MXPA99007267A - Preparation of vinyl-containing macromers - Google Patents

Abstract

Polymeric compositions of matter are described comprising olefin polymer chains having Mn of about 400 to 75,000, a ratio of vinyl groups to total olefin groups according to formula (1), where a=-0.24 and b=0.8, and where the total number of vinyl groups per 1000 carbon atoms is greater than or equal to 8000÷Mn. The invention includes a method for preparing these polymeric products comprising contacting one or more olefin comonomers with a catalyst system containing a transition metal catalyst compound and an alumoxane wherein the aluminum to transition metal ratio is from 10:1 to less than or equal to 220:1 (Al:Me). The process conditions of the invention permit predictable macromer characteristics of both molecular weight and vinyl unsaturation.

Description

PREPARATION OF ACRYLIC OUTS CONTAIN VINYL Field of the Invention The present invention relates to a method for the preparation of vinyl-containing macromers from olefins, using transition metal catalyst compounds with alumoxane co-catalyst activators. Background of the Invention It is known that vinyl terminated polymers, including, for the purposes of this application, oligomers, homopolymers, and copolymers synthesized from two or more monomers, are useful for post-polymerization reactions (or subsequent to oligomerization), due to the available ethylenic unsaturation in a polymer, at one chain end, or both. These reactions include addition reactions, such as those used to graft other ethylenically unsaturated fractions, and also insertion polymerization, wherein the vinyl terminated polymers are copolymerized with other monomers, such as α-olefins and / or other polymerizable monomers by insertion. In the latter case, vinyl-terminated polymers are often referred to as macro-monomers or macromers. Early work with metallocene transition metal catalyst compounds activated with alkylalumoxanes, such as methylalumoxane, led to observations that their use in the olefin polymerization resulted in unsaturated end groups in a higher percentage of the polymer produced, of which had typically been true of insertion polymerization using traditional Ziegler-Natta catalysts prior to the metallocene. See EP-A-0, 129, 638 and its equivalent, U.S. Patent No. 5,324,800. The latest work by Resconi et al., Reported in Olefin Polvmerization at Bis (pentamethylcyclopentadienyl) zirconium and -hafnium centers; Chain-Transfer Mechanisms, J. Am. Chem. Soc. 1992 114, 1025-1032, provided the observations that the use of bis (pentamethylcyclopentadienyl) zirconocene or hafnocene in the oligomerization of propylene favors the elimination of β-methyl on the β-hydride removal most commonly expected as the medium for the chain transfer, or the termination of the polymer chain. This was based on observations that the ratio of the vinyl end groups to the vinylidene end groups was on the scale of 92 to 8 for zirconocene, and 98 to 2 for hafnocene. In addition to these observations, the international publication WO 94/07930 refers to the advantages of including long chain branches in polyethylene, from the incorporation of vinyl terminated macromers in the polyethylene chains, where the macromers have weight Critical molecular majors of 3,800, or in other words, contain 250 or more carbon atoms. The conditions that are said to favor the formation of vinyl-terminated polymers are high temperatures, no comonomer, no transfer agents, and a process that is not in solution, or a dispersion, using an alkane diluent. It is also said that the increase in temperature during the polymerization produces a β-hydride product removed, for exe, while ethylene is added to form an "end cap" of ethylene. This document continues to describe a large class of metallocenes of both monocyclopentadienyl and bis-cyclopentadienyl, and suitable according to the invention, when activated by either alumoxanes or ionizing compounds, providing non-coordinating stabilizing anions. All exes illustrate the use of the Lewis acid activator of tris (perfluoro-phenyl) boron with bis (cyclopentadienyl) zirconium dimethyl at a polymerization temperature of 90 ° C. The copolymerization was conducted with ethylene and the two macromers, respectively, using the same catalyst systems that were used to form the macromers. Branched ethylene macromers are described in the international publication WO 95/11931. According to this disclosure, the vinyl groups will be greater than 75 mole percent, more preferably greater than 80 mole percent, of the total unsaturated groups, and the weight average molecular weight is said to be on the scale of 100 to 20,000. It is said that the method of manufacturing the described macromers is with a transition metal compound containing metals of groups 3 to 10; and it is said that the cyclopentadienyl derivatives of groups 4, 5, and 6 are of satisfactory utility in this respect. It is also said that these transition metal compounds are capable of forming ionic complexes suitable for polymerization by their reaction with ionic compounds, alumoxane, or Lewis acids. It is said that the proportion of the transition metal component to the alumoxane component is desirable when it is from 1/10 to 1 / 10,000, or more preferably from 1/30 to 1 / 2,000. Examples 1 to 7 illustrate the preparation of the ethylene macromer with proportions of the alumoxane compound to the transition metal compound of 240 and 2,000, respectively. Different patents refer to the use of metallocene catalysts with different levels of activating alumoxane cocatalysts. One is U.S. Patent No. 4,752,597, where relatively insoluble solid hydrocarbon reaction products of metallocenes and alumoxane are prepared by reacting the two in a suitable solvent, wherein the molar proportions of the aluminum metal to the metal of transition are between 12: 1 and 100: 1. The solid reaction product is then removed. It is said that this solid reaction product is useful for gas, paste, and solution phase polymerization.

