MXPA96006471A - Process for the production of branched channel poliolephines la - Google Patents

Abstract

A process for making a polyethylene having branched long chain by supplying ethylene and optionally an alpha-olefin having from 3 to 18 carbon atoms in a reaction zone containing a metallocene polymerization catalyst under polymerization conditions in the presence of a hydrocarbon coupling compound in an amount sufficient to provide a tangled chain or a long chain branched

Description

"PROCESS FOR THE PRODUCTION OF LONG CHAIN BRANCHED POLYOLEPHINES" This application claims the benefit of the Provisional Application of the United States Number 60 / 008,767, filed on December 15, 1995.

COUNTRYSIDE This invention relates to the polymerization of polyolefins, particularly polyolefins having long chain branching (LCB), more particularly, polyethylenes.

BACKGROUND U.S. Patent No. 5,317,036 discloses gas phase polymerization processes using unsupported catalysts, such as, for example, transition metal coordination catalysts. The catalysts are introduced into a reactor, such as a fluidized bed, in the form of a liquid such as in a solution. The patent further discloses the use of dienes as comonomers to produce polyolefins, such as ethylene-propylene-diene elastomers. Even though the manner of using a diene as a comonomer in the polyolefin polymerization or in activating a Ziegler-type catalyst is known (US Patent Number 5,021,382), the use of small amounts of a polyene, such as a diene, is not known. conjugated or unconjugated, a triene, naphthenics (e.g., cyclopentadiene) or other hydrocarbon crosslinking compounds having two or more carbon-to-carbon double bonds or are deformed in the ring with at least one additional double bond for increase or improve the long chain branching of a polyolefin during polymerization. Surprisingly, it has been found in the present invention that polyethylene polymers having long chain branching can be polymerized in a reaction zone containing a metallocene polymerization catalyst in the presence of a hydrocarbon crosslinking compound. In addition, the polyethylene product has improved processability and improved extrudability, toughness, strength and resistance to environmental stress cracking.

COMPENDIUM OF THE INVENTION According to the invention, there is provided a process for producing a homopolymer, copolymer or ethylene terpolymer having long chain branching comprising providing ethylene and optionally, at least one alpha-olefin having from 3 to 18 carbon atoms in a reaction zone containing a metallocene polymerization catalyst, under polymerization conditions in the presence of a hydrocarbon crosslinking compound, in an amount sufficient to provide a polyethylene polymer having chain entanglement. In one embodiment of the invention, there is provided a process for producing a polyethylene having long chain branching comprising contacting the ethylene and optionally at least one alpha-olefin of 3 to 8 carbon atoms in an area of reaction, under polymerization conditions in the presence of a hydrocarbon crosslinking compound in an amount sufficient to provide chain entanglement and a metallocene catalyst comprising a (i) a catalyst precursor having Formula I where: M is a transition metal, preferably Zr or Hf; L is a coordinating group linked with -'- 'substituted or unsubstituted, coordinated with M, preferably a cyclopentadienyl coordinating group; Q may be the same or different and is independently selected from the group consisting of -0-, -NR-, -CR2"and -S-; Y is either C or S; Z is selected from the group consisting of -OR, -NR2 ~, CR3-, -SR, -SIR3, -PR2 and -H, with the proviso that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR2, -SR, - SiR3, -PR and -H.n is 1 or 2, A is a univalent anionic group when n is 2 or A is a divaler anionic group, when n is 1, and R can be the same or different and is independently a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus, wherein one or more of the R groups can be attached to the substituent L, preferably R is a hydrocarbon group containing from 1 to 20 carbon atoms, preferably, an alkyl, cycloalkyl or an aryl group, or Formula II: where: M is a transition metal, preferably Zr or Hf; L is a coordinating group linked with 1, substituted or unsubstituted, coordinated with M, preferably, a cyclopentadienyl coordinating group; Q may be the same or different and is independently selected from the group consisting of -O-, -NR-, -CR2- and -S-; And it is either C or S; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SIR3, -PR2 and -H, with the proviso that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR, -SR, -SÍR3, -PR and -H; n is 1 or 2; A is a univalent anionic group when n is 2 and a is a divalent anionic group when n is 1; R may be the same or different and is independently a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus, wherein one or more of the R groups may be attached to the substituent L, preferably R, is a hydrocarbon group which contains from 1 to 20 carbon atoms, more preferably, an alkyl, cycloalkyl or an aryl group; T is a connecting bridge group, which is selected from the group consisting of an alkylene or arylene group containing from 1 to 10 carbon atoms optionally substituted with carbon or heteroatoms, germanium, silicone and alkylphosphine; and m is 1 to 7, preferably 2 to 6, most preferably 2 or 3; and (ii) a co-catalyst. Polymers are also provided, particularly polymers comprising ethylene, a hydrocarbon linking compound and optionally an alpha-olefin of 3 to 8 carbon atoms (e.g., and hexene-1 or butene-1) produced by the process of the invention.

DETAILED DESCRIPTION OF THE INVENTION In the long chain branching, the polymer has branching of sufficient length for chain entanglement, i.e., the length of a re-issuance is long enough, or contains enough carbon atoms to entangle with other polymer molecules. In general, the long chain branching involves a chain length of at least about 6 carbon atoms, usually 10 or more carbon atoms. The long chain branch can be as long as about the same length as the length of the basic structure of the polymer. The process of the invention is particularly suitable for preparing terpolymers of an ethylene-hexene-1-low-density hydrocarbon interlacing compound, terpolymers of low-density ethylene-butene-1-hydrocarbon interlacing compounds, and copolymers of a compound ethylene-low density hydrocarbon interlayer using a metallocene catalyst. The polymers prepared by the process of the invention have properties similar to a high pressure low density ethylene homopolymer, and copolymers of propylene and alpha olefin (of 3 to 18 carbon atoms).

