Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

• the invention relates to a catalyst composition for olefin polymerization and a process for polymerizing polyolefins, especially copolymers of ethylene-alpha olefins, ethylene-alpha olefin-dienes, and polypropylene using a metallocene catalyst. More particularly, the invention concerns the polymerization of polyolefins having less than 50% crystallinity using a metallocene catalyst containing a transition metal and an aluminoxane.
• metallocenes for poly olefin production.
• Many metallocenes for poly olefin production are difficult and time-consuming to prepare, require large amounts of alumoxane, and exhibit poor reactivity toward higher olefins, especially for making ethylene-alpha olefin copolymers and ethylene- alpha olefin-diene terpolymers.
• the ethylene-alpha olefin copolymers and ethylene-alpha olefin-diene terpolymers prepared using these metallocenes often have undesirably low molecular weights (i.e., Mw less that 50,000).
• the so-called "constrained geometry" catalysts such as those disclosed in EP 0 420 436 and EP 0 416 815 can provide a high comonomer response and a high molecular weight copolymer, but are difficult to prepare and purify, and, therefore, are expensive.
• Another drawback of the bridged amido-cyclopentadienyl titanium catalyst system is that in order to form an active oxide-supported catalyst, it is necessary to use fairly high levels of alumoxane (see, e.g., WO96/16092) or to employ mixtures of aluminum alkyl and an activator based on derivatives of tris(pentafluorophenyl)borane (see, e.g., WO95/07942), itself an expensive reagent, thus raising the cost of running the catalyst.
• alumoxane see, e.g., WO96/16092
• an activator based on derivatives of tris(pentafluorophenyl)borane see, e.g., WO95/07942
• the active catalyst may be formed starting from (C5Me5)Ti(OMe)3 and that the polymer formed has a relatively wide or broad compositional distribution.
• the present invention does not utilize this precursor.
• polyolefins such as EPRs and EPDMs are produced commercially using vanadium catalysts.
• those produced by the catalysts of the present invention have high molecular weight and narrower composition distribution (i.e., lower crystallinity at an equivalent alpha olefin content.
• the catalyst of the invention is unconstrained or unbridged and relatively easily and inexpensively prepared using commercially available starting materials. Further, the level of aluminoxane utilized can be lowered. That is, in the present invention, the precursor can be dried onto a support or dried with a spray drying material with Al:Ti ratios below 100:1 to form highly active catalysts with similar polymerization behavior to their unsupported analogs of the invention and polymerization behavior similar to constrained catalysts. Further, the catalyst of the present invention described herein has improved reactivity with methylaluminoxane (MMAO) which contains higher alkyl groups.
• MMAO methylaluminoxane
• toluene employed in the polymerization environment with light aliphatic hydrocarbons, since MMAO, unlike aluminoxane (MAO), is soluble in non-aromatic solvents.
• MMAO unlike aluminoxane (MAO)
• MAO aluminoxane
• Use of aliphatic hydrocarbons such as isopentane is often preferred to toluene because of the greater ease of purging it from the polymer after it leaves the reactor and also because of the adverse health concerns associated with aromatic solvents in general.
• the present invention provides a catalyst comprising:
• each R 2 or R is a C ⁇ -Cs alkyl
• the catalyst can additionally contain (D) a bulky phenol compound having the formula: (CgR ⁇ OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, a C ⁇ -Cg alkyl, an aryl, a heteroatom substituted alkyl or aryl, wherein two or more R ⁇ groups may be linked together forming a ring, and in which at least one R ⁇ is represented by a C3-C12 linear or branched alkyl located at either or both the 2 and 6 position (i.e., the ortho positions relative to the OH group being in position 1) of the bulky phenol compound.
• a bulky phenol compound having the formula: (CgR ⁇ OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, a C ⁇ -Cg alkyl, an aryl, a heteroatom substituted alkyl or aryl, wherein two or more R ⁇ groups may be linked together forming a ring, and in which at least
• a polymerization process employing the catalyst composition and a polymer produced using the catalyst.
• a cable composition is also provided.
• the catalyst contains a transition metal (titanium) precursor (Component A), an alcohol or carboxylic acid (Component B), an aluminoxane (Component C), and optionally a substituted bulky phenol (Component D),.
• the catalyst of the invention can be unsupported (that is, in liquid form), supported, spray dried, or used as a prepolymer. Support and/or spray drying material is described as optional Component E.