The additional technique refers to the preparation of unsaturated end chain polymers with different metallocenes under different conditions, each vinyl, vinylidene, vinylene, and trisubstituted unsaturation resulting from the reported processes. The difficulty to determine by the conventional characterization methods (1 H-NMR or 13 C-NMR) the total of saturated chain ends, has resulted in the acceptance in the art of the characterization of the unsaturated end group by the fraction of the total of each type of unsaturation to the total unsaturated ends. However, industrially efficient production methods would greatly benefit from high concentrations of unsaturated end group for the total population of end groups, i.e., including the saturated ends. Accordingly, the variations reported in molecular weight distributions, and the inability to precisely determine or predict the resulting type of chain ends, or the less favored production of unsaturated chain ends other than those of vinyl, limits the utility of the previous technique. It is generally accepted that vinyl chain ends are more reactive to chain end functionalization and insertion in the subsequent polymerization reactions than the other types, and are more highly preferred. In accordance with the above, additional work has been undertaken to improve the process of preparing the finished vinyl chain polymer, its predictability, and its utility for use in the preparation of branched polymers. SUMMARY OF THE INVENTION The invention comprises an olefin polymerization reaction product having olefin unsaturation which is predominantly vinyl. In these reaction product compositions, the molar concentration of the vinyl groups is greater than, or equal to, 50 percent of the total molar concentration of the polymer chain. In a more specific manner, as calculated from gel permeation chromatography (GPC), and from differential refractive index (DRI) measurements, the invention is a polymeric reaction product composition of material that comprising olefin polymer chains having number average molecular weights ("Mn") of from about 400 to about 75,000, a ratio of vinyl groups to total olefin groups satisfying the formula: (1) vinyl groups > [molar percentage of comonomer + 0.1] to olefin groups x 10a xb where a = -0.24, and b = 0.8 and where the total number of vinyl groups per 1,000 carbon atoms is greater than, or equal to, 8,000 -f- Mn . It also includes a surprisingly highly efficient method for the preparation of polymers having high levels of vinyl unsaturation, which comprises contacting 1 or more olefin monomers with a composition of a catalyst solution containing a transition metal catalyst compound and an alumoxane, wherein the ratio of aluminum to transition metal is from 10: 1 to 220: 1. Vinyl-containing chain yields can be achieved at levels greater than 70 percent of the total unsaturated chains, while high yields of unsaturated chains are simultaneously achieved in the total polymer chains, as calculated from gel permeation chromatography. and nuclear magnetic resonance. Accordingly, the use of the conditions of the process of the invention allows to have predictable macromer characteristics of both molecular weight and vinyl unsaturation, which further makes possible the preparation of branched polymers having custom-made characteristics, suitable for better processing applications, for example, where fusion processing is required, or industrially preferred, and in polymer blends where the choice of macromer constituents, monomer, or comonomer, may lead to better compatibilities or other characteristics of the polymer mixture. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates Examples 1 to 24 of the application, which show the vinyl yields as a percentage of the total olefinic groups in the polymer products, and their ratio according to the formula (I) below . The vinyl groups were characterized according to the 1H (NMR) methods, as described in the application. Detailed Description of the Invention The polymeric macromer material compositions according to the invention are the polymer chain reaction products of the polymerization by insertion or coordination of olefinic monomers. The means to achieve high proportions of the vinyl-containing chains relative to the total number of unsaturated chains in the polymerization reaction products were effectively achieved, and levels higher than 80 percent of vinyl-containing chains were reached, and still higher 90 percent. The highest levels, greater than 90 percent or even 95 percent, were reached with ethylene homopolymers. For the copolymers, the vinyl chain levels depended on the ratio of ethylene to the comonomer, as defined in equation (1). The polymer compositions or the reaction products contain chains with narrow polydispersities, from 1.5 to about 6, usually from 2 to 4, or even from 2 to 3.5. The number average molecular weight (Mn) of the polymeric macromers of the invention is usually from greater than or equal to 400 Daltons to less than 80,000 Daltons, more preferably less than 60,000 Daltons, more preferably less than or equal to a, 50,000 Daltons.

In formula I above, the values of A and B are within the preferred ranges expressed in Table A. Table A The total number of vinyl groups per 1,000 carbon atoms of the polymeric reaction product is usually greater than 0.13 and less than 9.85. The polymeric material compositions described in this way, exhibit higher numbers of vinyl-containing chains for the total polymeric reaction product, including both polymer chains having saturated groups, and those with unsaturated groups. In accordance with the above, these polymeric products can be effectively used for subsequent reactions, where reactive vinyl groups are needed. A measure of this effectiveness of the polymeric products of the invention is illustrated by the observed reaction efficiencies, i.e., the performance of the desired reaction products of the functionalized reactions or the macromer copolymerization reactions. The higher the content of total vinyl groups, the higher the yield of the functionalized polymer, or the yield of the copolymers-10-containing macromer branch. A wide range of polymeric reaction products of the invention containing vinyl macromers can be synthesized, including homopolymers, copolymers, and polymers containing three or more types of monomers, using the catalyst compositions of the present invention. Accordingly, monomers polymerized using these catalysts