Catalyst The practice of this invention is not limited to any specific class of the metallocene catalyst. Any metallocene catalyst useful for carrying out the olefin polymerization reactions is suitable for use in the practice of this invention. Metallocene catalysts that have been employed in slurry, solution, bulk, and gas phase polymerizations can be used in this invention. Generally, these metallocene catalysts will include a metal component and a co-catalyst. The metallocene catalyst can be introduced into the reaction zone in a solid support, in soluble form as a liquid, such as a solution or dispersion, spray-dried in the form of a prepolymer or formed in situ in the reaction zone. Particularly preferred among these is a metallocene catalyst that is spray dried or in soluble form. When the metal component is supported, typical supports may include, for example, silica, carbon black, polyethylene, polycarbonate crosslinked porous polyethyleneporous cross-linked polypropylene, alumina, thoria, zirconia or nagnesium halide (e.g., magnesium dichloride) as well as other well-known support materials and mixtures thereof. A supported metallocene catalyst composition, ie, a precursor of the catalyst and the activating co-catalyst, is impregnated in or deposited on the surface of the inert support substrate, such that the catalyst composition is between 1 one hundred and ninety percent by weight of the total weight of the composition of the catalyst and support. One type of precursor of the metallocene polymerization catalyst that can be used according to the invention are the metal coordination complexes corresponding to the formula: (III) '/ \ Cp Y M (For wherein: M is a metal of Group IIIB to VIII of the Periodic Table of the elements; Cp is a cyclopentadienyl or substituted cyclopentadienyl group bonded to M in a? 5-linked mode; Z is a residue comprising boron, or a member of Group IVB of the Periodic Table of Elements and optionally sulfur or oxygen, having the residue up to non-hydrogen atoms and optionally Cp and Z together form a fused ring system; X 'is an anionic coordinating group or a neutral Lewis base coordinating group having up to 30 non-hydrogen atoms; a is 0, 1, 2, 3 or 4, depending on the valence of M; and Y 'is an anionic or non-anionic coordinating group linked to Z and M and is nitrogen, phosphorus, oxygen or sulfur having up to 20 non-hydrogen atoms and optionally Y and Z together form a fused ring system. These metal coordination complexes are well known to those skilled in the art and are disclosed, for example, in Patents North American Numbers 5,026,798 and 5,055,438 and in the Application Europera published Number 0 416 815 A2. Illustrative, but not limiting examples of the compounds represented by the above formula are: Cp X M dimethyl-cyclopentat-butyl-chloride titanium silyl dienyl amido Methylphenoxyphenyl Phenylamide Methyl Zirconium Nysilyl diphenyl-indenyl cyclohexyl-hafnium silyl amido tetramethylethylene oxo ethylene tetramethylcyclopentadienyl diphenyl-methylene Typical organometallic co-catalysts other than aluminoxanes which are suitable for the purposes of the present invention are any of the compounds of the general formula: M3M vX2cR3b. (IV) where M3 is a metal of Groups IA, IIA and IIIA of the Periodic Table of Elements, M4 is a metal of Group IA of the Periodic Table of Elements; v is a number from 0 to 1; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b-c is, at least 1. Compounds having only one Group IA, IIA or IIIA metal that are suitable for the practice of the invention include those compounds having the formula: M3R3k (V) wherein: M3 is a metal of Group IA, IIA or IIIA, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium; k is equal to l, 2 or 3, depending on the valence of M3 whose valence in turn normally depends on the specific group (ie, IA, IIA or IIIA) to which M3 belongs; and Each R3 can be any monovalent hydrocarbon radical. Examples of the appropriate R3 groups include any of the R3 groups mentioned above in relation to the formula (V) The organometallic compounds of Groups IA, IIA and IIIA, such as methyl and butyl lithium, dihexylzinc, butylmagnesium, diethylcadmium, benzylpotasium, diethylzinc, tri-n-butylaluminium, diisobutyl ethylborobate, are entirely suitable for the purposes of the present invention. diethyl-cadmium, di-n-butylzinc and tri-n-amylboron and in particular, aluminum alkyls, such as trihexylaluminum, triethylaluminum, trimethylaluminum and triisobutylaluminum. In addition, the mono-organohalides and hydrides of the Group IIA metals and the mono- and di-organohalides and hydrides of the Group IIIA metals conforming to the general formula (VI) are also suitable. Specific examples of these compounds are diisobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylberyl chloride, ethylcalcium bromide, diisobutylaluminium hydride, methylcadmium hydride, diethylborohydride, hexylberylium hydride, dipropylborohydride, octylmagnesium hydride. , butylzinc hydride, dichloroborohydride, dibromoaluminum hydride and bromocadmium hydride. These organometallic co-catalysts compounds are well known to those skilled in the art and a more complete discussion of these compounds can be found in US Patent Numbers 3, 221,002 and 5,093,415. In another embodiment of the present invention, polyethylenes are produced using the catalytically active reaction product of one or more metallocenes with aluminoxane, which is introduced into the gas phase fluidized bed reactor. Metallocenes are organometallic compounds which are cyclopentadienyl derivatives of a Group IVB, VB, VIB or VIII metal of the Periodic Table and which includes mono-, di- and tri-cyclopentadienyls and their transition metal derivatives. Metallocene complexes of a Group IVB and VB metal, such as titanium, zirconium, hafnium and vanadium, are particularly desirable. Aluminoxanes are well known in the art and comprise linear and / or cyclic oligomeric alkyl aluminoxanes represented by the formula: R "- (Al-O).-AIR" (VI) I R " for oligomeric linear aluminoxanes; Y - [Al-O] - (VIi; IR "for oligomeric cyclic aluminoxanes, wherein s is from 1 to 40, preferably from 10 to 20, £ is from 3 to 40, preferably from 3 to 20, and R" is an alkyl group of 1 to 12 carbon atoms, preferably of a methyl radical and an aryl radical, such as a substituted or unsubstituted phenyl or naphthyl radical.Usually, in the preparation of the aluminoxanes starting from, for example, aluminum trimethyl and water, a mixture of linear and cyclic compounds is obtained.Al aluminoxanes can be prepared in a variety of ways.For example, aluminum alkyl can be treated with water in the form of a Alternatively, the aluminum alkyl, such as aluminum trimethyl, can be contacted with a hydrated salt, for example, ferrous sulfate hydrate, The latter method comprises treating a dilute solution of aluminum trimethyl, for example, in toluene with a suspension of sulfate heptahydrate It is also possible to form methylaluminoxanes by the reaction of tetraalkyldiluminoxane containing 2 carbon atoms or higher alkyl groups with trimethylaluminium, using an amount of trimethyumuminium which is less than a stoichiometric excess. The synthesis of methylaluminoxanes can also be achieved by reacting a trialkylaluminum compound or a tetraalkyldialuminoxane containing alkyl groups of two higher carbon atoms with water to form a polyalkyl aluminoxane which is then reacted with trimethylaluminum. In addition, the methylaluminoxanes which are also known as modified aluminoxanes can be synthesized by the reaction of a polyalkyl aluminoxane containing alkyl groups of 2 carbon atoms or higher with trimethylaluminum and then with water, as disclosed for example in the U.S. Patent Number 5,041,584. Another metallocene useful in the process of the invention can be represented by the general formula: (C5Rx) and R'z (C5Rm) MQ 'n-y-1 (VIII) wherein: M is a metal of Groups IIIB to VIII of the Periodic Table of the Elements; (C5RX) and (C5Rm) are the same or different cyclopentadienyl groups or substituted cyclopentadienyl groups linked to M; R is the same or different and is hydrogen or a hydrocarbyl radical, such as an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing 1 to 20 carbon atoms or two carbon atoms are joined together to form a ring of 4 to 6 carbon atoms; R 'is a unsubstituted or unsubstituted alkylene radical of 1 to 4 carbon atoms, a dialkyl or diaryl germanium or silicon or an alkyl or aryl phosphine or amine radical that connects two rings (C5RX) and (C5Rm); Q is a hydrocarbyl radical, such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms, the hydrocarboxy radical having from 1 to 20 carbon atoms, halogen, hydrogen, R "C02- and R" 2N wherein R "is a hydrocarbyl group containing 1 to about 20 carbon atoms and may be the same or different from one another, z is 0 or 1, Y is 0, 1 or 2; z is 0 when y_ is 0; n is 0, 1, 2, 3 or 4 depending on the valence state of M, and n-y_ is> 1. Illustrative, but not limiting examples of the metallocenes represented by the formula above, are the dialkyl metallocenes, such as bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, dimethyl and bis (cyclopentadienyl) diphenyl. ) hafnium, di-neopentyl of bis (cyclopentadienyl) titanium, di-neopentyl of bis (cyclopene) ntadienyl) zirconium, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) vanadium dimethyl; the monoalkyl metallocenes, such as bis (cyclopentadienyl) titanium metal chloride, bis (cyclopentadienyl) titanium ethyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, ethyl chloride of bis (cyclopentadienyl) zirconium, phenyl chloride of bis (cyclopentadienyl) zirconium, methyl bromide of bis (cyclopentadienyl) titanium; trialkyl metallocenes, such as cyclopentadienyltitanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienylzirconium trineopentyl, cyclopentadienylzirconium trimethyl, cyclopentadienylhafnium triphenyl, cyclopentadienylhafnium trineopentyl, and cyclopentadienylhafnium trimethyl; monocyclopentadienyl titanocenes, such as pentamethylcyclopentadienyltitanium trichloride, pentaethylcyclopentadienyltitanium trichloride; diphenyl of bis (pentamethylcyclopentadienyl) titanium, the carbene represented by the formula bis (cyclopentadienyl) titanium = CH2 and derivatives of this reagent; substituted bis (cyclopentadienyl) titanium (IV) compounds, such as: diphenyl or bis (indenyl) titanium dichloride, diphenyl or bis (methylcyclopentadienyl) titanium dihalides; dialkyl, trialkyl, tetraalkyl and penta-alkyl compounds of cyclopentadienyltitanium, such as diphenyl or bis (1,2-dimethylcyclopentadienyl) titanium dichloride, diphenyl or bis (1,2-diethylcyclopentadienyl) titanium dichloride, silicon, phosphine, amine or cyclopentadienyl complexes connected with carbon, such as diphenyl or dimethylsilyldicyclopentadienyltitanium dichloride, methylphosphine dichloride dicyclopentadienyltitanium, diphenyl or methylenedicyclopentadienyltitanium dichloride and other dihalide complexes and the like; as well as connected metallocene compounds such as isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (flurenyl) zirconium dichloride, diisopropylmethylene dichloride (cyclopentadienyl) (fluorenyl) zirconium, diisobutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diterbutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene dichloride (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene dichloride (cyclopentadienyl) (fluorenyl) hafnium, diisopropylmethylene dichloride (cyclopentadienyl) (fluorenyl) hafnium, diisobutylmethylene dichloride (cyclopentadienyl) (fluorenyl) hafnium, diterbutylmethylene dichloride (cyclopentadienyl) (fluorenil) hafnium, cyclo dichloride lohexylidene (cyclopentadienyl) (fluorenyl) afnio, diisopropylmethylene dichloride (2,5-dimethylcyclopentadienyl (fluorenyl) hafnium, isopropyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisopropylmethylene dichloride ( cyclopentadienyl) (fluorenyl) titanium, diisobutylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diterbutylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisopropylmethylene dichloride (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium, bis (1-indenyl) zirconium (IV) dichloride of racemic ethylene, bis (4,5,6,7-tetrahydro-l-indenyl) zirconium (IV) dichloride of racemic ethylene), dichloride of racemic dimethylsilyl bis (1-indenyl) zirconium (IV), bis (4,6,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride of racemic dimethylsilyl, bis (1-indenyl) zirconium dichloride ( IV) of 1, 1, 2, racemic 2-tetramethylsilanylene, bis (4,5,6,7-tetrahydro-l-indenyl) zirconium (IV) dichloride of racemic 1,1,2,2-tetramethylsilanylene dichloride, ethylidene dichloride ( l-indenyl tetramethylcyclopentadienyl) zirconium, bis (2-methyl-4-t-butyl-l-cyclopentadienyl) zirconium (IV) dichloride, racemic dimethylsilyl, bis (1-indenyl) hafnium dichloride (IV) of racemic ethylene, bis (4, 5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride of racemic ethylene, bis (1-indenyl) hafnium (IV) dichloride of racemic dimethylsilyl, dichloride of bis (4,5,6,7-tetrahydro-l-indenyl) hafnium (IV) of racemic dimethylsilyl, bis (1-indenyl) hafnium (IV) dichloride of 1, 1, 2, 2-tetramethylsilanylene, racemic, dichloride of bis (4, 5, 6, 7-tetrahydro-l-indenyl) hafnium (IV) of 1, 1, 2, 2-tetramethylsilanylene, racemic, ethylidene dichloride (l-indenyl-2,3,4,5-tetramethyl) -l-cyclopentadienyl) hafnium (IV), bis (1-indenyl) titanium (IV) dichloride of racemic ethylene, bis (4, 5, 6, 7-tetrahydro-l-indenyl) titanium (IV) ethylene dichloride racemic, bis (1-indenyl) titanium (IV) dichloride of racemic dimethylsilyl, bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV) dichloride of racemic dimethylsilyl, bis (1-) dichloride indenyl) titanium (IV) of 1, 1, 2, 2-tetramethylsilanylene racemic, bis (4, 5, 6,7-tetrahydro-l-indenyl dichloride ) racemic 1,1,2,2-tetramethylsilanylene titanium (IV) and ethylene dichloride (1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) titanium (IV). The reaction products of the metallocene and aluminoxane which are generally solid materials when produced in aliphatic solvent and solutions when they are produced in aromatic solvents can be recovered by any well known technique. For example, the solid material can be recovered from the liquid by vacuum filtration or decantation. The oils can be recovered by decanting and when dried they become vitreous solids. The recovered material is then dried under a stream of pure dry nitrogen, dried under vacuum or by any other convenient manner. The recovered solid is the catalytically active material. The amount of aluminoxane and metallocene employed with utility in the preparation of the catalytically active material, whether the active material is formed in situ as it is being introduced into the gas phase reactor or is formed in advance and introduced, such and as it is in liquid form, it can vary across a large scale. The molar ratio of aluminum atoms contained in the aluminoxane to metal atoms contained in the metallocene is, in general, within the range of about 2: 1 to about 100,000: 1, preferably within the scale of about 10: 1 to about 10,000: 1 and especially preferably within the range of about 50: 1 to about 2,000: 1. A metallocene is typically converted to an active catalyst with an ionization agent (also known as a catalyst activator), such as the aluminoxanes discussed above. This ionization agent reacts with the neutral metallocene to form a cationic metallocene which functions as the active catalyst. The ionization agent can be a cocatalyst compound, such as aluminoxane, or it can be an ionization ion complex that forms an anion that is not chemically reactive with the cationic metallocene. The anion is not coordinated or comfortably coordinated with the cationic metallocene. The use of these ionization agents containing non-reactive anions is disclosed, for example, in European Patent Application Publication Number 0 426 637, 0 426 638 and 0 427 697. Methods for generating cationic metallocenes are also disclose in the following publications: European Patent Application Publication Number 0 277 003 and 0 277 004; "Ethylene Polymerization by a Cationic Dicyclopentadienylzirconium (IV) Alkyl Complex", R.F. Jordán, C.S. Bajgur, R. Willett, B. Scott, J. Am. Chem. Soc., P. 7410-7411, Volume 108 (1986); "Synthesis and Insertion Reactions of Cationic Alkylbis (cyclopentadienyl) titanium Complexes", M. Bochmann, L.M. Wilson, J. Chem. Soc. Commun., Pages 1610-1611 (1986); "Insertion Reactions of Nitriles in Cationic Alkylbis (cyclopentadienyl) titanium Complexes ", M. Bochmann, L. Wilson, Organometallics, pages 1147-1154, volume 7 (1987); and "Multiple Metal-Carbon Bonds", R.R. Schrock, P.P. Sharp, J. Am. Chem. Soc. Pages 2389-2399, Volume 100 (1978). The ionization ionic agent is typically mixed with an equimolar amount of the neutral derivative of the metallocene producing the following reaction: (C5Rx) and R'z (C5Rm) MR "2 + [C] [A] - > [(C5Rx) and R * z (C5Rm) MR"] + [A] - + R "[C] wherein: [C] is a cation of carbonium, oxonium or sulfonium [A] is an anion that is not coordinated or only comfortably coordinated with the cationic metallocene and is not chemically reactive with the cationic metallocene. R 'and R "are the same or different and is hydrogen or a hydrocarbyl radical, such as an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a ring of 4 to 6 carbon atoms, M is a metal of Groups IIIB to VIII of the Periodic Table of the Elements; (c5 ^?) Y (c5Rm) are the same or different and are identical or different cyclopentadienyl groups or substituted cyclopentadienyl groups bonded to M; R 'is a substituted or unsubstituted alkylene radical of 1 to 4 carbon atoms, a dialkyl or aryl germanium or silico or an alkyl or aryl phosphine or an amine radical that connects two rings of (C5Rx) and (C5Rm); z is 0 or 1, y_ is 0, 1 or 2, and z is 0 when y_ is 0; Ionic ionization compounds containing a carbon, oxonium or sulfonium cation are applicable. Triphenylmethyltetrakis (pentafluorophenyl) borate is preferred. A catalyst system that does not require an aluminoxane includes metallocene complexes with one or more substituted dinegative coordinator groups for the non-negative cyclopentadienyl coordinating groups. The use of these compounds is disclosed in commonly assigned US Patent Application Serial Number 814,809, filed on December 31, 1991 and US Patent Application Serial No. 814,810, filed on December 31, 1991. The Examples of these polyolefin catalysts include: [C5 (CH3) 5] [C2B9H1; L] ZrCH3 and [[C5 (CH3) 5] ^ BgHn] Zr] 2-m-CH2 As discussed, the present invention is advantageous when two or more metallocene compounds are used. U.S. Patent No. 4,530,914 discloses the use of mixtures of at least two different metallocene compounds to control the molecular weight distribution. The catalysts of transition metal compound of mono- or bis-cyclopentadienyl being homogeneous produce polyolefins with limited molecular weight distribution and limited composition distribution. Changes in the substituents of the coordinating group or the metal component of the mono- or bis-cyclopentadienyl transition metal compound are known to affect the propagation of polymerization and the constants of the termination rate which in turn affect the molecular weight and the distribution of comonomer and the resulting polyolefin product. The proper selection of a mixture of a different mono- or bis-cyclopentadienyl transition metal compound allows control of the molecular weight distribution and distribution of the composition directly in the polymerization process without requiring intense energy mixing techniques after the polymerization. An especially preferred catalyst of the invention is generated by reacting a catalyst recursor of either Formula I or Formula II as signaled below with a co-catalyst, such as MAO or MMAO. - 2d Formula I wherein: M is a transition metal, preferably Zr or Hf; L is a coordinating group linked with substituted or unsubstituted coordinated with M, preferably a coordinating group of substituted cyclopentadienyl; Q may be the same or different and is independently selected from the group consisting of -O-, -NR-, -CR2- and -S-, preferably oxygen; And it is either C or S, preferably carbon; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SIR3, -PR2 and -H, with the proviso that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR2, -SR, -SIR3, ~ PR2 and -H, preferably Z is selected from the group consisting of -OR, -CR3 and -NR2; n is 1 or 2; A is a univalent anionic group when n is 2 or A is a divalent anionic group when n is 1, preferably W is a carbamate, carboxylate or other heteroalkyl residue described by a combination of X, Y and Z, and R can be same or different and is independently a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus wherein one or more of the groups of R can be attached to the substituent L, preferably R is a hydrocarbon group containing 1 to 20 carbon atoms and more preferably, an alkyl, cycloalkyl or an aryl group and one or more can be attached to the substituent L.

