Classifications

• • 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
  • 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
  • C08F210/16—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
  • 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
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

• M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidation state
• X is a monovalent anionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, ⁇ -bound ligand groups;
• the use of the indenyl and indecenyl catalysts as disclosed herein leads to the production of polymers having a high degree of vinyl termination.
• the resultant high level of vinyls/1000 carbons makes the polymers of the invention especially useful in applications wherein the polymers are subsequently functionalized.
• the resultant high level of vinyls/1000 carbons further makes the polymers able to achieve higher levels of long chain branching when appropriate polymerization conditions are employed.
• FIGURE 3 is a DSC endogram of the ethylene/octene interpolymer of Example 1a prepared using Catalyst One.
• FIGURE 7a are ATREF curves of two ethylene/octene interpolymers of the invention, prepared with Catalyst One (Example 1 b) and Catalyst Two (Example 2a), respectively, and of the ethylene/octene interpolymer of Comparative Example C-3a prepared with Catalyst Three.
• FIGURE 9b is a plot of the difference between the UST of various blends of ethylene/octene interpolymers prepared using Catalyst Three with the UST of interpolymers of the invention set forth in FIGURE 9a.
• DSC Differential scanning calorimetry
• Z is a divalent moiety bound to both A' and M via ⁇ -bonds, said Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen or phosphorus, wherein an aliphatic or alicyclic hydrocarbyl group is covalently bonded to the nitrogen or phosphorus via a primary or secondary carbon;
• M is preferably zirconium or titanium, and is more preferably titanium.
• R 3 , R 4 , R 5 , and R 6 independently are hydrogen or C, ⁇ alkyl
• Y is -NR ** -, -PR ** -;
• X' is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said X' having up to 40 carbon atoms and forming a ⁇ -complex with M.
• highly useful metal complexes for use in catalyst compositions for the copolymerization of ethylene, an ⁇ -olefin and a diene, especially ethylene, propylene and a nonconjugated diene, such as ethylidenenorbornene or 1 ,4-hexadiene, or the conjugated diene piperylene comprise the foregoing complexes (II) or (III) wherein R' is hydrogen, and R" is C-
• Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or a neutral Lewis base such as an ether or nitrile.
• a further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula: R 3 Si(X') q + A- wherein:
• silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof.
• Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443.
• the use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in USP 5,625,087.
• Suitable anions of the formula A d" include sterically shielded diboron anions corresponding to the formula:
• such L groups contain from 1 to 3 C 1 ⁇ M0 n-alkyl groups with a total of from 12 to 100 carbons, more preferably 2 C 1(M0 alkyl groups and from 21 to 90 total carbons.
• the presence of such oleophilic groups is believed to render the activator more soluble in aliphatic liquids thereby improving the effectiveness in catalyst activation.
• the catalyst activator may comprise a mixture of oleophilic groups of differing lengths.
• one suitable activator is the protonated ammonium salt derived from the commercially available long chain amine comprising a mixture of two C 14 , C 16 or C 18 alkyl groups and one methyl group.
• inventive polymers are further characterized as having a melt flow ratio (IIQ/'2) which may be varied independently of the polydispersity index, that is, the molecular weight distribution M w /M n .
• IIQ/'2 melt flow ratio
• M w /M n molecular weight distribution
• the polymers of the invention will have an l 10 /l 2 which is at least 10, preferably at least 15, with l 10 /l 2 values exceeding 20 being possible.
• the catalyst system may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent in which polymerization will be carried out by solution polymerization procedures.
• the catalyst system may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material.
• a catalyst support material such as silica gel, alumina or other suitable inorganic support material.
• silica silica as the support material.
• the heterogeneous form of the catalyst system is employed in a slurry polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble.
• solution polymerization conditions utilize a solvent for the respective components of the reaction, particularly the EP or EPDM polymer.
• Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures.
• Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar ETM, available from Exxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.
• the mixture was filtered using a funnel equipped with a glass frit having a pore size of 10 to 15 ⁇ m to give a clear solution (the molecular sieves were rinsed with additional dry methylcyclohexane).
• the concentration was measured by gravimetric analysis yielding a value of 16.7 weight percent.
• the resulting solution was removed from the reactor, and a hindered phenol anti-oxidant (irganoxTM 1010 from Ciba Geigy Corp.) was added to the resulting solution.
• a hindered phenol anti-oxidant irganoxTM 1010 from Ciba Geigy Corp.
• Polymers formed were dried in a vacuum oven set at 120°C for about 20 hours.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)

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• 1998
  • 1998-04-30 AR ARP980102043A patent/AR012645A1/es not_active Application Discontinuation
  • 1998-05-01 TW TW087106781A patent/TW375624B/zh active
  • 1998-05-01 AU AU71739/98A patent/AU742617B2/en not_active Ceased
  • 1998-05-01 KR KR1019997010050A patent/KR20010020425A/ko not_active Application Discontinuation
  • 1998-05-01 TR TR1999/02884T patent/TR199902884T2/xx unknown
  • 1998-05-01 PL PL98336594A patent/PL336594A1/xx not_active Application Discontinuation
  • 1998-05-01 JP JP54743598A patent/JP2001522399A/ja active Pending
  • 1998-05-01 CN CN98805626A patent/CN1112383C/zh not_active Expired - Fee Related
  • 1998-05-01 RU RU99125328/04A patent/RU2200169C2/ru not_active IP Right Cessation
  • 1998-05-01 EP EP98918908A patent/EP0977787A1/en not_active Withdrawn
  • 1998-05-01 CA CA002288893A patent/CA2288893A1/en not_active Abandoned
  • 1998-05-01 BR BR9808704-5A patent/BR9808704A/pt not_active Application Discontinuation
  • 1998-05-01 WO PCT/US1998/008859 patent/WO1998049211A1/en not_active Application Discontinuation
• 1999
  • 1999-10-29 NO NO995294A patent/NO995294L/no not_active Application Discontinuation

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