BLOCK COPOLYMERS FROM IONIC CATALYSTS

Abstract: A process for the production of block copolymers of ethylene and an alpha -olefin such as propylene by using an ionic catalyst system including a metallocene component and a component having a cation capable of donating a proton and a compatible non-coordinating anion. Novel block copolymers are produced.

Description: BLOCK COPOLYMERS FROM IONIC CATALYSTS SPECIFICATION Cross-Reference to Related Applications This application is a Continuation-in-Part of U.S. Patent Application No. 477,791 filed February 9, 1990. U.S. Patent Application No. 477,791 is in turn a Continuation-in-Part of copending U.S. Patent Application Nos. 133,052 filed December 21, 1987 and 133,480 filed December 22, 1987. Copending U.S. Patent Application No. 133,052 is in turn a Continuation-in-Part of U.S. Patent Application No. 011,471 filed January 30, 1987. Copending U.S. Patent Application No. 133,480 is in turn a Continuation-in-Part of U.S. Patent Application No. 008,800 filed January 30, 1987. FIELD OF THE INVENTION This invention relates to a method for preparing block and tapered copolymers by polymerizing ethylene and other oleflns In the presence of a catalyst which is a reaction product of a metal locene component with second component which comprises a cation capable of donating a proton and a compatible non-coordinating anlon. More particularly, this Invention relates to a process for the production of mutlblock and tapered copolymers of ethylenlcally unsaturated monomers. The invention also related to the multiblock. and tapered copolymers produced. BACKGROUND OF THE INVENTION Block copolymers are well known. They have been used commercially as components In adhesives, as melt processable rubbers, Impact resistant thermoplastics, and as compat1b1Hzers, or "surfactants", for emulsifying polymer-polymer blends. There has been widespread interest 1n polymer blends and alloys. Unfortunately, most homopolymer pairs are immiscible with one another and give rise to low strength materials due to the lack of interfadal adhesion between the separate phases. A block copolymer is created when two or more polymeric segments, or blocks, of different chemical composition are covalently bonded 1n an end-to-end fashion. Block copolymers have certain advantages over blends. Firstly, the segments are covalently bonded to each other, thereby eliminating the Interface problem. Secondly, block copolymers can be used to strengthen blends of immiscible polymers by serving as "emulsifiers," which encourage physical connections between the phase, and thus improve the interfadal adhesion and load transferring capability of the components. While a wide variety of block copolymer architectures are possible, most block copolymers of Interest Involve the covalent bonding of hard plastic segments which are crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber, glass-glass, and glass-crystalline block copolymers are also possible and may have commercial importance. Two common types of block copolymer structures are the diblock and triblock forms. However, multiblock copolymers, 1n which more than three segments are bonded together, are also desirable. Triblock and multiblock copolymers have the unique ability of behaving as thermoplastic elastomers, combining thermoplastic!ty with rubber-like behavior. The key requirements for achieving thermoplastic elastomeric behavior 1s the ability to develop a two-phase physical network. Such a system 1s composed of a minor fraction of hard block, having a glass transition temperature (Tg) or melting temperature (Tm) above room temperature, and a major fraction of a soft block, having a Tg below room temperature. The hard blocks associate to form small morphological domains that serve as physical crossϋnklng and reinforcement sites. These states are thermally reversible making it possible to process the polymer as a melt at temperatures above the Tg or T of the hard block. Block copolymers are 1m1lar to, yet distinct from, tapered polymers. In a tapered copply er the composition of comonomer Is gradually varied from one end of the polymer to the other. Tapered copolymers are commercially used as viscosity modifiers, oil additives, thermoplastic elastomers, and Impact-resistant plastics. Much work has been done in an attempt to synthesize olefinic block copolymers. The ideal catalyst system would produce a "living polymer." Unlike typical Ziegler-Natta polymerization processes living polymerization processes Involve only Initiation and propagation steps and are essentially devoid of terminating side reactions. This permits the synthesis of the predetermined and well-controlled structures required for effective block copolymerization. A polymer created 1n a "living" system can have an extremely narrow distribution of molecular weight and be essentially monodisperse. The living polymer technique 1s uniquely suited for the preparation of block copolymers. Living catalyst systems are characterized by an initiation rate which Is considerably higher than 9 the propagation rate, and the absence of termination or transfer 0 reactions. In addition, these systems are characterized by the 1 presence of a single type of active site. 2 Anionlc polymerization routes to ideal olefinic block 3 copolymers have been much studied. Butadlene-isoprene block 4 copolymers have been synthesized using the sequential addition 5 technique. In sequential addition, a certain amount of one of the 6 monomers 1s contacted with the catalyst, Once the monomer has reacted 7 to extinction, forming the first block, a certain amount of the second 8 monomer species 1s introduced and allowed to react to form the second 9 block. The process may be repeated as desired using the same or other 0 anionlcally poly erizable monomers. 1 Ethylene and other alpha-oleflns such as propylene and butene 32 are not directly block polymerizable by anionlc techniques. Another 33 technique 1s described by Falk and Schlott in Macromolecules. 1971 4, 34 152. The first step 1n the procedure involves preparing block 35 polymers containing polybutadiene and polylsoprene using anionlc I techniques. The low pressure catalytic hydrogentation of the block - polymer obtains the saturated block polymer. 3 The anionlc routes to ideal olefinic block copolymers provide 4 a clean route to model block copolymers. However, the method is 5 impractical and 1s not sufficiently versatile for commercial 6 purposes. For example, the anionlc route cannot be used to synthesize 7 HDPE or isotactlc polypropylene (1-PP) segments. 8 A coordination technique which has been used to synthesize 9 block copolymers involves the use of vanadium catalysts at low 10 temperatures. Doi et. al., in Macromolecules. 1986, 19, 2896, showed II that a catalyst prepared from 12 tris(2-methyll-l,3-butanedionato)vanad1um and AKC-HJ-Cl 1n 13 toluene has high reactivity 1n the living coordination polymerization 14 of propene and that a well-defined diblock copolymer of polypropylene 15 and ethyl ene-propylene rubber can be prepared by adding ethylene 16 monomer during the living polymerization of propene. 17 While the Do1 technique has the advantage over the anionlc 18 routes of dispensing with the hydrogenation step, it does require very 19 low temperatures. The block copoly erizations carried out by Doi et. 20 al. were performed at -70 and -60 C. Do1 also reported, In W. 21 Kaminsky and H. Sinn (Eds.), Transition Metals and OrqanometalHcs 22 Catalysts for Olefin Polymerization. Springer-Verlag 1988, the living 23 copolymerization, at -78 C, of propylene with 1.5-hexadiene. An 24 additional disadvantage of the technique is that it cannot be used to 25 produce 1-PP. Furthermore, and no reports of the production of high 26 density polyethylene (HDPE) via this method have appeared 1n the 27 literature. The catalyst Itself 1s poorly characterized and unstable. 28 Many claims in the prior art have been made for the 29 production of block polymers 1n the presence of Ziegler-Natta type 30 catalysts. For example, JP63-712 to Mitsubishi Petrochemicals claims 31 a method of producing a propylene block copolymer using a catalyst 32 including a solid titanium component containing magnesium, titanium, 33 halogen and an electron-donor with an organo-alumlnu cocatalyst to 34 prepare homopolypropyl ene 1n a first stage reaction, following which 35 in a second stage of reaction bis(cyclopentadienyl) titanium dl chloride i s added and polymeri zation 1 s continued 1n the presence of added ethyl ene . The propyl ene bl ock copolymers produced are sai d to have hi gh rigi di ty and Impact strength and good molding properti es U.S. Patent 4 ,408 ,0.9 to Bl unt relates to the use of a catalyst-activator system wherein titanium 1s the sole metal component to produce block copolymers of ethylene and propylene. The block copolymers have the general formula (AB) A wherein A Is a crystalline polypropylene block, each B 1, a random ethylene-propylene copolymer block, and n 1s an integer from 1 to about 12 The catalyst-activator Is described as a combination of titanium trichloride as the catalyst ind d1methylb1s ( methylcyclopentad1enyl ) t1tan1um as an activator The amount of ethylene In the block polymer is typically 40-65 wt X with 5-15 wt.l present In the ethyϊene-propylene segments. The thermoplastic block polymers are said to have superior tensile strength and lower compression set than prior art block polymers In discussing prior art catalysts. Blunt observes that the production of a true block polymer 1s dependent upon there being no permanent interruption in the growth of any given polymer chain until all of the blocks have been completed. Moreover, Blunt states that the traditional Ziegler-Natta catalysts based on titanium halldes in conjunction with alkylaluminum compounds do not provide a sufficient! y long chain lifetime to permit the formation of block copolymers of more than