include, but are not limited to: ethylene, α-olefin of 3 to 18 carbon atoms, isobutylene; cyclic olefins, for example norbornene, ethyl norbornene, cyclopentene; styrene, non-conjugated dienes, and cyclic dienes. As suggested in this list, any comonomer copolymerizable with ethylene by coordination or insertion polymerization will be suitable in accordance with the invention. Others include: internal olefins, such as 1-butene; substituted olefins, such as 3-methyl-1-pentene; multiply substituted olefins, such as 3,3-dimethyl-1-hexene, and aromatic olefins. The assembly of the monomers in the polymeric reaction products is not limited only to random copolymers or mixtures of random copolymers. It is known in the art that the monomer sequence and the comonomers in the chains can be controlled to impart useful properties by using different means, for example flow catalysts, or sequential polymerization processes. The method for the preparation of the polymeric vinyl-containing macromer product of the invention involves contacting one or more olefin monomers with a catalyst solution composition containing a transition metal catalyst compound and an alumoxane, in the preferred proportions. - from aluminum to transition metal. The catalyst solution preparation usually comprises contacting the alumoxane activator with the transition metal compound in a suitable solvent to form an activated catalyst solution. Toluene is a preferred solvent for the catalyst solution in view of the high solubility of alumoxane, and many transition metal compounds which are suitable as catalysts when activated therein. Other solvents that can solvate to a significant degree both the activator and the transition metal compound, as can be easily determined in an empirical manner, will also be suitable. Both aliphatic and aromatic solvents will be suitable, provided that the transition metal compound and the alumoxane activator are substantially soluble at the mixing temperatures used. The method for the preparation of the polymeric vinyl-containing macromer product of the invention depends mainly on the molar ratio of the aluminum in the activator of the alkylalumoxane to the transition metal. Preferably, this level is >; 20 and < 175; more preferably > 20 and < 140 >; and very preferably > 20 and < 100. The temperature, pressure, and reaction time depend on the selected process, but in general they are within the normal ranges for the selected process. Accordingly, temperatures can be from 20 ° C to 200 ° C, preferably from 30 ° C to 150 ° C, more preferably from 50 ° C to 140 ° C, and most preferably from 55 ° C to 135 ° C. Reaction pressures generally can vary from atmospheric to 305 x 103 kPa, preferably up to 182 x 103 kPa. For typical solution reactions, temperatures will normally be from ambient to 250 ° C, with pressures from ambient to 3,450 kPa. Reactions can be executed in batches. The conditions for the pulp type reactions are similar to the conditions in solution, except that the reaction temperatures are limited to the melting temperature of the polymer. In some reaction configurations, a supercritical fluid medium can be used with temperatures up to 250 ° C and pressures up to 345 x 103 kPa. Under conditions of high temperature reaction, a macromer product of lower molecular weight ranges is usually produced. Batch reaction times may vary from 1 minute to 10 hours, more preferably from 5 minutes to 6 hours, and more typically from 45 minutes to 90 minutes. The reactions can also be executed continuously. In continuous processes, the average residence times can vary similarly from 1 minute to 10 hours, more preferably from 5 minutes to 6 hours, and more typically from 45 minutes to 90 minutes. Transition metal catalysts suitable in the process of the invention for the preparation of the reaction products containing vinyl macromer include one or more transition metal catalyst precursor compounds having both 1) stabilizing auxiliary ligands, and 2) additional ligands that react with the alumoxane activators, such that an active transition metal catalyst complex is produced. Preferred compounds include metallocene compounds containing at least one substituted or unsubstituted cyclopentadienyl auxiliary ring ("Cp") as transition metal ligands. Here, "substituted" means that one or more of the hydrogen atoms bonded to the ring carbon atoms of one or both Cp rings, are replaced with one or more monovalent radicals capable of having sigma bond with the carbon atom of the ring. ring. Examples include hydrocarbyl radicals of 1 to 30 carbon atoms and their counterparts, wherein one or more carbon atoms is replaced with another Group 14 atom, for example Si or Ge. The term "substituted" includes both 1) bridging or linking radicals that are linked with two different Cp ligands, or with a Cp ligand and another transition metal ligand, such as a heteroatom ligand of Groups 15 or 16, as 2) fused ring configurations, wherein two Cp ring atoms are covalently linked by substituents as in the indenyl and fluorenyl ligands, which themselves may be further substituted and / or bridged. Examples include those compounds of the 4-6 monocyclopentadienyl and bis-cyclopentadienyl groups known to those skilled in the art as suitable for olefin polymerization. For the bis-cyclopentadienyl compounds, see, for example, U.S. Patent Nos. 5,324,800, 5,324,801, 5,441,920 and 5,502,124. For the exemplary monocyclopentadienyl metallocene compounds, see, for example, U.S. Patent Nos. 5,055,038; 5,264,505, and the pending United States patent applications with Nos. Serial No. 08 / 545,973, filed October 20, 1995, and 08 / 487,255, filed June 7, 1995 and published as the international publication WO 96 / 00244 For the purposes of this invention, additionally included in the definition of metallocene, the cyclopentadienyl analogs, wherein one or more ring carbon atoms are replaced with a heteroatom of Groups 14 or 15, or fused ring systems, such as indenyl and fluorenyl, in where one or more carbon atoms in any of the condensed rings is replaced in this way. Lists of suitable metallocenes include essentially any of those available in the patent literature, such as those mentioned above, and in the academic literature related to the polymerization of olefin, including specifically that which refers to amorphous homopolymers and copolymers, and semi -Crystalline and crystalline, of more than one monomer. In particular, these documents relating to polyethylene polymers and copolymers, and