Formula II where: M is a transition metal, preferably Zr or Hf; L is a coordinating group linked with substituted or unsubstituted coordinated to M, preferably a coordinating group of substituted cyclopentadienyl; Q may be the same or different and is independently selected from the group consisting of -O-, -NR-, -CR2- and -S-, preferably oxygen; And it is either C or S, preferably carbon; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SIR3, -PR2 and -H, with the proviso that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR2, -SR, -SIR3, -PR2 and -H, preferably Z is selected from the group consisting of -OR, -CR3 and NRH2; n is 1 or 2; A is a univalent anionic group when n is 2 or A is a divalent anionic group when n is 1, preferably it is a carbamate, carboxylate or other heteroalyl residue described by the combination of Q, Y and Z; R may be the same or different and is independently a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus, wherein one or more of the R groups may be attached to the substituent L, preferably R is a hydrocarbon group containing from 1 to 20 carbon atoms, more preferably an alkyl, cycloalkyl or an aryl group and one or more can be attached to the substituent L; T is a bridge group that selectively connects the group consisting of an alkylene or arylene group containing from 1 to 10 carbon atoms, optionally substituted with one carbon or heteroatoms, germanium, silicone and alkylphosphine; and m is 1 to 7; preferably 2 to 6, particularly preferably 2 3. The support substituent formed by Q, Y and Z is a unidirected, polydentate coordinating group which exerts electronic effects due to its high polarizability, similar to the group Cp '. In the especially preferred embodiments of this invention, disubstituted carbamates, and the carboxylates they are used A particularly preferred embodiment of the invention is the indenyl zirconium tris (diethylcarbamate). The catalyst precursor of the present invention can be produced using any conventional process; the manufacturing method is not critical. In a preferred method for making such a catalyst, a source of the cyclopentadienyl type coordinating group is reacted with a metal compound of the formula M (NR2I) wherein M and R are as defined above to introduce the type coordinating group of cyclopentadienyl in the metal compound The resulting product is then dissolved in an inert solvent, such as toluene, and the heteroocumulene as in this case CO2, is contacted with the dissolved product to be inserted into one or more of the bonds M-NR2 to form as in this case, a carbamate These precursors are then reacted with an activator, such as aluminoxane to form the active catalyst Examples of other catalyst precursors include indenyl zirconium tris (pivalate) or tris ( p-toluate) of indenyl zirconium, tris (pivalate) of zirconium, tris (p-toluate) of indenyl zirconium, tris (benzoate) of indenyl zirconium, tris (pivalate) of (1-methylindenyl) zircon io, tris (ditylcarbamate) of (2-methylindenyl) zirconium, tris (pivalate) (methylcyclopentadienyl) zirconium, tris (pivalate) cyclopentadienyl, tris (benzoate) (pentamethylcyclopentadienyl) zirconium. As mentioned above, the catalyst can be supported, spray dried or in liquid form. In a particularly preferred embodiment, the catalyst is sprayed or used in liquid form as a thick solution or suspension. As mentioned above, these catalyst precursors are used together with activating co-catalysts to form catalyst compositions for the production of polyethylenes. The activation co-catalyst is capable of activating the metallocene catalyst. Preferably, the activating co-catalyst is one of the following: (a) poly (branched or cyclic) poly (hydrocarbylaluminum) oxide containing recurring units of the general formula - (A] (R *) 0) -, in where R * is hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms or an aryl radical, such as a substituted or unsubstituted phenyl or naphthyl group; (b) ionic salts of the general formula [A +] [BR ** 4 ~], wherein A + is a Lewis or Bronsted cationic acid capable of abstracting an alkyl, halogen or hydrogen from the metallocene catalysts, B is boron and R ** is a substituted aromatic hydrocarbon, de - preferably, a perfluorophenyl radical; and (c) boron alkyls of the general formula 3R ** 3, wherein R ** is as defined above. Preferably, the activating co-catalyst for use with the metallocenes of Formulas I and II is a cyclic branched oligomeric hydrocarbylaluminum (polycarbonate oxide). Particularly preferably, the activation co-catalyst is an aluminoxane, such as methylaluminoxane (MAO) or isobutyl-modified methylaluminoxane (MMAO). As stated above, aluminoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxanes, represented by the formula: and oligomeric cyclic alkyl aluminoxanes of the formula: '-Al-O- where JS is 1-40, preferably 10-20; p_ is 3-40, preferably 3-20; and R *** is an alkyl group containing from 1 to 12 carbon atoms, preferably, a methyl or isobutyl radical, such as a substituted or unsubstituted radical. The catalyst composition may optionally contain one or more non-metallocene catalysts. These non-metallocene catalysts include, for example, any of the Ziegler-Natta catalysts containing a metal of groups IV (B), v (B) or VI (B) of the Periodic Table. Suitable activators for Ziegler-Natta catalysts are well known in the art and can also be included in the catalyst composition.