two copolymer blocks * While many patents and publications claim the synthesis of block copolymers from ethylene and propylene, there 1s no evidence that these products were obtained as well defined block polymers The known kinetic features of heterogeneous Ziegler-Natta catalysts suggest that It is unlikely that block polymers were synthesized in high concentrations. (J. Boor, Zleoler-Natfry Caϋ]^ Polymerization*, Academic Press 1979). According to Boor the reported propylene and ethylene block copolymers are most'llkely mixtures of largely Isotactic ' polypropylene, polyethylene, and either random, block, or tapered copolymers which are present in low concentrations, in the range of 0 to 20X. As reasons for his conclusion, Boor lists a large number of inherent barriers which must be overcome 1n using known Ziegler-Natta catalysts to synthesize block copolymers. For example, to synthesize ethyl ene/α-olef 1ns block copolymers the following conditions must be satisfied: 1) all of the T1 centers must become active simultaneously; 2) all the T1 centers must stay alive during the polymerization; 3) all the Ti centers must have equal activities for polymerizing propylene and ethylene; 4) all the T1 centers must be 9 equally accessible to the available olefin molecules; 5) the 10 cross-over propagation rates must be high for T1-propylene centers to 11 be efficiently converted into Ti-polyethylene centers; 6) the centers 12 must be Isotactic-specific for propylene polymerization and polymerize 13 all ethylene molecules to a linear polymer. 14 Several difficulties arise 1n the use of known catalysts for -- the block copoly erization of olefins. Among those are the fact that -m conventional catalysts are typically multi-sited, and a significant 17 fraction of the active sites are unstable. This leads to random chain 18 initiation and termination which, 1n turn, lowers the theoretical 19 block copolymer yield. What 1s desired, and what practice of this 20 invention provides, is a catalyst system with well-characterized 21 structure and reactivity which has a single active site. The system 22 should have well-defined and stable polymerization kinetics and be 23 free of aluminum alkyls or other chain transfer agents. SUMMARY OF THE INVENTION 24 The invention comprises a process for the production of novel 25 block copolymers of ethylene with an o-olefin and the polymers 26 obtained therefrom. The process includes sequentially contacting 27 ethylene with an α-olefin monomer 1n a suitable solvent at about 0*C 28 1n the presence of an ionic catalyst to produce a block copolymer. 29 Thus, for example, when a-PP-HDPE diblock is produced, the process 30 provides a diblock copolymer yield of 40-70X. The molecular weight of 31 the block copolymer may be controlled by varying the 32 catalyst-to-monomer ratio. The ionic catalyst which is a critical 33 component of the inventive polymerization process, comprises the reaction product of a first component which Is a bls(cyclopentadienyl) derivative of a metal of Group IV-B of the Periodic Table of the Elements, which metal is capable of forming a cation formally having a coordination number of 3 and a valence of +4; and at least one second component comprising a cation capable of donating a proton and a compatible non-coordinating anion which anion is bulky and labile, and capable of stabilizing the Group IV-B metal cation without interfering with the ability of said Group IV-B metal cation, or Its decomposition product, to polymerize α-olef1ns to form tapered polymers and ° multiblock polymers such as di- and tri-block homo-, and copolymers of 1 ethylene and propylene with one or more other alpha-oleflns. DESCRIPTION OF THE PREFERRED EMBODIMENTS 2 The Invention provides (1) novel non-random di-, tr1-, and 13 multi-block copolymers and tapered copolymers of ethylene, 1-olefins, 1 diolefins, cyclic olefins, acetylenes and other unsaturated monomers; *- and (2) the processes for polymerizing said non-random copolymers. Ionic Catalyst System - General Description 16 The process of this Invention is practiced with that class of 17 ionic catalysts referred to, disclosed, and described 1n our copending 18 U.S. Patent Application Nos. 133,052 and 133,480. The Ionic catalyst 19 1s prepared by combining at least two components. The first of these 20 1s a bls(cyclopentadlenyl) derivative of a Group IV-B metal compound 21 containing at least one Hgand which will combine with the second 22 component or at least a portion thereof such as a cation portion 23 thereof. The second component Is an Ion-exchange compound comprising 24 a cation which will Irreversibly react with at least one Hgand 25 contained in said Group IV-B metal compound and a noncoordinatlng 26 anion which 1s bulky, labile, and " stable. Upon combination of the 27 first and second components, the cation of the second component reacts 28 with one of the ligands of the first component, thereby generating an 29 1on pair consisting of a Group IV-B metal cation with a formal 30 coordination number of 3 and a vaslence of +4 and the aforementioned 31 anion, which anion is compatible with and non-coordinating towards the metal cation formed from the first component. The anion of the second compound must be capable of stabil izing the Group IV-B metal cation complex without interfering with the Group IV-B metal cation' s or its composition product's abil ity to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization. A. The Metal!ocene Component The Group IV-B metal compounds; i.e., titanium, zirconium 9 and hafnium etal!ocene compounds, useful as first compounds in 1° the preparation of the improved catalyst of this invention are 11 bis(cyclopentadienyl) derivatives of titanium, zirconium and -- hafnium. In general, useful titanocene, zirconocenes and 1 3 hafnocenes may be represented by the following general formulae: 15 2. (A-CpJMX^X^ 16 3. (A-Cp)ML 17 4. (Cp*)(CpR) MXi 18 wherein "Cp" represents a cyclopentadienyl radical which may be 19 substituted or unsubstituted, and" 20 (A-cp) is either (Cp)(Cp*) or Cp-A'-Cp* and Cp and Cp* are 21 the same or different cyclopentadienyl ring substituted with 22 from zero to five substituent groups R. 23 The substituent groups R may be, independently, selected 24 from a wide variety of classes of radical groups which form 25 covalent bonds to the carbon atoms of the Cp-rings. These 26 substituents act to modify the catalyst behavior by affecting the 27 symmetry, sterics, and electronics of the transition metal center. Illustrative but not limiting examples of suitable R substituents include hydrocarbyl radicals containing from 1 to 50 carbon atoms; substituted hydrocarbyl radicals wherein one or more of the hydrogen atoms is replaced by a halogen radical, an amido raidcal (X1X2N-), a phosphido radical (X^P-). an alkoxy radical (XjO) or any other radical containing Lewis acidic or basic functionality; hydrocarbyl substituted metalloid radicals wherein the metalloid is selected from the Group IV-A of the Periodic Table of elements; halogen radicals, amido radicals (X1X2 -), phosphido radicals (X1X2P-), alkoxy radicals (XjO), alkylborido radicals (X1X2B-), or any other radical containing Lewis acidic or basic functionality; or Cp and/or Cp* are a cyclopentadienyl ring in which two adjacent R groups are joined forming a C4 to C 0 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl , fluQ'renyl, or octahydrofluorenyl; A' is a covalent bridging group between the two cyclopentadienyl groups; M is titanium, zirconium or hafnium; L is an olefin, diolefin or aryne ligant; Xi and X2 are, independently, selected from the group consisting of hydride radical?, hydrocarbyl radicals having from 1 to about 20 carbon atoms, hydrocarbyl radicals wherein one or more of the hydrogen atoms are replaced with a halogen atom, organometalloid radicals comprising Group IV-A element wherein each of the hydrocarbyl substitutions contained in the organic portion of said organometalloid independently contain from 1 to about 20 carbon atoms and the like; X'j and X'2 are joined and bound to the metal atom to form a metaTlacycle, in which the metal atom, X'jand X'2 form a hydrocarbocyclic ring containing from about 3 to about 20 carbon atoms; and R is a substituent, preferably a hydrocarbyl; substituent, on one of the cyclopentadienyl radical.? which is also bound to the metal atom. Illustrative, but not limiting examples of b1s(cyclopentad1enyl)z1rcon1um compounds which may be used 1n the preparation of the Improved catalyst of this Invention are dihydrocarbyl-substituted b1s(cyclopentadienyl)zircon1um compounds such as bis(cyclopentadienyl)zircon1um dimethyl, bis(cyclopentad1enyl ) z1rcon1um diethyl, b1s(cyclopentad1enyl)zircon1um dlpropyl , bis(cyclopentadienyl)zirconium dibutyl, b1s(cyclopentad1enyl)zirconium diphenyl, bis(cyclopentad1enyl)zirconium dineopentyl, bis(cyclopentad1enyl)zircon1um di(m-tolyl), bis(cydopentadienyl)zirconium di(p-tolyl) and the Hke; (monohydrocarbyl-substituted cyclopentadienyDzirconium compounds such as (methylcyclopentad1enyl)(cyclopentad1enyl) and bis(methylcyclopentad1enyl)z1rcon1um dimethyl, (ethylcyclopentadienyl) (cyclopentadienyl) and b1s(ethylcyclopentadienyl)z1rcon1um dimethyl, (propylcyclopentadienyD(cyclopentadienyl) and bis(propylcyclopentadienyDzirconium dimethyl, (n-butylcyclopentadlenyl) (cyclopentadienyl) and bis(n-butylcyclopentad1enyl)z1rcon1um dimethyl, (t-butylcyclopentadienyl) (cyclopentadienyl) and bis(t-butylcyclopentad1enyl)zircon1um dimethyl, (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl) and bis(cyclohexylmethylcyclopentadienyl)zircon1um dimethyl, (benzylcyclopentadienyl) (cyclopentadienyl) and bis(benzylcydopentadienyl)zirconium dimethyl, (diphenylmethylcyclopentadienyl) (cyclopentadienyl) and b1s(diphenylmethylcyclopentad1enyl)z1rconium dimethyl, (methylcyclopentadienyl) (cyclopentadienyl) and b1s(methylcyclopentadienyl)z1rconium