those relating to stereoregular higher olefins, such as polymers and copolymers of isotactic and syndiotactic polypropylene, contain suitable descriptions. Any of the other transition metal olefin polymerization catalyst precursors, particularly those of the Group 4, 5, 6, 7, 8, 9, and 10 metals, known in the art as being capable of have activation with alumoxane; see, for example, the international publication WO 96/23010, U.S. Patent Nos. 5,504,049; 5,318,935, and the pending United States patent applications with Serial Nos. 08 / 473,693, filed June 7, 1995, and 60/019626, filed on June 17, 1996. All of which are referred to, e. incorporated as reference. Reactor configurations suitable for the present invention include continuous reactors, batch, and semi-batches. The conditions in solution phase, paste phase, and supercritical phase for olefin polymerizations using these catalysts are useful. Additionally, combinations of the above reactor types are explicitly intended in multiple reactors in series, and / or under multiple reaction conditions, and / or in multiple catalyst configurations. Preferred solvents for solution phase reactions are selected based on polymer solubilities, volatility, and safety / health considerations. Non-polar alkanes or aromatics are preferred. For supercritical fluid reactions, the reaction medium is generally composed of polymer, monomer, and comonomer, optionally with suitable supercritical cosolvents. For paste reactions, the diluent can be an inert liquid or liquid by volume comonomer. Solvents, cosolvents, and comonomers are normally purified by treatment with an absorbent material, including aluminas and molecular sieves. The impurities can also be deactivated by the addition of suitable scavengers well known in the art, including, but not limited to, metal alkyls and alumoxanes. Industrial Utility Branched polymers, wherein at least one of the branches is derived from the vinyl macromer-containing product of the invention, will be particularly useful, for example, for improved processing ethylene copolymers having branching derived from the macromer. The incorporation of vinyl macromer for the preparation of the branched polymer can be carried out by adding the polymer product of the invention to an environment of insertion polymerization, with a catalyst compound capable of incorporating monomer by volume. This includes the bridged mono- and bis-cyclopentadienyl metallocene catalyst compounds suitable for the insertion polymerization of bulky comonomers such as 1-octadecene, 3-methyl-1-pentene, and cyclic olefins, such as norbornene. See, for example, U.S. Patent Nos. 5,324,801; 5,444,145; 5,475,075 and 5,635,573 and the international application WO 96/000244. Other suitable catalyst systems include, but are not limited to, amido and imido derivatives of the metals of Groups 4, 5, 6, 7, 8, 9, and 10 in the aforementioned documents for polymer products containing macromer of vinyl of the invention. Also, the international publication WO 94/07930 mentioned in the background discloses the advantages of incorporating the macromer, and the means to do so. Each of these documents is also incorporated as a reference. For the preparation of both the vinyl macromer product and the branched copolymer, it is known that many methods and permutations of the addition order of the macromer and monomer species to the reactor are possible, some more convenient than others. For example, it is widely known in the art that the preactivation of the metallocene with alumoxane before addition to a continuous reactor in the solution phase produces higher activities than the continuous addition of metallocene and activator in two separate streams. In addition, it may be convenient to control the prior contact time to maximize the effectiveness of the catalyst, for example, by preventing excessive aging of the activated catalyst composition. Preferred branched copolymers of the invention are homopolymers and copolymers of ethylene with two or more comonomers. The most readily available comonomers are olefins, especially propylene, 1-butene, isobutylene, 1-hexene, and 1-octene. Other suitable comonomers include, but are not limited to: internal olefins, cyclic olefins, substituted olefins, multiply substituted olefins, and aromatic olefins, such as those described above for vinyl macromer products. The co-monomers are selected to be used based on the desired properties of the polymer product, and the metallocene employed will be selected for its ability to incorporate the desired amount of olefins. See U.S. Patent No. 5,635,573 which discloses different metallocenes suitable for ethylene-norbornene copolymers, and the pending U.S. patent application Serial No. 08 / 651,030, filed May 21, 1996, which describes monocyclopentadienyl metallocenes suitable for the ethylene-isobutylene copolymers. These documents are incorporated by reference.

For an improved tear of polyethylene film, a longer olefin comonomer, such as 1-octene, may be preferred over a shorter olefin, such as butene. For a better polyethylene film elasticity or barrier properties, a cyclic comonomer, such as norbornene, may be preferred over an olefin. The concentrations of comonomer in the reactor will be selected to give the desired level of comonomer in the polymer, more preferably from 0 to 50 mole percent. In addition, it is possible to react two or more polymeric macromer chains having the same or different comonomers and / or the same or different molecular weights, to derive new polymeric compositions with desirable properties. We have found that statistical mixtures or formulated mixtures of branching / block molecules derived by the binding of these macromer chains exhibit commercially useful properties. Optionally, it is possible to use dienes to control the incorporation of unsaturated chains into other unsaturated chains. Functionalization reactions for low molecular weight vinyl group containing polymeric products include those based on thermal or free radical addition, or grafting, of the vinyl group containing compounds and the ethylenically unsaturated compounds. A typical industrially useful example is that of subsequent grafting reactions with maleic acid, maleic anhydride, or vinyl acids or acid esters, for example acrylic acid, methyl acrylate, and the like. The addition of these groups allows for additional functionalization through amidation, imidation, esterification, and the like. For example, see U.S. Patent