• Component A a transition metal compound having the formula: wherein each Rl substituent is independently selected from the group consisting of hydrogen, a C ⁇ -Cg alkyl, an aryl, and a heteroatom-substituted aryl or alkyl, with the proviso that no more than three R-*- substituents are hydrogen; and wherein two or more Rl substituents may be linked together forming a ring; and each
• Y is independently selected from the group consisting of a C1-C20
• Illustrative compounds can include: cyclopentadienyltitanium tribenzoate; cyclopentadienyltitanium tris(diethycarbamate); cyclopentadienyltitanium tris(di-tert- butylamide); cyclopentadienyltitanium triphenoxide; pentamethylcyclopentadienyltitanium tribenzoate; pentamethylcyclopentadienyltitanium tri-pivalate; pentamethylcyclopentadienyltitanium triacetate; pentamethylcyclopentadienyltitanium tris(diethycarbamate); pentamethylcyclopentadienyltitanium tris(di-tert-butylamide); pentamethylcyclopentadienyltitanium tribenzoate; cyclopentadienyltitanium tris(diethycarbamate);
• Component B is an alcohol having the formula: R 2 OH or
• R 3 COOH wherein each R 2 or R 3 is a Ci-Cg alkyl.
• Illustrative R 2 OH compounds in which R 2 is alkyl can include, for example, methanol, ethanol, propanol, butanol (including n- and t- butanol), pentanol, hexanol, heptanol, octanol.
• R 2 is a methyl group.
• R COOH compounds are acetic acid, propionic acid, benzoic acid, and pivalic acid. Preferred among these are benzoic and pivalic acid.
• Component C is a cocatalyst capable of activating the catalyst precursor is employed as Component D.
• the activating cocatalyst is a linear or cyclic oligomeric poly(hydrocarbylaluminum oxide) which contain repeating units of the general formula -(Al(R*)O)-, 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.
• the activating cocatalyst is an aluminoxane such as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).
• Aluminoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxanes represented by the formula:
• Aluminoxanes may be prepared in a variety of ways. Generally, a mixture of linear and cyclic aluminoxanes is obtained in the preparation of aluminoxanes from, for example, trimethylaluminum and water.
• an aluminum alkyl may be treated with water in the form of a moist solvent.
• an aluminum alkyl, such as trimethylaluminum may be contacted with a hydrated salt, such as hydrated ferrous sulfate.
• the latter method comprises treating a dilute solution of trimethylaluminum in, for example, toluene with a suspension of ferrous sulfate heptahydrate.
• methylaluminoxanes by the reaction of a tetraalkyl- dialuminoxane containing C2 or higher alkyl groups with an amount of trimethylaluminum that is less than a stoichiometric excess.
• the synthesis of methylaluminoxanes may also be achieved by the reaction of a trialkyl aluminum compound or a tetraalkyldialuminoxane containing C2 or higher alkyl groups with water to form a polyalkyl aluminoxane, which is then reacted with trimethylaluminum.
• modified methylaluminoxanes which contain both methyl groups and higher alkyl groups, i.e., isobutyl groups, may be synthesized by the reaction of a polyalkyl aluminoxane containing C2 or higher alkyl groups with trimethylaluminum and then with water as disclosed in, for example, U.S. Patent No. 5,041,584.
• the mole ratio of aluminum atoms contained in the poly(hydrocarbylaluminum oxide) to total metal atoms contained in the catalyst precursor is generally in the range of from about 2:1 to about 100,000:1, preferably in the range of from about 10:1 to about 10,000:1, and most preferably in the range of from about 50:1 to about 2,000:1.
• Component C is an alumoxane of the formula
• R 5 is a methyl group
• R 6 is a Ci-C alkyl
• m ranges from 3 to 50
• n ranges from 1 to 20.
• R" is a methyl group.
• Component D is optional and is a bulky phenol compound having the formula: (CgR ⁇ 5)OH, wherein each R ⁇ group is independently selected from the group consisting of hydrogen, halide, a C ⁇ -Cg alkyl, an aryl, a heteroatom substituted alkyl or aryl, wherein two or more R ⁇ groups may be linked together forming a ring, and in which at least one R * * is represented by a C3-C12 linear or branched alkyl located at either or both the 2 and 6 position (i.e., the ortho positions relative to the OH group being in position 1) of the bulky phenol compound;.
• R 1 * groups is a methoxy group.