dihydride, (ethylcyclopentadienyl)(cyclopentadienyl) and bis(ethy1cyclopentadienyl)zirconium dihydride, (propy1cyclopentad1enyl)(cyclopentad1enyl) and b1s(propylcyclopentad1enyl)zirconium dihydride, (n-butylcyclopentadlenylKcyclopentadienyl) and bis(n-buty1cyclopentadienyDzirconium dihydride, (t-butylcyclopentadienyD(cyclopentadlenyl) and b1s(t-butylcyclopentad1enyl)zircon1um dihydride, (cyclohexylmethylcyclopentadlenyD(cyclopentadlenyl) and bis(cyclohexylmethylcyclopentad1enyl)zircon1um dihydride, (benzylcyclopentad1enyl)(cyclopentad1enyl) and bis(benzylcyclopentad1enyl)zirconium dihydride, (dlphenylmethylcy opentadienylKcyclopentadienyl) and b1s(diphenylmethylcyclopentadienyDzirconium dihydride and the Hke; (polyhydrocarbyl-substituted-cydopentadienyl) zirconium compounds such as (dimethylcyclopentadlenyl) (cyclopentadienyl) and bis(dimethylcydopentadlenyl) zirconium dimethyl, (trimethylcyclopentadienyl) (cyclopentadienyl) and bis(trimethylcyclopentadlenyl) zirconium dimethyl, (tetramethylcyclopentadienyl) (cyclopentadienyl) and bis(tetramethylcyclopentadienyl) zirconium dimethyl, (permethylcyclopentadlenyl) (cyclopentadienyl) and bis(permethylcyclopentadlenyl) zirconium dimethyl , (ethyltetramethylcyclopentadienyl) (cyclopentadienyl) and bis(ethyltetramethylcyclopentadienyl) zirconium dimethyl , (1ndenyl)(cyclopentad1enyl) and bisdndenyDzirconium dimethyl, 0 (dimethylcyclopentadlenyl) (cyclopentadienyl) and i bis(dimethylcyclopentadienyl) zirconium dihydride, 2 (trimethylcyclopentadienyl) (cyclopentadienyl) and 3 b1s(trimethylcydopentad1enyl) zirconium dihydride, 4 (tetramethylcyclopentadienyl) (cyclopentadienyl) and 5 bis(tetramethylcyclopentadienyl)z1rconium dihydride, 6 (permethylcyclopentadlenyl) (cyclopentadienyl) and 7 b1s(permethylcydopentad1enyl)zircon1um dihydride, 8 (ethyltetramethylcyclopentadienyl) (cyclopentadienyl) and 9 bis(ethyltetramethylcyclopentadienyl)z1rconium dihydride, 0 (1ndenyl)(cyclopentad1enyl) and bisdndenyDzirconium 1 (propylcyclopentadienyl) (cyclopentadienyl) and 2 b1s(propylcyc1opentadienyl)zirconium dihydride, 3 (n-butylcyclopentadlenyl) (cyclopentadienyl) and bis(n-butylcyclopentadienyDzirconium dihydride, 5 (t-butylcyclopentadienyl) (cyclopentadienyl) and b1s(t-buty1cyclopentad1enyl)zircon1um dihydride, (cyclohexylmethylcyclopentadlenyl) (cyclopentadienyl) and b1s(cyclohexylmethylcyclopentad1enyl ) zircon1um dihydride, (benzylcyclopentadienyl) (cyclopentadienyl) and bis(benzyl cyclopentadienyDzirconium dihydride, (diphenylmethylcyclopentadienyl) (cyclopentadienyl) and b1s(diphenylmethylcyclopentadienyl ) zirconium dihydride and the like; (polyhydrocarbyl-substitutεd-cyclopentadienyl) zirconium compounds such as (dimethylcyclopentadlenyl) (cyclopentadienyl) and bis(dimethylcydopentadienyl) zirconium dimethyl , (trimethyl cyclopentadienyl) (cyclopentadienyl) and bis(trimethylcyclopentadlenyl) zirconium dimethyl , (tetramethylcyclopentadienyl) (cyclopentadienyl) and bis(tetramethylcyclopentadienyl) zirconium dimethyl , (permethyl cyclopentadienyl) (cyclopentadienyl) and bis(permethylcyclopentadienyl) zirconium dimethyl , (ethyltetramethylcyclopentadienyl) (cyclopentadienyl) and b1s(ethyltetramethylcydopentadienyl)zircon1um dimethyl, ndenyl Kcyclopentadienyl ) and bisdndenyDzirconium dimethyl , (dlmethylcydopentadlenyD(cyclopentadienyl) and b1s(dimethylcyclopentad1enyl)z1rcon1um dihydride, (trimethyl cyclopentadienyl) (cyclopentadienyl) and b1s(tr1methylcyclopentadienyl)z1rcon1um dihydride, (tetramethylcyclopentadienyl) (cyclopentadienyl) and b1s(tetramethylcyclopentad1enyl)z1rconiua dihydride, (permethylcy opentadienyD(cyclopentadlenyl) and b1s(permethylcyclopentad1enyl)zircon1um dihydride, (ethyltetramethylcyclopentadienyD(cyclopentadlenyl) and bis(ethyltetramethylcyclopentad1enyl)z1rcon1um dihydride, (1ndenyl)(cyclopentad1enyl) and bis ndenyDzirconium dihydride and the like; (metal hydrocarbyl-substituted cyclopentadienyDzirconium compounds such as ( trlmethylsllylcyclopentadienylKcy opentadienyl) and b1s(trimethyls1lylcyclopentad1enyl)zirconium dimethyl, (trimethylgermylcyclopentadienyl)(cyclopentadienyl) and b1s(trimethylgermylcyclopentadienyl)zircon1um dimethyl, - 13 - 1 ( tr methylstannylcy opentadlenylKcyclopentadienyl) and bi s trimethylstannylcyclopentadienyDzirconium dimethyl, ( tr methylplumbylcyclopentadlenylKcyclopentadienyl) and bi s trimethylpiumbylcyclopentadienyl)zirconlurn dimethyl, 5 (tr methyls1lylcydopentad1enyl cyclopentadienyl) and b s trimethyls1lylcyclopentadienyDzlrconlurn d1hydride, 7 (tr methylgermylcyclopentadienyl cyclopentadienyl) and bi s trimethylgermylcyclopentadienyDzirconium dihydride, 9 (tr methylstannylcyclopentadienyl)(cyclopentadienyl) and 10 bi s trimethylstannylcyclopentadienyDzirconium dihydride, 11 ( tr methylpiumbylcyclopentadienyl)(cyclopentadienyl) and 12 bi s tr1methylplumbylcyclopentad1enyl ) zircon1um dihydride and the like; 13 (ha ogen-subst1tuted-cydopentad1enyl ) zirconium compounds such as 14 ( tr fluoromethylcyclopentadienylKcyclopentadienyl) and 15 bi s trlfluoromethylcyclopentadienyDzlrconium dimethyl 16 ( tr fluoromethylcyclopentadienylKcyclopentad enyl) and 17 bi s trifluoro ethylcyclopentadienyDzirconium dihydride and the like; 18 silyl-substltuted bis ( cydopentadienyl) zirconium compounds such as 19 bis cyclopentadienyl ) ( tr1methyls1lyl)(π.ethyl)z1rcon1um, 20 bis cyclopentadienyl ) ( tr1phenyls1lyD ( methyl)z1rcon1um! 21 bis cyclopentadienyl ) ttr1s(dimethy1s1lyl ) silyl](methyl)z1rconium, 22 bis cyclopentad1enyl ) [bis ( mes1tyl ) s1lyl] ( methyl ) zircon1um, cyc1opentad1enyl )( tr1methy1silyl ) tr1methy1s1lylmethyl) zirconium, cyclopentadienyl ) ( trimethylsilylbenzyl) and the like; dged-cyclopentadienyDzirconlum compounds such as ethylene eye1opentadienyl)zirconlurn dimethyl, 27 methylene ( cyclopentadienyl ) z1rcon1um dimethyl, ethylene' 28 b s cyclopentadienyDzirconium dimethyl, dimethylsilyl 29 bis cyclopentadienyDzirconium dihydride, ethylene 30 bis cyclopentadienyDzirconium dihydride and dimethylsilyl 31 bis cyclopentadienyDzirconium dihydride and the like; chiral and 32 ymmetlon compounds; "zlrconacycles": assymetrlcally 33 br1dged-dicylopentad1enyl-ι£ fnpounds such as 34 methy1ene(cyclopentad1enyl )(l-f1uorenyl )zi rcon1 um dimethyl , 35 dimethys1 ly ( cyclopentad1 enyl ) ( l-fluorenyl ) zi rcon1um dihydride , diphenylmethylene(cyclopentadienyl)(l-fluorenyl)zirconium dimethyl , isopropyl (cyclopentadi enyl )(l-fluorenyl)zirconium dimethyl, isopropyl (cyclopentadienyl) (l-octahydrofluorenyl)zirconium dihydride, dimethylsilyl (methyl cyclopentadi enyl (1-fluorenyl) zirconium dihydride, methyl ene(cyclopentad1 enyl ( tetramethyl cyclopentadienyDzirconium dimethyl and the like: racemlc and meso Isomers of symmetrically bridged substituted dicydopentadlenyl compounds such as ethyl eneblsOndenyDzirconium dimethyl, d1methyls1lybisdndenyl)z1rconium dimethyl, ethyleneb1s(tetrahydro1ndenyl)z1rconiuri dimethyl, dimethyl s1lyb1s(3-tr1methyls1 lyl cyclopentadi entyDzi rconium dihydride and the like; zlrconacycles such as b1s(pentamethyl cyclopentadi enyl) zirconacyclobutane, bls ( pentamethylcyclopentadienyl) zlrconacydopentane, bis(cyclopentad1enyl)zircona1ndane, l-b1s ( cyc1opentadienyl ) zircona-3-dimethyls1la-cydobutane and the like; olefin, diolefin and aryne Hgand substituted bis(cyclopentadienyDzirconium compounds such as bis(cyclopentadienyl) (1 ,3-butadiene)zirconium, bis(cyclopentadienyl) (2,3-dimethyl-l ,3-butadiene)zirconium, bis(pentamethyl cyclopentadi enyl )(benzyne)zi rconium and the like; (hydrocarbyl) (hydride) b1s(cyclopentadienyl)zirconium compounds such as bis(pentamethylcyclopentadienyl)zlrconi ' um (phenyD(hydride), bis(pentamethyl cyclopentadienyDzirconium ( ethylKhydride) and the like; and bls(cydopentadienyl) zirconium compounds in which a substituent on the cyclopentadienyl radical is bound to the metal such as (pentamethyl cyclopentadi enyl) (tetramethylcyclopentadlenylmethylene) zirconium hydride, (pentamethylcy opentadienyl) (tetramethylcyclopentadienylmethylene)zlrconium phenyl and the like. A similar list of illustrative bls(cyclopentadienyl) hafnium and bis(cyclopentad1enyl)t1tan1um compounds could be made, but since the lists would be nearly identical to that already presented with respect to bi s(cyclopentad1 enyl )zi rconium compounds, such lists are not deemed essential to a complete disclosure. Other bis(cyclopentadienyl)hafnium compounds and other bis(cyclopentad1enyl)titanium compounds as well as other b1s(cyclopentad1enyl)z1rconium compounds which are useful 1n the catalyst compositions of this Invention will, of course, be apparent to those skilled in the art. B. The Activator Component Compounds useful as an activator component 1n the preparation of the catalyst of this Invention will comprise a cation, which 1s a Bronsted add capable of donating a proton, and a compatible noncoordinatlng anion which anion is relatively large (bulky), capable of stabilizing the active catalyst species (the Group IV-B cation) which is formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by olefinic, diolefinlc and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers, nitriles and the like. In general , suitable anions for the second component may be any stable and bulky anionic complex having the following molecular attributes: 1) the anion should have a molecular diameter greater than 4A; 2) the anion should form stable ammonium salts; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing or oxidizing agent. Anions meeting these criteria - such as polynuclear boranes, carboranes, metal lacarbόranes, polyoxoanions and anionic coordination complexes are well described in the chemical literature. Two classes of compatible non-coordinating anions meeting these criteria have been disclosed in our copending US Patent Applications Nos. 133,052 and 133,480: 1) anionic coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core, and 2) anions comprising a plurality of boron atoms such as carboranes, metallacarboranes and boranes. in general, the activator compounds containing single anionic coordination complexes which are useful in this invention may be represented by the following.general formula: 5. [(L'-H) + ] d [(M') m+ Q 1 Q 2 ...Q n 3 d ~ 1 Wherei n : 2 L' is a neutral Lewis base; 3 H 1s a hydrogen atom; 4 CL'-H] Is a Bronsted add; 5 M' 1s a metal or metalloid selected from the Groups 6 subtended by Groups V-B to V-A of the Periodic Table of the Elements- 7 I.e., Groups V-B, VI-B, VII-B, VIII, I-B, H-B, III-A, IV-A, and V-A;' 8 Q j to Q n are selected, independently, from the 9 time, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, 1° substltuted-hydrocarbyl radicals, wherein one or more of the hydrogen H atoms 1s replaced by a halogen atom, containing from 1 to about 20 12 carbon atoms, hydrocarbyl-substituted metal (organometalloid) radicals 13 wherein each hydrocarbyl substitution contains from 1 to about 20 carbon atoms and said metal is selected from Group IV-A of the 5 Periodic Table of the Elements and the like. 16 In general, Ar and Ar 2 may, independently, be any 17 aromatic or substituted-aromatic hydrocarbon radical containing from 8 about 6 to about 20 carbon atoms. Suitable aromatic radicals Include, 1 9 but are not limited to, phenyl , naphthyl and anthracenyl radicals. 