No. 5,498,809, and international publications WO 94/19436 and WO 94/13715. Each relates to ethylene-1-butene polymers having vinylidene termination, and their functionalization into effective dispersants in lubricating oil compositions. See also EP-A-0, 513, 211 Bl, wherein similar copolymers are described in wax crystal modifier compositions effective for fuel compositions. The polymeric products of the invention useful in this manner will normally have an Mn of about 1,500 to 10,000 Mn, preferably of about 2,000 to 5,000 Mn. Each of these documents are incorporated as a reference. It is preferable to use polymeric products of high vinyl unsaturation of the invention, in such a way that they are functionalized or copolymerized immediately after being prepared. Highly reactive vinyl groups appear to be susceptible to the reactions of byproducts with adventitious impurities, and even dimerization or addition reactions with other polymer chains containing unsaturated group. Accordingly, maintenance in an inert environment cooled in dilute concentrations after the preparation, and immediate subsequent use, will optimize the effectiveness of the use of the vinyl macromer product of the invention. Therefore, a continuous process using series reactors, or reactors in parallel, will be effective, preparing the vinyl macromer product in one, and continuously introducing itself in the other. Examples General: All polymerizations were carried out in a 1 liter Zipperclave reactor equipped with a water jacket for temperature control. The liquids were measured by entering the reactor using calibrated windows. The high purity hexane (> 99.5 percent), toluene, and butene supplies were purified by first passing through activated basic alumina at a high temperature under nitrogen, followed by a 13x molecular sieve activated at a high temperature under nitrogen. Polymerization-grade ethylene was supplied directly in a nitrogen-clad line, and was used without further purification. Methylalumoxane (MAO) at 10 percent in toluene, transparent, was received from Albemarle Inc. in stainless steel cylinders, divided into 1 liter glass containers, and stored in a handling box with laboratory gloves at room temperature. Ethylene was added to the reactor as was necessary to maintain a total system pressure at the reported levels (operation in semi-batches). The ethylene flow rate was monitored using a Matheson mass flow meter (model number 8272-0424). To ensure that the reaction medium was mixed well, a flat paddle stirrer was used rotating at 750 revolutions per minute. Preparation of the reactor: The reactor was first cleaned by heating to 150 ° C in toluene, to dissolve any polymer residues, and then cooled and drained. Next, the reactor was heated using a water jacket at 110 ° C, and the reactor was purged with flowing nitrogen for a period of about 30 minutes. Prior to the reaction, the reactor was further purged using 10 cycles of nitrogen presurization / ventilation (at 100 psi), and 2 cycles of ethylene pressurization / ventilation (at 300 psi). The cycles served three purposes: (1) to fully penetrate all dead ends, such as pressure gauges, to purge fugitive contaminants, (2) to displace nitrogen in the system with ethylene, and (3) to Test the pressure of the reactor. Catalyst preparation: All catalyst preparations were carried out in an inert atmosphere with an H20 content of <1.5 ppm. In order to accurately measure the small amounts of catalyst, often less than 1 milligram, methods of solution / dilution of catalyst supply freshly prepared in the preparation of the catalyst were used. To maximize the solubility of the metallocenes, toluene was used as a solvent. The stainless steel transfer tubes were washed with MAO to remove the impurities, drained, and the activator and the catalyst were added with a pipette, first the MAO. Macromer synthesis: First the catalyst transfer tube was connected to a reactor gate under a continuous flow of nitrogen to purge the ambient air. The reactor was then purged, and the pressure was tested as described above. Then 600 milliliters of solvent was charged to the reactor, and heated to the desired temperature. Then the comonomer was added (if applicable), the temperature was allowed to equilibrate, and the base pressure of the system was recorded. The desired partial pressure of ethylene was added above the base pressure of the system. After allowing the ethylene to saturate the system (as indicated by the ethylene flow from zero), the catalyst was injected in a pulse, using a high pressure solvent. The progress of the reaction was monitored by reading the ethylene recovery in the electronic mass flow meter. When the desired amount of macromer was accumulated, the ethylene flow was terminated, and the reaction was terminated by rapid cooling (approximately 1 minute) and the addition of an excess of methanol, to precipitate the polymer product. The polymer / solvent mixture was dried in ambient air flowing. Characterization of the product: Samples of the polymer product were analyzed by gel permeation chromatography using a Waters high temperature system of 150 ° C equipped with a DRI detector, a Showdex AT-806MS column, and operating at a system temperature of 145 ° C. ° C. The solvent used was 1, 2, 4-trichlorobenzene, from which polymer sample solutions of a concentration of 0.1 milligrams / milliliter for injection were prepared. The total flow rate of the solvent was 1.0 milliliters / minute, and the injection size was 300 microliters. The gel permeation chromatography columns were calibrated using a series of narrow polystyrenes (obtained from Tosoh Corporation, Tokyo, 1989). For quality control, a wide standard calibration based on the NBS-1475 linear polyethylene sample was used. The standard was passed with each carousel of 16 jars. It was injected twice as the first sample of each batch. After elution of the polymer samples, the resulting chromatograms were analyzed using the Waters Expert Fuse program to calculate the molecular weight distribution and one or more of the averages of Mn, Mw, and Mz. The quantification of the long chain branching was carried out by the method of Randall, Rev. Macromo. Chem. Phys., C29 (2 and 3), pages 285-297. The NMR analyzes were performed using a Varian Unity model of 500 mHz operating at 125 ° C, using d2-tetrachloroethane as the solvent. The 13 C-NMR analyzes were performed using a Varian Unity Plus model at a frequency of 100 mHz, under the same conditions.