Compound of Hydrocarbon Interlacing A hydrocarbon crosslinking compound is employed in the process to increase or improve the long chain branching and / or chain entanglement. The hydrocarbon crosslinking compound may have two or more carbon-to-carbon double bonds or be deformed ring and have at least one double bond to effect long chain branching and / or chain entanglement during polymerization. Suitable hydrocarbon interlacing compounds may include a polyene, such as a diene, conjugated or non-conjugated, a triene, naphthenic (e.g., cyclopentadiene, cyclohexene and cyclo-octene) and mixtures thereof. The hydrocarbon crosslinking compound is an aliphatic, cyclic or aliphatic and cyclic hydrocarbon of at least 6 or 7 carbon atoms and at least two non-conjugated carbon-to-carbon double bonds. When the hydrocarbon crosslinking compound contains more than two double bonds, it is preferred that these additional double bonds are not reactive because they are a stable ring structure or because they are sterically hindered. Each of the two unconjugated carbon-to-carbon double bonds is independently: 1) a double vinyl bond or 2) the single carbon to carbon double bond in a ring containing five or less carbon atoms. Both of the two unconjugated carbon-to-carbon double bonds of the hydrocarbon crosslinking compound are Ziegler-Natta reagents; that is, both unconjugated carbon-to-carbon double bonds react with and are inserted into the growing polyolefin chains in the presence of the catalyst composition during the polymerization. In addition, the two unconjugated carbon-to-carbon double bonds of the hydrocarbon crosslinking compound have essentially equal Ziegler-Natta reactivity, ie, an essentially equal tendency to insert into a growing polyolefin chain, in the presence of the low catalyst composition. polymerization conditions. The requirement of the present invention that two carbon-to-carbon double bonds and the hydrocarbon crosslinking compound be reactive or exhibit an equal or essentially equal tendency to be inserted into a growing polymer chain is neither necessary nor desired nor is it know in processes in the art where compounds, such as dienes are used as comonomers. Of course, in the present invention, it has been found that the reactivity of a compound such as a diene towards copolymerization can vary widely. For example, diene ethylidene norbornene (ENB), used extensively in the EPDM rubber preparation, has a highly reactive deformed double ring bond and a non-reactive double bond. Butadiene (BD) and divinylbenzene (DVB) also exhibit behaviors of reactivity similar to ENB. In contrast, it may be seen that the structure presented below, the hydrocarbon crosslinking compounds of the present invention, such as norbornadiene (NBD) and 1,7-- octadiene (OCTN) have essentially reactive double bonds in an identical manner, while vinylnorbornene (VNB) has two double bonds of different reactivity.