20 Suitable substituents on the substituted-aromatic hydrocarbon 21 radicals, include, but are not necessarily limited to, hydrocarbyl 22 radicals, organometalloid radicals, alkoxy radicals, alkylamldo 23 radicals, fluoro and fluorohydrocarbyl radicals and the like such as 24 those useful as X^ and X 4 - The substituent may be ortho, meta 25 or para, relative to the carbon atoms bonded to the boron atom. When 26 either or both X % and X 4 are a hydrocarbyl radical, each may 27 be the same or a different aromatic or substituted-aromatic radical as 28 are Ar and Ar , or the same may be a straight or branched 29 alkyl, alkenyl or alkynyl radical having from 1 to about 20 carbon 30 atoms, a cyclic hydrocarbon radical having from about 5 to about 8 31 carbon atoms or an alkyl-substituted cyclic hydrocarbon radical having 32 from about 6 to about 20 carbon atoms. % and X 4 may also, 33 independently, be alkoxy or dialkylamido radicals wherein the alkyl 34 portion of said alkoxy and dialkylamido radicals contain from 1 to 35 about 20 carbon atoms, hydrocarbyl radicals and organometalloid 36 radicals having from 1 to about 20 carbon atoms and the like. As indicated above, Ar r and Ar 2 may be linked to each other. Similarly, either or both of Ar and Ar could be linked to either X. or X 4 . Finally, X t or X 4 may also be linked to each other through a suitable bridging group. Illustrative, but not limiting, examples of boron compounds which may be used as an activator component in the preparation of the Improved catalysts of this Invention are trialkyl-substHuted ammonium salts such as tr1ethylammonium tetra ( phenyl)boron, trlpropylammonium tetra(phenyl)boron, tr1 ( n-butyDammon1um tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra ( o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra ( o,p-dimethylphenyl)boron, tr1butylammonium tetra(m,m-d1methylphenyl)boron, tributylammonium tetra(p-tri-fluoromethylpheήyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron and the like; N,N-dialkyl anH1n1um salts such as N.N-dimethylanilinium tetra(pentafluoro phenyDboron, N.N-diethylanilinium tetra(phenyl)boron, N,N-2,4,6-pentamethylanil1nlum tetra(phenyl)boron and the like; dialkyl ammonium salts such as di -propyl)ammonium tetra ( pentafluorophenyl ) boron, dicyclohexylammonium tetra(phenyl)boron and the like; and triaryl phosphonlum salts such as trlphenylphosphonium tetra(pheny1 ) boron, trKmethylphenyDphosphonlum tetra ( phenyl ) boron, trKdimethylphenyDphosphonium tetra(phenyl)boron and the like. Similar lists of suitable compounds containing other metals and metalloids which are useful as activator components may be made, but such lists are not deemed necessary to a complete disclosure. In this regard, 1t should be noted that the foregoing list is not intended to be exhaustive and that other useful boron compounds as well as useful compounds containing other metals or metalloids would be readily apparent to those skilled 1n the art from the foregoing general equations . Activator components based on anions whi ch contain a plural i ty of boron atoms may be represented by the fol l owi ng general formul ae: 6. [L'-H] r c[(CX) a a)(M"X , ) m mX' h o] C" 7. [L' -H] d t [ [(CX 3 ) a l (M"X 4 ) m l (X 5 ) b l ] C,' ] 2 M n+ ] d" wherein [L'-H] 1s either H*. ammonium or a substituted ammonium cation having up to 3 hydrogen atoms replaced with a hydrocarbyl radical containing from 1 to about 20 carbon atoms or a substltuted-hydrocarbyl radical, wherein one or more of the hydrogen atoms Is replaced by a halogen atom, containing from 1 to about 20 carbon atoms, phosphonlum radicals, substituted-phosphonium radicals having up to 3 hydrogen atoms replaced with a hydrocarbyl radical containing from 1 to about 20 carbon atoms or a substltuted-hydrocarbyl radical, wherein 1 or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to about 20 carbon atoms and the like; C is carbon; M" is boron or phosphorus; each of X, X', X", X t X 4 and X $ are radicals selected, Independently, from the group consisting of hydride radicals, hallde radicals, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substltuted-hydrocarbyl radicals, wherein one or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to 20 carbon atoms, organometalloid radicals wherein each hydrocarbyl substitution In the organo portion contains from 1 to about 20 carbon atoms and said metal is selected from Group IV-A of the Periodic Table of the Elements and the like; M is a transition metal; "a" and "b" are integers.> 0; "c" is an integers 1; a + b + c - an even-numbered integer from 2 to about 8; and " " 1s an Integer ranging from 5 to about 22; "a"' and "b' M are the same or a different 1nteger_> 0; H c ,H 1s an integer .> 2; a' ♦ b' ♦ c' ■ an even-numbered Integer from 4 to about 8; "«'" Is an Integer from 6 to about 12; "n" is an integer such that 2c' - n - d; and "d" Is an Integer greater than or equal to 1. Illustrative, but not limiting, examples of second components which can be used 1n preparing catalyst systems utilized in the process of this invention wherein the anion of the second component contains a plurality of metalloid atoms (as in formulae 5 and 6) are ammonium salts such as ammonium 1-carbadodecaborate (using 1-carbadodecaborate as an Illustrative, but not limiting, counterion for the ammonium cations listed below): monohydrocarbyl-substituted ammonium salts such as methylammonium 1-carbadodecaborate, ethylammonium 1-carbadodecaborate, propylammonium 1-carbadodecaborate, Isopropyl ammonium 1-carbadodecaborate, (n-butyl) ammonium 1-carbadodecaborate, anilinium 1-carbadodecaborate, and (p-tolyDammonium 1-carbadodecaborate and the like; dlhydrocarbyl-substHuted ammonium salts such as dimethyl ammonium 1-carbadodecaborate, di ethyl ammonium 1-carbadodecaborate, d1 propyl ammonium 1-carbadodecaborate, d1 Isopropyl ammonium 1-carbadodecaborate, d1 (n-butyl) ammonium 1-carbadodecaborate, diphenyl mmonium 1-carbadodecaborate, d1(p-tolyDammon1um 1-carbadodecaborate and the like; trihydrocarbyl-substltuted ammonium salts such as tri ethyl ammonium 1-carbadodecaborate, tri ethyl ammonium 1-carbadodecaborate, tri propyl -ammonium 1-carbadodecaborate, trKn-butyl) ammonium 1-carbadodecaborate, trlphenyl ammonium 1-carbadodecaborate, trKp-tolyDammonium 1-carbadodecaborate, N,N-d1methylan1l1n1um 1-carbadodecaborate, N,N-d1ethylanil1n1um l-carbadodecaborate and the like. Illustrative, but not limiting examples of second compounds corresponding to Formula 5 [using tr1(n-butyl)ammon1um as an illustrative, but not limiting, counterion for the anions listed below] are salts of anions such as b1s[tr1(n-butyl)ammon1um] nonaborate, b1s[tr1(n-butyl)ammon1um]decaborate, b1s[tri(n-butyl) ammoniumlundecaborate, bis[tr1(n-butyl)ammon1um] dodecaborate, bisttri(n-butyl)ammon1um]decachlorodecaborate, tr1(n-butyl)ammonium dodecachlorododecaborate, tr1(n-butyl)ammonium 1-carbadecaborate, trKn-butyl) ammonium 1-carbaundecaborate, tr1(n-butyl)ammon1um l-carbadodecaborate, trKn-butyDammonium l-trimethyls1lyl-l-carbadecaborate, tri (n-butyl )ammoni urn dibromo-1-carbadodecaborate and the like; borane and carborane complexes and salts of borane and carborane anions such as decaborane(14), 7,8-d1carbaundecaborane(l3), 2,7-dicarbaundecaborane(13), undecahydd do-7 ,8-dimethyl -7 , 8-di carbaundecaborane , dodecahydr1do-ll-methyl-2,7-d1 -carbaundecaborane, trKn-butyl) ammonium undecaborate(14), trKn-butyl) ammonium 6-carbadecaborate(12), tri (n-butyl )ammoni urn 7-carbaundecaborate(13), tr1 (n-butyl )ammon1 urn 7,8-dicarbaundecaborate(12), tr1(n-butyl)ammon1um 2,9-dicarbaundecaborate(12), tri (n-butyl )ammon1um dodecahydrido-8-methyl-7,9-dicarbaundecaborate, trKn-butyl) ammonium undecahydrido-8-ethyl-7,9-d1carbaundecaborate, trKn-butyl) ammonium undecahydrido-8-buty1-7,9-dicarbaundecaborate, trKn-butyl) ammonium undecahydrido-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammon1um undecahydrido-9-trimethyls1lyl-7,8-d1carbaundecaborate, tr1(n-butyl)ammon1um undecahydrido-4,6-dibromo-7-carbaundecaborate and the like; boranes and carboranes and salts of boranes and carboranes such as 4-carbanonaborane(14), l,3-d1carbanonaborane(l3), 6,9-d1carbadecaborane(l4), dodecahydr1do-l-phenyl-l ,3-dicarbanonaborane, dodecahydrido-1 -methyl -1 ,3-d1carbanonaborane, undecahydr1do-l,3-d1methyl-l ,3-dicarbanonaborane and the like. Illustrative, but not limiting, examples of second compounds corresponding to Formula 7 [using tr n-butyl )ammoni urn as an Illustrative, but not limiting, counterion for the anions listed below] are salts of metal lacarborane and metallaborane anions such