Example 1 Catalyst Preparation: A stainless steel catalyst addition tube was prepared as described above. An aliquot of 0.25 milliliters of a 10% methylalumoxane (MAO) solution in toluene was added, followed by 0.5 milliliters of a toluene solution containing 1 milligram of Cp2ZrCl2, bis-cyclopentadienyl zirconium dichloride, per milliliter. The sealed tube was removed from the glove box, and connected to a reactor hatch under a continuous flow of nitrogen. A flexible stainless steel line was connected from the reactor supply manifold to the other end of the addition tube under a continuous flow of nitrogen. Homopoli erizasión: The reactor was purged simultaneously of nitrogen and the pressure was tested using two cycles of filling / purge of ethylene (at 300 psig) (2,170 kPa). The reactor pressure was then raised to approximately 40 psig (377 kPa) to maintain a positive reactor pressure during set-up operations. A water jacket temperature of 90 ° C was established, and 600 milliliters of toluene was added to the reactor. The agitator was set at 750 revolutions per minute. Additional ethylene was added to maintain a positive pressure of the reactor meter as ethylene was absorbed in the gas phase in the solution. The reactor temperature controller was set at 90 ° C, and the system was allowed to reach the continuous state. The ethylene pressure regulator was then set to 100 psig (791 kPa), and ethylene was added to the system, until a continuous state was reached, measured by zero ethylene recovery. The reactor was isolated, and a pressurized toluene pulse at 300 psig (2,170 kPa) was used to force the catalyst solution from the addition tube into the reactor. Immediately the ethylene supply manifold of 100 psig (791 kPa) was opened to the reactor, in order to maintain a constant reactor pressure as the reaction consumed ethylene. After 30 minutes of reaction, the reaction solution was cooled rapidly, and 200 milliliters of methanol was added to terminate the reaction and precipitate the polymer. The product was stirred into an open two liter tub, and dried in ambient air, producing 38 grams of homopolyethylene. A summary of the reaction conditions of Example 1 is given in Table 1. Examples 2-7 Catalyst preparation: The catalysts of MAO-activated Cp2ZrCl2 of Examples 2 to 7 were identical to that of Example 1, with the exception of that the amounts of catalyst solution (containing 1 milligram of Cp2ZrCl2 per milliliter of toluene), and the amounts of 10% MAO solution in toluene used were different. These catalyst formulations are summarized in Table 1.

Homopolymerization: The reaction conditions used in Examples 2 to 7 involved only minor modifications of the conditions used in Example 1. These variations are summarized in Table 1. Example 8 Preparation of the catalyst: The catalysts were prepared in a manner analogous to that of Example 1, differing only in the amounts of Cp2ZrCl2 and activator of MAO used. These catalyst preparations are summarized in Table 1. Copolymerization: The reactor was prepared as in Example 1, with the exception that nitrogen was used to fill the reactor prior to the addition of liquids. After the addition of toluene, 50 milliliters of butene was added, and the reactor temperature was allowed to equilibrate to 90 ° C. A base pressure of 25 psig (273 kPa) was recorded. Ethylene was added to bring the total equilibrium system pressure to 125 psig (963 kPa), or alternatively said, to produce an ethylene partial pressure of 100 psia (688 kPa). 10 minutes after the catalyst injection, the reaction was terminated by cooling and addition of methanol. 64 grams of ethylene / butene copolymer was isolated after drying. Examples 9-10 Catalyst Preparation: The amounts of Cp2ZrCl2 catalyst and MAO activator used in Examples 9 and 10 are summarized in Table 1. Addition tubes and catalyst solutions were prepared using the methods of Example 1. Copolymerization : Following the methods of Example 8, nitrogen, solvent, and butene were added to the reactor, and heated to 90 ° C. The base pressure was recorded, and the ethylene pressure regulator was set to add ethylene in order to raise the partial equilibrium pressure of ethylene to 100 psia (689 kPa). After saturating the system with ethylene (measured by zero ethylene recovery), the catalyst was injected. The reaction was terminated by adding methanol after the elapsed times of Table 1. Example 11 Catalyst Preparation: An aliquot of 2.5 milliliters of 10 percent MAO in toluene was added to the stainless steel catalyst addition tube prepared as previously. Then 2 milliliters of a toluene solution containing 0.5 milligrams of (C5Me4Si-Me2NC12H23) TiCl2, (tetramethylcyclopentadienyl dimethylsilyl cyclododecamido) titanium, per milliliter, was added to the addition tube. Homopolymerization: The polymerization was carried out using essentially the same procedures as Example 1, with the exception that the conditions specified in Table 1 were used. After drying, 17 grams of the homopolymer was obtained. Examples 12-15 Catalyst Preparation: The catalyst and activator were prepared using the procedures of Example 11. Only the amounts of MAO catalyst and activator solution were different (see Table 1). Homopolymerization: The procedures used in Examples 12 to 15 were identical to those of Example 11, but with slightly different conditions summarized in Table 1. Examples 16-19 Catalyst Preparation: Catalyst and activator were prepared using the methods of Example 11. See Table 1, for the amounts of activator and catalyst used. Copolymerization: Solvent was added, followed by 1-butene, to a reactor filled with nitrogen. The reactor was heated to the desired reaction temperature (see Table 1), and the pressure recorded. The ethylene feed regulator was adjusted to provide ethylene at a pressure necessary to maintain the absolute partial pressure of ethylene tabulated. The ethylene feed was then opened to the reactor, until equilibrium was reached, as indicated by zero ethylene flow. The reactor was sealed, and the catalyst was injected using high pressure solvent (toluene or