• suitable R ⁇ groups can include, for example, t-butyl, isopropyl, n-hexyl and mixtures thereof.
• Component E Preferably, the catalyst of the invention is unsupported. However, optionally, one or more of the above-described catalyst components may be impregnated in or deposited on a support, or alternatively spray dried with a support material. These support or spray drying materials are typically solid materials which are inert with respect to the other catalyst components and/or reactants employed in the polymerization process.
• Suitable support or spray drying materials can include silica, carbon black, polyethylene, polycarbonate, porous crosslinked polystyrene, porous crosslinked polypropylene, alumina, thoria, titania, zirconia, magnesium halide (e.g., magnesium dichloride), and mixtures thereof.
• Preferred among these support materials are silica, alumina, carbon black, and mixtures thereof. These are composed of porous particulate supports that usually have been calcined at a temperature sufficient to remove substantially all physically bound water.
• the molar ratio of Component B to Component A ranges from about 2:1 to 200:1; preferably about 2:1 to 50:1; and, most preferably, is about 2:1 to 20:1.
• the molar ratio of Component D to Component A ranges from about 5:1 to 1000:1; preferably about 10:1 to 300:1; and, most preferably is about 30:1 to 200:1.
• the molar ratio of Component C to Component A ranges from about 10:1 to 10,000:1, preferably about 30:1 to 2,000:1, and most preferably, is about 50:1 to 1000:1, with the provisos that (1) the ratio of Component B to Component C does not exceed 0.7:1, and is preferably between 0.001:1 to 0.050:1; and (2) the ratio of Component D to Component C does not exceed 1:1, and is preferably below 0.7:1.
• Component E is employed as a support or spray drying material, it is employed in an amount ranging from about 7 to 200 g/mmol, preferably 12 to 100 g/mmol, and most preferably 20 to 70 g/mmol (grams of Component E per millimole Component A).
• the individual catalyst components can be combined in any order prior to polymerization.
• the individual catalyst components can be fed to the polymerization reactor such that the catalyst is formed in-situ.
• the active catalyst is prepared as follows.
• Step 1 Components A and B are mixed in an inert hydrocarbon solvent suitable for dissolving Components A through C, and optionally also D, under an inert atmosphere (e.g., nitrogen) for at least 15 minutes or longer (e.g., up to 3 days).
• the components are combined such that Component A is mixed with at least three molar equivalents of Component B.
• Typical inert solvents can include, for example, toluene, xylene, chlorobenzene, etc. Preferred among these solvents is toluene.
• Step 2 Component C (or Component C and Component D, when employed) is mixed in one of the above-described inert hydrocarbon solvents, preferably the same solvent employed in Step 1, under an inert atomosphere (e.g., nitrogen and/or argon) for at least 15 minutes or longer (e.g., for up to 3 days).
• the ratio of aluminum (in the aluminoxane, Component C) to phenol of the bulky phenol compound (Component D) ranges from 1.4:1 to 1000:1; preferably 3:1 to 100:1; most preferably 3:1 to 10:1.
• the support or spray drying material can be added to any of the above-described solutions, mixtures, and/or slurries.
• Component E the mixing should take place for about 30 minutes or more and the ratio of aluminum to support material is in the range of about 0.5 to 10 mmo /g., preferably, 2 to 5 mmol./g.
• Step 3 the mixture of Components A and B is combined with the mixture of Components C (or Components C and D, when D is employed) (and optional E) in such proportion that the molar ratio of aluminum to transition metal is about 5 to 5000, preferably 30 to 1000, and the molar ratio of Component B to aluminum is less than 0.5.
• the mixture is stirred for at least about 5 minutes.
• the mixture can be used as a liquid for direct injection into the polymerization reactor, or, if Component E is present, may be dried in vacuo to a free-flowing powder or spray-dried in an inert atmosphere. If Component E is not present, the catalyst is then fed to the reactor in liquid form. If Component E is present and the catalyst is in solid form, it may be introduced into the reactor by a variety of methods known to those skilled in the art such as by inert gas conveyance or by injection of a mineral oil slurry of the catalyst.
• the function of the two protic reagents is to prevent the degradation of the cationic titanium (IV) active site.
• the aluminum trialkyl (A1R3) compounds will rapidly reduce the oxidation state of titanium from +4 to +3.