as tri (n-butyl )ammonium b1s(nonahydrido-l ,3-dicarbanonaborato) cobaltate(III), trKn-butyl )ammoni urn b1s(undeca-hydr1do-7,8-dicarbaundecaboratoferrate(III), trKn-butyl) ammonium b1s(undecahydr1do-7,8-dicarbaundecaborato ) cobaltate(III) , tri (n-butyl )ammoni urn bis(undecahydrido-7,8-dicarbaunaborato) nlkelate(III), tri(n-butyl)ammon1um bis(nonahydrido-7, 8-dimethyl-7,8-d1carbaundecaborato)ferrate(III), trKn-butyl )ammoni urn bis(nonahydrido-7,8-d1methyl-7,8-dicarbaundecaborato ) chromate(III), trKn-butyl )ammon1um bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III), trKn-butyDammonium bls(dodecahydridodicarbadodecaborato) cobaltate(III), tris[tri(n-butyDammonium] bis (undecahydrido-7-carbaundecaborato)chromate(III) , bis[tr1(n-butyl) ammonium] b1s(undecahydrido-7-carbaundecaborato)manganate(IV), b1s[trKN-butyl)ammon1um] b1s(undecahydr1do-7-carbaundecaborato) cobaltate(III), b1s[tr1 (n-butyl)ammonlum] . bis(undecahydrido-7-carbaundecaborato) n kelate(IV) and the like. A similar list of representative phosphonium compounds can be recited as Illustrative second compounds, but for the sake of brevity, it 1s simply noted that the phosphonium and substltuted-phosphonium salts corresponding to the listed ammonium and substituted-ammonlum salts could be used as second compounds in the present Invention. Choice of Metallocene-Actlvator Pairs In general, and while most metal locene components Identified above may be combined with most activator components Identified above to produce an active olefin polymerization catalyst, 1t 1s Important for continuity of the polymerization operations that either the metal cation initially formed from the etallocene component or a decomposition product thereof be a relatively stable catalyst. It is also Important that the anion of the activator compound be stable to hydrolysis when an ammonium salt 1s used. Further, 1t Is important that the addity of the activator component be sufficient, relative to the metallocene component, to facilitate the needed proton transfer. Activator compounds containing aryl -ammonium salts such as N,N-d1methylanilium are more addle than trialkylammonium salts and therefore are useful with a wider variety of metallocene components. The basicity of the metal complex βust also be sufficient to facilitate the needed proton transfer. In general, bis(cyclopentadienyl)metal compounds which can be hydrolyzed by aqueous solutions can be considered suitable as netallocene components to form the catalysts described herein. The chemical reactions which occur may be represented by reference to the general formulae set forth herein as follows: A. (A-Cp)MX x X 2 ♦ [L'-H] + [B']~- t(A-Cp)MX ι ] + [B'] " + HX^L' or [(A-Cp)MX 2 ] + [B , ] HX ι +L' B. (A-Cp)M)(^X , 2 ♦ [L'-H] + [B'] ' - [(A-Cp)MX' ι X , 2 H] + [B , ] " +L' or [(A-Cp)MX' 2 X , ι H] + [B , ] " + L' C. (A-Cp)ML + [L'-H] + [B'3~- [(A-Cp)M(LH)] + [B'] L » D. (Cp*)(RCp)MX χ + [L' or In the foregoing reaction equations, the letters A-D correspond to the numbers 1-4, respectively, set forth in combination with the general equations for useful metallocene compounds. B' represents a compatible 1on corresponding to the general formulae outlined 1n formulae 5, 6 and 7 above. When the metallocene and activator components used to prepare the improved catalysts of the present invention are combined 1n a suitable solvent or diluent, all or a part of the cation of the activator (the addle proton) combines with one of the substituents on the metallocene compound. In the case where the metallocene component has a formula corresponding to that of general formula 1, a neutral compound is liberated, which neutral compound either remains in solution or 1s liberated as a gas. In this regard, it should be noted that if either X χ or X In the metallocene component 1s a hydride, hydrogen gas may be liberated. Similarly, 1f either X χ or X 2 is a methyl radical, methane may be liberated as a gas. In the cases where the first component has a formula corresponding to those of general formulae 2, 3 or 4 (optional), one of the substituents on the metallocene component 1s protonated but no substituent 1s liberated. In general, the stability and rate of formation of the products in the foregoing reaction equations will vary depending upon the choice of the solvent, the acidity of the [L*-H] + selected, the particular L' , the anion, the 9 temperature at which the reaction 1s completed and the particular 0 cyclopentadienyl derivative of the metal selected. 1 With respect to the combination of the metallocene component 2 with the activator component to form a catalyst of this invention, it should be noted that the two Compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the anion to the metal cation, thereby formi ng a catalytl cal ly i nactive species. Thi s could 'be done by sterlc hi ndrance , resul ti ng from substi tutions on the cyclopentadi enyl carbon atoms as wel l as substi tutions on the non-coordi nating anion. It fol lows , then , that the metal locene components compri sing perhydrocarbyl-substi tuted cyclopentadi enyl radi cal s could be effectively used wi th a broader range of activator compounds than could metal locene components compri sing unsubsti tuted cyclopentadi enyl radi cal s . As the amount and size of the substitutions on the cyclopentadienyl radicals are reduced, however, more effective catalysts are obtained with activator compounds containing non-coordinating anions which are larger in size and more resistant to degradation. In the case where the non-coordinating anion 1s an anionic coordination complex, such as a tetraphenylboron derivative, substitutions on the phenyl rings can be used to prevent the transfer of a proton or an entire phenyl group from the anion to the metal. This can be accomplished by alkyl substitution in the ortho positions of the phenyl groups, or, more preferably, by perfluoro-substitutlons on the anion. Thus, anionic coordination complexes containing perfluorphenyl-, trifluoro ethylphenyl-, or bls-trlfluormethylphenyl rings are preferred for this subgenus of activator components. When the non-coordinating anion contains a plurality of boron atoms as described 1n general formulae 6 and 7, more effective catalysts are obtained with activator compounds containing larger anions, such as those encompassed by Equation 7 and those having larger m values 1n Equation 6. In these cases it is further preferable when using second compounds which are encompassed by Equation 6, that a + b + c - 2. Second compounds 1n which a + b + c ■ even-numbered Integers of 4 or more have acidic B-H-B moieties which can react further with the metal cation formed, leading to catalytlcally inactive compounds. As indicated supra, most metallocene compounds will combine with most activator compounds to give an active polymerization catalyst. The initially formed catalyst is not, however, always sufficiently stable as to permit its separation and subsequent identification. However, catalysts which are thermally stable are preferred for the production of block or tapered copolymers. Three structurally distinct forms of thermally stable 1on1c catalysts have been Identified by NMR spectroscopy and are shown below in equation 8. 8a. [A-CpMX ι 3[(C 2 B j H ιι ) 2 Co3 8b. [A-CpMX ι (L')][B(C t F 8 ) j (X j )3 8c. [(A-CpMX χ ) 2 X ι 3[B , 3 in the foregoing reactions the symbols A-Cp, M, X , L* and X correspond to the definitions set forth in equations 1-4 and 5-5a, respectively; B' represents a compatible non-coordinating anion corresponding to the general formulae set forth in equations 5, 6 and 7. In example 8a, NMR spectroscopy indicates that the metallacarborane anion Is weakly bound to the metal center; the biproduct L' does not form an observable coordination complex with the metallocene center. In 8b, NMR experiments indicate that the fluorinated boron anion is completely non-coordinating and that L', weakly coordinates to and stabilizes the metallocene cation when the tertiary amine (L 1 ) is an aniline derivative. The ability of L' to coordinate to the metal 1s important to the stability of the catalyst systems which have highly noncoordlnatlng anions. The Lewis basicity of the L' can affect the rate of polymerization and other polymerization parameters. Experience has shown that when the bulk of the amine or the metallocene cation is increased by substitutions on the nitrogen atom or the cyclopentadienyl ligands respectively, the ability for the amine to coordinate to the metal center decreases. Addition of excess metallocene ACρM(X χ ) 2 to 8a or 8b results in displacement of the anion in 8a or the aniline Hgand 1n 8b to form a stable dimerlc cation 8c. Preferred Catal ysts For the Production of Block and Tap ed Copol ymers Ideal catalyst systems for the production of block copolymers are single-sited living catalysts. Living catalysts are those systems 1n which chain transfer 1s nonexistent and the rate of Initiation 1s fast compared to propagation. Catalysts which have finite chain transfer rates may also be useful for the production of block and tapered copolymers if the rate of propagation 1s fast relative to termination. It 1s also important that the average chain lifetimes are reasonably long ( minutes to hours) 1n order to permit adequate time for modifications of the reactor conditions (e.g. changing monomer feed streams ) . While most reasonably stable 1on1c catalysts described above will under suitable conditions produce block and/or tapered copolymers of nonpolar oleflns. It 1s preferred that the catalyst be: 1) thermally stable (recoverable as a single organometallic complex), 2) versatile In terms of random copolymer synthesis (i.e. capable of preparing HDPE, 1-PP, s-PP, EP-rubber, LLDPE etc.), 3) capable of producing high molecular weight polymers at reasonable temperatures and pressures, 4) high activity (fast propagation catalysts) and 5 ) slow 1n chain termination reactions so that few chains of polymer product are produced per hour per site. Ionic catalysts of the fora [A-CpMMe(L')3[B(C F ) (X )] are the preferred catalysts for the produέt on of block and tapered copolymers of ethylene. 