ENB BD DVB NBD VNB OCTDN The hydrocarbon crosslinking compound of the invention, for example, may be a non-conjugated linear diene containing only two vinyl carbon-to-carbon double bonds, both of which are reactive to Ziegler-Natta. Alternatively, the hydrocarbon crosslinking compound of the invention may contain in addition to the two reactive non-conjugated carbon-to-carbon double bonds, one or more additional double bonds that are generally not reactive in the present process, i.e., double bonds of a -C = C-internal aromatic or cis / trans. One or more of one of the hydrocarbon crosslinking compounds can be used in the process. Examples of useful hydrocarbon crosslinking compounds include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, norbornadiene (NBD), 1,6-octadiene, 1,7-octadiene. (OCTDN), 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, vinylnorbornene, such as 5-vinyl-2-norbornene (VNB), 5- (2-propenyl) -2-norbornene, dicyclopentadiene , trivinylbenzene, 1, 4, 4a, 5, 8, 8a-hexahydro-1,4,4,8-dimethanonaphthalene; branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene; single ring acyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene, 1,5-cyclo-octanediene and 1,5-cyclododecadiene; and fused alicyclic and ring-linked multiple ring dienes, such as bicyclopentadiene, bicyclo- (2, 2, 1) -hepta-2, 5-diene, alkenyl norbornenes, alkylidene, cycloalkenyl and cycloalkydiene, such as 5-methylene- 2-norbornene, 5-vinyl-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene and norbornadiene. Preferably, the hydrocarbon crosslinking compound is selected from 1,6-octadiene, 1,11-dodecadiene, 1,9-decadiene, 1,7-octadiene, norbornadiene, vinylnorbornene, such as 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, dicyclopentadiene and mixtures thereof. Particularly preferably, the hydrocarbon crosslinking compound is norbornadiene (NBD), 1,7-octadiene, vinylnorbornene or mixtures thereof. It is preferred that when a diene is used as the hydrocarbon crosslinking compound it is not also used as a comonomer in the polymerization. The amount of the hydrocarbon crosslinking compound used in the gas phase process preferably ranges from about 0.001 percent to about 5 weight percent based on the total monomer feed to the process, ie, the total ethylene and alpha -olephine optional used. Preferably from 0.05 percent to about 4 percent by weight of the total monomer feed is the hydrocarbon crosslinking compound. Particularly preferably from about 0.1 percent to about 3.5 percent by weight of the total monomer feed is the hydrocarbon crosslinking compound. In slurry polymerization processes, the amount of the hydrocarbon crosslinking compound can be employed at a somewhat higher concentration, for example, in an amount ranging from about 0.001 percent percent to about 10 percent by weight based on the total monomer feed, preferably from about 0.1 percent to about 7.5 percent and especially preferably from about 0.5 percent to about 6 percent by weight. In an especially preferred embodiment, the unreacted hydrocarbon crosslinking compound is removed from the polymer product by purging the system with an inert gas (e.g., nitrogen) or purging with an inert gas and steam or oxygen or heating under vacuum using techniques well known to those skilled in the art.

Polymerization Polymerization using the catalyst and the hydrocarbon crosslinking compound described herein, may be carried out in the gas phase in a fluidized or stirred bed reactor or in a slurry phase reactor using the process equipment well known in the art. Preferably, polymerization is carried out in the gas phase as disclosed in U.S. Patent Nos. 4,588,790; 4,988,783; 4,994,534; 5,317,036; 5,453,471 and 5,462,999. Particularly preferably, the polymerization of the invention is carried out in a condensation mode as disclosed in US Pat. Nos. 4,528,790 and / or 5,462,999. The ethylene, the higher alpha-olefins, optionally other monomers and the hydrocarbon crosslinking compound, are contacted with an effective amount of the metallocene catalyst at a temperature and pressure sufficient to initiate the polymerization. The process can be carried out in a single reactor or in two or more multiple reactors in series (or in stages). The process is carried out essentially in the absence of catalyst contaminants, such as moisture, oxygen, carbon dioxide and acetylene, since only small amounts (ie, <2) parts per million of these materials have been found to they detrimentally affect polymerization. The polymerization of the present invention can further be carried out in the presence of an inert particle material, as described in US Pat. No. 4,994,534. When hydrogen is used as the chain transfer agent in the process, it is used in amounts ranging from about 0.001 to about 10 moles of hydrogen per mole of the total monomer feed. Also, as desired for system temperature control, the gas stream, any inert gas with respect to the catalyst composition and the reagents may also be present. Organometallic compounds can be used as purifying agents for the components in order to increase the activity of the catalyst. Examples of these compounds are metal alkyls, preferably aluminum alkyls, more preferably triisobutylaluminum. The use of these depuration agents is well known in the art.

Produced Polymers The polyolefins that can be produced according to the present invention are the ethylene polymers, the hydrocarbon crosslinking compound and optionally the higher alpha olefins containing from 3 to about 12 carbon atoms, such as propylene, 1-butene , 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene, with densities ranging from about 0.86 to about 0.96 gram per cubic centimeter, preferably from about 0.89 to about 0.94 gram per cubic centimeter. Of these, the ethylene-hydrocarbon-hexene-1-ethylene crosslinking compound-hydrocarbon-butene-1 interlacing compound and ethylene-hydrocarbon-propylene crosslinking compound are preferred. Optionally, the ethylene-hydrocarbon-propylene entanglement composition may further contain a diene, such as ENB and an inert particulate material, such as carbon black and / or silica. When produced as described in the invention, the processing capacity of the polyolefin is appreciably improved by the presence of long chain branches whose branches approximate in length the basic structure of the polymer molecule. In addition to LCB, these essentially non-linear polymers can have short chain branches (SCB) that are produced from the added monomer, such as hexen-1 or buten-1. Particularly preferably, the final polymer is LDPE (density 0.91 to 0.93 gram per cubic centimeter) having at least 0.3 to 4 LCB per 1,000 units of CH2 and approaching in structure to a dendritic configuration. The polymers produced in this way can be stabilized by post reaction using conventionally obtainable stabilizers.. , such as Irgano? (R) 1035. The molecular weight of the polymers can be controlled by the use of a chain transfer agent such as hydrogen. These polymers have utility in films and molded plastic products among other uses. The ethylene-hydrocarbon interlacing compound and the ethylene-hydrocarbon-hexene interlacing compound produce transparent, crystalline, essentially gel-free films. All of the patents cited herein are incorporated by reference. The following examples further illustrate the intention. All parts and percentages are by weight unless otherwise specified.

EXAMPLES Glossary: The density in grams per cubic centimeter is determined in accordance with Method 1505 of the American Society for the Testing of Materials, based on method D-1928, procedure C of the American Society for the Testing of Materials, preparation of plates. A plate is produced if it is conditioned for one hour at 100 ° C to approximate the equilibrium crystallinity and then carried out in the measurement for density in a density gradient column.

MAO is a solution of methyl aluminoxane in toluene, approximately 1.8 molar in aluminum, which is obtained from Ethyl Corporation (Baton Rouge, LA). MMAO in isopentene is a solution of modified methyl aluminoxane containing isobutyl groups in isopentane obtained from Akzo Nobel (Chicago, Illinois). TMA is trimethylaluminum TEAL is triethylaluminum TIBA is triisobutylaluminum TNBAL is tri (n-butyl) aluminum MFR represents melt flow ratio, which is the ratio of the flow index to the melt index. It relates to the molecular weight distribution of the polymer. MI represents melt index that is reported as grams per 10 minutes determined according to method D-1238, condition E of the American Society for the Testing of Materials at 190 ° C. Fl represents a flow rate that is reported as grams per 10 minutes, which is determined according to method D-1238, condition F of the American Society for the Testing of Materials and is measured at 10 times the weight used in the text of the fusion index.

Procedures: SEC-Visco etria for Measuring Long Chain Branch Polyethylene chains with long chain branches show less spatially shaped spatial arrangements in a diluted solution than linear polyethylene chains of the same molar mass. Therefore, the former have lower limit viscosity numbers than the latter, due to their reduced hydrodynamic size. The theoretical relationships that allow the calculation of the long chain branching statistics of the ratio of the limit viscosity number of a branched polymer to that of its linear duplicate have been developed. See, for example, the article called "Determination of Long-Chain Branching Distributions of Polyethylenes" by Mirabella, F.M., Jr .; and Wild, L. in Polymer Characterization ,. Amer. Chem. Soc. Symp. Ser. 227, 190, page 23. In this way, by measuring the limit viscosity of the polyethylene containing long chain branches as a function of the molecular weight and comparing the results with the corresponding data measured for the same amount of a linear polyethylene, provides an estimate of the number of long chain branches in the branched polyethylene.

Determination of Molecular Weights, Molecular Weight Distribution and Long Chain Branch A Waters 150-C liquid chromatography apparatus equipped with gel permeation chromatography (GPC) columns for molecular weight measurements and a Viscotek 150R viscometer for viscosity measurements are those used. Gel permeation chromatography provides the molecular weight distributions of the polyethylene samples, while the viscometer together with the infrared GPC detector and the determined concentrations and viscosities. For size exclusion (SEC) chromatography, a 25-centimeter-long preliminary column of Polymer Labs, which has a nominal pore size of 50 angstrom units, is used, followed by a 25 cm long Shodex A-80 M column. / S (Showa) with a nominal pore size of 80 angstrom units, followed by a 25 cm long Shodex A-80 M / S (Showa) column with a nominal pore size of 80 angstrom units. Both columns are of a material similar to styrene-divinylbenzene. 1,2,4-Trichlorobenzene is used as the solvent and the chromatographic eluent. All measurements are carried out at a temperature of 140 + 0.5 ° C. A detailed discussion of the methodology of the SEC-Viscometry technique and the equations used to convert GPC and viscometry data into long-chain branching and corrected molecular weights is given in the article by Mirabella and Wild, which is referenced in the foregoing.