• A1R3 or aluminoxanes present during polymerization to serve as scavengers of catalyst poisons which adhere to reactor surfaces or are introduced by reaction media such as monomers, inert gases, and (if appropriate) solvents. Therefore, the catalyst of the invention represents a solution to the titanium reduction problem which allows the presence of alkylaluminum species.
• the first step in the activation of titanium by cocatalyst is alkylation, that is, the exchange of two or more titanium substituents with alkyl groups on aluminum atom(s).
• alkylation that is, the exchange of two or more titanium substituents with alkyl groups on aluminum atom(s).
• the reason the catalysts based on titanium carboxylates are more active than their trihalide analogs under certain polymerization conditions is that the aluminum carboxylates which are immediately formed from the alkylation reaction of the tricarboxylates serve as bulky groups. It is believed that these bulky groups prevent a close interaction of the aluminum species with the alkylated titanium species, thus hindering the reduction and complexation reactions.
• the above-described catalyst composition can be used for the polymerization of monomers (e.g., olefins, diolefins, and/or vinyl aromatic compounds) in a suspension, solution, slurry, or gas phase process using known equipment and reaction conditions, and it is not limited to any specific type of reaction.
• the preferred polymerization process is a gas phase process employing a fluidized bed.
• the gas fluidized bed reactor can be assisted by mechanical stirring or agitation means.
• Gas phase processes employable in the present invention can include so-called "conventional" gas phase processes, "condensed-mode,” and, most recent, "liquid-mode” processes.
• a scavenger in the reactor to remove adventitious poisons such as water or oxygen before they can lower catalyst activity.
• a scavenger in the reactor to remove adventitious poisons such as water or oxygen before they can lower catalyst activity.
• trialkylaluminum species e.g., TIBA
• methylalumoxane be employed for such purposes.
• Condensed mode polymerizations including induced condensed mode, are taught, for example, in U.S. Patent Nos. 4,543,399; 4,588,790; 4,994,534; 5,317,036; 5,352,749; and 5,462,999.
• condensing mode operation is preferred.
• Liquid mode or liquid monomer polymerization mode is described in U.S. Patent No. 4,453,471; U.S. Serial No. 510,375; and WO 96/04322 (PCT/US95/09826) and WO 96/04323 (PCT/US95/09827).
• liquid mode or liquid monomer polymerization the temperature in the polymerization zone of the reaction vessel is maintained below the dew point of at least one of the monomers employed.
• Fluidization is achieved by a high rate of fluid recycle to and through the bed, typically in the order of about 50 times the rate of feed of make-up fluid.
• the fluidized bed has the general appearance of a dense mass of individually moving particles as created by the percolation of gas through the bed.
• ethylene-propylene copolymer e.g., EPMs
• ethylene-propylene-diene terpolymer e.g., EPDMs
• diolefin e.g., butadiene, isoprene
• inert particulate materials are described, for example, in U.S. Patent No. 4,994,534 and include carbon black, silica, clay, talc, and mixtures thereof. Of these, carbon black, silica, and mixtures of them are preferred.
• these inert particulate materials When employed as fluidization aids, these inert particulate materials are used in amounts ranging from about 0.3 to about 80% by weight, preferably about 5 to 50% based on the weight of the polymer produced.
• the use of inert particulate materials as fluidization aids in polymer polymerization produces a polymer having a core-shell configuration such as that disclosed in U.S. Patent No. 5,304,588.
• the catalyst of the invention in combination with one or more of these fluidization aids produces a resin particle comprising an outer shell having a mixture of a polymer and an inert particulate material, wherein the inert particulate material is present in the outer shell in an amount higher than 75% by weight based on the weight of the outer shell; and an inner core having a mixture of inert particulate material and polymer, wherein the polymer is present in the inner core in an amount higher than 90% by weight based on the weight of the inner core.
• these resin particles are produced by a fluidized bed polymerization process at or above the softening point of the sticky polymer.
• the polymerizations can be carried out in a single reactor or multiple reactors, typically two or more connected in series, can also be employed.
• the essential parts of the reactor are the vessel, the bed, the gas distribution plate, inlet and outlet piping, at least one compressor, at least one cycle gas cooler, and a product discharge system.
• the vessel above the bed, there is a velocity reduction zone, and in the bed a reaction zone.
• all of the above modes of polymerizing are carried out in a gas phase fluidized bed containing a "seed bed" of polymer which is the same or different from the polymer being produced.
• the bed is made up of the same granular resin that is to be produced in the reactor.