1-olefins, dienes, cyclic olefins and other unsaturated monomers. Ionic catalysts of this form where M - Hf are 6 the most preferred catalyst systems because they are more stable, produce higher molecular weight copolymers, and have longer chain lifetimes than corresponding Zr or Ti-based systems. Polymerizations 9 using hafnium systems of this form under standard random copolymer 0 conditions as described in our copending U.S. Patent Application No. i 133,480 produce high molecular weight HDPE, LLDPE, a-PP, 1-PP, s-PP, 2 and EP-rubber at rates comparable to similar Zr-based catalysts. 3 Tapered and block copolymers containing these segments can be 4 produced using the appropriate hafnium 1on1c catalyst using the 5 techniques and process conditions set forth 1n the following sections. Processes For the Production of Block and Taoered Copolymers Many procedures for modifying the reactor conditions and monomer feeds for the production of block copolymers have been developed and ' applied using conventional Ziegler-Natta catalysts. The patent literature concerning block copolymer from Ziegler-Natta catalysts disclose a variety of processes for altering reactor conditions. The processes Include batch reactors and sequential additions techniques, series batch reactors, loop and tubular reactors, and fluidized bed reactors. A review of the processes and patents is given in chapter 4 of "Block Copolymers" [D. C. Allport and W. H. Oames; Oohn Wiley and Sons, New York 19733. As Indicated supra, the application of these processes using conventional catalysts in general produces broad molecular weight distributions of poorly defined polymer blends. In principle, the catalysts of this Invention can be used 1n any of the processes described above for the production well-defined block copolymers of higher purity than obtained using conventional Ziegler-Natta catalysts. The most demanding process, that is the process which requires the longest chain lifetimes, 1s the sequential addition. When the catalyst or initiator produces growing chains with sufficiently long lifetimes, the sequential addition technique allows for the production of block copolymers having non-tapered transitions between different polymer segments. Sequential addition techniques are commonly used to produce styrenic block copolymers (Kraton for example) using anionic Initiators. In the first step of the sequential addition process employed in accordance with this invention the catalyst 1s placed 1n a well stirred batch reactor in a suitable solvent and first segment of the block copolymer 1s grown by adding a specific number of molar equivalents of monomer(s). The catalyst consumes all of the monomer(s) prior to addition of the second monomer(s) (a different set of monomers than 1n the first step). This procedure can be repeated to prepare multiblock copolymers. Sequential Addition Conditions For a given catalyst and target block or tapered copolymer a solvent, temperature and catalyst concentration must be chosen so that 1) narrow molecular weight distribution, high molecular weight copolymer segments can be synthesized; and 2) the molecular weight of the copolymer segments can be controlled by varying the catalyst-to-monomer molar ratio. Under these conditions the system 1s behaving in a quaslliving fashion (I.e. slow chain transfer) and narrow molecular weight block copolymers can be prepared in high yield. Methods for choosing'the conditions for a particular catalyst system are given below. Solve t Preferably, the solvent should normally disperse or dissolve the catalyst to form a well-mixed system. The most preferred catalysts for block copolymer synthesis, [ACpHfMe(L')3[B(C t F β ) 4 3, are prepared 1n toluene and form non-mislble, toluene-dispersible phases. This two-component phase contains the catalyst and a particular amount of toluene; the concentration of toluene in the catalyst phase depends on temperature and the structure of the catalyst. Addition of an aliphatic hydrocarbon to the toluene-catalyst emulsion causes immediate precipitation of the catalys from solution to give a soft waxy, non-dispers1ble catalyst deposit. While aliphatic hydrocarbons, fluorinated hydrocarbons, and chlorinated aromatic hydrocarbons may be used in this invention, the preferred solvents for the preparation of block copolymers from the most preferred catalysts are aromatic hydrocarbons such as toluene, xylene, ethyl benzene and the like. The lack of solubility or compatibility of the catalyst phase in the aromatic solvent does not present significant problems 1n terms of molecular weight broadening because the phase Is highly dlspersible even at lower temperatures. Temperature The reactor temperature strongly affects the yield of block copolymer and must be adjusted depending on the type and concentration of monomers and catalyst used. The general procedure for determining this condition is to 1) find the maximum temperature where high molecular weight polymer segments can be prepared and 2) confirm the molecular weight is controlled by the catalyst-to-monomer ratio at this temperature. The general trend is that higher temperatures cause chain transfer to be more rapid relative to propagation and therefore give lower block copolymer yields. The process may be carried out at temperatures of -80*C to 80*C, however, It is preferred that the temperature be In the range of -10*C to 20 * C. Concentration of Catalyst The concentration should be high enough to produce significant rates of polymerization under the generally low pressure 0 conditions of sequential addition. The concentration should not be 1 so high as to produce uncontrollable exotherms upon exposure to the 2 monomer. The exotherm can be controlled, however, by adjusting the 3 rate of monomer addition during the formation of a block segment. 4 This level of control allows for a large range of acceptable 5 catalysts concentrations. The process may be carried out at catalyst 6 concentrations ranging from about 6 x 10~* to about 6 x 10 "2 7 moles of catalyst/liter of solution, however it 1s preferred that 8 catalyst levels be in the range of 1 x 10~ 4 to about 3 x 10 " * 9 moles of catalyst/liter of solution. Monomer Concentration 0 The amount of monomer added depends on the molecular weight 1 of the targeted polymer and the moles of active catalyst 1n the 22 reactor. Molar ratios of monomer to catalyst may be in the range of 3 about 10:1 to about 10,000:1. The monomers may be added quickly or 24 may be metered In to the reactor to control exotherms. Order of Monomer Addition 25 Precipitation of polymer (with catalyst attached) causes 26 undesirable broadening of the molecular weight distribution due to 27 mass transport limitations and poor mixing. It is therefore ς preferred to prepare the soluble block (generally the elastomeric 29 segment) in the first stage of the reaction. Thus, as indicated in 30 the examples, when ethylene is added 1n the first step 1n the 3i synthesis of a HDPE-b-atactic-PP diblock copolymer the Initially -- formed polyethylene precipitates with the catalyst and the final - 29 - I molecular weight distribution of crude block copolymer product is - rather broad (Mw/Mn - 3.0). Addition of propylene In the first step 3 produces a system which remains homogeneous throughout the block copolymer synthesis, yielding a crude product having a much narrower 5 MwMn - (1.7 - 1.8). Preparation of Taoered and Random Copolvers 6 Addition of stolchlo etric amounts of a mixture of two 7 olefins to the reactor under block copolymer conditions will 8 naturally produce tapered copolymer because the monomers will 9 generally have different reactivities with the catalyst. Thus, the 10 head of the polymer will be rich in the more reactive comonomer while II the polymer tail will contain larger amounts of the slower reacting comonomer. The extent of tapering will depend on magnitude of the 13 difference of monomer reactivity. The extent of tapering can be 14 controlled by metering the two monomers Into the reactor at different 15 rates. 16 Random copolymers such as non-crystalline ethyl ene-propylene rubber can be made under block copolymer conditions by adding the 18 fast monomer (ethylene) to the catalyst/propylene mixture at a rate 19 where the desired amount of ethylene has been added when all the 20 propylene has been consumed. This procedure is exemplified for a 21 ethyl ene-propylene elastomer containing 50 mole 1 propylene. piock Copolymer Products 22 The novel polymer products of this Invention are olefinic 23 block and tapered copolymers having narrow molecular weight 24 distributions and well defined di-, tr1-, multiblock or tapered 25 structures. The polymer segments which can be Incorporated into 26 these architectures include 1) elastomers such as atactlc 27 polypropylene, atactlc poly-1-olefins, and ethylene/1-olefin 28 copolymers wherein the ethylene comonomer is a C -C 29 α-olef1n such as ethyl ene-propylene, ethylene butene, and 30 ethyl ene-octene copolymers ethyl ene-propylene-diene terpolymers and 31 other crosslinkable elastomeric olefins; 2) thermoplastics such as 32 high density polyethylene, linear low density polyethylene having 33 melting points from 80-135*C (e.g. e * thyl ene-propylene and other ethyl ene-l-ol ef1n copolymers wherein each l-ol ef1 n has from about 4 to 20 carbon atoms) , ethyl ene/d1 ene copolymers such as ethyl ene/ethyldi ene-norbornene copolymers , I sotactic polypropyl ene having melting points from 100 * C-165 * C, syndiotacti c polypropyl enes havi ng mel ting points from 100*C-165 * C, hemi -I sotactic polypropylenes and other crystalline 1-olefin homo and copolymers ; and 3) glasses such as homo-polycyclopentene, homopolynorbornene