Differential Scan Colorimetry and Heat of Fusion A DSC thermogram is acquired by measuring the differential heat flux between the sample and the reference both placed in flanged aluminum trays using a temperature ramp that is increased using a controller.

DSC IA-2910 and an A21W data station.

Determination of Al, Zr and Si in Polyethylene The polyethylene samples are weighed in platinum crucibles, ignited, and then placed in a muffle furnace (580 ° C) until all the carbon has burned. After cooling, hydrochloric acid is added to the residue and heated gently to aid in the dissolution. The crucibles are cooled and the floric acid is added to ensure a total dissolution of the silicon. The samples are then transferred quantitatively and diluted to 15 milliliters with deionized water and analyzed using an Inductively Coupled Plasma (Atom 25 Scan, Thermo Jarrell Ash).

Analysis of the Distribution of the Composition of the Ethylene Copolymer by Fractionation of Elution of Temperature Elevation.

Fractional Elevation of Temperature Elution or TREF has been established as the main method to measure the distribution of the composition (or short chain branching) for ethylene / alpha-olefin copolymers. A solution of copolymer diluted in a solvent such as 1, 2, 4-trichlorobenzene, at 0.1 percent-0.5 percent by weight / volume, is loaded at high temperature into a packed column. The column is then allowed to cool to room temperature in a controlled manner so that the polymer crystallizes towards the package in the order of the increased branching (or decreased crystallinity) with the temperature decreased. The column is then heated in a controlled manner to more than 140 ° C with a constant solvent flow through the column. The fractions of the polymer as they elute have decreased branching (or increased crystallinity) with increasing temperature. A concentration detector is used to monitor the concentrations of the effluent. Profiling the polymer concentration as a function of the elution temperature yields the so-called TREF thermogram. Reference: Wild, L. and others, J. Polym. Sci. , Polym, Phys. Ed., 20, p. 441 (1982).

Branch by Carbon Nuclear Magnetic Resonance-13 A concentration of 8 percent by weight / volume is prepared by dissolving the polyolefin in orthodichlorobenzene (ODCB) in a Nuclear Magnetic Resonance tube. A closed capillary tube of deuterium oxide is inserted into the Nuclear Magnetic Resonance tube as an image frequency lock. The data is collected in Bruker AC 300 at 115 ° C using improved NOE conditions with a PW of 30 ° and a repetition time of 5 seconds. The number of carbon scans usually varies from 1,000 to 10,000 with the highest branching samples requiring shorter acquisitions. The area of each of the maxima is measured together with the area of the total aliphatic region. The areas of the carbons contributed by the comonomer are averaged and related with respect to the area of the basic structure to provide the mole fraction. This number is then converted to branching frequency.

Method for the Determination of Unsaturation in Polyethylene Through IR The band outside the CH plane of the unsaturated group is sensitive to the nature of the double bond substitution. Therefore, it is possible to distinguish between three different types of unsaturation: vinyl absorptions (910 cm-1), vinylidene (890 cm-1) and trans-vinylidene (965 cm-1); however, cis-vinylidene is not measurable due to the interference of CH2 vibrations at 720 cm-1. The degree of total unsaturation is determined by adding all three previously mentioned. The procedure uses the following equation for the branching frequency per 1,000 groups of CH2 (BF): BF = [A / te] * [14.0 / 2.54 x 10-3] where: A is the maximum height in units of absorbency, t is the thickness in millimeters, and is the extinction coefficient in liter / centimeters * mol. The values of the extinction coefficients were taken from the work of Anderson and Seyfreid (1). The bromination process (2) was used to eliminate the interference of the butyl branches. This involved the use of brominated films as references.

References: 1. J.A. Anderson and W.D. Seyfreid, Anal. Chem. 20, 998 (1948). 2. D.R. Rueda, F.J. Balta-Calleeja and A. Hidalgo, Spectrochim. Acta 30A, 1545 (1974).

Preparation of the Catalyst Catalyst BIEZr (Oipr) 3 1,2-Bis (indenyl) ethane (BIE) was dissolved in toluene containing an equimolar amount of tetrakis (isopropoxide) zirconium. An aliquot of this was added to MMAO in heptane in such a way that the ratio of Al / Zr of the resulting mixture was 1,000 (moles).

BIEZr Catalyst (Q? CNEt?) ^ 1, 2-Bis (indenyl) ethane (BIE) was reacted at 125 ° _ / 2 hours with an equimolar amount of tetrakis (diethylamide) zirconium and the resulting diethylamide was pumped. The residue was dissolved in toluene and gaseous carbon dioxide was added at 0 ° and atmospheric pressure (3C02 / Zr). An aliquot of this solution was added to MMAO in heptane in such a way that the Al / Zr ratio of the resulting mixture was 1,000 (moles).

Catalyst of indenylzirconium tris (diethyl carbamate) [? S-IndZr (Q? CNEt?) 3] The tetrakis (diethylamide) zirconium was reacted at atmospheric pressure of 120 ° _ / under a nitrogen atmosphere with 150 percent excess of indene for 2 hours while diethylamide was distilled (one mole of Et2NH / Zr was fired). This yielded quantitatively the tris (diethylamide) of zirconium of 5-indenyl. This was diluted to a 5 weight percent concentration solution with dry toluene and this was contacted with carbon dioxide (0 ° _ / atmospheric pressure). Approximately 3 moles of carbon dioxide were absorbed per mole of the zirconium compound. An aliquot of this was reacted with MMAO such that the final mixture had an Al / Zr of 1,000 (moles).

Catalyst BIEZr (OpCCfiHs) Bis (indenyl) ethane and tetrakis (diethyl) amide zirconium were reacted as above to produce the BIEZr (NEt2) 3. This was dissolved in toluene to form a diluted solution and three moles of benzoic acid / mol of BIEZr (NEt2 ) 3, also as a solution diluted to -78 ° _, slowly. The resulting solution of the tris (benzoate) was reacted with MMAO, Al / Zr of 1,000 (moles) to form the active catalyst.

Used Dienes OCTDN - 1, 7-octadiene VNB - 5-vinyl-l-norbornene NBD - norbornadiene Product Stability of Diene Terpolymers An apparatus was used to measure the melt index in order to test the post-reaction stability of the polymer product (s). The normal procedure is to heat the polymer of the instrument for 5 minutes before the extrusion of 1P or 10P. In order to test the melt stability, the polymer was preheated for 5 and 15 minutes before the 1P extrusion: Fusion index (1P) Preheat time 5 minutes 15 minutes 6.61 6.64 4.27 4.01 3.42 3.55 2.60 2.70 0.99 1.17 With the exception of the last test, MIs were all within the "noise level" of the data. The serious crosslinking-gelling must have decreased the MI considerably during the prolonged preheating.

Extractions This was a procedure similar to the D-2765-84 method of the American Society for Testing Materials. A small bag of a 120 mesh SS screen was made and a carefully weighed amount of the polymer was placed inside this bag. The exact weights of the empty and full bag were determined. This was now hung in a solution of 1,500 milliliters of xylene and 5 grams of BHT and extracted at reflux temperature (-135 ° _) for 4 hours. The bag was dried (110 ° _ / overnight in an air oven) and reweighed. For polymers that do not contain diene, the weight loss is 99.9 percent to 100.1 percent.

Polymerizations in Agitated Thickened Suspension Reactor (Tests A to N) These polymerizations were carried out in a 1.8 liter stirred reactor using the following procedure. After being baked at -100 ° _ under flowing N2, the reactor was cooled (under a flow of N2). One liter of hexanes, 100 milliliters of hexen-1 (distilled CaH2), a manifested amount of diene and 1.14 milliliters of TIBA (1.0 millimol of Al) were added and the reactor was closed. The temperature was adjusted to 85 ° _, the amount of hydrogen added (0-1,000 milliliters of STP) and the reactor was pressurized to 14.06 kilograms per square centimeter with ethylene (approximately 1.8 moles). Then, the catalyst solution was injected through a pressure syringe that initiated the polymerization reaction. The reaction time was usually 30 minutes even when using very active catalysts was only 10 minutes. The reaction was terminated by the injection of one milliliter of isopropanol at the reaction conditions. After cooling and discharging, 0.2 gram of Irganox-1035 in acetone was added as a stabilizer. The slurry of the polymer was dried in air and stored in polyethylene bags.