• the bed is fluidized using a fluidizing gas comprising the monomer or monomers being polymerized, initial feed, make-up feed, cycle (recycle) gas, inert carrier gas (e.g., nitrogen, argon, or inert hydrocarbon such as methane, ethane, propane, isopentane) and, if desired, modifiers (e.g., hydrogen).
• a fluidizing gas comprising the monomer or monomers being polymerized, initial feed, make-up feed, cycle (recycle) gas, inert carrier gas (e.g., nitrogen, argon, or inert hydrocarbon such as methane, ethane, propane, isopentane) and, if desired, modifiers (e.g., hydrogen).
• inert carrier gas e.g., nitrogen, argon, or inert hydrocarbon such as methane, ethane, propane, isopentane
• modifiers e.g., hydrogen
• the polymerization conditions in the gas phase reactor are such that the temperature can range from sub-atomos- pheric to super- atmospheric, but is typically from about 0 to 120°C, preferably about 40 to 100°C, and most preferably about 40 to 80°C.
• Partial pressure will vary depending upon the particular monomer or monomers employed and the temperature of the polymerization, and it can range from about 1 to 300 psi (6.89 to 2,0067 kiloPascals), preferably 1 to 100 psi (6.89 to 689 kiloPascals). Condensation temperatures of the monomers such as butadiene, isoprene, styrene are well known. In general, it is preferred to operate at a partial pressure slightly above to slightly below (that is, for example, + 10°C for low boiling monomers) the dew point of the monomer.
• Olefin polymers that may be produced according to the invention include, but are not limited to, ethylene homopolymers, homopolymers of linear or branched higher alpha-olefins containing 3 to about 20 carbon atoms, and interpolymers of ethylene and such higher alpha-olefins, with densities ranging from about 0.84 to about 0.96.
• Homopolymers and copolymers of propylene can also be produced by the inventive catalyst and process.
• Suitable higher alpha-olefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4- methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-l-hexene.
• the olefin polymers according to the invention can also be based on or contain conjugated or non-conjugated dienes, such as linear, branched, or cyclic hydrocarbon dienes having from about 4 to about 20, preferably 4 to 12, carbon atoms.
• Preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2- norbornene, 1,7-octadiene, 7-methyl-l,6-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene and the like.
• Aromatic compounds having vinyl unsaturation such as styrene and substituted styrenes, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyl trialkyl silanes and the like may be polymerized according to the invention as well.
• Specific olefin polymers that may be made according to the invention include, for example, polyethylene, polypropylene, ethylene/propylene rubbers (EPR's), ethylene/pro- pylene/diene terpolymers (EPDM's), polybutadiene, polyisoprene, and the like.
• the present invention provides a cost-effective catalyst and method for making compositionally homogeneous, high-molecular weight ethylene-alpha olefin copolymers with very high levels of alpha olefin.
• One advantage is that the catalyst has a very high comonomer response, so the ratio of alpha olefin to ethylene present in the reaction medium can be very low, which increases the partial pressure of ethylene possible in the reactor. This improves catalyst activity. It also lessens the level of residual comonomer which must be purged or otherwise recovered from the polymer after it exits the reactor.
• the catalyst is also suitable for incorporation of non-conjugated dienes to form completely amorphous rubbery or elastomeric compositions.
• the catalyst's very high comonomer response also makes it a good candidate for the incorporation of long-chain branching into the polymer architecture through the insertion of vinyl-ended polymer chains formed via ⁇ -hydride elimination.
• the ethylene copolymers produced by the present invention have polydespersity values (PDI) ranging from 2 to 4.6, preferably 2.6 to 4.2.
• Polymers produced using the catalyst and/or process of the invention have utility in wire and cable applications, as well as in other articles such as molded and extruded articles such as hose, belting, roofing materials, tire components (tread, sidewall, inner-liner, carcass, belt).
• Polyolefins produced using the catalyst and/or process of the invention can be cross-linked, vulcanized or cured using techniques known to those skilled in the art.
• a cable comprising one or more electrical conductors, each, or a core of electrical conductors, surrounded by an insulating composition comprising a polymer produced in a gas phase polymerization process using the catalyst of the invention.
• the polymer is polyethylene; a copolymer of ethylene, one or more alpha-olfins having 3 to 12 carbon atoms, and, optionally, a diene(s).