hexane, depending on the solvent used for the reaction). After the indicated reaction times, the product was rapidly cooled, quenched using methanol, and dried in ambient air. Examples 20-22 Catalyst Preparation: Solutions in toluene containing 1 milligram of ((CH3) 2Si (C9H6) 2HfCl2, dimethylsilyl-bis (indenyl) hafnium dichloride, per milliliter of solution, were added to 10% MAO solutions. percent in toluene for the catalyst formulation The amounts used are summarized in Table 1. Copolymerization: The copolymerization reactions used identical methods to those used in Examples 16 to 19, with the exception of Example 21, where hydrogen was added The hydrogen was supplied as follows: toluene and butene were added to a clean reactor containing nitrogen, the reactor was heated to 90 ° C, and the pressure (base) of 30 psig (308 kPa) was recorded. hydrogen to raise the system pressure to 130 psig (998 kPa) (hydrogen partial pressure of 100 psia (689 kPa)). The ethylene regulator was then set to 230 psig (1, 687 kPa), to provide the system with a partial pressure of 100 psia (689 kPa) of ethylene. The reaction was then carried out in a manner analogous to Example 20. Examples 23 and 24 Catalyst preparation: Toluene solutions of Cp2ZrCl2 and (C5Me4SiMe2NC12H23) TiCl2, described in Examples 1 and 11, respectively, were used. First MAO (10 percent in toluene) was added to the catalyst addition tube, followed by a solution of (C5Me4SiMe2NC12H23) TiCl2, and subsequently by a solution of Cp2ZrCl2. Homopolymerization: The same procedures were used essentially as in Example 1. Only the conditions were different (Table 1). Analysis of the polymer: The molecular weight, the content of co-monomer, and the structural distributions of unsaturated groups of the reaction products are reported in Table 2. It was found that the concentrations of unsaturated groups (total olefins per 1,000 atoms of carbon), as well as the selectivities of vinyl groups, are increased by decreasing the proportions of aluminum: metal, all other factors being equal. The concentrations of olefin (comonomer) can be further increased by decreasing the concentration of ethylene in solution (decreasing the partial pressure of ethylene, or increasing the temperature).

Table 1. Summary of Reaction Conditions. * a = Cp2ZrCl2 b = (C5Me4SiMe2NC12H23) TiCl2 c = ((CH3) 2Si (C9H6) 2HfCl2 ** MAO = 10 weight percent methylalumoxane in toluene.

Table 2. Summary of Polymer Analysis.

The following examples illustrate the preparation of macromers according to the invention, and their copolymerization with copolymerizable monomers, to form long chain branching copolymers. Example I Catalyst Preparation: A stainless steel catalyst addition tube was prepared as described above. An aliquot of 1 milliliter of 10% methylalumoxane (MAO) solution in toluene was added, followed by 16 milligrams of a solution of Cp2ZrCl2 in toluene. The sealed tube was removed from the glove box, and connected to a reactor hatch under a continuous flow of nitrogen. A flexible stainless steel line was connected from the reactor supply manifold to the other end of the addition tube under a continuous flow of nitrogen. Synthesis of the macromer: The 1 liter reactor was simultaneously purged of nitrogen, and the pressure was tested using two ethylene fill / purge cycles (at 300 psig (2170 kPa)). The reactor pressure was then raised to approximately 20 psig (239 kPa) to maintain a positive reactor pressure during set-up operations. The temperature of the water jacket was set at 90 ° C, and 600 milliliters of toluene was added to the reactor. The agitator was set at 750 revolutions per minute. Additional ethylene was added to maintain a positive pressure of the reactor meter as ethylene was absorbed in the gas phase in the solution. The reactor temperature controller was set at 90 ° C and the system was allowed to reach the continuous state. The ethylene pressure regulator was then set at 20 psig, and ethylene was added to the system, until a steady state was reached, as measured by zero ethylene recovery. The reactor was isolated, and a pressurized toluene pulse was used at 300 psig (2170 kPa) to force the catalyst solution from the addition tube into the reactor. Immediately the ethylene supply manifold was opened at 20 psig (239 kPa) to the reactor, in order to maintain a constant reactor pressure as the reaction consumed the ethylene. After 8 minutes of reaction, the reaction solution was heated rapidly to 150 ° C for 3 minutes to kill the catalyst, and then cooled to 90 ° C. A small sample of macromer was removed by means of an addition gate. Analysis by 13 C-NMR indicated that there were no measurable long chain branches present in the macromer. The number-average and weight-average molecular weights of the macromer were 9.268 and 23.587 Daltons, respectively, with 81.7 percent of olefins as vinyls. Example II Preparation of branched polymer: 25 grams of a solution of norbornene at 80.7 percent in toluene was added to the reactor content of Example I, immediately after sampling the macromer. A catalyst addition tube containing 0.5 milliliters of a solution of 10% MAO in toluene, and 1 milligram of CpCp * ZrCl2 was connected to the addition gate. The total pressure in the reactor at 90 ° C was raised to 100 psig (791 kPa), adjusting the ethylene supply regulator, and allowing the system to reach equilibrium, as indicated by zero ethylene flow to the reactor. The catalyst was injected using a toluene pulse at 300 psig (2170 kPa). After 20 minutes of reaction time, the system was ventilated and cooled rapidly. The sample was quenched using an excess of methanol, and evaporated to dryness. 