymers commercially obtained. ? > to o Table 26. Physical Properties of the Polymers l \ - > "Comparative, it is not an example of the invention.

Examples 34-36, Comparison QS The reaction conditions of Examples 1 to 4 are substantially repeated to prepare copolymers of ephelene and a variety of aromatic and cycloaliphatic comonomers (styrene, cyclopentene, and bicyclo [2.2.1] hep-2-) eno). The chain linker used is diethyl zinc (SA1). MMAO is used to replace the chain agent for the Comparative U-S. The details of the polymerization are given in Table 27. The properties of the polymers are given in Table 28. Table 27. Process Data t t O Table 28. Physical Properties of the Polymer "Comparative, it is not an example of the invention.? \ 3

Claims (27)

1. CLAIMS 1. A composition comprising the mixture or the reaction product resulting from the combination of: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers that differ in their chemical or physical properties of the polymer prepared by the catalyst (A) under equivalent polymerization conditions, and (C) a chain-linking agent.
2. 2. A composition according to claim 1, wherein the catalyst (B) has a comonomer incorporation index lower than the comonomer incorporation index of the calibrator (A).
3. 3. A composition according to claim 1, wherein the binding agent is a compound of aluminum, zinc, or gallium, containing at least one hydrocarbyl substituent having 1 to 12 carbon atoms.
4. 4. A catalyst composition according to claim 3, wherein the bonding agent is trietyl-aluminum or diethyl-zinc.
5. A composition according to claim 1, wherein the catalyst (A) comprises a complex comprising a transition metal selected from Groups 4 to 8 of the Periodic Table of the Elements, and one or more ligands p - delocalised links or polyvalent Lewis base ligands.
6. 6. A composition according to claim 5, wherein the catalyst (A) corresponds to the formula: wherein: it is selected from alkyl, cycloalkyl, heteroalkyl, cyclohep- roalkyl, aryl, and inert derivatives thereof thereof, which contain from 1 to 30 atoms without counting hydrogen, or a divalent derivative thereof; T1 is a group of divalenfe bridging from 1 to 41 different hydrogen spheres; and R12 is a heeroaryl group of 5 to 20 carbon atoms containing Lewis base functionality; M1 is a Group 4 metal; X1 is a group of anionic, neutral, or dianionic ligand; x 'is a number from 0 to 5, which indicates the number of these groups X1; and the links, optional links, and electron donation interactions, are represented by lines, punched lines, and arrows, respectively.
7. 7. A composition according to claim 8, wherein the cafalizador (B) corresponds to the formula: where: M2 is a melal from Groups 4 to 10 of the Periodic Table of the Elements; T2 is a group that contains niógeno, oxygen, or phosphorus; X2 is halogen, hydrocarbyl, or hydrocarbyloxy; t is one or two; x "is a number selected to provide charge equilibrium, and T2 and N are linked by a binder ligand
8. 8. A process for preparing a multi-block copolymer, which comprises putting into or not one or more polymerizable monomers by addition, under addition polymerization conditions, with a composition according to claim 1.
9. 9. A multiple block copolymer, which comprises, in a polymerized form, ethylene and one or more copolymerizable comonomers, said copolymer containing the same two or more segments or blocks that differ in comonomer content, crystallinity, density, melting point, or crystal transition temperature 1 0.
10. An olefin interpolymer having at least one melting point, Tm , in degrees Celsius, and a density, d *, in grams / cm3, where the numerical values of the variables correspond to the relation: Tm > -2002.9 + 4538.5 (d *) - 2422.2 (d * ), and where the interpolymer has an Mw / Mn of 1.7 to 3.5. eleven .
11. An olefin interpolymer having an Mw / M n of 1.7 to 3.5, a delta amount (highest DSC peak minus highest CRYSTAF peak) greater than the quantity, and *, defined by the equation: y * > -0.1 299 (? H) + 62-81, and a heat of fusion of up to 1 30 J / g, where the peak of CRYSTAF is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent. percent of the polymer has an identifiable CRYSTAF peak, then the temperature of CRYSTAF is 30 ° C, and? H is the numerical value of the heat of fusion in J / g.
12. 12. An olefin inferpolymer having a fraction strength greater than 10 MPa, and a breaking elongation of at least 600 percent, at a crosshead separation rate of 1 1 centimeter / minute.
13. 1 3. An olefin in-polymer that has a delta amount (highest DSC peak (measured from baseline) minus CRYSTAF peak plus alio) greater than 48 ° C, and a heat of fusion greater than or equal to 1 30 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has a CRYSTAF peak idenifiable, then the CRYSTAF temperature is 30 ° C .
14. 14. An olefin interpolymer having a storage modulus ratio, G '(25 ° C) / G' (1 00 ° C) from 1 to 50, and a Cured by compression at 70 ° C less than 80 percent.
15. 1 5. An olefin interpolymer having a heat of fusion less than 85 J / g, and a blockage strength of the granule equal to or less than 1 00 pounds / square foot (4,800 Pa).
16. 1 6. A non-crosslinked elastomeric olefin polymer which comprises, in a polymerized form, at least 50 mole percent ethylene, which has a compression setting at 70 ° C of less than 80 percent.
17. 1 7. A polymer according to any of claims 9 to 16, or which can be prepared by the method of claim 8, which confers a single crystalline melting point (Tm) measured by DSC.
18. 1 8. A polymer according to any of claims 9 to 16, which can be prepared by the method of claim 8, which has a penetration depth of the thermomechanical analysis of 1 millimeter at a temperature of at least 90 ° C, and a flexural modulus of 3 kpsi (20 M Pa) at 1 3 kpsi (90 MPa).
19. 1 9. A polymer according to claim 1, which has a depth of penetration of the thermomechanical analysis of 1 millimeter at a temperature of at least 90 ° C, and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa).
20. 20. A polymer according to any of claims 9 to 16, or that can be prepared by the method of claim 8, which has a volume loss by abrasion resistance according to ISO 4649 less than 90 mm3. twenty-one .
21. A polymer according to claim 1, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 mm3.
22. 22. A polymer according to any of claims 9 to 16, or that can be prepared by the method of claim 8, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 mm3, and which is a storage module, GS such that the record (G ') is greater than 0.4 M Pa, at a temperature of 1 00 ° C.
23. 23. A polymer according to claim 1, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 mm3, and which has a storage modulus, GS such that registration ( G ') is greater than or equal to 0.4 M Pa at a temperaure of 1 00 ° C.
24. 24. A polymer according to claim 20, which has a volume loss due to abrasion resistance according to ISO 4649 less than 90 mm3, and which has a storage module, GS fails the registration (G '). ) is greater than or equal to 0.4 MPa at a temperaure of 1 00 ° C.
25. 25. A polymer according to claim 21, which has a volume loss by abrasion resistance in accordance with ISO 4649 less than 90 mm3, and which has a storage module, GS such that the record (G ') ) is greater than or equal to 0.4 M Pa at a temperaure of 1 00 ° C.
26. 26. A crosslinked derivative of a polymer according to any of claims 9 to 16, or that may be prepared by the method of claim 8.
27. 27. A polymer according to any of claims 9 to 16, or that may be prepared according to the method of claim 8, or a composition comprising the same in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-spun fabric, an injection molded article, a blow molded article, a roto-molded article, or an adhesive.