• additives which can be introduced into the cable and/or polymer formulation, are exemplified by antioxidants, coupling agents, ultraviolet absorbers or stabilizers, antistatic agents, pigments, dyes, nucleating agents, reinforcing fillers or polymer additives, slip agents, plasticizers, processing aids, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extenders oils, metal deactivators, voltage stabilizers, flame retardant fillers and additives, crosslinking agents, boosters, and catalysts, and smoke suppressants.
• Fillers and additives can be added in amounts ranging from less than about 0.1 to more than about 200 parts by weight for each 100 parts by weight of the base resin, for example, polyethylene.
• antioxidants are: hindered phenols such as tetrakis[methylene(3,5-di-tert- butyl-4-hydroxyhydrocinnamate)]- methane, bis[(beta-(3,5 di-tert-butyl-4-hydroxybenzyl)-methylcarb- oxyethyl)] sulphide, 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thio- bis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(4-methyl-6-tert-butyl- phenol), and thiodiethylene bis(3,5 ditert-butyl-4-hydroxy)hydro- cinnamate; phosphites and phosphonites such as tris(2,4-di-tert-butyl- phenyl) phosphite and di-tert-butylphenyl-phosphonite; thio compounds such as dilau
• Antioxidants can be used in amounts of about 0.1 to about 5 parts by weight per 100 parts by weight of polyethylene.
• the resin can be crosslinked by adding a crosslinking agent to the composition or by making the resin hydrolyzable, which is accomplished by adding hydrolyzable groups such as -Si(OR)3 wherein R is a hydrocarbyl radical to the resin structure through copolymerization or grafting.
• Suitable crosslinking agents are organic peroxides such as di- cumyl peroxide; 2,5-dimethyl- 2,5-di(t-butylperoxy) hexane; t-butyl cumyl peroxide; and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3. Dicumyl peroxide is preferred.
• Hydrolyzable groups can be added, for example, by copoly- merizing ethylene with an ethylenically unsaturated compound having one or more -Si(OR)3 groups such as vinyltrimethoxy- silane, vinyltri- ethoxysilane, and gamma-methacryloxypropyltrimethoxysilane or grafting these silane compounds to the resin in the presence of the aforementioned organic peroxides.
• -Si(OR)3 groups such as vinyltrimethoxy- silane, vinyltri- ethoxysilane, and gamma-methacryloxypropyltrimethoxysilane
• the hydrolyzable resins are then crosslinked by moisture in the presence of a silanol condensation catalyst such as dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, stannous acetate, lead naphthenate, and zinc caprylate.
• a silanol condensation catalyst such as dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, stannous acetate, lead naphthenate, and zinc caprylate.
• Dibutyltin dilaurate is preferred.
• hydrolyzable copolymers and hydrolyzable grafted copolymers are ethylene/ vinyltrimethoxy silane copolymer, ethy- lene/gamma- methacryloxypropyltrimethoxy silane copolymer, vinyltrimethoxy silane grafted ethylene/ethyl acrylate copolymer, vinyltrimethoxy silane grafted linear low density ethylene/1-butene copolymer, and vinyltrimethoxy silane grafted low density polyethylene.
• the cable and/or polymer formulation can contain a polyethylene glycol (PEG) as taught in EP 0 735 545.
• PEG polyethylene glycol
• the cable of the invention can be prepared in various types of extruders, e.g., single or twin screw types. Compounding can be effected in the extruder or prior to extrusion in a conventional mixer such as Brabender TM mixer or BanburyTM mixer. A description of a conventional extruder can be found in U.S. Patent No. 4,857,600.
• a typical extruder has a hopper at its upstream end and a die at its downstream end. The hopper feeds into a barrel, which contains a screw. At the downstream end, between the end of the screw and the die, is a screen pack and a breaker plate.
• the screw portion of the extruder is considered to be divided up into three sections, the feed section, the compression section, and the metering section, and two zones, the back heat zone and the front heat zone, the sections and zones running from upstream to downstream.
• the length to diameter ratio of each barrel is in the range of about 15:1 to about 30:1.
• the die of the crosshead feeds directly into a heating zone, and this zone can be maintained at a temperature in the range of about 130 C to about 260°C, and preferably in the range of about 170°C to about 220°C.
• ICP inductively coupled plasma method for elemental analysis
• Irganox Irganox® 1076 a product of Ciba-Geigy
• Kemamine Kemamine® AS-990 a product of Witco Corp.