42 grams of the ethylene-norbornene copolymer product containing branched polymers, with homopolyethylene branches and the ethylene-norbornene base structure were isolated. The 13C NMR analysis of the product indicated that there were 0.085 long chain branches per 1, 000 carbon atoms present. Example III Catalyst Preparation: A stainless steel catalyst addition tube was prepared as described above. An aliquot of 2 milliliters of a solution of 10% methylalumoxane (MAO) in toluene was added, followed by 32 milligrams of a solution of (C5Me4Si-Me2NC12H23) TiCl2 in toluene. The sealed tube was removed from the glove box, and connected to a reactor hatch under a continuous flow of nitrogen. A flexible stainless steel line was connected from the reactor supply manifold to the other end of the addition tube under a continuous flow of nitrogen. Synthesis of the macromer: The 2 liter reactor was simultaneously purged of nitrogen, and the pressure was tested using two ethylene fill / purge cycles (at 3000 psig) (2170 kPa). The reactor pressure was then raised to approximately 40 psig (377 kPa) to maintain a positive reactor pressure during set-up operations. The temperature of the water jacket was set at 90 ° C, and 1,200 milliliters of toluene and 20 milliliters of butene were added to the reactor. The agitator was set at 750 revolutions per minute. Additional ethylene was added to maintain a positive pressure of the reactor meter, as the ethylene in gas phase was absorbed into the solution. The reactor temperature controller was set at 90 ° C, and the system was allowed to reach the continuous state. Then the ethylene pressure regulator was set at 40 psig (377 kPa), and ethylene was added to the system, until a steady state was reached, measured by zero ethylene recovery. The reactor was isolated, and a pressurized toluene pulse at 300 psig was used to force the catalyst solution from the addition tube into the reactor. The ethylene supply manifold was opened immediately at 40 psig (377 kPa) to the reactor, in order to maintain a constant reactor pressure as the reaction consumed ethylene. After 25 minutes of reaction, the reaction solution was heated rapidly to 147 ° C for 15 minutes to kill the catalyst, and then cooled to 90 ° C. The system was continuously ventilated and purged with nitrogen to dryness, to remove both the solvent and the ethylene and butene monomers. Then 1,200 milliliters of toluene were added, and the system equilibrated at 90 ° C. A sample of ethylene-butene macromer was removed for analysis by the addition gate. The number-average and weight-average molecular weights of the macromer were 22,394 and 58,119, respectively. The comonomer content of the macromer, obtained by FTIR measurements, was 6.6 mole percent of butene. Example IV. Preparation of the branched polymer: The content of the reactor of Example III (at 90 ° C) was pressurized to 100 psig, by adjusting the ethylene supply regulator, and allowing the system to reach equilibrium, as indicated by zero flow of ethylene to the reactor. A catalyst addition tube containing 2 milliliters of 10% MAO solution in toluene, and 2 milligrams of a solution of (C5Me4SiMe2NC12H23) TiCl2 in toluene, was connected to the addition gate. The catalyst was injected using a toluene pulse at 300 psi. After 10 minutes of reaction time, the system pressure was raised to 300 psig (2170 kPa). After 23 minutes of reaction time, the system was ventilated and cooled rapidly. The sample was quenched using an excess of methanol, and evaporated to dryness. 69.5 grams of the product were isolated, and analyzed by FTIR as the homopolyethylene base structures having 56 weight percent branches of the ethylene-butene macromer of Example III. Chain branching was measured by separating the high molecular weight branched material from the low molecular weight macromer using gel permeation chromatography methods, and then quantifying by means of FTIR the amount of butene in both the macromer and the high molecular weight branched polymer. Accordingly, the average butene content in the high molecular weight branched material was 3.7 mole percent, as opposed to that of the macromer product with 6.6 mole percent butene. The level of branching was calculated from the following equation:% of butene in the high molecular weight fraction% by weight of branches = x 100%% of butene in the action of the macromer Table 1. Summary of Reaction Conditions * a = Cp2ZrCl2; b = Cp ((Me5) Cp) ZrCl2; c = (C5Me4? iMe2NC12H23) TiCl2 ** MAO = 10 weight percent methylalumoxane in toluene.

Claims (11)

1. CLAIMS 1. A composition of matter, comprising polymer chains of ethylene having an Mn value of 1,500 to 25,154, a molecular weight distribution by gel permeation chromatography (145 ° C) and a differential refractive index of
2. 2 to 4, a ratio of vinyl groups to total olefin groups according to formula (1) vinyl groups = [mol% co-monomer + 0.1] ax 10a xb olefin groups where a = -0.24, b = 0.8, and where the total number of vinyl groups per 1,000 carbon atoms is greater than or equal to 8,000 ^ -Mn, the measurement of vinyl groups being taken by gel permeation chromatography (145 ° C) and XH NMR (125 ° C). 2. The composition of claim 1, wherein a = -0.20.
3. 3. The composition of claim 1, wherein a = -0.18 and b = 0.83. 4. The composition of claim 1, wherein a = -0.15 and b = 0.83. The composition of claim 1, wherein said olefin polymer comprises one or more of the group consisting of ethylene, C3-C12 α-olefins, isobutylene and norbornene. A method for preparing ethylene polymers of claim 1, comprising contacting, under batch polymerization conditions, in solution, ethylene and, optionally, one or more olefin co-monomers with a catalyst solution composition which it contains a transition metal catalyst compound and an alumoxane, wherein the molar ratio of aluminum to transition metal is from 10: 1 to 158: 1. The method of claim 6, wherein the ratio of aluminum to transition metal is from 20: 1 to 140: 1. The method of claim 6, wherein the ratio of aluminum to transition metal is from 20: 1 to 100: 1. The method of claim 6, wherein the transition metal catalyst compound is one of a metal of group 4, 5, 6, 7, 8, 9, 10, which is capable of activation with alumoxane for polymerization of olefins. The method of claim 9, wherein the transition metal catalyst compound is a metal compound of the 4-biscyclopentadienyl group. The method of claim 9, wherein the transition metal catalyst compound is a metal compound of monocyclopentadienyl group
4. 4.