and the l ike. The average molecular weight of the polymer segments i ncluded 1n the novel block copolymers of thi s i nvention can be i n the range of from 100-1 ,000,000 daltons , preferably from 30,000 to 200,000 daltons. The mol ecular weight di stri butions (Mw/Mn) of the crude and/or fractionated block copolymer are in the range from about 1 .0 to about 5.0, preferabl e from about 1 .1 to about 2.0. As I ndicated above and 1 n the exampl es fol lowing the percentage of block copolymer 1n the crude product can vary from about lϊ to 1001, preferably from about 50X to about 90% depending on the application and the condi tions of the experiment . The block copolymers of thi s invention can be represented by the fol lowing general formulae: (A ι )(A 2 )(A J ) (A n ) wherein each A is a polymer segment having an average molecular weight from about 100 to about 1,000,000 daltons chosen Independently from homopolymers consisting of HDPE, homo and copolymers of cyclic olefins, such as polycydopentene and polynorbornene, and isotactic, atactlc, and syndiotactic poly-1-oleflns such as atact1c-PP, isotact1c-PP, syndiotactic-PP; random copolymers of 1-olefins and diolefins such as ethylene-propylene rubber, ethylene-propylene-hexadlene rubber, ethylene-butene rubber, linear low density polyethylenes, such that no adjacent segments are the same polymer composition. Novel block copolymers of this invention include but are not limited to diblock copolymers such as (HDPE)(EP), (1-PP(EP), (LLDPE)(a-PP), (HDPE)(a-PP), (LLDPE(HDPE) and the like, and triblock copolymers such as (HDPE) (EP) (HOPE) , (HDPE) (a-PP) (HDPE) , (HDPE) (EP)LLDPE) , (LLDPE) (a-PP) (LLDPE) , (HDPE) (a-PP) (LLDPE) , (i-PP)(EP)(i-PP), (s-PP)(EP)(s-PP) and the like. It will be recognized to those well versed in the field that the Isotactic polypropylene 5 segments contained in the block copolymers of this invention have 6 icrostructure defects which are not observed in conventional i-PP 7 materials prepared using titanium Ziegler-Natta catalyst. The 8 microstructure defects which are unique to isotactic polypropylenes 9 prepared using metallocene catalysts arise from 1-3 and 2-1 additions to 10 propylene. The melting points of such materials can vary from 60°C to 11165°C depending on the total number total defects. 12 The tapered copolymers can be represented by similar general 13 formula where the transitions between idealized polymer segments A 14are gradual. These gradient transitions between segments are 15 represented by arrows. 15 (Ai)—>(A2 —>(Ai)—> (An). 17 An example of thi s would be a polymer prepared by reacti ng a 50-50 18 mi xture of ethyl ene and propyl ene wi th a l i vi ng catalyst whi ch has a 19 hi gh preference for ethyl ene over propyl ene . The tapered polymer 20 obtai ned in such an experiment would be desi gnated by the fol lowi ng 21 formul a: 22 HDPE >EP — >a-PP EXAMPLES Catal yst Preparation. The catalyst used in the fol lowing examples was prepared in dry, deoxygenated toluene (5.0 cc) by reacting Cp2HfMβ2 with one equivalent of [DMAH3 [B(pfp)43 (where DMAH - Ph e2NH+ and pfp - C6F5) at room temperatur for 5-10 minutes. The reaction is known to cleanly produce methane gas and a single ionic catalyst [Cp 2 HfMe(PhNMe 2 ) ] [B(pfp)43. Example 1 First Ethylene then Propylene. The reactor was cooled to 0°C and charged with 400 is of toluene and 0.30 mmoles of catalyst. Ethylene (4.0 grams; 0.143 9 moles) was added to the reactor. After all the ethylene was 1° consumed, propylene (6 grams; 0.139 moles) was added; after 30 11 minutes the reactor was dropped and the product collected. The 12 crude product contained 50 mole % propylene, had an 13 M n - 87,000 with a molecular weight distribution of 3.0. The 1 4 crude product was washed with hexane at room temperature to remove 5 any -PP which was not in the form of block copolymer. The hexane l β insoluble material contained cyrstalline HDPE (as determined by 17 IR) and 30 mole % propylene; the M n was 144,000 with a molecular 18 weight distribution of 1.89. The hexane soluble fraction was - 19 PP, did not contain ethylene (by IR), and had an M n of 63,000 with 20 a molecular weight distribution of 1.47. Based on the extraction 21 studies, it was concluded that 50-60% of the -PP chains were 22 incorporated into a block coplymer under these conditions. M - 87,000 with a molecular weight distribution of 3.0. The crude product was washed with hexane at room temperature to remove any α-PP which was not 1n the form of block copolymer. The hexane insoluble material contained crystalline HDPE (as determined by IR) and 30 mole % propylene; the M fl was 144,000 with a molecular weight distribution of 1.89. The hexane soluble fraction was α-PP, did not contain ethylene (by IR), and had a M fi of 63,000 with a molecular weight distribution of 1.47. Based on the extraction studies, it was concluded that 50-60% of the α-PP chains were Incorporated into a block copolymer under these conditions. Example i First Propylene Then Ethylene The procedure of Example 1 was repeated except propylene was added first. The crude product had 41 mole X propylene (IR), a M of 170,000 with a molecular weight distribution of 1.78. A pad was pressed and extracted with hexane for 4 hours. At this point, the material contained 37 mole X propylene and very crystalline HDPE. The pad was further extracted with toluene at room temperature for 50 hours with no loss of weight. The extracted "diblock" had a ).__ of * 230,000 and a molecular weight distribution of 1.48 (the hexane , solubles were α-PP having a Mn of 125,000 and a molecular weight distribution of 1.72). Example 3 Molecular Height Control In Block Copolymer Synthesis i Using the procedure 1n Example 2, 3.0 grams of propylene 2 (0.070 moles) were added to 0.30 mmole of the hafnium catalyst. 3 After the propylene (0.071 moles) was completely consumed, 2.0 grams 4 of ethylene were added to the system. The resulting product was 5 washed with hexane at room temperature to remove any α-PP. The 6 resulting block copolymer had a Mn of 107,000 and a molecular weight 7 distribution of 1.68, and contained 42 mole X propylene by IR 8 spectroscopy. Example 4 Effect of Temperature If the temperature is raised the effect is to lower the efficiency of the block formation. The temperature was raised from O'C to 10*C and the blocking efficiency was reduced to less than 10X to 65X. When the temperature was lowered to -5*C, the blocking efficiency improved 78%. Example 5 The Effect of Increasing the Time Between the Addition of Monomers A series of block copolymer1zat1ons were run at O'C and the time between the addition of propylene and ethylene was varied from 6 to 42 minutes. The crude products were collected, analyzed by GPC and IR, then extracted with hexane at room temperature for 65 hours to remove unblocked α-PP. In a well-behaved system wherein the extraction technique removes all of the α-PP, a logrithmlcally increase 1n the percent of hexane extractables with time would be expected. The data of this example Is shown in Fig. 1 in graphical form. The Y-axis represents the percent of polypropylene which 1s Incorporated Into the block copolymer. The extractables were Isolated and analyzed by GPC and IR; they were all pure α-PP. . The correlation 1s close to the linear result expected so that this technique can be used to evaluate the kinetics of chain loss under a variety of conditions. This result confirms the ability to make true block copolymers, and confirms that hexane extraction is a good measure of block copolymer efficiency for this polymer system. Example 6 Preparation of EP In this example, 1.6 grams of propylene (0.037 moles) were added to [Cp 2 HfMe(L)3[B(pfp) 4 3 (0.30 mmole) in 400 cc of toluene at 0 * C. Immediately after the propylene addition, 1.1 grams of ethylene (0.039 moles) was metered in over 3 minutes. After six minutes, the product was recovered yielding 2.7 grams of amorphous EP rubber. The product was non-crysta111ne by IR; the polymer had a M of 96,000 and a molecular weight distribution of 1.69. Example 7 Preparation of EP In this example, 3.2 grams of propylene (0.074 moles) was added to [Cp 2 HfMe(L)3[B(pfp) 4 3 (0.30 mmole) in 400 cc of toluene at 0*C. Ethylene (2.2 grams; 0.078 moles) was added to the reactor over 5.5 minutes. The product was recovered yielding 5.7 grams of EP rubber having a M of 155,000, and a molecular weight distribution of 1.48. The IR showed some degree of PE-crystallinity. Example 8 Preparation of EP-b-HDPE Example 6 was repeated to prepare "living" EP-rubber. After all the monomer had been consumed, ethylene (1.1 grams) was added to prepare the desired block copolymer. The product was recovered yielding 4.25 grams of copolymer. The IR showed PE crystallinity and the polymer had thermoplastic-like properties. The onset of Tg was -52.9 * C and the product had a melting point of 119*C. The M of the crude product was 161,000 with a molecular weight distribution of 1.59. Example 9. The intention of this example is to demonstrate that slow chain transfer can be used to catalytically prepare block copolymers. This is an example of in-situ catalyst recycle leading to the production of mixtures of small amounts of homopolymer and mixtures of multiblock copolymers (AB, ABA, BAB etc) . The reactor was cooled to 0°C and charged with 400 mis of toluene and 0.15 mmole of catalyst. In step 1, propylene (1.5 grams) was added to the well stirred reactor causing a pressure increase of 7 psi. After 7 minutes the pressure in the reactor dropped to zero and the reactor was vented through a nujol bubbler to remove any residual propylene in the system. In step 2, ethylene (1.0 grams) was added. The ethylene was consumed in less than one minute. After all the ethylene was consumed the reactor was vented. These sequential steps were repeated 5 more times resulting in similar monomer conversion rates. The reactor was dropped