Polymerizations in a Mechanically Agitated Gas Phase Reactor (Test O to T) On the night before each reaction, a pre-bed of 1.36 kilogram capacity was loaded into the reactor and then purged under nitrogen pressure three times to 7.03 kilograms per square centimeter gauge. The jacket temperature was adjusted to retain the material at about 80 ° C during the night, while it was under a nitrogen flow purge of 1.36 to 1.82 kilograms per hour at the reactor pressure of 7.03 kilogram per square centimeter gauge. Prior to testing each morning, the reactor was pressurized once at 21.09 kilograms per square centimeter and then 50 milliliters of the co-catalyst solution was charged to further passivate the reactor. The reactor was then pressurized four times more at 7.03 kilograms per square centimeter gauge. The raw materials were charged to establish the initial gas phase concentrations of ethylene, hexen-1 and nitrogen; Gas phase concentrations were normally retained near these initial values throughout the batch. The solution or slurry of the catalyst was fed to the reactor for the first 2.5 hours continuously (from 0.3 to 0.5 millimol of Zr) using a solution of the aluminum alkyl co-catalyst as a carrier and the nitrogen as a dispersant. The monomers and hydrogen were continuously fed, as required to maintain the gas phase composition throughout the batch. A small vent stream was used to prevent buildup of the nitrogen that was added with the catalyst. The reactor was operated intermittently whereby the batch was terminated when the bed weight approached 11.35 - 13.62 kilograms. During the completion of the batch, the feeds were suspended and the reactor was rapidly discharged at atmospheric pressure. The reactor was then purged under pressure five times at 7.03 kilograms per square centimeter with dry nitrogen. The resin was then discharged and exposed to the atmosphere. A two-nozzle purge manifold was inserted into the resin in order to purge the hydrocarbons and deactivate the catalyst with nitrogen saturated with water overnight at room temperature. TABLE I Results of the NBD Terpolymerizations Hexeno-1-Ethylene Using the BIE-Zr (Oipr) 3 / MMAO Catalyst Operating Periods of the Polymer A B C Catalyst type BIEZr (Oipr) 3 > > Added Hydrogen (milliliters of STP) 0 150 450 Catalyst Quantity (millimoles) 0. 33 0. 65 0. 65 Diene (grams) 0 0. 81 0. 80 Polymer Performance (grams) 74.2 59.4 53.8 Activity (grams of PE / hour-millimol Zr-7.03 kilograms per square centimeter of C2 =) 225,000 183,000 165,000 Properties of Polymer BBF (butyl / 1, 000 CH2) 17.6 16.8 16.9 Hexen-1 (weight percentage) 9.9 9.5 9.5 SEC (Shape) Monomodal NA > Mn 31,900 PDI 1.9 Recovery (percentage MI 6.63 0.8 (MF) 0.43 MFR 19.0 95 TREF (Form) NA Limited Bimodal Wide LD (< 60_, percentage) - 15.3 16.3 HD (> 90_, percentage) - 1.1 16.6 Extr. (percentage of sol.) __ 100.1 100.2 Infrared (percentage by weight) of NA Trans. NA NA .004 Vinyl .72 = CH2 .029 DSC (second warm-up) Shape Pronounced F. Wide NA Melting temperature (°) 110.8 109.5 Crist. (percentage) 38.3 19.6 LCB (per 1,000 C)) 0 1.4 2.0 Intrinsic Viscosity 1.15 0.86 TABLE I (CONTINUED) Periods of Polymer Functionality D E F Catalyst Type > > > Added Hydrogen (milliliters of STP) 600 800 800 Quantity of Catalyst (millimoles) 0.55 0.63 0.49 Diene (grams) 1.25 1.29 1.77 Polymer yield (grams) 41.9 51.8 44.3 Activity (grams of PE / hour-millimole Zr-7.03 kilograms per square centimeter of C2 =) 152,700 82,200 90,400 Properties of Polymer BBF (butyl / 1, 000 CH2) 18.0 NA NA Hexen-1 (weight percentage) 10.1 SEC (Form) > > Monomodal Mn - 4,680 PDI 38.3 Recovery (percentage) 92.6 MI 0.39 1.79 0.57 MFR 140 77.2 176.5 TREF (Form) Bi-modal Biased Wide LD (< 60, percentage) 24.7 18.3 31.6 HD (> 90, percentage) 8.7 1.4 1.1 Extr. (percentage of sol.) 99.4 99.97 99.67 Infrared (percentage by weight) of NA Trans. .012 NA .004 Vinyl 1.50 - .050 = CH2 .031 - .020 DSC (second warm-up) Form F. Pronounced Broad Wide Melting temperature (°) 108.2 107.6 105.9 Crist. (percentage) 36.4 43.9 37.9 LCB (per 1,000 C) 4.7 4.6 11.8 Intrinsic Viscosity 0.77 0.72 0.69 TABLE II Results of the OCTDN-Hexen-1-Ethylene Terpolymerizations Using BIEZr Catalysts (OpCC ^ Hc,) 3 / MMAO Operating Period of Polymer G H Catalyst (19170-) 36-1 > Type of Catalyst BIEZr (02CCgH5) 3 > Catalyst Quantity (millimoles) 0.72 0.81 Diene (grams) 0 0.8 Polymer Performance (grams) 82.2 91.9 Activity (corrected for [Zr]) (grams of PE / hour-millimeters of Zr-7.03 kilograms per square centimeter of C2 113,800 112,000 Properties of Polymer BBF (butyl / 1, 000 CH2) 16.7 19.2 Hexen-1 (percentage by weight) 9.4 10.7 SEC (Form) Simple > Mn 28,400 28,500 PDI 2.1 2.0 Recovery (percentage) MI 6.61 4.27 MFR 19.9 25.4 TREF (Form) NA > LD (< 60_, percentage) HD (> 90_, percentage) JWN Extr. (percentage of sol.) (19457-113) 100 100 Infrared (percentage by weight) Trans. .01 NA Vinyl .077 = CH2 .015 DSC (second heating) Simple Simple Form F. Pronounced Slightly Wide Fusion Temperature (°) 111.6 109.8 Crist. (percentage) 38.8 41.9 LCB (Ramifications / 1, 000 C) 0 0.8 Intrinsic Viscosity 0.88 1.07 TABLE II (CONTINUED) Polymer Working Period I J Catalyst (19170-) 36-2 36-3 Catalyst Type > > Catalyst Quantity (millimoles) 0.67 0.69 Diene (grams) 1.5 3.0 Polymer Yield (grams) 81.6 69.8 Activity (corrected for [Zr]) (grams of PE / hour-millimeters of Zr-7.03 kilograms per square centimeter of C2 116,000 101,000 Properties of Polymer BBF (butyl / 1, 000 CH2) 17.7 15.2 Hexen-1 (weight percentage) 9.6 8.6 SEC (Form) > > Mn 29,400 29,800 PDI 2.0 2.1 Recovery (percentage) MI 3.42 2.60 MFR 28.0 31.3 TREF (Form) > > LD (< 60_, percentage) HD (> 90_, percentage) JWN Extr. (percentage of sol.) (19457-113) 100 100 Infrared (percentage by weight) Trans. > > Vinyl = CH2 DSC (second heating) Simple > Form F. Pronounced Fusion Temperature (°) 110.4 112.0 Crist. (percentage) 40.0 42.0 LCB (Ramifications / 1, 000 C) 0.7 1.0 Intrinsic Viscosity 1.11 1.11 TABLE III Results of the VNB-Hexen-1 and Ethylene Terpolymerizations Using BIEZr (0 CNEt?) 3 / MMAO Catalysts Polymer Working Period K ^ L & Catalyst type BIEZr (02CNEt2) 3 > 120 milliliters of H2 No. TIBA Catalyst Quantity (millimoles) 0.20 0.52 Diene (grams) 0 6.5 Polymer Performance (grams) 89.5 52.4 Activity (grams of PE / hour millimole of Zr-7.03 kilograms per square centimeter of C2 =) 447,000 104,800 Properties of Polymer BBF (butyl / 1, 000 CH2) 19.0 13.4 Hexen-1 (weight percentage) 10.6 7.4 SEC (Form) Bimodal Mono Mn 26,100 25,400 PDI 1.9 6.90 Recovery (percentage) MI 9.7 2.75 MFR 21.2 33.6 TREF (Shape) Mono NA LD (< 60, percentage) 15.8 HD (> 90, percentage) 2.1 JWN Extr. (percentage of sun.) Infrared (percentage by weight) Trans. .003 .026 Vinyl .068 1.36 = CH2 .015 .039 DSC (second warm up) Tail form Mono- Long V. wide Fusion Temperature (°) 111.0 100.7 Crist. (percentage) 52 23.5 LCB (per 1,000 C) 0 2.2 Intrinsic Viscosity 1.05 TABLE III (CONTINUED) Operating Period of Ma'b Na Polymer Type of Catalyst > > Catalyst Quantity (millimoles) 1.92 1.88 Diene (grams) 13.0 18.4 Polymer Performance (grams) 87.5 44.0 Activity (grams of PE / hour-millimole of Zr-703 kilograms per square centimeter of C2 =) 43,700 23,400 Properties of the Polymer BBF (of butyl / 1, 000 CH2) 13.5 11.0 Hexen-1 (weight percentage) 7.3 6.0 SEC (Form) Bimodal Bimodal Mn 20,000 19,000 PDI 11.2 9.33 Recovery (percentage) MI 0.32 0.47 MFR 59.7 59.5 TREF (Form) V. broad NA LD (< 60_, percentage) 40.3 HD (> 90_, percentage) 6.2 JWN Extr. (percentage of sun.) Infrared (percentage) Trans. .029 .037 Vinyl 2.05 2.19 = CH2 .065 .048 DSC (second heating) Large V. shape > Bimodal Fusion Temperature (°) 89.9 / 113.1 87.7 / 116.3 Crist. (percentage) 13.5 / 5.6 11.9 / 10.6 LCB (per 1,000 C) 0 3.0 3.6 Intrinsic Viscosity 1.07 1.02 to BHT stabilized products: b Positive tested sample for LCB by extensional viscometry TABLE IV Some Physical Properties Fudamentales of the Products of the Reactor of Phase of Gas Operating Period 0 Pc Qd NBD in Hexen-1 in PR-1 0.8 1.6 Feeding (percentage by weight) MI 2.96 4.04 2.71 MFR 30.0 36.8 30.4 Appearance of Material Rough Semi-Rough Extruded smooth Thickness Smooth TREF LD (percentage <60_) 14.7 12.2 11.8 HD (percentage> 90_) 10.7 14.2 11.3 Lw / Ln 4.26 3.79 3.04 Broad Bimodal Appearance > > SEC Mw / Mn 2.88 3.10 3.02 MN 24,200 22,600 23,800 Symmetric Appearance > > Recovery (percentage) k 96.2 97.4 97.4 Intrinsic Viscosity 1.20 1.22 1.25 LCB / 1,000 CH2 0.6 0.4 0.3 Infrared (percentage by weight of C = C) Trans. .024 .024 .029 Vinyl .014 .012 .014 = CH2 .038 .033 .049 Zr in Polymer (parts per million) 2.6 3.8 3.8 TABLE IV (CONTINUED) Operating Period R Sa T NBD in Hexen-1 in PR-1 3.2 6.4 12.8 Feeding (percentage by weight) MI 1.29 0.31 0.47 MFR 47.5 67.7 50.0 Appearance of Material Very Extruded Rough TREF LD (percentage <60_) 14.3 23.8 21.8 HD (percentage> 90_) 11.6 12.3 14.2 Lw / Ln 3.31 4.57 4.52 Appearance > V. Broad > SEC Mw / Mn 3.42 3.05 2.73 MN 20,000 20,500 21,000 Appearance > > > Recovery (percentage) b 94.9 93.6 87.2 Intrinsic Viscosity 1.18 1.02 0.87 LCB / 1,000 CH2 0.4 1.5 3.8 Infrared (percentage by weight of C = C) Trans. . 026 032. 030 Vinyl 012 024 031 = CH2. 039 047 047 Zr in Polymer (parts per million) 3.0 2.9 3.0 a Very low catalyst activity, unknown ratio, 95 + 2 percent recovery that is normal for a gel-free polymer. BBF - 13.4; 7.6 weight percent of hexene incorporated. BBFG - 12.7; 7.2 percent by weight of hexene incorporated.