• MAO methylalumoxane (Ethyl/Albemarle, solution in toluene, 1.8 or 3.6 moles Al L)
• Pentamethylcyclopentadienyltitanium trichloride and indenyl titanium trichloride were obtained from Strem Chemicals Inc., and used without further purification.
• a toluene solution of (C5Me5)Ti(O2CPh)3 containing 0.83 eq. benzoic acid (0.025 g in 5 mL, 7.7 mmol Ti L) was prepared under nitrogen.
• the reactor had a removable two-baffle insert and a variable speed propeller- shaped impeller, which was run at 800 rpm.
• the reactor was heated to 40°C and vented to release most of the nitrogen, then resealed.
• the reactor was heated to 70°C and pressurized with ethylene (100-120 psig, ca. 0.7-0.8 MPa).
• ethylene 100-120 psig, ca. 0.7-0.8 MPa.
• a sample of the (C5Me5)Ti(O2CPh) 3 /MeOH mixture (0.33 mL, 1.92 x 10 ⁇ 6 mol Ti) was injected into the reactor and the temperature allowed to rise to 85°C. The temperature was held between 80 and 85°C for the remainder of the test, during which time ethylene flowed to make up monomer lost to polymerization.
• the reaction was quenched with methanol and the reactor vented.
• DSC of the copolymer showed melting points at 35.2, 65.9, and 115.9°C, with the last peak being about 3% as tall as the dominant peak (65.9°C) and a total crystallinity of 17.3%; the peak recrystallization temperature was found to be 52.9°C.
• a toluene solution of (C5Me5)Ti(O2CPh)3 containing 1.4 eq. benzoic acid (0.025 g in 5 mL, 7.0 mmol Ti/L) was prepared under nitrogen.
• the reactor was heated to 40°C and vented to release most of the nitrogen, then resealed.
• the reactor was heated to 70°C and pressurized with ethylene (100-120 psig, ca. 0.7- 0.8 MPa).
• DSC of the copolymer showed melting points at 35.8, 70.1, and 115.9°C, with the last peak being less than 10% as tall as the dominant peak (70.1°C) and a total crystallinity of 15.1%; the peak recrystallization temperature was found to be 41.6°C.
• a toluene solution of (C5Me5)Ti(O2CPh)3 containing 1.4 eq. benzoic acid (0.025 g in 5 mL, 7.0 mmol Ti/L) was prepared under nitrogen.
• the reactor was heated to 40°C and vented to release most of the nitrogen, then resealed.
• the reactor was heated to 70°C and pressurized with ethylene (100-120 psig, ca. 0.7-0.8 MPa).
• DSC of the copolymer showed melting points at 34.6, 67.5, and 116.7°C, with the last peak being about 3% as tall as the dominant peak (67.5°C) and a total crystallinity of 14.8%; the peak recrystallization temperature was found to be 45.5°C.
• the filtrate was reduced to an orange oil in vacuo which then crystallized, from which 2.86 g was obtained (85%).
• the nmr peaks for the titanium complex are as follows ( ⁇ , solvent CD 2 Cl2): ( 1 H nmr) 1.94 (15H, s), 1.09 (27H, s); (13C ⁇ lH ⁇ nmr) 194.4, 130.3, 38.7, 26.5, 11.2.
• a toluene solution of (C5Me5)Ti(O2CCMe3)3 (0.025 g in 5 mL, 10.3 mmol Ti/L) was prepared under nitrogen.
• the reactor had a removable two-baffle insert and a variable speed propeller-shaped impeller, which was run at 800 rpm. The reactor was heated to 40°C and vented to release most of the nitrogen, then resealed.
• the reactor was heated to 75°C and pressurized with ethylene (100 psig, 0.7 MPa).
• a sample of the (C5Me 5 )Ti(O 2 CCMe3)3/MeOH mixture (0.33 mL, 2.5 x 10"6 mol Ti) was injected into the reactor and the temperature allowed to rise to 80°C, where it stayed for the remainder of the test, during which time ethylene flowed to make up monomer lost to polymerization.
• the reaction was quenched with methanol and the reactor vented.
• a small oven dried glass vial was charged with magnetic stirbar and 0.025 g (C5Me5)Ti(O2CPh)3 containing 0.83 eq. benzoic acid. This vial was sealed and brought out of the glovebox. Toluene (5 mL) was added to the vial to form a solution with a concentration of 7.7 mmol/L. In another oven dried glass vial sealed under nitrogen, 0.05 mL methanol (MeOH) was mixed with 10ml toluene resulting in a 0.123 mol/L concentration MeOH/toluene solution.