and the the product was collected yielding 15 grams after drying. The crude product was analyzed by GPC and had a Mn = 122K and a MWD = 2.2. The melting point was 126°C by DSC and the IR indicated the presence of high crystallinity polyethylene. A thin pad weighing 1.25 grams was compression molded and extracted with hexane a room temperature for 72 hours at room temperature. The pad was removed, dried and weighed yielding 1.13 grams of insoluble material. The insoluble material was analyzed by GPC and DSC and had a Mn = 171K, a MWD = 1.8 and a melting point of 126 β C. The soluble material was isolated (0.12 grams) and was identified as atactic PP. The extraction data indicated that 84% of the polypropylene is bonded to insoluble polyethylene segments. The data are not sufficient to detect homo-polyethylene, or to quantify the ratios of the various possible multiblock copolymers. The observation, however, that the Mn of the crude and extracted products in this experiment are only slightly higher than is typical of a standard A-B sequential addition (Mn = 1201-140K) at the same monomer : catalyst ratio suggests that the chain lifetimes are not sufficiently long to produce high amounts of triblock or other higher order block copolymers. F.yamp.e 10. The reactor was cooled to 0 β C and charged with 400 mis of toluene and 0.15 mmole of catalyst. In step 1, propylene (1.5 grams) was kdded to the well stirred reactor causing a pressure increase of 7 psi. After 7 minutes the pressure in the reactor dropped to zero and the reactor was vented through a nujol bubbler to remove any residual propylene in the system. In step 2, ethylene (1.0 grams) was added. The ethylene was consumed in less than one minute. After all the ethylene was consumed the reactor was vented and in step 3 propylene (1.5 grams) was added. The propylene was consumed in 7 minutes and after an addition 20 minute waiting period steps 1,2 and 3 were repeated. The reactor was dropped and 4 grams of crude dry product was isolated. The crude product was analyzed by GPC and had a Mn = 140K and a MWD = 1.7. The IR spectrum indicated the presence of high crystallinity polyethylene. A thin pad weighing 1.07 grams was compression molded and extracted with hexane a room temperature for 72 hours at room temperature. The pad was removed, dried and weighed yielding 0.87 grams of insoluble material. The insoluble material was analyzed by GPC had a Mn = 192K, a MWD = 1.4. - The soluble material was isolated (0.20 grams) and was identified as atactic PP by IR and NMR spectroscopy. The extraction data indicated that 81% of the polypropylene is bonded to insoluble polyethylene segments. Example H ^ In this example we describe an attempt to prepare an ABA triblock copolymer where the A-block is high density polyethylene and the B-block is elastomeric atact ic polypropylene . We disclose a technique where a small amount of propylene (5% of the amount added in the B-step) is added n a prepolymerizat ion step . The e ffect of th is is to solubilize the insoluble polyethylene A-segment and prevent precipitation of the living polymer . When this procedure is used a clear , appa rent l y homogeneous react ion mixture i s formed . Simi lar experiments where the prepolymerizat ion step is not used gives a heterogeneous react ion mixture, lower b locking e f f ic ienc ies and broade r mo le cu lar we i ght distributions . The reactor was cooled to 0 β C and charged with 400 mis of toluene and 0.15 mmole of catalyst. In a prepolymerization step 1, propylene (0.15 grams) was added to the well stirred reactor. After 7 minutes the pressure in the reactor dropped to zero and the reactor was vented through a nujol bubbler to remove any residual propylene in the system. In step 2, ethylene (0.5 grams) was added. After 2 minutes, propylene (3.0 grams) was added to the well stirred reactor causing a pressure increase of 7 psi. The propylene was consumed in 4 minutes at which point the reactor was vented and ethylene (0.5 grams) was added. The reactor was dropped and approximately 4 grams of crude dry product was isolated. The crude product was analyzed by GPC and DSC and had a melting point of 122°C, a Mn = 173K and a MWD « 1.9 (with a bi odal shape). A thin pad weighing 1.295 grams was compression molded and extracted with hexane a room temperature for 72 hours at room temperature. The pad was removed, dried and weighed yielding 1.17 grams of insoluble material. The resulting material has thermoplastic elastomeric properties. The extraction data indicated that 86% of the polypropylene is bonded to insoluble polyethylene segments. Examplel2. The reactor was cooled to 0°C and charged with 400 mis of toluene and 0.15 mmole of catalyst. In a prepolymerization step 1, propylene (0.15 grams) was added to the well stirred reactor. After 7 minutes the pressure in the reactor dropped to zero and the reactor was vented through a nujol bubbler to remove any residual propylene in the system. In step 2, ethylene (0.25 grams) was added. After 2 minutes, propylene (3.0 grams) was added to the well stirred reactor causing a pressure increase of 7 psi. The propylene was consumed in 4 minutes at which point the reactor was vented and ethylene (0.25 grams) was added. The reactor was dropped and approximately 3.5 grams of crude dry product was isolated. The crude product was analyzed by GPC and DSC and nad a melting point of 122°C, a Mn = 160K and a MWD = 1.8 (with a bimodal shape). A thin pad weighing 1.288 grams was compression molded and extracted with hexane a room temperature for 72 hours at room temperature. The extremely swollen pad was removed, dried and weighed yielding 1.165 grams of insoluble material. The resulting material has thermoplastic elastomeric properties. The extraction data indicated that 88% of the polypropylene is bonded to insoluble polyethylene segments. The insoluble product was analyzed by GPC and had a Mn = 184K and a MWD = 1.6 (with a bimodal shape)

Claims: CLAIMS 1. A process for the production of block copolymers comprising: (I) contacting a first olefinic monomer(s) with a catalyst which Is the reaction product of: (a) a metallocene component, and (b) a second component having a cation capable of donating a proton and a compatible non-coordinating anion to produce a first living polymer; and (II) sequentially adding to said living polymer at least a second monomer(s) to copolymerize with said first polymer to produce a ulti block copolymer; and (III) recovering a block copolymer 2. The process of claim 1 wherein the block copolymer 1s a diblock copolymer. 3. The process of claim 1 wherein the block copolymer is a triblock. 4. The process of claim 1 wherein the catalyst reaction product 1s of the formulae: [A-CpMX ι ][(C 2 B f H n ) 2 Co] [A-CpMX 1 (L , )][B(C i F | ) J (X 2 )] [ A-CpMX^^HB'] wherein: M is ti tanium, zi rconium or hafni um; (A-Cp) i s ei ther (Cp)(Cp*) or Cp-A'-Cp* and Cp and Cp* are the same or di fferent substi tuted or unsubsti tuted cyclopentadi enyl radical s ; A' I s a covalent bridging group containing a Group IV-A el ement; L' is a neutral Lewis base; X χ I s a hydride radical , hydrocarbyl radical having from 1 to about 20 carbon atoms, substltuted-hydrocarbyl radical , wherein 1 or more of the hydrogen atoms are replaced wi th a halogen atom, having from 1 to about 20 carbon atoms, or organo-metalloid radical comprising a Group IV-A element wherein each of the hydrocarbyl substituents contained in the organo portion of said organo-metalloid, independently, contain from 1 to about 20 carbon atoms; C -C and X 2 1s a hydride, hallde, hydrocarbyl radical, a 1 -C 2Q hydrocarbyl radical wherein one or more of the hydrogen atoms is replaced by a halogen atom, organometalloid radical wherein each hydrocarbyl substitution 1n the organo portion contains from 1 to 20 carbon atoms and the metal is a Group IVA metal. 5. The process of claim 4 wherein the catalyst reaction product is represented by the formula: [A-CpMX * L' )3[B(C » F 9 3 (X 3 )] 6. The process claim 1 , wherein the catalyst i s the reaction product bi s(cyclopentadi enyl ) hafni um dimethyl and N .N-dimethyl ani l ini um tetraki s(pentafluorophenyl )boron. 7. The process of claim 1 wherei n said steps of reacting, copoly erizing, introduci ng and repeating are carri ed out at a temperature of from about -5 * C to about lO'C. 8. The process of claim 1 wherein any of said monomers is sel ected from ethylene, propylene, 1-butene. 9. Olefinic block copolymers having a Mw/Mn of from about 1 to 5 represented by the formula: (A x )(A 2 ) (A 3 ) (An) wherein each A represent a polymer segment havi ng an average of Mw of from 100 to about 1 ,000,000 dal tons , each adjacent A represents a different olefinic polymer segment , A being sel ected from HDPE, atactlc-1-oleflns, I sotactic 1-ol efins , syndiotacti c 1-ol efins , homo- and copolymers of cyclic olefins, and random copolymers of l-olef1ns and dioleflns. 10. The olefin block copolymers of claim 9 wherein the polymer segments are selected from are atactic-polypropylene, isotactic-polypropylene and syndiotactic-polypropylene. 11. Olefin block copolymers of claim 11 wherein said block copolymers is a diblock. 12. Olefin block copolymers of claim 11 selected from (HDPEKEP), (1-PP)(EP), (LLDPE)(a-PP), (LLDPE)(HDPE). 13. Olefin block copolymers of claim 10 wherein said block copolymer is a triblock. 14. Olefin block copolymers of claim 13 selected from (HDPE)(EP)(HDPE), (HDPE)(EP)(LLDPE), (LLDPE)(a-PP)(LLDPE)(HDPE)(a-pp)(LLDPE), (i-PP)(EP)(i-PP)(s-pp)(EP)(s-PP). 15. Mixtures of homόpolyolefins, and di- and triblock copolymers, said block copolymers produced by the process of claims 2 and 3.

Inventors: HLATKY GREGORY GEORGE, TURNER HOWARD WILLIAM, HLATKY, GREGORY, GEORGE, TURNER, HOWARD, WILLIAM
Applicants: EXXON CHEMICAL PATENTS INC, EXXON CHEMICAL PATENTS INC.
Application year: 1991
Main classification: C08F297
IPC codes: C08F4, C08F297