TABLE V Summary of the Gas Phase Reactor Polymerization Data Operating Period O P Q NBD in Hexen-1 Feeding (percentage by weight) 0 0.8 1.6 Reaction Conditions Pressure (kilograms per square centimeter gauge) 25.36 > > Temperature (° C) 80 > > Relations (C6 / C2) .022-.029 .020-.03. 020-.025 Ethylene pressure (kilograms per square centimeter gauge) 14.86 > > Production Regime Max. (kilograms / hour) 1.63 2.04 1.54 Min. Shirt Temperature (° C) 68 67 70 Condensation Temperature Max. (° C) 44 44 40 (BWR Equ.) Catalyst Catalyst Type P-24-U > > (19170-95-) H Cat. Feed (millimoles) 350 449 481 Cat Feeding Time (hours) 2.0 2.5 2.5 Catalyst Carrier and Co-catalyst 15% MMAO / iC5 > > Diet of the Co-cat. (milliliters / hour) 150 - > > Ratio of Al / Zr (moles) 1,000 > • - > Feeding mode Pre-bed + 5 MI LLDPE Pre-bed passivation (TIBA mi.) 50 > > Product Weight (pre-bed weight) (kilograms) 12.26 10.76 11.21 TABLE V (CONTINUED) Period of Operation R S T NBD in Hexen-1 Feeding (percentage by weight) 3.2 6.4 12.8 Reaction Conditions Pressure (kilograms per square centimeter gauge) > > > Temperature (° C) > > > Relations (Cg / C) .025-.03 .026-.029 .023-.030 Ethylene pressure (kilograms per square centimeter gauge) > > > Production Regime Max. (kilograms / hour) 1.36 .68 1.50 Min Shirt Temperature (° C) 68 79 70 Condensation Temeprature Max. (° C) 44 45 45 (BWR Equ.) Catalyst Catalyst Type > > > (19170-95-) G G I Cat. (millimoles) 404 302 431 Cat Feeding Time (hours) 2.0 1.5 3.0 Catalyst Carrier and Co-catalyst > > > Diet of the Co-cat. (milliliters / hour) > > > Ratio of Al / Zr (moles) - > > - > Feeding Mode Pre-bed + R O Pre-bed passivation (my from TIBA) > > > Product Weight (pre-bed weight) (kilograms) 12.26 9.31 11.89 + 1.36 kilograms of the designated operating period.

Claims (10)

R E I V I N D I C AC I O N E S;

1. A process for producing a polyethylene homopolymer, copolymer or terpolymer having long chain branching comprising providing ethylene and optionally an alpha-olefin having from 3 to 18 carbon atoms, in a reaction zone containing a polymerization catalyst of metallocene under polymerization conditions in the presence of a hydrocarbon crosslinking compound in an amount sufficient to provide long chain chain or branching entanglement.

2. The process according to claim 1, wherein the hydrocarbon crosslinking compound is selected from the group consisting of a diene, a triene, a naphthenic compound and mixtures thereof; and wherein the catalyst comprises (i) a catalyst precursor selected from the group consisting of and mixtures thereof; wherein: M is Zr or Hf; L is a 1-linked, substituted or non-substituted coordinating group; Q may be the same z different and is independently selected from the group consisting of -O-, -NR-, -CR2- and -S-; And it is either C or S; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SIR3, -PR2 and -H, with the proviso that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR2, -SR, -? ÍR3, -PR2 and -H; n is 1 or 2; A is a univalent group when n is 2 or A is an anionic group divalent.te when n is 1; R may be the same or different and is independently a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus and one or more R groups may optionally be attached to the substituent L; T is a bridging group selected from the group consisting of an alkylene or arylene group containing from 1 to 10 carbon atoms, germanium, silicone and alkylphosphine; and m is 1 to 7; and (ii) a co-catalyst.

3. The process according to claim 2, wherein the hydrocarbon crosslinking compound is selected from the group consisting of 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,1-dodecadiene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, norbornadiene, dicyclopentadiene, 1, 4, 4a, 5, 8, 8a-hexahydro-l, 4, 5, 8-dimethanonaphthalene and mixtures thereof.

4. The process according to claim 2, wherein Q is oxygen, and es is carbon, Z is selected from the group consisting of -OR, -CR3, and -NR2, R is a hydrocarbon group having 1 to 20 carbon atoms, L is a coordinating group of substituted cyclopentadiene, T is a group of ethylene or a group of silicone; m is 2 or 3; and wherein the co-catalyst selected from the group consisting of (a) branched or cyclic oligomeric poly (hydrocarbylaluminum oxide) containing repeat units of the general form - (Al (R ') O) -, wherein R' is an alkyl radical containing from 1 to about 12 carbon atoms, or an aryl radical such as a substituted or unsubstituted phenyl or naphthyl group and (b) borates.

5. The process according to claim 4, wherein the catalyst precursor is preactivated with an amine.

6. The process according to claim 1, wherein the hydrocarbon crosslinking compound is employed in an amount ranging from about 0.001 percent to about 5 percent by weight of the total monomer feed. The process according to claim 1, wherein the process is carried out in the gas phase and the catalyst is spray-dried or in liquid form. 8. The process according to claim 1, wherein the process is carried out in a condensation mode. 9. A polyethylene composition according to the process of claim 1. 10. An injection molded article or a film comprising the composition of claim 9.