• MeOH MeOH
• a third small oven dried glass vial 2.06 g of DTBP and 20mL toluene were added under nitrogen to form a DTBP/toluene solution with concentration of 0.5 mol/L.
• a small oven dried glass vial with a stir bar was sealed under nitrogen.
• 0.5 mL of (C5Me5)Ti(O2CPh)3/toluene solution 0.00385 mmol Ti
• a 100 mL glass oven dried bottle with a stir bar was sealed with a septum and purged with nitrogen.
• the activated catalyst mixture made above was transferred to the reactor by nitrogen overpressure.
• the reactor was sealed and the temperature was brought to 60°C.
• the polymerization was carried out for 1 hour after the introduction of the monomer gases.
• Two charges of ENB (0.5 mL) were injected to the reactor under pressure at polymerization times of 10 min and 30 min. Therefore 3 mL total ENB was charged to the reactor.
• a small oven dried glass vial was charged with magnetic stirbar and 0.025 g (C5Me5)Ti(O2CPh)3 containing 0.83 eq. benzoic acid. This vial was sealed and brought out of the glovebox. Toluene (5 mL) was added to the vial to form a solution with a concentration of 7.7 mmol L. In another oven dried glass vial sealed under nitrogen, 0.05 mL methanol was mixed with 10 mL toluene resulting in a 0.123 mol/L concentration MeOH/toluene solution.
• DTBP 2,6-di-t- butylphenol
• a 100 mL glass oven dried bottle with a stir bar was sealed with a septum and purged with nitrogen.
• the following components were added under nitrogen: 50ml of hexane; 0.30 mL MAO (3.36 mol/L in toluene); 1.0 mL of DTBP/toluene solution; 0.66 mL of (C5Me5)Ti(O2CPh)3/MeOH mixture made above and 2 mL of ENB.
• ENB 0.5 mL
• Polymerization was terminated by injecting 2 mL of ethanol killing solution (0.5 g BHT, 1.0 g Kemamine, 0.5 g Irganox in 125 mL of ethanol).
• the polymer was scooped out, blended in methanol and dried in a vacuum oven at 40°C overnight.
• the collected polymer weighed 59.7 g, for catalyst activity of 15.5 kg(EPDM)/mmol Ti/hr.
• a small oven-dried glass vial was charged with magnetic stir bar and 0.024 g (C5Me5)Ti(O2CCMe3)3. This vial was sealed and brought out of the glove box. Toluene (5 mL) was added to the vial to form a solution with a concentration of 0.01 mol/L. In another oven-dried glass vial sealed under nitrogen, 0.05 L methanol was mixed with 10 mL toluene resulting in a 0.123 mol/L concentration MeOH/toluene solution.
• DTBP 2,6-di-t-butylphenol
• a 100 mL glass oven-dried bottle with a stir bar was sealed with a septum and purged with nitrogen.
• the following components were added under nitrogen: 50 mL of hexane; 0.30 L MAO (3.36 mol/L in toluene); 1.0 mL of DTBP/toluene solution; 0.66 mL of (C5Me5)Ti(O2CCMe3)3/MeOH mixture made above and 2 mL of ENB.
• ENB 0.5 mL
• Polymerization was terminated by injecting 2 mL of ethanol killing solution (0.5 g BHT, l.Og Kemamine, 0.5 g Irganox in 125 mL of ethanol).
• the polymer was scooped out, blended in methanol and dried in a vacuum oven at 40°C overnight.
• the collected polymer weighed 34.1 g, for catalyst activity of 6.82 kg(EPDM)/mmol Ti/hr.
• the polymer contained 51.2 wt % propylene and 4.5 wt % ENB.
• Example 10 An experiment similar to Example 10 was conducted except that 0.57 mL MMAO (1.74 mol(Al)/L in heptane) was used in place of MAO.
• the collected polymer weighed 26.2 g, for catalyst activity of 5.24 kg(EPDM)/mmol Ti/hr. The polymer did not flow because of high molecular weight.
• Example 6 A similar experiment as Example 6 was carried out except that (C5Me5)TiCl3 precursor instead of (C5Me5)Ti(O2CPh)3 was used. After polymerization only 0.8 g of polymer was collected. This experiment shows that (C5Me5)TiCl3 is not active with MMAO cocatalyst for EPDM polymerization at a high aluminum: titanium ratio.

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